Synthetic polymers with quaternary nitrogen atomsÃ¢â‚¬â€Synthesis and ...

Progress in Polymer Science 35 (2010) 511–577 

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Progress in Polymer Science 

journal homepage: www.elsevier.com/locate/ppolysci 

Synthetic polymers with quaternary nitrogen atoms—Synthesis and 

structure of the most used type of cationic polyelectrolytes 

Werner Jaeger ∗ , Joerg Bohrisch ∗,1 , Andre Laschewsky ∗,2 

Fraunhofer Institute of Applied Polymer Research, Geiselbergstr. 69, D-14476 Potsdam, Germany 

article info 

Article history: 

Received 15 June 2009 

Received in revised form 14 January 2010 

Accepted 21 January 2010 

Available online 28 January 2010 

Keywords: 

Polyelectrolytes 

Ammonium 

Quaternary 

Cationic 

Contents 

abstract 

This paper reviews the advances during the last decade in the synthesis and chemical structures 

of the important class of charged polymers that bear quaternary ammonium moieties. 

The synthetic pathways to these polycations are discussed, comprising chain growth and 

step growth polymerization of suitable cationic monomers as well as chemical transformations 

of uncharged reactive precursor polymers. Attention is paid to the new methods of 

controlled polymerization, in particular of controlled radical polymerization. The focus of 

the review is on linear and branched structures including linear macromolecules with flexible 

chains, conjugated polymers, block copolymers, statistically branched and dendritic 

polymers, whereas crosslinked materials are out of the scope. In addition to the structural 

and synthetic aspects, application properties of the new polymers are noted. 

© 2009 Elsevier Ltd. All rights reserved. 

1. Introduction ........................................................................................................................ 512 

2. Principles and processes of the synthesis ......................................................................................... 513 

3. Structure of synthetic polymers with quaternary nitrogen atom ................................................................. 516 

3.1. Linear macromolecules with flexible chains ............................................................................... 516 

3.1.1. Polymeric diallylammonium compounds ........................................................................ 516 

3.1.2. Polymers containing aromatic or heterocyclic structures ....................................................... 520 

3.1.3. Acrylic and methacrylic polymers ............................................................................... 523 

3.2. Block copolymers........................................................................................................... 529 

3.2.1. Synthesis and structure .......................................................................................... 535 

3.2.2. Properties and application ....................................................................................... 537 

3.3. Ionenes ..................................................................................................................... 537 



3.4. Cationic conjugated polyelectrolytes ...................................................................................... 543 



∗ Corresponding authors. Tel.: +49 332 032 2951. 

E-mail addresses: wjaeger@gmx.net (W. Jaeger), joerg.bohrisch@iap.fraunhofer.de (J. Bohrisch), andre.laschewsky@iap.fraunhofer.de (A. Laschewsky). 

1 Tel.: +49 331 568 1331; fax: +49 331 568 2520. 

2 Tel.: +49 331 568 1327; fax: +49 331 568 3000. 

0079-6700/$ – see front matter © 2009 Elsevier Ltd. All rights reserved. 

doi:10.1016/j.progpolymsci.2010.01.002

512 W. Jaeger et al. / Progress in Polymer Science 35 (2010) 511–577 

3.5. Nonlinear polymers ........................................................................................................ 548 

3.5.1. Statistically branched and crosslinked polymers ................................................................ 548 

3.5.2. Dendritic polymers ............................................................................................... 554 

3.6. Polymeric surfactants ...................................................................................................... 559 



4. Conclusions ........................................................................................................................ 563 

References ......................................................................................................................... 564 

Nomenclature 

4(2)-VP 4(2)-vinylpyridine 

�-CD �-cyclodextrin 

AAM acrylamide 

AIBN 2,2 ′ -azobis(2-methylpropionitrile) 

AmphBC amphiphilic block copolymers 

AMPS 2-acrylamido-2-methyl-1-propane sulfonic 

acid 

AN acrylonitrile 

ATAC acryloyloxyethyltrimethylammonium 

chloride 

ATRP atom transfer radical polymerization 

BA butyl acrylate 

BIEE 1,2-bis-(2-iodoethoxy)ethane 

CP conjugated polyelectrolytes 

CRP controlled free radical polymerization 

CT charge transfer 

DADMAC diallyldimethyl ammonium chloride 

DHBC double hydrophilic block copolymers 

DMA dodecyl methacrylate 

DMSO dimethyl sulfoxide 

EGDMA ethyleneglycol dimethacrylate 

EHA 2-ethylhexyl acrylate 

EO ethylene oxide 

FRET fluorescence resonance energy transfer 

GMA glycidyl methacrylate 

HEA 2-hydroxyethyl acrylate 

HEMA 2-hydroxyethyl methacrylate 

HPMA hydroxypropyl methacrylate 

kp/kt ratio of the rate constants of propagation 

and termination 

LCST lower critical solution temperature 

MA methyl acrylate 

MADBAC N-methacryloyl-oxyethyl-N,Ndimethyl-N-benzylammonium 

chloride 

MADIX macromolecular design via interchange of 

xanthates 

MAPTAC 3-(methacrylamido)propyltrimethylammonium 

chloride 

MATAC methacryloyloxyethyltrimethylammonium 

chloride 

MBA N,N ′ -methylenebisacrylamide 

MDEA N-methacryloyl-N,N-diethylamin 

MDMA N-methacryloyloxyethyl-N,Ndimethylamin 

MM N-(methacryloyloxyethyl)morpholine 

MMA methyl methacrylate 

NIPAM N-isopropyl acrylamide 

NLO nonlinear optics 

NMVA N-methyl-N-vinylacetamide 

NVP N-vinylpyrrolidone 

PAA poly(acrylic acid) 

PAMAM poly(amideamine) 

PEC polyelectrolyte complex 

PEG poly(ethylene glycol) 

PPE poly(p-phenylene ethynylene) 

PPI poly(propylene imine) 

PPP poly(p-phenylene) 

PPV poly(p-phenylene-vinylene) 

RAFT reversible addition fragmentation chain 

transfer 

ST styrene 

t-BMA tert-butyl methacrylate 

TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl 

UCST upper critical solution temperature 

VBC vinylbenzyl chloride 

VBTMC vinylbenzyltrimethylammonium chloride 

1. Introduction 

Polymeric quaternary ammonium compounds represent 

a class of polyelectrolytes that derive unique 

properties mainly from the density and distribution 

of positive charges along a macromolecular backbone. 

The resulting behavior is not merely a superposition of 

macromolecular and electrolytic properties. Long-ranged 

Coulomb interactions are additional influences to be considered 

in the chain conformation of these polyelectrolytes 

and their peculiarities in aqueous solution. Furthermore, 

the typical properties of the quaternary polymers do not 

depend exclusively on the electrostatic forces. The flexibility 

of the polymer chain as well as the formation 

of H-bonds, hydrophobic interactions or charge transfer 

interactions also play a major role in questions of scientific 

interest and practical importance. 

Like other polyelectrolytes the quaternary ammonium 

polymers find manifold application in industrial processes 

and daily life. Therefore, they have been the subject of 

extensive investigations for several decades and still continue 

to be an active area of research in diverse fields 

such as chemistry, physics, biology, environmental pro-

tection, medicine, materials science, and nanotechnology. 

Most of the great number of technical applications and 

scientific developments are based on attractive Coulomb 

forces between the charged macromolecules and oppositely 

charged macro-ions, surfactants, colloid particles, or 

solid surfaces resulting in different structures: solids, membranes, 

different particulate structures, modified surfaces, 

coated particles, etc. However, up to now the fundamentals 

of many of these processes are not well understood and 

many open questions persist. Together with a widespread 

interest to optimize known applications of the cationic 

polyelectrolytes and to open new applications, this leads 

to a continuously growing number of investigations for a 

better understanding of their behavior and properties often 

based on new tailor-made polymers with well-defined 

molecular architecture. 

In comparison to this scientific challenge and the enormous 

potential in commercial application the number of 

reviews dealing with cationic polyelectrolytes is rather 

low. They are, e.g., mentioned in hand- and textbooks [1,2] 

as well as in the summary of a research center on polyelectrolytes 

of the German Science Foundation DFG [3] and 

in the proceedings of several symposia on polyelectrolytes 

[4–9] mainly focused on the physicochemical and physical 

properties of these polymers. Synthesis and structure are 

listed with one exception [10] only in elder papers [11–15] 

or briefly in special reviews [16,17]. Some articles review 

selected groups of cationic polyelectrolytes like ionenes 

[18,19] or rigid-rod structures [20]. 

This article will summarize the developments and 

progress in synthesis and structure of polymeric permanently 

quaternary ammonium compounds made during 

the last decade. Besides linear polymers with flexible or 

rod-like chains, also polymeric surfactants, block and graft 

copolymers and ionenes as well as conjugated and nonlinear 

structures are included. Not mentioned are highly 

crosslinked materials like ion exchangers and hydrogels, 

which could be the subject of individual reviews because 

of the great number of publications in this field. Furthermore, 

some special species of cationic polymers such as 

certain “polycationic” dyes covering surfaces of electrodes 

after electropolymerization are not discussed due to their 

undefined structures. 

2. Principles and processes of the synthesis 

Cationic charges in organic compounds are in practice 

provided by a very limited number of functional groups, 

due to reasons of accessibility and/or stability. The most 

used groups are shown in Scheme 1. The majority of the 

reported syntheses and applications are covered by quaternary 

nitrogen containing structures. Reasons are the easy 

synthetic access, good hydrophilicity for aqueous applications 

and an adequate chemical and thermal stability of 

most of these structures. Hence this paper focuses on structures 

with functional groups as displayed in the left and 

middle column of Scheme 1. 

A great number of macromolecular chemical structures 

can be transformed into a cationic polyelectrolyte structure 

by covalently attaching a sufficient number of quaternary 

ammonium groups to the polymer backbone. The number 

W. Jaeger et al. / Progress in Polymer Science 35 (2010) 511–577 513 

of different cationic substituents is comparatively small, 

but the huge variability of the polymer backbone leads to 

cationic polyelectrolytes with a wide variety of structures 

and properties. 

Cationic polyelectrolytes with quaternary ammonium 

groups are accessible by two different synthetic routes: 

- the chain or step polymerization of suitable monomers 

(Scheme 2), or 

- the cationic functionalization of reactive precursor polymers 

(Scheme 3). 

The first method leads to polymers with 100% functionality, 

but the molecular characterization of the polyelectrolytes 

is often difficult due to the sensitivity of their conformation 

in aqueous media to the ionic strength and due 

to interactions with other matter, e.g., chromatographic 

columns [1,2]. The second route has the advantage of a 

mostly simple polymerization of the precursor monomers 

resulting in reactive polymers with adjustable molecular 

parameters whose characterization usually is easy to 

conduct. Provided high conversions during the functionalization 

reaction, well-defined cationic polyelectrolytes are 

available, but this premise is not valid in any case. 

Most of the known cationic quaternary polyelectrolytes 

are synthesized by free radical polymerization in water. 

The polymerization in aqueous media has the advantage 

of a very low chain transfer to the solvent and a protection 

of the propagating polymer radical by a strongly 

bound hydration shell, thus hindering the termination 

reaction [21]. Furthermore, the formation of hydrogen 

bonds between monomer and water may increase the 

monomer reactivity [22], while the electrostatic repulsion 

between the charged growing macroradicals becomes 

more important in aqueous media [23]. Altogether, the 

result is a remarkable increase of the kp/kt ratio and thus 

of the molar mass in water compared to other solvents 

[24]. However, solution polymerization is limited to low 

monomer conversion because of the high viscosity of the 

final polymer solution, if a high degree of conversion is 

desired. In contrast a broad variation of the initial monomer 

feed, as, e.g., used in the synthesis of model polymers 

with different molecular parameters, requires the termination 

of the reaction at comparatively low conversion [25]. 

Highly concentrated monomer solutions can be radiationinitiated 

polymerized on a continuous belt resulting in a 

final product of high solid content containing much precipitated 

polymer. 

Kinetic investigations must consider several possibilities 

of side reactions like those between the initiator 

and the counterion of the monomer, polymerization of 

monomer associates and an influence of the ionic strength 

on the rate of polymerization [26,27]. 

Today’s commercial cationic polyelectrolytes are 

mainly synthesized by polymerization in inverse emulsion. 

This process has several significant advantages: 

- High monomer concentration in the aqueous droplets 

distributed in an organic phase leading to high molecular 

weight of the polymers in the range of several millions 

g/mol.


Scheme 1. Typical examples for permanently cationic functional groups in organic compounds 

- Good heat transfer in the reactor and low viscosity of the 

final dispersion resulting in a high polymer content in the 

final product. 

- Easy handling of the inverse latexes. 

Another process of commercial importance is the 

inverse suspension polymerization leading to polymers 

as a powder. The inverse microemulsion polymerization 

results in very stable latexes with comparatively small 

particle size. As the molecular weight of the polymers 

is very high this technique is a promising method for 

the preparation of both dispersions and polymers with 

interesting properties, although the ratio of surfactant to 

monomer is rather high. With selected surfactants the limiting 

case of one single macromolecule per particle can be 

reached. 

In the last years controlled free radical polymerization 

(CRP) as a key method for the synthesis of well-defined 

molecular architectures with predictable and narrowly 

distributed molecular weight [28,29] has been extended 

to aqueous systems, too [24,30,31]. Atom transfer radical 

polymerization (ATRP) and in particular the reversible 

addition fragmentation transfer (RAFT) have been successfully 

extended to the synthesis of cationic homo- and block 

copolymers as tailor-made polyelectrolytes with adjusted 

structure and molecular parameters [32–42]. The narrow 

molecular weight distribution of the polymers prepared 

by CRP, improve the precision of any physicochemical or 

physical measurement thus supporting their application in 

structure-property investigations. 

Chain polymerization of cationic vinyl monomers 

mostly results in polyelectrolytes bearing the cationic 

charge not directly on the backbone, but in the side chain 

(pendant type) (I in Scheme 2). However, the cyclopolymers 

from diallylammonium monomers (Section 3.1.1) are 

an exception to the rule. In contrast, synthesis of cationic 

polymers by step polymerization often leads to polymers 

carrying the cationic charge as a part of the polymer 

backbone (integral type) (III and IV in Scheme 2). Typical 

example is the synthesis of ionenes:

- by either the Menshutkin reaction of bis-tertiary amines 

and dihalides or by the reaction of an aminoalkylhalide 

with itself. or 

- by the polyaddition of dimethylamine or bis-tertiary 

amines with epichlorohydrin in the presence of HCl. 

These reactions result in comparatively low molecular 

weight polymers not exceeding 10 5 g/mol. Other examples 

Scheme 3. Typical cationic functionalization of reactive precursor polymers. 


Scheme 2. Typical polymerization routes to polycations. 

of a polyaddition are the synthesis of ionenes by reaction of 

methylviologene and terephthalaldehyde [43], or by radical 

thiol/ene addition reaction [44]. 

Very few cases of ring-opening polymerization leading 

to cationic polymers of the integral type are known (II 

in Scheme 2). An example is the polymerization of N,Ndialkylazetidinium 

salts upon heating resulting in ionenes 

via the Menshutkin reaction of the intermediate N,Ndialkyl-3-halopropylamine 

[45]. 

Many cationic polyelectrolytes were synthesized by 

functionalization of reactive precursor polymers. As the 

local concentration of functional groups of a macromolecule 

is very high even in diluted solution neighboring 

effects may involve complex reaction kinetics during the 

chemical modification, and sometimes the reaction cannot 

be carried out to 100%. The solubility of the polymer may 

change during the polymer-analogous reaction, leading to 

a hindrance of the accessibility of the functional groups. 

Then transport phenomena can become important and the 

kinetics is diffusion controlled. Nevertheless, in most cases 

this strategy leads to well-defined polyelectrolytes. Using 

different reagents, polymers with constant degree of polymerization 

but varied chemical structures are available. 

These polymers are useful models, e.g., for investigations 

of structure-property-performance relationships. 

The most significant reactions to introduce quaternary 

nitrogen in the polymer are well-known ways of quaternization 

(see Scheme 3): 

- The quaternization of a halogen containing polymer with 

a tertiary amine.


Fig. 1. General structure of poly-DADMAC 1. 

- The quaternization of a polymeric tertiary amine with an 

alkyl or aryl halide. 

- The base-catalyzed Mannich reaction of a polymeric 

amide with formaldehyde and dimethylamine followed 

by quaternization. 

- The quaternization of polymers containing OH-groups 

by appropriate agents like 2,3-epoxypropyltrimethylammonium 

chloride. 

The quaternization reaction needs a solvent with a high 

dielectric constant, able to dissolve all components of the 

reaction—initial polymer, alkylating agent and modified 

polymer. These conditions are often difficult to fulfill simultaneously. 

Narrowly distributed polyelectrolytes and polyelectrolyte 

block copolymers were synthesized via CRP 

or anionic living polymerization of reactive precursor 

monomers. Examples are the nitroxide mediated polymerization 

of 4-vinylpyridine [46,47] and vinylbenzyl chloride 

[46,48] followed by different quaternization reactions, 

analogous reactions of RAFT polymerization of the latter 

monomer [49,50], and the anionic living polymerization of 

several tertiary aminostyrenes again followed by quaternization 

[51]. 

3. Structure of synthetic polymers with quaternary 

nitrogen atom 

3.1. Linear macromolecules with flexible chains 

3.1.1. Polymeric diallylammonium compounds 

3.1.1.1. Synthesis and structure. The free radical polymerization 

of diallyldimethylammonium chloride (DADMAC) 

was the first case of cyclopolymerization of a nonconjugated 

diene leading to a linear soluble polymer [52,53]. 

Fig. 2. Chemical structure of poly-DADMAC at low conversion. 

Since that pioneering work of Butler a great number 

of papers dealing with synthesis, properties and mostly 

application of poly-DADMAC 1 (Fig. 1) were published 

and summarized in several reviews [2,54,55]. A simple 

monomer synthesis by twofold alkylation of dimethylamine 

with allyl chloride [54] and a high hydrolytic 

stability of monomer and polymer due to the a priori 

absence of potentially labile carbon–heteroatom bonds 

lead to versatile applications of this polyelectrolyte as processing 

aids and as additives to establish special properties 

in polymer products. Thus, poly-DADMAC became the most 

often used cationic polyelectrolyte for this kind of investigations. 

The cyclopolymerization of DADMAC and derived 

monomers results in water soluble cationic polyelectrolytes 

(Figs. 1–4). 

Structural units are configurational isomers of pyrrolidinium 

rings (cis–trans ratio 6:1) linked by ethylene groups 

[2,54,56] (Fig. 2). 

At low conversion the polymers contain up to 3% 

of pendant double bonds [2,54,56] resulting either from 

chain propagation without cyclization or transfer to the 

monomer [2,23,57]. At high initial monomer feed and high 

conversion also these less reactive double bonds take part 

at the reaction leading to branched structures. 

The kinetics of the polymerization show several 

deviations from the ideal overall kinetics and also 

from the behavior of other cationic vinyl monomers 

[2,23,25–27,54,57]: 

- Chain propagation via monomer cation associates. 

- Increase of the polymerization rate with increasing ionic 

strength due to the formation of ion pairs between the 

growing polymer radical and a monomer cation thus 

reducing their electrostatic repulsion. 

- Side reactions by initiation with peroxides, e.g., in the 

case of peroxidisulfate a monomer activated initiator 

decomposition and the formation of both initiating and 

terminating chlorine atoms. 

Considering these findings several kinetic models 

are available fitting the experimental data well 

[2,23,26,27,54,57]. Based on these data it is easily possible 

to synthesize narrowly distributed polymers with 

adjusted molecular parameters by either polymerization 

to a calculated conversion [25] or by feeding the monomer 

to the polymerizing system thus keeping the monomer

concentration constant [58]. The attainable molecular 

weight of poly-DADMAC is lower in comparison to the 

values obtained with cationic esters or amides of acrylic or 

methacrylic acid, caused by a greater effective electrostatic 

repulsion due to the nearness of the reactive and charged 

parts of monomer and growing polymer. For an efficient 

application as a flocculant the molecular weight can be 

enhanced by adding a crosslinking agent at the end of the 

polymerization followed by a reactive kneading processing 

[74]. 

A great number of copolymers of DADMAC with 

non-ionogenic and ionogenic comonomers have been syn- 


Fig. 3. Structures of diallylammonium compounds 2–19. 

thesized (Fig. 3). The elder structures are summarized by 

Butler [55]. The most common comonomer is acrylamide 

(AAM) with the objective to vary the charge density of the 

copolyelectrolyte 2 using a cheap component. The published 

data on the kinetics of the copolymerization in both 

aqueous solution and inverse emulsion are discussed by 

Wandrey [54], who first observed the marked difference 

between the r-values of both monomers (r DADMAC ≪ r AAM) 

[75]. The copolymerization of DADMAC and AAM can be 

classified as non-ideal non-azeotropic. The synthesis of 

normally distributed copolymers with various charge densities 

but having similar molar masses needs a semi-batch


procedure with a time-dependent dosage of the much more 

reactive AAM [58]. These results are in contrast to the reactivity 

ratios of the copolymerization of AAM with other 

cationic monomers like the quaternary esters or amides 

of acrylic or methacrylic acid. The differences are much 

lower and the cationic monomer even may react preferentially. 

This can be explained by a less electrostatic repulsion 

between the charged monomer and the charged radical 

chain end due to the location of the charge far from the reactive 

double bond in the case of the acrylic and methacrylic 

compounds [54]. 

Unlike with AAM, the copolymerization of DADMAC 

with N-methyl-N-vinylacetamide (NMVA) proceeds as 

nearly ideal copolymerization in aqueous solution with an 

overall monomer concentration not exceeding 2 mol/l [77]. 

Thus, cationic polyelectrolytes 3 with in a broad range variable 

charge density on adjustable levels of the molecular 

weight are easily available. The same is true for copolymers 

of DADMAC with other small vinylamides, such as 

N-methyl-N-vinylformamide 4 [90]. Copolymers 4–6 were 

synthesized by free radical polymerization in aqueous solution. 

Copolymers 7 were synthesized in methanol in a 

non-ideal non-azeotropic reaction [94]. The water soluble 

products can be easily functionalized via hydrolysis 

followed by acetalization and acylation. The associating 

water soluble terpolymers 9 containing up to 7.5 mol% of 

the hydrophobic component were synthesized by AIBNinitiated 

polymerization in DMSO [95]. A copolymer 8 

displaying both conducting and hydrophobic properties 

was obtained by random copolymerization of DADMAC 

with chlorotrifluoroethylene [618]. 

The cyclopolymerization strategy was used for the 

synthesis of very different cationic polyelectrolytes 

(Figs. 3 and 4). An interesting extension is the polymerization 

of allyl acrylate quaternary ammonium salts [96,97]. 

The monomers N,N-dialkyl-N-2(alkoxycarbonyl)allyl-Nallylammonium 

chloride were prepared by reaction of 

Fig. 4. Structures of diallylammonium compounds 20–24. 

N,N-dialkyl-N-allylamine with the corresponding alkyl 

�-chloromethyl acrylates. The methyl and ethyl ester 

monomers showed high cyclization efficiencies leading 

to 10. The t-butyl ester derivatives showed crosslinking 

tendencies. In any case soluble polymers were obtained 

by copolymerization with DADMAC. During photopolymerization 

the allyl acrylate monomers were much more 

reactive than DADMAC. Polymers 11 and 12 were prepared 

as intermediates on the synthetic pathway to 

mostly amphiphilic polycarbobetaines, which were easily 

obtained after hydrolysis of the ester group [99]. 

The synthesis and properties of 11 (R 1 =CH 3,R 2 =C 2H5, 

n = 1) were extensively discussed in [100,102,114]. Also 

13 and its copolymer with SO 2 [101], 11 (R 1 =R 2 =CH 3, 

n =6) [102] and the 1,6-hexanediamine-based polymers 

14 [103] serve as betaine precursors. The polymerization 

of 1,1-diallyl-4-formylpiperazinium chloride with subsequent 

acid hydrolysis resulted in 15 and 16. The properties 

of the homopolymers and their copolymers with SO 2 were 

discussed extensively [104–106]. 

Diallylguanidinium salts were synthesized in good 

yields by reaction of diallylamine and cyanamide. The 

homopolymerization is limited due to a high degradative 

chain transfer to the monomer, but the copolymerization 

with DADMAC resulted in soluble copolymers [110]. 

The polymerization of N,N-diallylpyrrolidinium bromide 

[107], N,N-diallylisoquinolinium chloride [112], and 

N,N-diallylmorpholinium bromide [108] results in 17–19 

with spiro structures. The latter also was copolymerized 

with SO 2. The polymeric spiro compound 19 and 

its crosslinkable derivative 20, available after Hoffmann 

elimination and methylation of 19, are employed for 

polyelectrolyte multilayer films with inorganic polyions, 

too. Using 20 the hybrid multi-layers were easily 

crosslinkable by exposure to UV-light [111]. These investigations 

were continued using the polycations 21 [112] 

and both the homopolymers 22 bearing via a spacer

4-methylcoumarin and 4-cyanobiphenyl as fluorescent 

and mesogenic side groups, and their copolymers with 

DADMAC [113]. In agreement with results of other substituted 

diallylammonium polymers, e.g., 11 (R 1 =CH 3, 

R 2 =C 2H5, n = 4, 10) [114], high monomer and initiator 

concentrations were needed for successful polymerization, 

while the conversions are much lower compared 

to the standard poly-DADMAC system. Also propargyl 

groups may take part in the cyclopolymerization 

process. Dimethyl allyl propargyl ammonium chloride 

results in water-soluble 24 and corresponding copolymers 

with SO 2. The diallyl propargyl derivative afforded 

crosslinked homo- but water soluble SO 2-copolymers. 

The monomer containing two propargyl groups did not 

undergo cyclopolymerization [115]. The copolymerization 

of tetraallylpiperazinium dibromide and diallylmorpholinium 

bromide results in fully cationic nonhydrolizable 

hydrogels 23 containing residual unsaturation up to 8% 

[559]. 

Several other polymeric diallylammonium compounds 

are listed in the sections on block copolymers and polymeric 

surfactants (see Tables 4, 6 and 8). 

3.1.1.2. Properties and application. Well-designed 

DADMAC-polymers with adjusted molecular parameters 

are used as models for investigations of the influence 

of their molecular data on the interaction with other 

matter, e.g., the formation of coacervates with proteins 

and mixed micelles [59–65], the stability of complexes 

with different polyanions [66], the formation of polyelectrolyte 

multi-layers [67] and the colloidal stability and 

flocculation of dispersions [68–73]. Copolymers of DAD- 

MAC and NMVA respectively N-methyl-N-vinylformamide 

are used as models for investigations of the influence of 

the charge density on adjustable levels of the molecular 

weight on different chemical, physical or physicochemical 

processes. Examples with 3 are the adsorption on and 


flocculation of colloids [68,72,73], the formation and salt 

stability of polyelectrolyte complexes [78], the structure 

formation in polymer modified liquid crystals [77,79], 

the buildup and properties of multilayer films formed 

by sequential adsorption of alternating layers of 3 and 

polyanions [80–85], the formation and biological activity 

of complexes with DNA [86] and the formation and 

properties of freestanding foam films [87–89]. 

The copolymers 4 of DADMAC with N-methyl-Nvinylformamide 

of different composition and thus charge 

density were used in studies of the role of charge on 

growth of polyelectrolyte multi-layers via layer-by-layer 

self assembly with poly(styrenesulfonate) from pure aqueous 

solutions [90] (Scheme 4). 

Scheme 4 displays the principle procedure of the filmforming 

procedure using layer-by-layer technique. Copolymers 

with N-methyl-N-(n-dodecyl)ammonium chloride 5 

were used for investigations of the influence of different 

counterions on their aggregation behavior [91]. The 

copolymers 6 with N-isopropylacrylamide are soluble in 

water at room temperature but form colloidal particles 

at higher temperature and serve as temperature-sensitive 

flocculants [92]. The copolymerization of DADMAC with 

small amounts of vinyl trimethoxysilane and the terpolymerization 

with additional AAM leads to polymers with 

good flocculation properties [93]. The copolymers of DAD- 

MAC with allyl acrylate quaternary ammonium salts were 

efficient flocculants, too [98]. Copolymers of DADMAC 

with chlorotrifluoroethylene 8 were used in solid alkaline 

fuel cells [618]. Copolymer 14 is a powerful corrosion 

inhibitor. The copolymerization of diallylguanidinium salts 

with DADMAC resulted in soluble copolymers with good 

biocide activity [110]. The spiro polymer 17 forms hybrid 

clay-based multi-layers by electrostatic self-assembly with 

a synthetic hectorite [109]. The unsaturated hydrogels 23 

can be used as model gels to examine pure Coulomb effects 

[559]. 

Scheme 4. Principle of the alternating layer-by-layer self-assembly of oppositely charged polyelectrolytes.


3.1.2. Polymers containing aromatic or heterocyclic 

structures 

3.1.2.1. Synthesis and structure. Though polycations containing 

aromatic or heterocyclic structures can be based 

on various skeletons (Figs. 5–7), most examples known 

are derived from polystyrene and poly(vinylpyridine)s. The 

synthesis of the intensely studied poly(vinylbenzyl trialkyl(aryl)ammonium 

chloride)s 25–27 mainly proceeds 

via alkylation of poly(vinylbenzyl chloride) (poly-VBC) 

with different tertiary amines [10,11,48,116], only a 

minor amount was prepared by polymerization of the 

quaternary monomers. An example is the RAFT polymerization 

of vinylbenzyl trimethylammonium chloride in 

solution [37,38], and the surface modification of plasmamodified 

poly(dimethylsiloxane) [117], or the preparing 

of block copolymers, the blocks of which being statistical 

copolymers themselves, for polysoaps [35]. Another 

example is the polymerization of vinylbenzyl dimethyl (3formylaminopropyl) 

ammonium chloride 25h, which after 

hydrolysis yields a polycation bearing simultaneously quaternary 

ammonium and primary amine groups [118]. 

Older kinetic investigations of the alkylation reaction 

of poly-VBC are summarized in [10]. The principles of 

the polymer synthesis [116] and the characterization by 

NMR-spectroscopy are discussed by Vogl et al. [119]. The 

synthesis of the precursor poly-VBC by nitroxide mediated 

CRP leads after functionalization to narrowly distributed 

polymers 25a,b,e–g, 26, 27 [48,120,121]. Also, alternative 

growth procedures for polyelectrolyte multilayers with 

dichroic dyes were achieved by a two-step crosslinking 

alkylation of poly-VBC with hydroxystilbazol. Thus, structure 

28 is an interesting example for reactive polycations 

for further coupling procedures [124]. Copolymers 30 were 

prepared under microwave irradiation of VBC, styrene (ST) 

Fig. 5. Structures of polymers containing aromatic or heterocyclic structures 25–33.


Fig. 6. Structures of polymers containing aromatic or heterocyclic structures 34–45. 

and tri(n-butyl)amine [125] or by conventional copolymerization 

of VBC and ST with subsequent quaternization 

[126]. 

Copolymers of 25a and ST with different charge density 

were synthesized by direct copolymerization of the 

corresponding monomers in ethanol. 

The synthesis of poly(4-vinylpyridinium salt)s (poly- 

4-VP) 31 may proceed by free radical polymerization of 

the corresponding monomers, provided, the monomer 

concentration is above 1 mol/l. Otherwise ionene structures 

are obtained following a complicated mechanism 

[10,11]. Alternatively the polymer synthesis can be carried 

out by alkylation of a polymeric pyridine [10,11]. The 

quaternization is remarkably influenced by the conformation 

of the polymer during the reaction [128]. A variety 

of N-alkyl derivatives for absorption studies is described 

in [129]. The well-known bactericidal activity of poly-4- 

VP can be enhanced by hydrophilic modification through 

copolymerization of 4-VP with hydroxyethyl methacrylate 

or poly(ethylene glycol) methylether methacrylate 

and quaternization with hexylbromide 32 [130]. Using 

nitroxide mediated CRP again a narrowly distributed 

poly-VP precursor is available [46,131] and can be 

quaternized resulting in 31 (R=CH 3). 2-VP [132] and 3- 

VP [133] were polymerized and quaternized similarly. 

The ferrocene attached poly-4-VP 33 was prepared by 

alkylation of poly-4-VP with the reaction product of N,Ndimethylaminomethyl 

ferrocene with 1,2-dibromoethane 

and used as part of an amperometric enzyme electrode 

[134].


Fig. 7. Structures of polymers containing aromatic or heterocyclic structures 46–53. 

The terthiophene-functionalized poly-4-VP 34 was 

obtained by quaternization of the pyridine moiety along 

the poly-4-VP backbone with 5-(6-bromohexyl)-2,2 ′ ,5 ′ ,2 ′′ - 

terthiophene [135]. 

Redox active polymers 35 have been synthesized by 

copolymerization of diaryl-4-(1-trifluoromethylvinyl)aryl 

amines with 4-VP [136]. The stepwise quaternization of 

poly-4-VP first with VBC and second with bromoethane 

resulted in the crosslinkable polycation 36, used for the 

reactive modification of polyelectrolyte multilayer assemblies 

[137]. The copolymer 38 is available by alkylation 

of poly-4-VP with 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8iodooctane 

[139]. 

Copolymers 42 of the very reactive 

4-vinylbenzylcinnamate and 4-vinylbenzyltriethylammonium 

chloride are highly efficient water soluble 

crosslinking systems [144]. Imidization of styreneor 

acrylamide–maleic anhydride copolymers with 3dimethylaminopropylamine 

followed by quaternization 

with methyl iodide resulted in alternating copolymers 43 

whose aqueous solution properties were studied in dependence 

of type and concentration of added salt [145,146]. 

The quaternization of polychloroethylvinylether with 

4,4 ′ -bipyridine followed by reaction with benzyl chloride 

is a comfortable synthetic pathway to polymers containing 

viologen moieties 45a which are used as electron-transfer 

catalysts for the reduction of substituted nitroarenes 

[148]. Functionalization of those polymers with ionic 

liquid moieties yielded materials 45b and 45c with an 

(LCST)-type phase separation in organic media [619]. 

Another example is the viologen-functionalized poly-4- 

VP 46, prepared by reaction of an excess of the viologen N- 

1-(2-bromoethyl)-N-methyl-4,4 ′ -bipyridinium with poly- 

4-VP. Polymers 47 were obtained from anionic synthesis of 

poly[5-(N,N-dialkylamino)isoprene]s by quaternization of 

the tertiary amino group [150]. Ring-opening metathesis 

polymerization (ROMP) of an oxanorbornene educt with a 

Grubbs third generation catalyst yielded material 48 [623]. 

The poly(ferrocenylsilane)s 49 and 50 are available via 

different convenient multi-step syntheses including a ringopening 

polymerization step of a strained silicon-bridged 

ferrocenophane [153,154]. Cationization of a commercial 

polysulfone via chloromethylation leads to structures 51 

[622]. 

3.1.2.2. Properties and application. The poly(Nvinylbenzyl-N,N,N-trialkyl(aryl)ammonium 

chloride)s 

25a,b, and 26 are used as flocculants [120] and for investigations 

of the counterion activity (25a,b,f,g, 26) [121]. 25a 

was applied for the preparation of microcapsules by onestep 

complex surface precipitation [122]. Polyelectrolyte 

multilayers as nanocontainers for functional hydrophilic

molecules like coumarin-based dyes were prepared from 

25c and poly(styrene sulfonate) [123]. The fluorophore 

functionalized copolymers 29 were used for Foerster 

energy transfer studies in polyelectrolyte multilayers [37]. 

Copolymers 30 were successfully used as phase transfer 

catalysts [125,126]. Copolymers of 25a and ST form aggregates 

in water which were used as paper sizing agents 

[127]. The terthiophene-functionalized poly-4-VP 34 was 

incorporated as a reductant to form Au nanoparticles 

within hydrogen-bonded complexed multilayer thin films 

[135]. The redox-active polymers 35 have been applied 

successfully for electrochemical oxidations [136]. The 

crosslinkable polycation 36 was used for the reactive 

modification of polyelectrolyte multilayer assemblies 

[137]. The azobenzene containing copolymer 37 is a 

versatile analytical tool to study the assembling process of 

oppositely charged polyelectrolytes [138]. Copolymer 38 

was used as part of polyelectrolyte multilayer films which 

are employed to support attachment of vascular smooth 

muscle cells [139]. 

Partially quaternized poly(vinylimidazole) 39 was 

proved for investigations of the stability of polyelectrolyte 

multilayers [140] and to control the electroosmotic 

flow in microchannels using pH-responsive polyelectrolyte 

multilayers [141]. Ritter et al. [620,621] investigated the 

microwave-assisted decomposition of fully quaternized 

derivatives 39. The alternately coating of a solid substrate 

with the water-soluble NLO-active side chain polymer 40 

with an NLO-active main chain polyanion leads for the 

first time to NLO films prepared from two active components 

[142]. In a related approach, reactive polymeric 

�-picolinium salts 41 have been employed for the preparation 

of NLO thin films by an alternative polyelectrolyte 

multilayer approach before [143]. The fully water-soluble 

charged polysilane 44 was used for spectroscopic observations 

of surfactant induced conformational changes from 

a coil-like to a rod-like state [147]. The viologen moieties 

containing polymers 45a are used as electron-transfer catalysts 

for the reduction of substituted nitroarenes [148]. The 

redox polymer 46 was used for the production of a novel 

bioelectrode [149]. Polymers 47 serve as phase transfer 

catalysts [150]. 

The poly(ferrocenylsilane)s 49 and 50 were used for 

the tuning of the optical properties of photonic crystals 

by iterative coating with 49 and a similar polyanion [151] 

and for the first layer-by-layer construction of macroporous 

architectures from semi-flexible double-stranded 

DNA and flexible 50 [152]. Material 48 shows a remarkable 

antibacterial and hemolytic activity [623], and structures 

51 display biocide properties useful for membranes [622]. 

Copolymers containing hemicyanine dyes 52 and 53 were 

synthesized for NLO applications [434,435]. 

3.1.3. Acrylic and methacrylic polymers 

3.1.3.1. Homopolymers. 

3.1.3.1.1. Synthesis and structure. The lion’s share of 

cationic polyelectrolytes is represented by derivatives 

(homo- and copolymers) of acrylic or methacrylic acid 

(Figs. 8–10). A few existing reviews predominantly summarizing 

earlier papers have to be mentioned such as Dragan 

et al. [10], Locheux et al. [11] and McCormick et al. [15]. 


The main route leading to cationic acrylic monomers 

is the coupling of an activated carbonyl group bearing 

acrylic derivative with an O or N nucleophile forming an 

ester or amide. In most cases this nucleophile carries the 

quaternary or a tertiary amine functionality subsequently 

to be quaternized. Syntheses using special functionalized 

acrylates (e.g., HEMA, GMA, glycerol dimethacrylate) 

are performed less frequently. Reaction with glycidyl trialkylammonium 

salts (HEMA), direct addition of tertiary 

amines (GMA) or Michael analogous addition of suitable N 

nucleophiles to double bonds lead to the required products. 

Cationic acrylic homopolymers can be synthesized 

using two general procedures. Polymerization of charged 

monomers (Scheme 2, I) guarantees a strictly uniform 

polymer structure along the chain, whereas subsequent 

polymer analogous quaternization of acrylate polymers 

containing primary, secondary or in most cases tertiary 

amine function (Scheme 3, II) may lead to incompletely 

quaternized polymers. Strictly seen, products of incomplete 

quaternization have to be considered as statistical 

copolymers and will be discussed in Section 3.1.3.2. So 

in this section we review papers from the mid-1990s up 

to now containing polymerizations starting from cationic 

acrylic monomers. Most of the “standard” acrylic polycations 

are of commercial interest and therefore synthesized 

via free radical polymerization in discontinuous or less 

frequently continuous processes. One of the far-reaching 

changes in polymerization methodology was the development 

of different methods to control molecular weight 

and its distribution by additives. The synthesis principle 

of controlled radical polymerization (CRP) is discussed in 

a compacted form in Section 2. Detailed considerations to 

different CRP methods are to be found in the specialized 

literature [24,28–33]. 

Most of the papers concerning acrylic polycations 

describe synthesis, properties and/or applications of 

derivatives of the commercial acrylic monomers such 

as methacryloyloxyethyltrimethylammonium chloride 

(MATAC) 54 and 3-(methacrylamido)propyltrimethylammonium 

chloride (MAPTAC) 55. Different anions are 

used generating specific properties (Fig. 8). 

A large number of other cationic acrylic monomers 

has been polymerized and studied. Figs. 8 and 9 display 

these structures of exclusively amides and esters of 

(meth)acrylic acid. One special derivative of a methacrylic 

carboxylate 64, bearing the functional unit at the 

�-carbon has been reported and investigated for antimicrobial 

behavior [197]. However, cationically substituted 

fumarates as �-carbon functionalized acrylates couldn’t 

be polymerized [216]. Wandrey et al. published polymerization 

details of bis-1,3-(N,N,N-trimethylammonium)- 

2-propylmethacrylate dichloride 66, a doubly charged 

methacrylic monomer [219]. 

Synthetic aspects are investigated while applying controlled 

methods like ATRP [193,196] and RAFT [211,626] 

or template polymerization [182]. Using RAFT method 

interesting “ionic liquid” moieties containing macroinitiators 

67 and 68 could be obtained. An alternative 

synthetic method studied is the polymerization to 54c with 

an electrochemically generated redox system Sn 2+ /EDTA 

[183,185,212]. Molotkov et al. reported new methods in


order to obtain cationic methacrylates 54f with ultra-high 

molecular weight [213]. 

3.1.3.1.2. Properties and application. Many of the 

papers are dealing with physicochemical aspects of 

charged polymer structures in solution and on surfaces. 

Fehervari et al. studied the pH dependent rapid “switch” 

from cation to anion by hydrolysis under basic conditions 

[194]. Conformational changes of 54m dependent 

on various parameters such as salt concentration were 

investigated via AFM methods [192,195,207] or in the case 

of 54f with light scattering [186]. Quaternization of tertiary 

amine functionality with long chain n-alkyl bromides 

to 57c implements the ability to micellar organization in 

Fig. 8. Cationic (meth)acrylic homopolymers 54–58. 

aqueous media [215] or to increasing antibacterial activity 

of 59–61 with increasing alkyl chain length [204]. Film formation 

and surface coating both with single components 

and polyelectrolyte complexes with structures 54e and 62 

[206,210] are topics with still increasing importance in 

polyelectrolyte research. Layer-by-layer self assembly (see 

Scheme 4) with 54d, 55e, f and 63a yielding photo-active 

films was discussed by Laschewsky et al. [188,191,198]. 

According to Bazuin et al. similar structures 63b,c display 

thermotropic behavior [217,218]. Surface chemistry 

control via photochemical grafting of micro patterns and 

interaction with macrophages of 55b was studied by DeFife 

et al. [200,201]. Fluoroalkylated end-capped oligomers of

polycations 56 displayed a variety of interesting properties 

like highly viscoelastic behavior [189]. Adsorption of 

differently charged polyacrylamides 54m on SiO 2 surfaces 

was investigated by ellipsometry [203]. Furthermore, polyacrylic 

cations have been used as carriers for photo-active 

functionality 58 [202] and for a single component photoimaging 

system [180,190]. Compound 65 was found to 

show liquid crystalline behavior [214]. Besides these relatively 

new application areas also “classical” functions of 

acrylic polycations as ion exchange material 54i [187], flocculant 

54m, 55a [181,71], and polymeric phase transfer 

catalyst 57a [205] or as CO 2 absorber in a polyionic liquid 

like material 54h [208] were studied. 

3.1.3.2. Copolymers. The by far largest group of nitrogen 

containing polycations is represented by copolymers of 

(meth)acrylic monomers (Tables 1–10). Why copolymers? 

Charge density is an essential parameter for polycations. 

Hence copolymerization is a suitable method to control 

this property. Likewise copolymerization allows certain 

monomers to be polymerized, which are not reactive 

in homopolymerizations. With appropriate comonomers 

additional functionality can be established in the material. 

After all, many of the copolymers mentioned in this section 


Fig. 9. Cationic (meth)acrylic homopolymers 59–68. 

are a result of incomplete polymer analogous reactions (see 

Scheme 3), therefore representing an “accidental” mixture 

of cationic and educts functionality. 

3.1.3.2.1. Synthesis and structure. The copolymers 

have been synthesized by two general approaches. One is 

the direct copolymerization of nearly all commonly used 

monomers with cationically modified acrylic monomers. 

Alternatively polymer analogous quaternization of previously 

uncharged copolymers leads to products with 

varying cationization degree. Tables 1–3 display the derivatives 

of MATAC 54 and MAPTAC 55. As part of copolymers 

they are numbered as 69 and 70. For purposes of clarity the 

real structure concerning R groups at chain and nitrogen 

atom and counterion is to be found in the reference given 

in the right column. More special structure variations are 

shown in Fig. 10. 

There are some papers focusing on synthetic aspects 

of the copolymerization using new comonomers such as 

vinylcarbazole in 69f [228], different amino acid monomers 

in 70l [256], C 16 or C 18 units containing ionomers as in 78 

[259] or unusual cationic monomers as in 80, 82 and 85 

[250,269,624]. The problem of an appropriate polymerization 

solvent for polar cationic monomer and hydrophobic 

butyl acrylate in 70p was solved using alcohols [268], or


Fig. 10. Cationic (meth)acrylic copolymers 71–86 (84 and 86 show the cationic monomer). 

recently, employing ionic liquids [633,634]. Copolymers 

of acrylamides and acrylic acid 74 were esterified with 

photo reactive stilbene derivatives [248]. Materials 69b, 

69ag displaying low surface tension have been synthesized 

using monomers with fluorocarbon chains [221,275], in 

70i with randomly methylated �-cyclodextrin as solubilization 

aid [253]. Tieke et al. reported a copolymerization 

of (2-methacryloyloxyethyl) dodecyl dimethylammonium

Table 1 

Copolymers 69a–69s of MATAC (54). 


Cationic part of the copolymer R/X Comonomers Selected references 

bromide with HEMA 69m in a lyotropic mesophase upon 

�-ray irradiation [240]. Furthermore, many different techniques 

of heterophase polymerization were performed, 

i.e., copolymer synthesis in emulsion using a surfmer for 

69d and 69ai [252,278], inverse emulsion for 69a and 

69q [220,227,251,260], microemulsion for the synthesis 

of 79 [274], inverse microemulsion for 69a [222,233] and 

miniemulsion for 69g [246]. Controlled polymerization 

protocols leading to cationic block copolymers are discussed 

in Section 3.2. 

3.1.3.2.2. Properties and application. Some of the 

papers contain basic research such as for materials with 

LCST behavior as in 83b, 69i and 79 [209,232,274], an UCST 

gel as in 69ak [279], adsorption phenomena at silica surfaces 

with 70m and 70e [257,263] and interaction of soft 

microcapsules with red blood cells of 69ad, 69ae and 69af 

[272]. 

Most of the cited references contain studies aiming 

at a variety of different applications of these polymer 

materials. Fields of application with increasing importance 

R 1 =H,Me; a AAM [220–222,227,233,237,245, 

247,251,260,267] 

R 2 = Me, Et, Pr, C8H17, C12H25, CH2Ph; 

X = Cl, Br, I; [221] 

c NaAMPS [222] 

d MMA [224,230,238,244,252,261] 

e AN [226] 

, [228] 

g Alkyl (Et,Bu)-(meth)acrylate [230,236,246,265] 

[231] 

i NIPAM [232] 

k 4-VP [236,266] 

l NVP [238] 

m HEMA [240] 

[242] 

o GMA [244] 

[137] 

q N,N-Dihexylacryl-amide [247] 

r Na acrylate [251] 

s ST [252] 

are biomedicine and pharmacy. This is proved by several 

papers dealing with controlled drug release using 69g and 

70b [225,230], polyelectrolyte complexes containing 69d 

[224] or nanoparticles from 70e [262] as drug carriers, gene 

delivery using 69d and 69l [238], and amperometric peroxidase 

detection using toluidine blue copolymer 86 [436]. 

Stepanek et al. developed hydrophilic reactive terpolymers 

69al for derivatization of biological systems [625]. 

The properties of membranes and thin films containing 

70h, 70q or 74a,b [188,243,248] are strongly 

governed by different nonionic comonomers. So, NVP 

leads to polymers 70g forming films which strongly 

withstand polar solvents [241]. Membranes from 70f 

with 4-VP as comonomer display retentive properties 

towards ions of heavy metals especially Hg 2+ [235]. 

Fast transport of ferric ions in a cationic terpolymer 

membrane of 70c,d containing 2,3-epithiopropyl 

methacrylate has been reported [229]. Terpolymers with 

t-BMA or AMPS 70n were found to show a good anti-fog 

effect on a glass surface [258]. Lipophilic polyelec-


Table 2 

Copolymers 69t–69al of MATAC (54) derivatives. 


trolyte gels 71a and 71b were obtained by copolymerization 

of N-acryloyloxyethyl-N,N,N-trihexylammonium 

tetrakis[3,5-bis(trifluoromethyl)phenyl] borate, neutral 

acrylate monomers with different alkyl chain length and 

R 1 =H,Me; t HEA [255] 

R 2 = Me, Et, Pr, C8H17, C12H25, CH2Ph; u MA, t-BMA [258] 

[261] 

X = Cl, Br, I; [265] 

x EHA [64] 

[266] 

z HPMA [270] 

[210] 

[237] 

[267] 

ad N,N-Dimethylacryl-amide, [272] 

ae Aminomethyl-ST, [272] 

[272] 

[275] 

[276] 

[278] 

ak EGDMA [279] 

[625] 

EGDMA, useful as superabsorbent polymers for nonpolar 

organic solvents [560,561]. 

Another important field of research comprises the formation 

of polyelectrolyte complexes (PEC) with 70e and

Table 3 

Copolymers 70 of MAPTAC (55) derivatives. 



surfactants [234], 69t and PAA [255], 69aa and poly-AMPS 

sodium salt [210] or 69ac or 69z and DNA [267,270]. One 

of the PEC applications with 69v,d (in a membrane on a 

glass substrate) is the usage as humidity sensor [261]. Generally, 

electrical properties of layers containing different 

cationic copolymers such as 69g,k, 70o and 73a,b are used 

for humidity sensing [236,264–266,271]. 

Photo-physical properties are of growing scientific 

interest, especially with regard to photo-reactive multilayers 

containing 69p, 70h,r [137,191], fluorophore 

containing materials with 70h and 77 [198] and photoinitiation 

systems using 69h,n and 70s [231,242,273]. 

Further application oriented research is directed 

towards flocculation efficiency with structures 69a,e 

R 1 =H,Me; a AAM [223,256] 

R 2 = Me, Et, C12H25, b HEMA [225] 

X = Cl, Br, MeOSO3 c DMA [229] 

d Thio-GMA [229] 

f 4-VP [235] 

g NVP [241] 

[234,262,263] 

[188,191,198,243,257] 

[253] 

NIPAM [254] 

[256] 

MAA [257] 

n NaAMPS, t-BMA [258] 

o MMA [264] 

p BA [268] 

[188] 

[191,277] 

[273] 

[220,226,245] and general paper applications using 69a,ab 

and 69g [237,246], a platinum catalyst for gas phase reduction 

of aromatic compounds with 70a [223], absorption 

of CO 2 using 69o [244], thickening properties of 69a,q 

[247,260], dye based halide sensing of structure 75 [249], 

usage of 70k as a stationary phase in capillary electrochromatography 

[184,254] and antibacterial activity of 72, 

76, 81, 83a,b and 84 [204,209,239,280]. 

3.2. Block copolymers 

Block copolymers containing a block of quaternary 

ammonium compounds (Tables 4–9) can be divided 

into double hydrophilic block copolymers (DHBC) and


Table 4 

Double hydrophilic cationic block copolymers 87–97. 

Polymer Type Cationic block Nonionic block Reference 

87 ABA [27,48,354,385,386] 

88 AB [27,48,193,386, 

388,390–392,394,401] 

89 ABC [387] 

90 (AB)n [387] 

91 AB [388] 

92 AB [390] 

93 AB [393] 

94 AB [38]

Table 4 (Continued ) 



95 AB [397–403] 

96 AB [395,396] 

97 AB [193] 

Table 5 

Double hydrophilic cationic block copolymers 98–100. 


98 AB [193] 

99 AB [403] 

100 AB [626]


Table 6 

Amphiphilic cationic block copolymers 101–104 containing cationic polysoap blocks. 

Polymer Type Cationic block B Nonionic block A Reference 

101 ABA [343,404] 

102 AB [343] 

103 AB [310] 

104 AB [405,406] 

amphiphilic block copolymers (AmphBC), depending on 

the chemical structure of the nonionic block. DHBCs consist 

of two water soluble blocks of different chemical nature 

[378]. In aqueous solution, DHBCs behave like usual polyelectrolytes 

and show no characteristics of an amphiphile 

like micelle formation or lowered surface tension of their 

solutions at all. In some cases amphiphilicity may be 

induced, e.g., by interaction with a nanosized substrate 

and subsequent complex or superstructure formation. In 

Table 7 

Amphiphilic cationic block copolymers 105–106 containing two cationic polysoap blocks. 

principle, change of pH, ionic strength or temperature 

may turn one block to hydrophobic leading to an AmphBC 

[378]. These DHBCs represent switchable amphiphiles. 

Typical examples are block copolymers containing a block 

of tertiary amines which is hydrophilic at low pH and 

hydrophobic at high pH [379,381]. In contrast, Amph- 

BCs contain a hydrophilic and a hydrophobic block, in 

this context the hydrophilic one is a block of quaternary 

ammonium monomers. The most outstanding feature of 

Polymer Cationic block Cationic block Reference 

105 [35,407] 

106 [327]

Table 8 

Amphiphilic cationic block copolymers 107–116 containing hydrophobic nonionic blocks. 



107 AB [409] 

108 AB [47,404,410] 

109 AB [411,412] 

110 AB [413,414] 

111 AB [36,415] 

112 ABC [50] 

113 AB [416] 

114 AB [626] 

115 AB [417]


Table 8 (Continued ) 


116 AB [418] 

AmphBCs is their association behavior, leading to different 

types of micelles in aqueous solution. The micellar structure 

of these so-called macrosurfactants is determined by 

various parameters like block length, ionic strength, pH and 

solvent quality. Depending on these parameters and the 

Table 9 

Amphiphilic cationic block copolymers 117–121 containing tertiary amine blocks. 

molecular architecture of the individual blocks not only 

spherical micelles but also more complicated structures 

like cylindrical micelles and vesicles may be formed, and at 

high concentrations aggregation of the primary aggregates 

into lyotropic mesophases may take place [380,381]. 

Polymer Cationic block Nonionic block Reference 

117 [419–423] 

118 [424] 

119 [40,425] 

120 [426] 

121 [428]


Table 10 

Amphiphilic cationic block copolymers 122–123 from precursor of shell-crosslinked micelles. 

Polymer Cationic block Nonionic block Reference 

122 [427] 

123 [384,429] 

3.2.1. Synthesis and structure 

The synthesis of the polyelectrolyte block copolymers 

proceeds similarly to uncharged block copolymers and to 

polyelectrolytes in general [380–382]. Living anionic and 

cationic as well as group transfer polymerization has been 

applied, mostly for the synthesis of a block copolymer containing 

a precursor block which then was modified into 

the polycation. Typical examples are the quaternization 

of block copolymers of N,N-dimethylacrylamide and N,Ndimethylvinylbenzylamine 

[383] and of block copolymers 

of N-methacryloyloxyethyl-N,N-dimethylamin (MDMA) 

and N-(methacryloyloxyethyl)morpholine (MM) [384], 

synthesized by the RAFT respectively ATRP process. The 

precursors are often easy to characterize, but the disadvantage 

of this procedure may be a functionalization 

less than 100%. Great success in the synthesis of tailormade 

polyelectrolyte block copolymers came with the fast 

development of CRP techniques within the last decade, 

particularly with the application of novel water-soluble 

RAFT agents allowing successful RAFT polymerization in 

water solution [loc. cit. [381]]. Now quaternary ammonium 

monomers can be applied. Then no final polymer modification 

is necessary. Polymerizations with macroinitiators 

carrying one block of the final polymer are relevant but of 

minor importance. 

Cationic DHBCs mostly contain poly(ethylene glycol) 

(PEG) as the nonionic block (Tables 4 and 5). Here the radical 

polymerization of a cationic vinyl monomer using linear 

macroazoinitiators containing PEG of variable chain length 

is a very convenient method to synthesize the desired polymers 

[27,48,354,385–387]. The structure of these block 

copolymers is dependent on the mode of termination of 

the monomer involved. Combination results in ABA block 

copolymers, disproportionation in AB blocks. As the termination 

of DADMAC occurs only by combination [2,26] (see 

Section 3.1.1) the macroinitiated polymerization of DAD- 

MAC gives triblock copolymers 87 [27,48,354,385,386]. 

Using macroazoinitiators of different molecular weight 

a set of block copolymers containing blocks of compa- 

rable length is available [27,354,386]. Initiation of the 

DADMAC-polymerization with an OH-terminated PEGmacroazoinitiator 

leads at first to PEG-DADMAC-PEG 

triblock copolymers with OH-end groups. Using now Ce 4+ 

to initiate the polymerization of N-methacryloyloxyethyl- 

N,N,N-trimethylammonium chloride (MATAC) results in 

polymer 89 containing 3 blocks of different chemical structure 

[387]. Furthermore, the polymerization of DADMAC 

with poly(macroazoinitiators) [387] as well as the initiation 

with Ce 4+ on PEG with two OH-end groups [389] leads 

to multiblock polymers 90. 

Block copolymers 88 (R=CH 3) were also synthesized 

using PEG-macroazoinitiators [27,48,386]. Another route 

to 88 (R=CH 3) includes the initiation of the polymerization 

of the tertiary amine MDMA with PEG-macroazoinitiators 

followed by quaternization with methyl iodide. Similar 

products (88, R=C 4H 9) were obtained using 1bromobutane 

[391]. An only partial quaternization gives 

polymers 92 with a cationic block of a statistical copolymer 

of tertiary amine and quaternary ammonium structure. 

PEG—poly-MDMA block copolymers are also available by 

ATRP of MDMA using �-(2-bromoisobutyrate-�-methyl- 

PEG as macroinitiator, quaternization again leads to 88 

[388,392]. An analogous reaction yielded product 91 [388]. 

The first ATRP of MATAC in aqueous media opened the 

gate for the direct synthesis of 88 by ATRP using an appropriate 

PEG-macroinitiator [193,394]. The subsequent ATRP 

of MATAC and glycerol monomethacrylate respectively 

VBTMC monomer resulted in polymer 97 and a diblock 

copolymer 98 built from two cationic blocks [193]. 

The DHBC 93 was synthesized by the RAFT method 

in two steps: first preparing a poly-RAFT agent from 

N-acryloyl-N,N,N-trimethylammonium chloride (ATAC) in 

water, followed by RAFT polymerization of poly(ethylene 

oxide) monomethyletheracrylate [393]. Aqueous RAFT 

polymerization with new water-soluble RAFT agents was 

successfully used for the preparation of polymer 94 containing 

blocks of polydimethacrylamide and poly-VBTMC 

[38]. A RAFT-process in methanol/water using macroini-


tiators 67 and 68 (see Fig. 9) lead to new DHBC structures 

100 and 114 [626]. The block copolymers 96 of acrylamide 

and ATAC are available by the so-called MADIX-process, a 

variation of the RAFT method using xanthate compounds as 

chain transfer agents in aqueous solution [395]. The block 

copolymer 95 can be synthesized by coupling of poly[N- 

(2-hydroxypropyl) methacrylamide] terminated with a 

reactive N-hydroxysuccinimidyl ester group with poly- 

MATAC terminated with a primary amino group [400]. 

The hydrophobic part of a cationic AmphBC may derive 

from one (Table 6) or two (Table 7) cationic polysoap blocks 

or from a hydrophobic nonionic block (Table 8), especially a 

tertiary amine block (Table 9). Special structures of the latter 

both serve as precursors for shell-crosslinked micelles 

(Table 10). 

Block copolymers containing a cationic polysoap block 

and a nonionic hydrophilic, mostly PEG, block, represent 

a novel type of micellar polymers. Typical examples 

are listed in Table 6. Both the head structure 101 and 

the tail-end structure 102 were synthesized by polymerization 

of the cationic surface active monomers with 

a PEG-macroazoinitiator [343,404]. The cationic block 

of 101 must be built as a statistical copolymer with 

a DADMAC content ≥ 60%, otherwise the polymers are 

insoluble in water. Polymers 103 were synthesized by 

sequential anionic polymerization of the cationic soap 

monomer and ethylene oxide [310]. Polymer 104 can 

be prepared by CRP using new nitroxides as control 

agents allowing the synthesis of high molecular weight 

poly-N,N-dimethylacrylamide, which then was used as a 

macroinitiator for the chain extension by 4-vinylpyridine. 

Finally, the amine block was quaternized [405,406]. 

AmphBCs containing two cationic polysoap blocks are 

listed in Table 7. Polymer 105 was made by RAFT in two 

steps. First, the block B was made by statistical copolymerization 

of the both monomers involved. Second, the 

resulting macromolecular chain transfer agent was used 

for the statistical copolymerization of the second monomer 

pair [35,407]. The cationic ionene block copolymers 106 

bearing hydrophobic hydrocarbon or fluorocarbon side 

chains were prepared in a multi-step sequence. 

It should be mentioned that the CRP using TEMPOcapped 

poly(sodium 4-styrenesulfonate) as macroinitiator 

for the chain extension with VBTMC leads to an insoluble 

zwitterionic complex [408]. 

Another group of cationic AmphBCs contains a 

hydrophobic nonionic besides the cationic block. The 

hydrophobic parts often are polystyrene or derivatives of 

polystyrene (Table 8). The block copolymer 107 containing 

a conjugated and strongly hydrophilic cationic polyacetylene 

block attached to a hydrophobic polystyrene block 

was synthesized by initiation of the living anionic polymerization 

of an N-methyl-2-ethynylpyridinium salt with 

polystyryl-Li + [409]. Polymer 108 with low polydispersity 

and different block lengths and block length ratio is easily 

available by TEMPO-mediated CRP via polymerization 

of styrene with N-oxyl terminated VBC macromonomers 

followed by reaction with trimethylamine [47,48,386,404]. 

The precursor block copolymer of VBC and styrene 

was further synthesized via nitroxide mediated CRP 

using phosphonylated nitroxides [411] as well as by the 

RAFT method [412]. In both cases 109 is available by 

subsequent reaction with triethylamine [411,412]. The 

synthesis of 110 was carried out by carbodiimide coupling 

of block copolymers of styrene and acrylic acid 

with N,N-dimethylethylenediamine followed by quaternization 

[413]. 111 is available via a RAFT agent of 

poly(butylacrylate) with good correlation between the 

molar masses obtained and the theoretical expected ones 

[36]. The linear triblock copolymer 112, consisting of a 

long cationic hydrophilic block and two short consecutive 

hydrophobic blocks, was synthesized using a three-step 

RAFT process to obtain a reactive precursor followed 

by quaternization with N-methylmorpholine [50]. Polymer 

113 was obtained by quaternization of the precursor 

synthesized by a group transfer polymerization of the 

corresponding tertiary amine and methylmethacrylate. It 

serves as mimic of the biopolymers implicated in biosilica 

formation [416]. 115 bearing a polyisobutene and a 

polyelectrolyte block was prepared by bromination and 

quaternization of a block copolymer of 4-methylstyrene 

and isobutene [417]. The polymer 116 containing a liquid 

crystalline polyacrylate block was obtained using double 

bond containing poly-DADMAC as a macromonomer [418], 

but it is not clear whether the polymer has the linear block 

structure 116 or a branched or graft structure, because the 

double bonds of the polycation mainly are pendant from 

uncyclized structures [2,54] (see Section 3.1.1). 

In some cases the nonionic hydrophobic block is a 

polymeric tertiary amine (Table 9). MDMA was block 

copolymerized with three other tertiary amines later 

forming the nonionic block in 117 using group transfer 

polymerization (GTP). The MDMA residues of each of these 

diblock copolymers were selectively quaternized using 

both methyl iodide and benzyl chloride [419]. Block copolymers 

118 and 119 were prepared using the RAFT process 

in aqueous media [40,424]. Polymer 120 with very narrowly 

distributed molecular weight was synthesized again 

by the RAFT method in water [426]. 121 was obtained 

by sequential monomer addition in an oxy-anion-initiated 

polymerization of the two tertiary amines with good MWcontrol 

for both blocks followed by selective quaternization 

[428]. 

The self-assembly of amphiphilic block copolymers 

into polymer micelles followed by crosslinking of side 

chain functionalities along the block composing the 

shell of the polymer micelles results in nanometer-sized 

amphiphilic core-shell spheres, often referred to as 

knedel-like structure [427]. Such structures resemble 

dendrimers in the basic structural components, and have 

the advantage of a rapid synthetic approach of larger and 

broader size ranges. Polymers 122 and 123 are typical 

cationic precursors able to crosslink in the shell thus 

preparing the amphiphilic spheres. 122 was synthesized 

by anionic block copolymerization of styrene and 4-VP 

and then quaternization of the pyridyl nitrogen with pchloromethylstyrene, 

thus incorporating a polymerizable 

double bond to be used for the crosslinking [427]. Partial 

quaternization of the MDMA-block in the precursor of 

117 [419] results in polymer 123. Reaction with a bifunctional 

quaternizing agent, 1,2-bis-(2-iodoethoxy)ethane 

(BIEE), results in knedel-like micelles with temperature-

variable core hydrophilicity [384,429]. Another route 

to shell-crosslinked micelles with pH-responsive cores 

uses ABC triblock copolymers. Successive ATRP polymerization 

of MDMA and N-methacryloyl-N,N-diethylamin 

(MDEA) using PEG-based macroinitiators results in PEG- 

MDMA-MDEA triblocks forming three-layer “onion-like” 

micelles at pH > 7 comprising MDEA cores, MDMA inner 

shells, and PEG coronas. Selective quaternization of the 

MDMA residues by BIEE leads to increased hydrophilicity 

and colloidal stability for the shell-crosslinked micelles 

[431]. Similar results were obtained with the selective 

crosslinking by bifunctional quaternization of the triblocks 

PEG–MDMA-tert(butylamino)ethylmethacrylate 

[428], PEO–MDMA–MM [429] and poly(propylene oxide)– 

MDMA-methoxy-capped oligo(ethyleneglycol)methacrylate 

[430]. 

3.2.2. Properties and application 

Both the intra- and the intermolecular aggregation of 

101 containing a cationic polysoap block depend on the 

block composition and the alkyl chain length [343,404]. 

Polymers 105 give rise to not only microphase separation 

between the hydrophilic polar parts and the hydrophobic 

apolar parts of the macromolecules, but also seem 

to be able to undergo additional microphase separation 

[35,407]. The poor compatibility of the perfluorocarbon 

and hydrocarbon micellar blocks results in aqueous solution 

in a microphase separation into hydrocarbon-rich 

and fluorocarbon-rich hydrophobic domains, thus yielding 

multicompartment micelles [327]. Simple spheres, large 

micelles and more complex architectures result from the 

self-assembling of 110 which where applied to serum 

cholesterol reduction [414]. Micelle-like aggregates were 

found in water and inverse micelles in organic media using 

111 [36,415]. The self assembly of 112 in aqueous media 

results in multicompartment micelles [50]. Polymer 113 

serves as mimic of the biopolymers implicated in biosilica 

formation [416]. After selective quaternization of 117 

the resulting set of block copolymers exhibit reversible pH- 

, salt-, and temperature induced micellization in aqueous 

media [419] and a pH-controlled adsorption at solid/liquid 

interfaces [420,421]. They form micelles with a highly 

charged corona [422]. Silica deposition results in hybrid 

copolymer-silica particles with well-defined core-shell 

morphologies [423]. The pH-dependent micellization of 

119 and 120 was extensively studied in dependence on 

the length of the amine block [425] and by different methods 

[426]. Polymers 108 form micellar solutions in water 

as well as in organic solvents, forming frozen micelles 

in the former case [404]. They are efficient stabilizers 

in the emulsion polymerization of styrene resulting in 

monomodal cationic dispersions extremely stable against 

dilution and at high ionic strength, obviously due to a 

charged corona formed by the cationic block [404]. The 

complexation of polyacrylic acid by 108 results in a mesomorphously 

ordered material [410]. 109 was successfully 

tested as an electrosteric stabilizer in emulsion polymerization 

[411,412]. 

The triblock copolymers 87 are powerful stabilizers 

in the emulsion polymerization of styrene resulting 

in monodisperse cationic latexes [354]. Block copoly- 


mers 88 are very efficient stabilizers in the precipitation 

polymerization of cationic vinyl monomers with slightly 

hydrophobic properties like N-methacryloyl-oxyethyl- 

N,N-dimethyl-N-benzylammonium chloride (MADBAC) in 

aqueous solution of high ionic strength. This process results 

in dispersions of fine particles with excellent colloidal 

stability which can be transformed in aqueous polymer 

solutions by simple dilution [27,386]. Polymers 92 containing 

a cationic block of statistical copolymer of tertiary 

amine and quaternary ammonium structure were used for 

delivery of DNA. They spontaneously assemble with DNA to 

give in aqueous medium micellar structures with physicochemical 

properties appropriate for in vivo applications 

[390,391]. Polymers 90 and 91 are used for the formation 

of polyion complex micelles by sequential complexation of 

the polyions with oppositely charged DNA [392] or heparin 

[388], followed by the self-association of the complexes 

into micelles. Polymers 88 were used for investigations 

of the influence of polymer molecular weight and charge 

density on the complexation of antisense oligonucleotides 

[394]. Stoichiometric complexes with sodium decanoate 

and sodium perfluorodecanoate were prepared by selfassembly 

using the DHBC 93. Both complexes are soluble 

in water forming core-shell nanoparticles [393]. 

The polymer 96 forms with oppositely charged surfactants 

colloidal complexes with core-shell microstructure 

[396]. Polymer 95 can self-assemble with DNA to form 

complexes capable of gene delivery [397]. The resulting 

clusters were characterized by light scattering methods 

[398–401]. Furthermore, 95 was used for the self-assembly 

with antisense oligonucleotides in order to improve their 

biocompatibility and of their pharmacokinetics for greater 

therapeutic usefulness [402] as well as for studies of the 

ionic coupling with oligophosphates as a model for the 

repeating phosphate groups in DNA [403]. 

3.3. Ionenes 


Ionenes are polyelectrolytes in which ionic groups are 

part of the polymer backbone (Table 11, Figs. 11–14). Still, 

the use of the term is mostly confined to polycations 

carrying the quaternary nitrogen as the charged species 

[487]. Generally, the synthesis proceeds via a polyaddition 

reaction (see Scheme 2, IV), such as the Menshutkin 

reaction of bis-tertiary amines (x) and dihalides (y) leading 

to polymers 124 [10,18], the self-condensation of 

aminoalkyl halides to polymers 125 [10,18] or the reaction 

of bis-tertiary amines or secondary amines (mostly 

dimethylamine) with epichlorohydrin to polymers 126 in 

the presence of HCl [18]. Often the synthetic pathway follows 

the pioneering recipes of Rembaum [loc.cit. in [10,18]] 

after the first synthesis of an ionene 85 years ago by Marvel 

[438]. This development led to more than 300 papers 

in general up to 1995 [439]. The most important elder 

results are reviewed by Dragan [10] and Noguchi [18]. A 

typical problem of this synthetic route is the occurrence of 

side reactions, such as Hoffmann degradation and cyclization 

reactions, which makes it difficult to achieve high 

molar masses [488]. Nevertheless, the Menshutkin reaction 

can easily be tuned to obtain ionenes with varying


Table 11 

Aliphatic ionenes 124–127. 

Structure R x, y Reference 

groups between the quaternary nitrogens (x and y in 124) 

as well as the side groups (R 1 and R 2 in 124). These parameters 

enable to modify the physical properties broadly. 

Also, the molecular weight may influence the molecular 

dynamics markedly, as for instance, Tg of ionene 124o 

strongly depends on the chain length [449]. Examples of the 

amine components comprise such with long alkyl chains 

or aromatic amines, examples of the dihalides can contain 

functional groups like hydroquinone or catechol [18]. 

As for all polycations, the properties depend strongly 

on the low molar mass counterion, too [10,18]. Still, most 

reported ionenes are bromides, as the alkylating agent 

is mostly a bromide [10,18,19]. Occasionally, the alkylating 

partner may be a tosylate, mesylate or triflate, but 

rarely a chloride. Due to the lower polarizability and leaving 

group ability, the reactivity of ordinary dichlorides is 

too low to allow a Menshutkin reaction to proceed to reasonable 

conversions, and thus to achieve sufficient molar 

masses. The generally low reactivity can be overcome by 

applying activated dichlorides, e. g. such in benzyl or allyl 

positions, such bearing electron withdrawing groups, or 

such prone to S Ni mechanisms like bis(2-chloroethyl)ether 

R 1,2 = Alkyl varying [10,18] 

R 1,2 =CH3 a: 2,4 [447] 

b: 2,6 [439] 

c: 2, 8 [447] 

d: 2,12 [440] 

e: 3,3 [442,443] 

f: 3,10 [441] 

g: 3,12 [441] 

h: 3,16 [444–446] 

i: 3,22 [441,444,445] 

k: 4,12 [440] 

l: 5,10 [441] 

m: 6,4 [440,442,443] 

n: 6,6 [439,440,442,443] 

o: 6,10 [449] 

p: 6,12 [440,442,443] 

q: 10, 6 [439] 

r: 12,12 [442,443] 

R 1,2 = Alkyl varying [10,18] 

R 1,2 =CH3 a:x=6 [16,451] 

[448] 

R=C16H33 a: 6,3 [450] 

R=C16H33 b: 6,4 [450] 

R=C16H33 c: 6,6 [450] 

R=C16H33 d: 6,10 [450] 

R=C14H29 e: 6,6 [450] 

R=C18H37 f: 6,6 [450,451] 

R=C20H41 g: 6,6 [450] 

[19]. Alternatively, counterion exchange gives access to 

all sorts of ionene salts from a given polymer structure 

[18,450,489,490]. 

The reaction of methyl viologen and terephthalaldehyde 

provides an alternative polyaddition strategy to ionenes 

[18]. Chain growth reactions such as the ring-opening polymerization 

of azetidinium salts, or the modification of 

living poly(2-methyl-2-oxazoline) are examples for further 

unconventional reactions [18]. Furthermore, the quaternary 

nitrogen may be introduced by polymer modification 

[18,441,491]. 

As listed in Table 11 and Figs. 11–14 ionenes are 

polyelectrolytes with an enormous structural versatility. 

Ionenes 124f,g,i,l were prepared via reaction of the 

chlorides of �,�-alkylenediacids to the corresponding 

dimethylamides, reduction to the amines and quaternization 

by �,�-dibromoalkanes. Ionenes 124m,n,e,p,r were 

obtained by classical synthetic procedures. Ionenes 129 

were obtained by copolymerization of bis-chloromethyl 

compounds and ditertiary amines [352]. Comb-like ionenes 

127a–g with aliphatic side chains of different length have 

been synthesized by the Menshutkin reaction under condi-

tions of extremely high monomer concentrations in order 

to compensate the low reactivity of the diamines. 

Polymers with aromatic or rigid-rod moieties are listed 

in Fig. 11. A series of polyimides containing aromatic 

bipyridinium salts 136 were synthesized by first reaction 

of 4,4 ′ -(1,4-phenylene)-bis(2,6-diphenyl pyrylium) 

with aromatic diamines and second reaction of these 

monomers with various tetracarboxylic dianhydrides 

[455]. Ionenes 137 are made by solution polycondensation 

of N,N,N ′ ,N ′ -tetraphenyl-xylylenediamine with suitable 

dihalides. The viologene polymers 131, 138, 139 with 

bromide, tosylate or triflimide as counterions were prepared 

by either the Menshutkin reaction or metathesis 


Fig. 11. Aromatic and “Rigid-Rod” ionenes 128–141. 

reaction in a common organic solvent and characterized 

mainly concerning their thermotropic liquid-crystalline 

and fluorescent properties [457]. The polymerization of 

p-bis[4-(2,6-diphenylpyrylium)]benzene ditriflate with a 

series of aromatic diamines results in polymers 144, soluble 

in polar aprotic solvents [459]. A similar reaction 

leads to 145 with tosylate or triflimide as counterion 

[460]. 

Fig. 13 summarizes ionenes containing azo benzene 

chromophores, where the azobenzene itself may bear 

charged or ionizable groups, as in 146–149, or may be 

uncharged, as in 150–154. The azobenzenes typically carry 

donor–acceptor substituents.


A number of other functionalized ionenes are shown 

in Fig. 14. 155 and 156 that carry a hydrocarbon and a 

fluorocarbon side chain, were synthesized by reaction of 

1,4-dibromobut-2-ene with the corresponding N,N-di(3- 

(dimethylamino)propylamide. Appropriately end-capped, 

155 and 156 were used to prepare block copolymer 

157 in two steps [321]. The synthesis and characterization 

of some novel cationic siloxane copolymers 

containing quaternary ammonium groups in the backbone 

are described in [476]. Another type of micellar 

polymer, 3,22-ionenes 164 with pendant chiral groups, 

was synthesized by the reaction between the tosyl 

derivatives of the carbohydrates involved and the tertiary 

3,22-polyamine obtained by selective demethylation 

of the corresponding ionene [357]. Ionenes 165 with 

semifluorinated side chain were prepared by reduction 

of poly(N,Nǐ-dimethylhexamethyleneadipamide) followed 

by quaternization of the resulting polyamine with semifluorinated 

1-bromoalkanes. 

The very water-soluble 158 was obtained by polycondensation 

of epichlorohydrin with dimethylamine 

and N,N-1,3-diaminopropane [472]. Incorporating additionally 

primary amines with nonpolar chains, such as 

hexyl- or decyloxypropylamine 159 was made similarly 

[473,474]. Low molecular weight ionenes 163 with 

pendant allyl groups are available by condensation of N,Nǐbisallylpiperazine 

with organic dihalides. They can easily 

be crosslinked to give transparent hydrogels [481]. 

The coordinating polymer 161 was synthesized classically 

from 4,4ǐdibromomethyl-2,2 ′ -bipyridine and 1,3- 

N,N,NǐNǐ-tetramethyl-1,3-diaminopropane [477]. 

Polymers 166–169 illustrate the scope of useful 

polymerization strategies to structurally related ionene 

polyethers. The poly(oxytetramethylene) ionenes 166 

were made by cationic living polymerization of THF followed 

by chain extension with a trimethylsilyl activated 

secondary amine [483]. Similarly, 169 was synthesized via 

Fig. 12. Structure of ionenes with “rigid rod” building blocks 142–145. 

cationic living polymerization of THF and chain extension, 

now using 4,4 ′ -bipyridine [486]. In contrast, 168 

was made by reacting trans-1,2-bis(4-pyridyl)ethylene and 

the corresponding di- or tri(ethylene glycol)-di-p-tosylate, 

which were characterized for their thermotropic LC and 

light-emitting properties [485]. Unusual 12,12-ammonium 

ionenes with cinnamate endgroups 170 allow chain extension 

and crosslinking via UV irradiation [437]. 


The structural versatility of ionenes results in multifold 

uses. Ionenes are useful antibacterial agents [10,18]. 

A typical example is 125a whose bacteriostatic and bactericidal 

activity increase with increasing molecular weight 

[16]. Investigations of the effects of charge density and 

hydrophobicity of aliphatic ionenes 124e,m,n,p,r and aromatic 

ionenes 128 on cell binding and viability indicate 

critical numbers of carbon atoms to induce effective cell 

disruption and cell binding [443]. 

The interaction of 124d,k,m,n,p synthesized via the successive 

Menshutkin reaction of diamine and dibromide in 

DMF, with sodium dodecylsulfate leads to water soluble 

aggregates. The viscosity of the solution depends strongly 

on the x, y values of the ionene due to the formation 

of hydrophobic domains [440]. The lyotropic and thermotropic 

phase transitions in films of complexes of ionenes 

124f,g,i,l with different alkyl sulfates were investigated by 

means of DSC, TG and ATR-IR [441]. The interaction of 

124m,n,p,r with anionic surfactants results in both stoichiometric, 

insoluble complexes and non-stoichiometric, 

soluble complexes [442]. Ionenes with short methylene 

segments exhibit behavior typical of polyelectrolytes in 

aqueous solution. In contrast, amphiphilic ionenes with 

long methylene segments such as 124f and 124p prefer 

globular conformations, forming microdomains via 

intra- or interpolymeric aggregation of the long segments 

[444]. Because of their micelle-mimetic properties, these


Fig. 13. Ionenes 146–154 containing azobenzene.


Fig. 14. Functionalized ionenes 155–171.

amphiphilic ionenes found a variety of applications in analytical 

chemistry. Examples are the catalysis of an alkaline 

hydrolysis by 124i immobilized on silica [444], the preparation 

of stationary phases for HPLC by attaching 124h,i 

to aminopropyl silica [445] and the in situ generation 

of stationary phases using 124h [446]. The adsorption of 

ionenes 125a and 127f on oppositely charged surfaces 

was investigated by in situ surface plasmon spectroscopy 

[451]. Furthermore, aliphatic ionenes 124b,n,q as well 

as aromatic ones 128 were immobilized on a cationic 

polystyrene resin resulting in novel high-performance stationary 

phases for the anion chromatography [439]. The 

terminal amino groups of 124a,c were alkylated with pnitrotoluene 

bromide. The modified polymers are easily 

detectable by UV-measurements, thus supporting many 

analytical investigations [447]. The OH-groups containing 

ionene 126 and the aromatic polymers 128, 130 

and 131 served successfully as modifiers in the synthesis 

of polyelectrolyte sorbents for ion chromatography 

[448]. Ionenes 129 form physical hydrogels and displaying 

unique thixotropic behavior [352]. From comb-like ionenes 

127a–g highly ordered films of layered structure have been 

obtained by solution casting [450]. Polymers with aromatic 

or rigid-rod moieties are listed in Figs. 11 and 12. Many of 

them were used to investigate the formation of complexes 

with polyanions (“symplexes”). The stability of complexes 

of 128 and poly(acrylic acid) or poly(methacrylic acid) 

depends mainly on the concentration cs of added low 

molecular weight salt. Low cs leads to nonstoichiometric 

water-soluble complexes, while intermediate cs results in 

insoluble complexes, and high cs induces redissociation 

into the single strands [452]. Aromatic ionenes 132–135 

[137] served to investigate the effect of linear charge 

density on the growth of stable ionene/poly(vinylsulfate) 

multilayers, which required a critical value. Several ways 

to overcome this limitation are discussed [453,454]. 

The azobenzene chromophores with donor–acceptor 

substituents containing ionenes of Fig. 13 are versatile 

analytical tools to study the alternating layer-by-layer 

assembly of 146–152 with polyanions, and to control 

the film quality [138,277,461–465,467]. In particular, 152 

served to study the interaction of polycations with an 

exfoliated synthetic hectorite [466], as well as aggregation 

phenomena in polyelectrolyte multilayers [480]. The photoisomerization 

behavior of 153 and its photoorientation 

upon irradiation with linearly polarized visible light were 

studied in multilayers, too [468,469]. Polymers 154 (n =6, 

10, 12) were used to prepare internally ordered multilayers 

[470] as well as photochromic hollow shells by multilayer 

formation using the anionic polyelectrolyte Carrageenan 

[471]. 

In analogy to ionenes 127a–g, polymers 155 and 

156 behave as micellar polymers of the polysoap type 

[321,327]. Hence, compounds 155 were used as pseudostationary 

phases for electrokinetic chromatography [371]. 

The very water-soluble 158 was used for the formation 

of multilayers with several anionic azo dyes whose 

built up was monitored by UV-VIS-spectroscopy [472]. 

159 was used for the flocculation of montmorillonite 

[473,474]. The thermal behavior of 160 and its complexes 

with poly(acrylic acid) is reported in [475]. By 


interaction of 161 either with a polyanion or through 

metal ion coordination, multilayers were prepared. The 

former systems reversibly accept and release transition 

metal ions [477]. Improved antimicrobial properties were 

reported using novel modified main chain guanidine polymers 

171 [629]. Polymers 137 are too hydrophobic to 

dissolve in water, but show normal polyelectrolyte behavior 

in ethanol [456]. 145 exhibits both thermotropic 

liquid-crystalline and fluorescence properties [460]. The 

electrolytic conductivity of 140-143, where quaternary 

nitrogens are attached with chloranil and xylylene moieties 

and connected with phenothiazine or bipyridyl linkages, 

was investigated in several solvents [458]. Polymers 165 

exhibit self-organizing materials with low surface energy 

[482]. Polymers 162 were subject of voltammetric studies 

at a polarizable nitrobenzene/water interface [478]. 

Cationic polyether urethanes bearing hydroquinone [479] 

and anthraquinone [480] groups in the main chain show 

tensile and thermal properties similar to other elastomeric 

polyurethanes. 

The morphology of 166 was analyzed in the nanometer 

scale [483]. The segregation of the polar units of the 

similar polymers 167 was studied by SAXS and SANS measurements 

[484]. The microphase separated structure of 

the resulting elastomeric polymer films prepared from 169 

consists of three phases [486]. 

3.4. Cationic conjugated polyelectrolytes 

Conjugated polyelectrolytes (CP) (Figs. 15–19), also 

referred as rodlike or rigid-rod polyelectrolytes, are characterized 

by a �-conjugated backbone and functional groups 

that ionize in high dielectric media, thereby making the 

polymers soluble in water and polar organic solvents [155]. 

Both cationic and anionic polymers have been synthesized 

during mainly the last 10 years, with an increasing 

share of cationic CPs. The work until 1996 was summarized 

by Rehahn [20]. Cationic CPs are of interest for two 

reasons. First, these polymers are ideal model systems to 

study the behavior of polyelectrolytes in aqueous solution, 

because their conformation is independent of the 

ionic strength. Hence, all effects observed on changing the 

ionic strength can be attributed to electrostatic interactions, 

so that the interaction of the counterions with the 

macroion can be studied without any superposed conformational 

effects as in the case of flexible polymers 

[492,493]. Secondly, cationic CPs embody the properties of 

polyelectrolytes with, e.g., optical and electronic functions 

of organic semiconductors which are largely determined 

by chain conformation and interchain contacts [156]. 

They are under consideration for potential uses in various 

technologies, despite their complex structure/property 

relationships [157]. 


Some cationic CPs were already mentioned in foregoing 

sections (cf. Section 3.3, Fig. 11). Figs. 15 and 16 

list cationic CPs such as 172–187 with an intrinsically 

rodlike poly(p-phenylene) (PPP) backbone. They were 

exclusively synthesized by polycondensation under Pdmediated 

Suzuki cross-coupling conditions of monomers


Fig. 15. Poly(p-phenylene) based cationic conjugated polymers 172–184.

containing solubilizing side chains. Mostly, the precursor 

strategy is used, where the polycondensation of monomers 

with non-ionic side chains leads to uncharged polymer 

precursors which can be readily characterized. Then the 


Fig. 16. Poly(p-phenylene) based cationic conjugated polymers 185–187. 

precursor is transformed into well-defined cationic PPPs, 

sometimes via an activated intermediate. The direct strategy, 

i.e., a Suzuki reaction of charged monomers has been 

rarely applied, mostly because the molecular characteriza- 

Fig. 17. Poly(p-phenylene vinylene) based cationic conjugated polymers 188–194.


Fig. 18. Poly(p-phenylene acetylene) and poly(acetylene) based cationic conjugated polymers 195–203. 

tion of the resulting ionic polymers is difficult [492,493]. 

Polymers 172–175 were synthesized with precursors carrying 

reactive ethers (or oligoethylene oxides in the case 

of 176) as solubilizing groups which are easily modified 

to ionic groups [492]. The kinks in the backbone of CP 184, 

showing a range of regiochemistry were created by varying 

ratios of p- and m-phenylene bisboronic acids in a Suzuki 

copolymerization [506]. 

Next to the PPP family, a number of cationic CPs is 

derived from poly(p-phenylene-vinylene) (PPV), as shown 

in Fig. 17. The PPV backbone is made mostly by Heck coupling 

[177,178,510,512,514,524] or by the Gilch reaction 

[511,513], or by the Wittig reaction [511]. The cationic PPV 

192 was synthesized via the precursor route [513]. 

Though rarely used, several routes to cationic CPs 

are based on chain reactions. The 1,4-topochemical polymerization 

of functional diynes leads to 199 and 200 

[518,519]. Another approach is the ring-opening metathesis 

polymerization of ionically functionalized cyclooctatetraenes. 

For example, the copolymerization with the 

non-ionic trimethylsilylcyclooctatetraene leads to 201 

[520]. 

Cationic water-soluble conjugated polymers based on 

polysilanes 206 were synthesized using sonochemical 

methods [158]. The steric crowding of the densely substituted 

Si-Si backbone results in relatively rigid polymer 

chains. 

Various cationic CPs have backbones built by heterocycles. 

Cationic poly(pyrrole)s are accessible by oxidative 

coupling of the corresponding monomers. 210 was synthesized 

by electrochemical or chemical polymerization 

of N-hexyl-cyclopenta[c]pyrrole [163], while 209 and 211 

are available by anodic coupling of the corresponding 

substituted 2,2 ′ -bipyrroles [164]. The oxidative polymerization 

of pyrrole substituted by (ferrocenyl)ammonium 

groups leads to polymers 207 showing pronounced electroactive 

properties, which were studied extensively 

[160,161]. Analogously, cationic poly(thiophene)s 204 

were prepared by oxidation of the charged thiophene 

with anhydrous FeCl 3 [165]. Polymers 144 (Section

3.3) were synthesized by polymerization of p-bis(4-(2,6diphenylpyrylium))benzene 

ditriflate with a series of 

aromatic diamines [459]. Material 212 has been obtained 

by nucleophilic substitution of the neutral precursor 

(palladium-catalyzed Stille copolymerization) or by exposure 

of films with trimethylamine gas [630]. 


The optical and electronic properties of ionic 

CPs can easily be tuned by designing the structure 

of the conjugated polymer backbone considering 

appropriate ionic functionalities, leading to versatile 

application in optoelectronic and biological research 

([433,496–499,501–509,511,512,517] and references 

therein). Thus, ionic CPs are the basis for polymeric 

optoelectronic devices. Examples are ink-jet and screen 

printing techniques. Furthermore, ionic CPs are a unique 

platform for highly sensitive chemical and biological 

sensors, based on specific properties like a high absorption 

cross section in the UV-visible, high photoluminescence 

efficiency in the visible spectrum and amplified fluorescence 

quenching of fluorescent CPs, as first reported for 


Fig. 19. Cationic conjugated polymers with heterocyclic structure 204–212. 

cationic CPs in 1999 [496]. Later, the relationship between 

the chemical structure and its corresponding ability for 

biosensing was intensely studied [506,526,527]. The 

various detection schemes include, e.g., assays for DNA, 

proteins and metal ions. 

172–174 and 176 served for an extensive study of 

the behavior of polyelectrolytes in aqueous solution 

[492,493,494], while 175 and similar copolymers of 173 

and 174 containing also uncharged phenylene moities are 

insoluble in water. 172 was also investigated with regard 

to the adsorption on oxidized silicon surfaces [495]. 

The use of fluorescent CPs for amplified sensing of 

chemical and biological analytes is of increasing interest 

[497–499]. The fluorescence quenching of 177 [522] by 

several anionic quenchers proceeds with high efficiency 

[496]. Alternatively, the light-harvesting properties of CPs 

provide enhanced fluorescence signals for chromophorelabeled 

nucleic acids or DNA probes via fluorescence 

resonance energy transfer (FRET) after selective binding 

to the polycation [503]. Polymer 186 was part of a study 

of the energy levels of different CPs as a function of the 

type of charge and the effect of charge compensating


counterions [179,505]. Furthermore its interaction with 

DNA was investigated by various spectroscopic methods 

[631]. Electrostatic complexes of 178 (m = 85, n = 15) with 

the anionic CP poly[9,9-bis(4 ′ -sulfonatobutyl)fluorene-coalt-1,4-phenylene] 

were tested as FRET donor to labeled 

single-stranded DNA according to a two-step FRET process 

[500]. Polymers 179 and 180 [523] allow the quantification 

of heparin by FRET [501]. Polymers 181 with different 

charge density show similar optical properties in aqueous 

solution, but differences in FRET to labeled DNA demonstrate 

the strong influence of the molecular architecture on 

the energy transfer process [502]. Cationic CPs have proven 

useful for strand-specific DNA detection [503,507–509]. 

Noteworthy, CP 184 with a range of backbone regiochemistries 

was a more efficient excitation donor than the 

analogous strictly linear polymers. 

When the imidazole moieties containing highly fluorescent 

CP 183 coordinates to Cu 2+ ions, its fluorescence is 

effectively quenched. This process is inhibited in the presence 

of NO, thus leading to an effective assay to detect this 

biological messenger molecule and other biologically relevant 

reactive nitrogen species [504].CP182 was developed 

as an electron injection layer for polymer light-emitting 

diodes [76]. The cationic polyfluorene copolymers 185 containing 

2,2 ′ -bipyridine moieties in the backbone are good 

fluorescent probes for Cu 2+ ions [433]. Generally, the optical 

properties of ionic CPs are strongly influenced by the 

counterions, which control inter-chain contacts and charge 

transport in polymer 187 [157]. 

PPV 194 exhibits unique pH-dependent optical properties 

in aqueous solution, due to changes in composition of 

two distinct polymer conformations [159]. While cationic 

PPVs 189 and 190 emit green light [511], analogs 191 and 

193 emit intense blue-greenish light with relatively high 

photo luminescence, thus offering potential application as 

sensors [514]. Aiming for instance at a biosensor [512], 

the energy transfer processes of the cationic highly watersoluble 

poly(fluorenevinylene-co-phenylenevinylene) 191 

[525] were studied. The cationic PPV 192 served as highly 

sensitive biosensor for iron-sulfur protein detection [513]. 

Further, 188 [177,510,524] supports the detection of the 

shape-specific conformation of DNA based on FRET [178]. 

Similar investigations were carried out with 186 [179]. The 

analogous electrostatic interaction is the base for monolayers 

of cationic CPs adsorbing on negatively charged 

solid surfaces [528–531]. Multilayered assemblies of 188 

and hexa(sulfobutyl)fullerenes were investigated concerning 

the photoinduced charge transfer property in the 

film [510]. Similar to the cationic PPV analogs, poly(pphenylene 

ethynylene)s (PPEs) 197 and 198 carrying 

side chains with different hydrophilicity were investigated 

extensively concerning their pH and ionic strength 

influenced conformational change and the related optical 

behavior [517]. The cationic PPE 195 shows light-induced 

biocidal activity which appears effective due to the ability 

of the CP to form a surface coating on different bacteria 

[515]. PPE 196 is part of a chemosensor in which the 

fluorescence intensity is turned on from an initially low 

level [516]. The cationic polyacetylene derivative 202 [172] 

enabled fundamental studies of the electrical behavior 

of conjugated polymeric mixed ionic-electronic conduc- 

tors [173,174]. The amphiphilic polyacetylene 203 was 

used to prepare ultrathin films [175] and multilayers with 

alumosilicate [176]. 199 exhibits a remarkable high thirdorder 

nonlinear optical susceptibility [518]. 201 shows 

self-limited electrochemical doping [520]. Cationic watersoluble 

CPs based on polysilanes 206 are discussed as 

highly sensitive materials for chemo- and biosensors [158]. 

Self-assembled monolayers and electrostatically assembled 

multilayers of the soluble polypyrroles 209–211 were 

produced on gold and platinum electrodes and used for 

investigations of molecular junctions [162]. 

The cationic poly(thiophene) 204a was used for 

supramolecular chiral insulated molecular wires by selfassembly 

with a natural polysaccharide [16] and of 

biosensors [170]. The sequential layer-by-layer adsorption 

(see Scheme 4) of204b with poly(styrene sulfonate) 

leads to functional films [166], while the combination with 

an anionic poly(alkoxythiophene) results in conducting 

and electroactive polyelectrolyte multilayers [165–167]. 

Charge carriers formed under oxidation were studied in 

situ by ESR/UV-VIS-NIR spectrochemical methods [168]. 

The self-assembly of the polythiophene 205 with a similar 

polyanion on ITO/glass and gold electrodes resulted in 

layers with unprecedented regularity [521]. The ferrocenefunctionalized 

cationic polythiophene 208 allows the 

label-free electrochemical detection of DNA [171]. 

3.5. Nonlinear polymers 

Cationic polyelectrolytes with nonlinear structure 

(Figs. 20–24) comprise very different architectures: 

branched structures and brushes as well as more defined 

structures like star shaped and dendritic polymers. Some 

of them are shown in Scheme 5. 

These various types of polymers will be referred briefly. 

Not included are highly crosslinked materials like ion 

exchangers and hydrogels, which usually are prepared 

from well-known cationic vinyl monomers. These materials 

are discussed in hundreds of papers and by far out of 

the scope of this review. 

3.5.1. Statistically branched and crosslinked polymers 

3.5.1.1. Synthesis and properties. Soluble branched polyelectrolytes 

(such as 213–218) can be synthesized 

by graft techniques, or by copolymerization using 

macromonomers. Independent of the synthetic strategy, 

they may carry either the ionic groups in the backbone, 

or in the grafted chains. In the former case, the charge is 

mostly separated by a spacer from the backbone. Polymers 

215–217 are typical examples of the first group, 

whereas polymers 213–214 are typical examples of the 

second group. 

Copolymer 213 was synthesized by free radical copolymerization 

of poly-DADMAC bearing two diallyl end groups 

and N-vinylformamide, measuring kinetic parameters of 

the polymerization process [532,533]. The unquaternized 

macromonomers were made by anionic polymerization 

[533]. In a “grafting-to” approach, branched polymers 

with cationic side chains were prepared by grafting of 

low molecular weight poly-DADMAC onto high molecular 

weight poly-AAM by combination of radicals generated in

oth polymers, which were generated by �-irradiation of 

a mixture of both polymers [534–536], or by reactive processing 

of the polymers using organic peroxide initiators in 

the presence of glycerol as plasticizer [537]. A shortcoming 

of such procedures is the simultaneous formation of 

gels as well as of combination products of the homopolymers 

[535,536]. In a similar “grafting-from” approach, a 

series of vinyl monomers containing ammonium groups 

was polymerized from poly(vinyl alcohol) (PVA) using ceric 

ammonium nitrate as redox partner [538]. The resulting 

polymers 214 were characterized by standard methods, 

but possible side reactions like formation of homopolymers 

were not investigated. 

Branched polycations with uncharged side chains 

were prepared by copolymerization of cationic vinyl 

monomers and uncharged macromonomers. Polymer 

215 for instance is made by copolymerization of MATAC 

and poly(ethyleneglycol monomethylether methacry- 


Fig. 20. Selected nonlinear cationic polyelectrolytes 213–218. 

late) [539,540,574]. Analogously, amphiphilic graft 

copolymers were synthesized from MATAC and a poly(�methyl-�-valerolactone) 

macromonomer [542]. This 

strategy can be extended to more complex copolymer 

such as 217 that is obtained by terpolymerization of 

N-methacryloylamidopropyl-N,N,N-trimethylammonium 

chloride, AAM and an acryloyl terminated poly-AAM 

macromonomer [543]. Polymer 216 represents another 

variant of this type of branched polyelectrolytes, as 

made by copolymerization of a cationic vinyl monomer 

and a cationic endcapped, but otherwise uncharged 

macromonomer. The copolymerization in isopropanol has 

a high tendency to crosslinking [541]. The inverse emulsion 

polymerization of AAM and ATAC with semi-batch 

addition of several ppm MBA resulted in copolymers with 

homogeneous branching [245]. 

Another efficient processing aid are cationic poly-AAM 

microparticles with side chains of poly-EO. They were


synthesized via inverse microemulsion polymerization of 

AAM, ATAC, poly-EO macromonomer and N,N ′ -methylene 

bisacrylamide (MBA) [555]. 

Polycation graft structures are also of interest for the 

modification and functionalization of surfaces. Tailormade 

surfaces of solid materials are accessible by ultrathin 

coatings in the 1–500 nm thickness regime, which can be 

prepared by grafting polymers carrying reactive endgroups 

to the surface (“grafting-to” approach), or by surface initiated 

graft polymerization (“grafting-from” approach) 

Fig. 21. Selected cationic dendritic structures 219–223. 

[544]. Surface-initiated CRP in particular is a versatile 

method to achieve a maximum control over graft density, 

polydispersity and composition and allows the formation 

of block copolymers on the surface. If the grafting density 

is very high, the macromolecules are strongly stretched 

away from the surface and the coated films are usually 

referred to as polymer brushes [544]. Whereas so far 

only comparatively few examples have been reported 

for molecular polycation brushes [3,34,566,574,635] 

(Scheme 5a), such surface attached brushes are increas-

ingly studied. The “grafting-to” approach enabled the 

modification of gold surfaces with thiol-terminated 

poly-VBTMC [545]. But mostly, polycation brushes were 

prepared by surface initiated polymerization of cationic 

monomers, or of monomers which were reacted to cationic 

units once grafted. Covalently attached poly(4-vinyl-Nmethylpyridinium 

iodide) layers on silicon were obtained 



by immobilization of a silyl-functionalized azo initiator 

on the surface, bulk polymerization of 4-VP and quaternization 

[562,571]. The thickness of the resulting cationic 

monolayer can be controlled in a wide range, starting from 

2 nm to more than 1000 nm in the solvent-free state [571]. 

Polycation brushes on gold surfaces were obtained by ATRP 

of MATAC as well as of MATAC and MMA [564,572]. MATAC


brushes prepared via ATRP from gold, Si or glass substrate 

carrying a thiol (gold) or a 3-bromoisobutyric acid (Si, 

glass) initiator [566] were loaded with [AuCl 4] − precursor 

ions followed by their in situ reduction to Au nanoparticles 

[567]. Spherical cationic polyelectrolyte brushes 

result from the photoinitiated polymerization of ATAC on 

poly(styrene) latexes carrying a thin shell of a photoinitiator 

polymerized on these cores [568,569]. The grafting 

from solid surfaces is often initiated by high energy irradiation, 

as by UV-, e-beam or �-radiation. The latter method 

was, e. g., used to prepare ion-exchange membranes 

by grafting of glycidyl methacrylate onto poly(olefine)s 

followed by modification with triethylamine [546] as 

well as by grafting of VBTMC onto poly(ethylene) [547]. 

Another example is the modification of polyamide fibers 

by grafting MATAC and N-methacryloyloxyethyl-N,N- 


dimethyl-N-dodecyl ammonium chloride [548]. Plasma 

activation to generate surface radicals allowed the grafting 

of MATAC, MADBAC, VBTMC and DADMAC, resulting in 

ultrathin polyammonium coatings on poly(ethylene) films 

[549]. The alternative strategy uses the oxygen plasma 

induced formation of oxygen functional groups on the 

surface to attach polyelectrolytes with reactive anchor 

groups [549]. Irradiation by electron beam induced the 

grafting of N-methacryloyloxyethyl-morpholine, which 

was subsequently quaternized with benzyl chloride, 

onto poly(propylene) fabrics [550]. UV-induced graft 

copolymerization fixed poly(N-methacryloyloxyethyl- 

N,N-dimethylamine) onto the surface of poly(ethylene 

terephthalate) films, followed by quaternization with n-C 3, 

n-C 4, n-C 8, n-C 10 and n-C 12 alkyl bromides [551]. Films of 

electroactive polymers, such as poly(aniline) and poly(3-


Fig. 24. Selected cationic dendritic structures 234–237.


Scheme 5. Unusual polycationic architectures: (a) polycation brush; (b) hyperbranched polycation; (c) polycation dendrimer (cationic end groups); (d) 

polycation dendrimer (cationic focal points). 

alkylthiophene)s are readily functionalized via thermal 

or near UV-light induced surface graft copolymerization 

[552]. Photo-initiated graft polymerization of MATAC 

onto poly(acrylonitrile) membranes in the presence of 

benzophenone provided low-fouling ultrafiltration and 

nanofiltration membranes [553]. Graft polymerization of 

MATAC initiated by cuprate(III)-complexes inside macroporous 

poly(acrylamide) gels enabled to vary the properties 

in a broad range [554]. 

Self-crosslinkable polyelectrolytes possessing humidity 

sensitive properties were prepared by copolymerization 

of 5–15 mol% 3-(trimethoxysilyl)propyl methacrylate with 

MATAC or ATAC [556]. 

Copolymers of methyl vinylbenzyl pyrrolidinium chloride 

and MMA exhibit thermally induced self-crosslinking 

with the formation of chemical links between both 

monomer units and splitting of N,N-dimethylpyrrolidinium 

chloride [557,558]. Polyhedral oligomeric 

silsesquioxane (POSS) compounds were quaternized to 

218 [632]. 

3.5.1.2. Properties and application. Several results indicate 

polyelectrolytes bearing cationic side chains to be more 

efficient processing aids in solid-liquid separation processes 

than the corresponding linear macromolecules. 

Copolymers 213 were found to be more effective flocculants 

than linear random cationic copolymers [532]. 

Polymers prepared by grafting of low molecular weight 

poly-DADMAC onto high molecular weight AAM performed 

better than the homopolymers in flocculation and 

sludge dewatering [535,536]. Furthermore, copolymers 

with homogeneous branching as synthesized by inverse 

emulsion polymerization of AAM and ATAC with semibatch 

addition of several ppm MBA are more efficient 

in flocculation of suspended solids than the traditional 

batch-wise MBA-added copolymers [245]. The solution 

properties of the polycation 215 carrying uncharged side 

chains strongly depend on the grafting degree [539]. The 

complexes of 215 with anionic block copolymers carrying 

poly(ethylene oxide) blocks are water soluble even 

at a charge ratio of 1:1 [540], due to the hydrophilicity 

of the non-ionic graft chains and blocks. Polymer blends 

containing amphiphilic graft copolymers of MATAC and 

poly(�-methyl-�-valerolactone) macromonomer showed 

both low surface resistance and low volume resistivity 

[542]. Complex formation of 217 with the sodium salt of 

poly(acrylic acid) leads to nanoparticles consisting of a 

hydrophobic complex core and a protective hydrophilic 

poly-AAM corona [543], as discussed analogously for the 

polyelectrolyte complexes of 215. Silicon containing covalently 

attached poly(4-vinyl-N-methylpyridinium iodide) 

brushes were used to investigate the complexation with 

oppositely charged polyelectrolytes [563]. Poly-MATAC 

brushes on gold surfaces can be easily deformed in water 

in both extended and collapsed conformation, provided 

the ionic strength is low. Otherwise the brushes become 

very rigid [565]. The conformational changes of the MATAC 

brushes were investigated extensively and discussed as a 

goal to chemically controlled actuators [572]. The adsorption 

of spherical cationic polyelectrolyte brushes (ATAC on 

poly(styrene) latexes) on negatively charged mica can be 

controlled in situ by the ionic strength of the suspension 

[570]. Furthermore, they serve as models for a systematic 

study of the interaction of sterically stabilized particles 

with solid substrates by means of AFM [573]. 

The grafting of quaternary vinyl cations on polymer 

surfaces results in materials with antibacterial properties. 

Typical examples are the modification of polyamide 

fibers with MATAC and N-methacryloyloxyethyl-N,Ndimethyl-N-dodecyl 

ammonium chloride [548], the 

coating of poly(ethylene) films with MATAC, MAD- 

BAC, VBTMC and DADMAC [549] and the grafting of 

N-methacryloyloxyethyl-morpholine, which was subsequently 

quaternized with benzyl chloride, to produce 

poly(propylene) fabrics with improved hydrophilicity 

and antimicrobial properties [550]. Also polymers 218 

were investigated regarding their antimicrobial activity in 

solution and on coatings [632]. 

3.5.2. Dendritic polymers 

3.5.2.1. Synthesis and structure. Polycations with defined 

branches comprise star-shaped (one common branching 

point) and dendritic (multiple, regularly spaced branching 

points) architectures (Scheme 5b–d). Polycations of both

architectures are relatively rare yet. Precursors of starlike 

strong cationic polyelectrolytes with up to 24 arms 

were synthesized by ATRP of N-methacryloyloxyethyl- 

N,N-dimethylamine employing a core-first attempt using 

oligofunctional initiators based on glucose, saccharose, 

�-cyclodextrin (�-CD) and (diglycidylamino)propylfunctional 

silsesquioxane containing 2-bromoisobutyryl 

initiating fragments. Quaternization of the stars transformed 

the precursors into well-characterized strong 

polyelectrolytes [575]. Using the above mentioned oligofunctional 

�-CD initiator directly in the ATRP of monomer 

MATAC in aqueous solution yielded strong polyelectrolyte 

stars. However, the limited solubility of a fully functionalized 

�-CD initiator in water leads to a fairly unsatisfactory 

control of the molecular weight [576]. As the poly-MATAC 

stars collapse in solutions of multivalent counterions due 

to the marked decrease of the osmotic pressure within the 

macroion, the conformation of the stars can be manipulated 

by photoreduction of [Co III (CN) 6] 3− counterions 

[577]. The cationic molecules 224 incorporating 4-benzoyl- 

N-alkylpyridinium moieties serve as models of redox 

dendrimers [606]. 

Dendritic polymers include both dendrimers 

(Scheme 5c and d) and hyperbranched macromolecules 

(Scheme 5b). Numerous synthetic strategies have been 

reported for the preparation of these materials leading 

to a broad range of dendritic structures [578–585]. Den- 


Scheme 6. Example for a divergent growth of dendrimers. 

drimers are synthesized by multistep procedures (step 

growth, chain growth, living chain growth) of ABn (n ≥ 2) 

monomers, in a convergent or divergent approach. Perfect 

dendrimers are true monodisperse macromolecules with 

an unique core-shell structure made of a core, an interior 

of shells (generations) consisting of repeating branch-cell 

units, and a generation dependent, non-linear growing 

number of terminal functional groups forming the outer 

shell. In contrast, hyperbranched polymers are typically 

prepared by a single step reaction (polycondensation, ring 

opening, or polyaddition reaction) of multifunctional ABn 

(n ≥ 2) monomers or of macromonomers. The resulting 

polymers are characterized by a high polydispersity and a 

lower degree of branching than an analogous dendrimer. 

Furthermore, the terminal groups are scattered throughout 

the macromolecules, and not confined to the outer shell. 

3.5.2.2. Cationic dendrimers. 

3.5.2.2.1. Synthesis and structure. An example for the 

general construction of dendrimers is given in Scheme 6. 

Here an AB 2 type repeat unit is used. The continuous alternation 

between coupling reaction (growth, upper row) and 

reactivation step (lower row) leads to a controlled growth 

under permanent branching. 

Due to the particular architecture, cationic dendrimers 

may be classified according the location of the charged 

groups (Figs. 21–23): in the core (e.g., 219, 220, 227, 228),


within the shells (e.g., 224, 225, 226), at the surface (e.g., 

221, 222, 229), or distributed over the whole molecule (e.g., 

223). Many of the cationic materials were synthesized by 

modification of preformed reactive dendritic structures, 

taking advantage of the two main, commercially available 

dendrimer types, namely poly(amideamine)s (PAMAM) 

and poly(propylene imine)s (PPI). These polymers are 

based on tertiary amines as branching units, and mostly 

bear primary amines as terminal groups, which conveniently 

serve as precursors for modification reactions to 

introduce cationic groups. Accordingly, the derived dendrimers 

bear cationic groups in the shells, and/or at the 

surface. 

Typical examples for dendrimers with a cationic core 

are 219, 220, 227, 228, which were made by the convergent 

approach. The reaction of trans-1,2-bis(4-pyridyl)ethylene 

with two dendron bromides (first to third generation) gave 

polymer 219 [586]. Cationic dendrimers 220 have a tetracationic 

core that is surrounded by a hydrophobic layer 

of dendritic wedges. They were synthesized similarly to 

219 by quaternization of tetraarylsilane building blocks 

containing tertiary amine groups with suitable dendrons 

containing a benzyl bromide focal point. 

Cationic dendrimers carrying the charged groups within 

the shells are mostly synthesized by quaternization of 

preformed PAMAM and PPI. For instance, the internal tertiary 

amines of hydroxyl-terminated PAMAM (PAMAMOH) 

were modified by methylation to introduce a more 

cationic character due to an easily adjustable amount 

of quaternary groups [591]. Complete methylation and 

quaternization of dendritic PAMAM results in cationic dendrimers 

quaternized in both the interior shells and at the 

surface [599]. Similarly, low-generation PPI-dendrimers 

were functionalized to fully quaternized species possessing 

hydrophobic n-dodecyl groups. The surfactant-like species 

form micelles through self-association or behave even as 

unimolecular micelles [603,604]. The direct access to dendrimers 

with cationic shells is exemplified by polymer 223, 

which was prepared by a high yield Menshutkin reaction: 

the benzylic CH 2Br-groups at the focal point of the 

growing dendritic wedges alkylate the benzylic tertiary 

amine of the monomer, thereby producing cationic sites 

[605]. The coupling of amines with powerful alkylating 

agents during dendrimer growth to provide cationic shells 

can be varied widely. The chiral cationic dendrimers 226 

are formed by quaternizing both nitrogen atoms of 1,4diazabicyclo[2.2.2]octane 

[609]. Dendrimer 225 was grown 

by reaction of benzyl bromides with bipyridyls [608]. 

Viologen functionalized PAMAM dendrimers 221 up 

to generation 6 were constructed by an amidation 

reaction between the succinimide ester of 1-ethyl-1 ′ - 

(3-propionic acid)-4,4 ′ -bipyridylium dibromide and the 

primary amine groups of the dendrimer surface, resulting 

in dendrimers with a cationic surface. The degree of 

endgroup functionalization was 13–34% [588]. Also, the 

surface of PAMAM was quaternized via a Michael reaction 

of the primary amine groups with ATAC [589]. Inan 

alternative strategy, cationic dendrimer-type surfactants 

were obtained by quaternization of the surface NH 2groups 

of PAMAM with glycidyldimethyloctylammonium 

bromide [600–602]. Analogously, quaternized PPI den- 

drimers are made by reaction of its external NH 2-groups 

with glycidyltrimethylammonium chloride, introducing 

simultaneously �-hydroxyamine moieties [590]. A similar 

reaction was carried out to introduce dimethyldodecylammonium 

groups into the surface of the 3rd generation 

of a PPI-dendrimer [594,595]. Cationic organophosphorus 

dendrimers up to generation 4 containing a phosphorous 

based core and pyridinium chloride [596,597] as well 

as tetraalkylammonium chloride [596–598] as terminal 

groups were synthesized in a quantitative yield by reacting 

the corresponding aldehyde-terminated dendrimers 

with Girard-P or Girard-T reagent, respectively [599]. A 

completely different approach was used to prepare novel 

star-shaped copolymers 229, by graft polymerization of Nmethyl-2-ethynylpyridinium 

triflate on the primary amine 

terminal groups of a PAMAM dendrimer [610]. 

3.5.2.2.2. Properties and application. Dendrimer 219 

was investigated with respect to its photo-responsive and 

redox-active properties [586]. 220 bearing a tetracationic 

core has been investigated for its ability to form assemblies 

with anionic guest molecules [587], as were cationic 

dendrons 227 and 228, encapsulating a porphyrin tetrasulfonate, 

or a tungstate cluster, respectively [582]. The 

interaction of cationic dendrimers carrying the charged 

groups within the shell with DNA resulted in the formation 

of highly condensed neutral polyplexes [583]. 

Dendrimer 225 forms strong host–guest complexes with 

the dianion of eosin, such that each viologen unit binds 

to one eosin molecule [608]. Electroactive dendrimers 

consisting of a viologen skeleton that contains electrochemically 

accessible 4,4 ′ -bipyridinium subunits show a 

novel, dendrimer generation-dependent and electrochemically 

switchable CT complexation [607]. Quaternization 

of the surface of PAMAM results in efficient flocculants 

[589]. Analogously, quaternized PPI dendrimers were considered 

for pH-controlled release systems [590] and serve 

as powerful biocides [594,595]. Poly(glycerol-succinate) 

dendrimers 222 with terminal quaternary ammonium 

groups [592] are amphiphilic and form strong electrostatic 

interactions with DNA [593]. Cationic organophosphorous 

dendrimers were used as new gelators in water 

[596], show thermoreversible properties [597], and support 

the surfactant-induced synthesis of mesostructured 

nanoporous silica [598]. The adsorption properties of the 

commercially available cationic polyesteramide 231 were 

investigated as a function of pH, ionic strength, etc. and 

compared to poly-DADMAC [614]. 

3.5.2.3. Cationic hyperbranched polymers. Hyperbranched 

polymers can be prepared by a one shot reaction from 

many commercially available monomers with functionalities 

larger than 2. Though imperfectly branched, the ease 

of synthesis renders such polymers particularly attractive 

for a plethora of different fields [611,612]. Again, cationic 

hyperbranched polymers may carry the cationic groups 

only in the core, or distributed over the whole macromolecule. 

Different from dendrimers, no clear distinction 

between “shell” and “surface” exists due to the statistically 

(instead of regularly) branched architecture. Despite 

the basic ease of synthesis and the frequently encountered 

tertiary polyamine motifs, hyperbranched polymers with


Fig. 25. (Meth)acrylate homopolymers 238–245 as surfactants (241, 245 as monomers).


permanently cationic groups have been surprisingly rarely 

up to now (see Figs. 23 and 24). 

Multibranching anionic ring opening polymerization of 

tris(hydroxymethyl)-propane followed by reaction with 

epoxide terminated PEG-monomethylether leads to hyperbranched 

polymers based on poly(glycerol) (PG) and 

poly(ethylene glycol) (PEG). Multivalent cationic sites are 

added to these polymers by postamination and quaternization 

leading to 230 due to the two-step formation, the 

Fig. 26. (Meth)acrylate copolymers 246–250 as surfactants. 

polymer approaches a core-shell structure with a cationic 

shell [613]. Hyperbranched poly(ethylene imine)s were 

concurrently functionalized to 237 with cationic and reactive 

groups by epoxides and cyclic carbonates [322]. 

Hyperbranched compounds 232 and 233 containing 

pyridine moieties were prepared by step growth 

polymerization, namely by poly-N-alkylation of the AB 2 

monomers 3,5-bis(bromoalkyl)pyridine hydrobromide 

232 [615] and 3-[4 ′ -(bis-(4 ′′ -bromobutanoyloxyethyl)


Fig. 27. Polystyrene derivative homopolymers 251–253 as surfactants (252 and 253 as monomers). 

aminophenylazo]pyridine 233 [137,138]. Alternatively, 

chain growth polymerization, such as selfcondensing 

vinyl copolymerization of 2-(2-bromoisobutyryloxy)ethyl 

methacrylate with dimethylaminoethyl methacrylate via 

ATRP followed by quaternization with methyliodide led to 

water-soluble cationic highly branched structures [616]. 

Hyperbranched polyglycerole, prepared by anionic 

ring-opening polymerization of glycidol and thus containing 

a large number of reactive OH-groups was 

functionalized to cationic polyelectrolytes 234a and 234b 

by reaction with �-bromoacylchlorides in the presence of 

pyridine or 1,2-dimethylimidazol [617]. 

Hyperbranched polysoaps of the ionene type 235 and 

236 consisting of individual surfactant fragments were 

prepared by polyreaction of the corresponding monomers 

containing one alkylating and two tertiary amine groups 

[292]. 

3.5.2.3.1. Properties and application. The hyperbranched 

polymer 230 condenses DNA to highly compact 

nanoparticles in the range 60–80 nm [613]. The colored 

233 was used in the assembly of alternating polyelectrolyte 

multilayers [137,138]. Hyperbranched polysoaps 235 and 

236 behave similar to classical “head-type” polysoaps 

[292]. 

3.6. Polymeric surfactants 

Polycations which contain a large number of hydrophobic 

groups become amphiphilic, and behave as macro- 

molecular surfactants and emulsifiers (Figs. 25–32). They 

display characteristic properties such as surface activity, 

foaming power, solubilization or dispersion ability, and the 

ability to self-assemble, e.g., into micelles. A large variety 

of such cationic homo- and copolymers has been prepared 

and examined in the past decade. Aspects as synthesis, 

properties, self-assembly and (potential) applications of 

polymeric surfactants have been reviewed occasionally 

[375–377]. Ref. [375] provides a comprehensive list (until 

1995) of the cationic surfactant monomers (“surfmers”) 

used in this context. While numerous articles describe 

the synthesis and characterization of surfactant properties, 

application oriented reports are less frequent in the 

scientific literature. Main uses for polymeric surfactants 

comprise stabilizers in emulsion based processes, ingredients 

in specialty detergent formulations, or biocides. 


Considering the chemical structure of polycationic surfactants, 

it is helpful to distinguish different architectures; 

in particular the so-called macrosurfactants such as 246b 

and 257b [353,354] from the so-called polysoaps (see all 

homopolymers in Figs. 25–32). 

The former are best exemplified by graft and block 

copolymers with separate cationic and hydrophobic blocks, 

or grafts and backbone, respectively. In contrast, the latter 

are characterized by repeat units which by themselves 

are already amphiphilic. They are typically constructed by


chemical transformations of reactive precursors, by statistical 

copolymerization of classical cationic monomers and 

uncharged hydrophobic monomers, or directly using polymerizable 

surfactants or lipid analogs, so-called “surfmers”. 

Characteristically, micellization of the monomers results 

Fig. 28. Polystyrene derivative copolymers 254–256 as surfactants. 

Fig. 29. Poly-(diallyl) compounds 257 as surfactants. 

in increased local concentration and preorganization of 

the polymerizable moieties, thus increasing the reactivity 

(Scheme 7). Moreover, even if the resulting hydrophobically 

modified polycations cannot be redispersed in water, 

after isolation, the in-situ prepared polycations generally

exhibit stable colloidal solutions [[375] and references 

therein]. 

Details of these syntheses can be found in the sections 

with the corresponding basic polymer structures. Though 

self-sufficient to obtain cationic polysoaps by homopolymerization, 

surfmers have been often copolymerized, 

too, either to adjust the properties of the polysoaps, 

or as reactive stabilizers in heterophase polymerization 

processes, preferentially in emulsion, miniemulsion and 

microemulsion polymerization as with 238a, 238c and 

251a [276,282,289,300]. Typically, statistical copolymerization 

is preferred. Still in recent years, the number 

of reports on block copolymers like 238k, 246f and 


Fig. 30. Ionenes 235, 236, 258–261 as surfactants. 

Fig. 31. Poly-p-aromatics 262 and 262 as surfactants. 

255 containing surfmers has increased [35,310]. Some 

reviews dealing with special surfactant structures such 

as multicompartment micelles have to be considered too 

[324,372]. 

Figs. 25–32 summarize various types of cationic 

polysoaps with respect to their basic polymer structures, 

namely as poly(meth)acrylics (Figs. 25 and 26), polystyrene 

derivatives (Figs. 27 and 28), poly(diallyl ammonium) salts 

(Fig. 29), ionenes (Fig. 30), conjugated polymers (Fig. 31), 

and other backbone structures (Fig. 32). 

In the past decade many new syntheses of potential 

surfactants und unusual architectures of amphiphiles 

have been developed. Derivatives of standard polymers


such as different kinds of terpolymers 246e,i [293], acrylates 

238b,c,f,h, 240 and 246d [278,325,350], maleates 

267, 268 [326,344,349], vinylamide derivatives 269 [305], 

tail-end pyridinium (meth)acrylates 242c,d [217,342], 

poly-DADMAC block copolymers 257b,d,f,g [343,354] and 

poly(vinylimidazolium) derivatives 270b,c [367] as well 

as more unusual polyelectrolyte structures such as hyperbranched 

235, 236 [292] or chiral [357] ionenes based 

on 261 or siloxane copolymers 250a,b and 271 [358,365] 

were reported. Special procedures such as �-ray initiated 

Fig. 32. Various polymer structures 264–274 as surfactants. 

polymerization were developed due to its homogeneous 

penetration of the sample at room temperature without 

any additional initiator to be needed. This was successfully 

applied using 238a,i or 264 in liquid crystalline phases 

[296,301,306,348]. 

These papers are mainly focused on synthetic aspects 

and investigation of general surfactant properties such as, 

for example, critical micelle forming concentration, aggregation 

tendency and interaction with different anionic 

substrates.


Scheme 7. Polymerization behavior of ionic polymerizable surfactants (“surfmers”) as function on the association state: (a) isolated surfactant with normal 

polymerization reactivity; (b) aggregation at concentrations above the critical micellization concentration (cmc) results in increased local concentration 

and preorganization of the polymerizable moieties, thus increasing the reactivity; (c) polymerized surfmers form typically stable colloidal solutions, even 

if the isolated polymer cannot be redispersed in water. 


A variety of methods is used to characterize the physical 

properties of surfactants. Examples are the fluorescence 

spectroscopy using pyrene labeled compounds 249, 251h, 

257a, 270a,b or 273 [283,303,328,363,366,369], SAXS for 

the determination of the phase curvature in mixtures of 

surfactants with 238a,d [309,312], drop shape analysis of 

fluorine containing films with 258a,b [321,327] or 1 Hnmr 

spectroscopy for the investigation of intermolecular 

association in 251b,c [335]. Numerous applications display 

polymeric surfactants as processing aids and/or constituent 

in polymeric materials. 

One of the main applications uses the stabilizing properties 

of polymeric surfactant and/or surfmers. Stable 

emulsions are used to polymerize MMA with 238a or 

244a [346,347], ST using 238a,c, 244b, 246a,k, 251b,c, 

254b,d or 266 [276,289,298,323,351,359,432], to produce 

pH-sensitive gels with 240 [320] or membranes for ultrafiltration 

using 238a,c or 252 [290,300,319]. Furthermore 

surfmers such as 238a,b,d, 239 or 251a are applied for radical 

micellar copolymerization [282,284,304] and of liquid 

crystalline phases in the case of 238i,l, 246g or 264a,b,c 

[285,286,291,311,315]. Amphiphilic structures like 241 are 

known to form lyotropic liquid crystalline phases, which 

can build ionic channels [331]. Polymerizations with 246h 

in a lyotropic mesophase [240] or using 253 in a lamellar 

phase [333] and a photopolymerization of a lyotropic liquid 

crystal with 238i [332] are reported. Thermotropic liquid 

crystalline complexes containing 242a,b are discussed, 

too [218,329]. A further research area of enormous interest 

comprises interactions of amphiphiles with inorganic 

matter. Multilayers containing TiO 2 and 238m [337], composites 

of fluorescent nanocrystals of CdTe with polymer 

251e or 254c [313,334], polystyrene-clay nanocomposites 

using 238n, 251f,g or 270a,d [316,318,339,340] and 

adsorption phenomena of polymer amphiphiles 254f on 

silica [356] are reported. In general polysoaps such as 247, 

259 and 260 can serve as polycation in layer-by-layer self 

assembly investigations [191,295,330]. 

Special surfactant architectures including fluorinated 

comonomers like 248, 256 or 258b are needed to form multicompartment 

micelles [50,294,297,327]. Laschewsky et 

al. compared different polymer architectures of fluorinated 

copolymers 255 (block vs. statistical) in terms of properties 

like microphase separation [35]. High antibacterial activity 

of special fluorine containing co-oligomers 246l compared 

to non-fluorinated species was reported by Sawada et al. 

[373]. Antimicrobial modification of polyurethane surfaces 

was achieved using co-telechelics 274 which have ammonium 

and fluorine-containing moieties [628]. 

Furthermore application oriented papers discuss polymeric 

surfactants 257c in terms of micellar catalysis of 

enzymic reactions [281], stationary phases for electrokinetic 

capillary chromatography in the case of 246c, 258a 

or 265 [302,371], enantioselective hydrogenation support 

using 243 [341] and viscosity management with 246e, 

250c or 273 [307,368,370]. Finally some special applications 

of polymer surfactants have to be mentioned such as 

stabilization of catanionic vesicles with 238e [206], polymer 

modification of colloid particles using 251g [318] and 

stimuli-responsive polysoap hydrogel of 257e in an electric 

field [360]. 

4. Conclusions 

Synthetic—mostly water soluble—polymeric quaternary 

ammonium compounds cover nowadays a wide range 

of molecular architectures. These include linear macromolecules 

with flexible chains, conjugated polymers, 

polymeric surfactants, statistical, graft and block copolymers 

as well as hyperbranched and dendritic structures. 

These various chemical structures are accessible using 

well-known techniques of polymer synthesis, namely by 

chain or step polymerization of suitable monomers as 

well as by the functionalization of reactive precursor polymers. 

The synthesis proceeds most conveniently by free 

radical polymerization either in aqueous solution or, especially 

on the technical scale, heterogeneous media such 

as in inverse emulsion. The new methods of controlled 

free radical polymerization have facilitated the synthesis 

of well-defined homo- and blockcopolymers. These 

are of growing interest, so far mainly to prepare model 

polymers with adjusted chemical structure and molecular 

parameters for fundamental investigations, as needed 

in life sciences or for establishing structure-property relationships 

which are valid for any application. Furthermore, 

the wealth of routes to ammonium polymers offers plentiful 

possibilities to introduce additionally special functional 

groups, thus imparting individual, tailor-made properties 

to them. The rich synthetic possibilities have resulted in a 

continuously increasing number of polycation structures, 

and clearly, this will carry on in the future. 

The impressive developments of the synthetic quaternary 

ammonium polymers are closely linked to the broad


range of properties of these polyelectrolytes, which are 

more than a mere superposition of the properties of neutral 

macromolecules and simple electrolytes. The variability 

of the polymer properties leads to manifold applications 

in industrial processes, biosciences, and daily life. The 

formidable diversity of applications can be deduced from 

some physicochemical key properties such as electrostatic 

interaction, ability for complex and network formation, 

stabilization of colloids, modification of rheological and 

interfacial behavior, solubilization and induced phase separation. 

The extreme versatility of these polycations will stimulate 

further developments concerning both molecular 

architectures and applications. 

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