Fluorine containing self‐crosslinking acrylic latexes with reduced flammability and their application as polymer binders for heterogeneous cation‐exchange membranes

In this study, self‐crosslinking core–shell latexes comprising copolymerized perfluorethyl groups and a novel flame retardant based on phosphazene derivative were prepared by the semi‐continuous non‐seeded emulsion polymerization of 2,2,2‐trifluorethyl methacrylate, methyl methacrylate, butyl acrylate, methacrylic acid, and hexaallylamino‐cyclo‐triphosphazene as main monomers. For interfacial crosslinking, diacetone acrylamide was copolymerized into the shell layer of latex particles to provide sites for subsequent reaction with adipic acid dihydrazide. The heterogeneous cation‐exchange membranes were obtained by dispersing commercial strong acid cation‐exchange resin powder in the latex binder and casting the mixture followed by keto‐hydrazide crosslinking reaction. It was found that the increased concentration of fluorine atoms and phosphazene units in the macromolecular structure of interfacially crosslinked emulsion polymers resulted in a significant enhancement of their flame resistance and shape stability in aqueous environment. Moreover, the easily prepared heterogeneous cation‐exchange membranes based on latexes with higher amounts of fluorine and phosphazene units were shown to exhibit satisfactory physicochemical and electrochemical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45467.     

Preparation and properties of reactive polyurethane polyacrylate blends based on carbonyl‐hydrazide reaction

A new reactive polyurethane/polyacrylate (PU/PA) blend was developed by mixing a core–shell polyacrylate latex containing keto groups in shell layer and a polyurethane dispersion incorporating multiple hydrazide groups which was synthesized by introducing the poly‐hydrazide groups into the end of the vinyl‐terminated polyurethane chains. Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC) results indicated that poly‐hydrazide groups had been incorporated in the polyurethane chains. Transmission electron microscopy (TEM) micrograph revealed that polyacrylate particles had a clear core–shell structure. The results of FTIR, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) indicated that the crosslinking reaction between two polymer systems had happened and crosslinking structure could effectively improve the compatibility between PA and PU. Thermogravimetric analysis (TGA) and mechanical tests results suggested that crosslinking structure could enhance the thermal stability and mechanical properties of blends. The influence of the PA content and the n(? CO? )/n(? NHNH₂) ratio on the hardness, water resistance, solvent resistance, and gel fraction of the blend films were comprehensively studied. The optimal PA content and n(? CO? )/n(? NHNH₂) ratio was 30% and 1.5:1 in this experiment, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44443.     

Crosslinking of isocyanate functional acrylic latex with telechelic polybutadiene. III. Application of a diffusion model

The diffusion and reaction of amino-telechelic polybutadiene (PBD-NH₂) in poly(styrene/n-butyl acrylate/TMI®) (PSBT) was studied. A monodisperse poly(St/BA/TMI) seed latex was prepared by semicontinuous emulsion polymerization. Two core/shell latices were also prepared semicontinuously, using the seed latex as the core and poly(St/BA) as the shell. These monodisperse latices were mixed with equivalent amounts of the telechelic PBD-NH₂ artificial latex before casting into films. The consumption of the TMI in these films was monitored by FTIR as a function of time and the NH₂/TMI ratio. The results showed that without the PSB shell, the PSBT particles (80 nm radius) could be penetrated by the PBD-NH₂ completely. A 24 nm PSB shell was found to act effectively as a barrier to preventing the penetration of the PBD-NH₂ inside the particles. This was consistent with previous TEM results, indicating that the crosslinking between the isocyanate in the PSBT particles and the amine in the PBD-NH₂ particles provided the driving force for the chain diffusion. A diffusion model was established for the PSBT/PBD-NH₂ system. Assuming steady-state diffusion, the effective diffusion coefficients were calculated based on the experimental data. This lead to the estimation of the surface coverage of the PBD-NH₂ on the PSBT particles in the latex films. A film formation and crosslinking mechanism was proposed for the PSBT/PBD-NH₂ latex blend system. In the absence of crosslinking reactions, the two incompatible polymers tended to completely phase separate during the film formation. However, with the crosslinking reactions, the PBD-NH₂ will be bound to the PSBT particle surfaces, forming a PSBT-PBD copolymer interphase. This interphase facilitates the diffusion of the PBD-NH₂ into the PSBT particles. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 985–993, 1998     

Preparation and properties of core [poly(styrene‐n‐butyl acrylate)]–shell [poly(styrene–methyl methacrylate–vinyl triethoxide silane)] structured latex particles with self‐crosslinking characteristics

Structured latex particles with a slightly crosslinked poly(styrene‐n‐butyl acrylate) (PSB) core and a poly(styrene–methacrylate–vinyl triethoxide silane) (PSMV) shell were prepared by seed emulsion polymerization, and the latex particle structures were investigated with Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, transmission electron microscopy, and dynamic light scattering. The films that were formed from the structured core (PSB)–shell (PSMV) particles under ambient conditions had good water repellency and good tensile strength in comparison with films from structured core (PSB)–shell [poly(styrene–methyl methyacrylate)] latex particles; this was attributed to the self‐crosslinking of CH₂?CH? Si(OCH₂CH₃)₃ in the outer shell structure. The relationship between the particle structure and the film properties was also investigated in this work. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1824–1830, 2006     

Effect of crosslinked core on minimum film formation temperature and morphology of composite microspheres

Effect of crosslinking on minimum film formation temperature (MFT) and particle morphology was investigated using the latices composed by the combination of crosslinked soft core-hard shell. n-Butyl acrylate (nBA) and ethylene glycol dimethacrylate (EGDMA) were used to prepare crosslinked rubber with methylmethacrylate (MMA) or styrene (ST) as a hard plastic component. Ordinary batch (flooded with secondary monomer) and semicontinuous (starved feed) operations were employed to compare the thermal properties of composite latices resulting from the different mode of secondary polymerization. As the degree of crosslinking increases, MFT of the latices obtained by batch operation became higher than those by semibatch operation. Observation of microtomed sections of particles stained with RuO₄ did not reveal much difference in particle morphologies between the two operations. There was a definite relationship between MFT and molecular weight of THF soluble fraction of composite polymers regardless the mode of operation.     

Preparation and properties of porous L‐tryptophan imprinted latex membrane from core‐shell emulsion

Molecularly imprinted latex membrane (MILM) is prepared by core‐shell emulsion technique in the presence of a template molecule (L ‐Tryptophan). A hard inward and soft outward microstructure latex particle is designed to obtain MILM with both flexibility and impact strength. Molecularly imprinted layer with high crosslinking degree is grafted on the surface of core‐shell latex particles. NaCl, glucose, urea, polyethylene glycol, M_w 300, etc., are added during the film‐forming process to produce porous microstructure in MILM. Fourier transform infrared spectroscopy (FTIR) and Scatchard analysis are used to investigate the interaction between L ‐Tryptophan and MILM and the binding ability of the resultant MILM, respectively. The functional binding and separation performances in aqueous medium towards template are carried out. The results reveal that the content and type of porogen and the shell composition have significant effects on adsorption capacity and separation ability. MILM with glucose as porogen shows high recognition towards the template with adsorption separation factor reaching 9.06. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of photo‐crosslinkable polyfluorene with acrylate side‐chains

A photo‐crosslinkable polymer, poly[2,7‐(9,9‐dioctylfluorene)‐co‐2,7‐(9‐hexyl‐9‐(2‐acrylate ethyl)‐9H‐fluorene)] (P3), was synthesized and the photo‐crosslinkable acrylate groups were introduced into the side‐chains of the polyfluorene derivative after its polymerization. This method avoids the possible crosslinkage of the crosslinkable groups on the monomers during polymerization in the traditional synthesis route by the polymerization of the monomers with the crosslinkable side‐chains. The soluble and processable polymer P3 could be crosslinked via the acrylate groups in its side‐chains upon exposure to UV light in nitrogen atmosphere. The crosslinking was confirmed by IR spectroscopy: the IR peak of C?C bond at 1635 cm^?1 decreased and that of the vinyl C? H bond at 742 cm^?1 disappeared after the UV exposure. The absorption spectra of P3 remain unchanged after crosslinking, but a longer wavelength emission at 517 nm appeared in the photoluminescent and electroluminescent spectra of the crosslinked P3, which could be attributed to the formation of keto defects during the photo crosslinking. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2336–2342, 2006     

Two‐component “Onionlike” micelles with a PPO core,a PDMAEMA shell and a PEO corona: formation and crosslinking

BACKGROUND: Chemical or physical crosslinking of supramolecular assemblies gives them stability in a wide range of environments. Much attention is paid to multilayer (onion‐like) polymeric micelles because their functionality is higher than classic core‐shell micelles. This work reports on the formation and crosslinking of onion‐like micelles prepared by mixing two different block copolymers containing a crosslinkable poly(dimethylaminoethyl methacrylate) (PDMAEMA) block. RESULTS: Block copolymers of a crosslinkable PDMAEMA block were synthesized by atom transfer radical polymerization of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) from poly(propylene oxide) (PPO) or poly(ethylene oxide) (PEO) macroinitiators. The (PDMAEMA₁₃)‐block‐PPO₆₉‐block‐(PDMAEMA₁₃) triblock formed wormlike core‐shell micelles, which were converted into ellipsoidal onion‐like micelles on mixing with the PEO₄₅‐block‐P(DMAEMA₈‐co‐MMA₄) diblock. Onion‐like micelles were crosslinked by quaternization of DMAEMA units. CONCLUSION: Formation of onion‐like micelles by mixing two different AB (ABA) and B′C block copolymers and their subsequent crosslinking is a valuable approach towards stabilized supramolecular assemblies of a higher complexity and functionality than the individual constitutive components. Copyright © 2008 Society of Chemical Industry     

自交联封闭性乳液的合成与性能

以双丙酮丙烯酰胺（DAAM）、甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）和甲基丙烯酸（MAA）为共聚单体,采用半连续种子乳液聚合工艺合成自交联封闭性聚丙烯酸酯乳液（PAE）,考察了DAAM和复合乳化剂对乳液聚合稳定性以及涂膜性能的影响。研究发现：随着DAAM含量的增加,乳液聚合稳定性下降,粒径增大,涂膜的耐介质性能和交联度提高,合适的DAAM加入量为总单体质量的3.0%,DAAM和己二酰肼(ADH)的最佳摩尔比为2∶1。采用SDBS+OP-10+OP-40为复合乳化剂体系,选用乳化剂的含量为2.35%,阴/非离子乳化剂质量比为1∶1.25;复合乳化剂在种子、核、壳比例为1.5∶1∶2,制备的乳液具有较好的聚合稳定性（乳液凝胶率低和单体转化率高）,乳液耐电解质（钙离子）稳定性好,涂膜具有优异的封闭性。傅里叶红外光谱（FTIR）表明在涂膜形成过程中DAAM的酮羰基与ADH的酰肼基反应生成腙（C=N）,TEM分析显示乳液的乳胶粒子呈核壳结构,TGA分析发现DAAM改性的PAE降低了涂膜的热稳定性。     

Surface structure and properties of water‐based polymer coating materials prepared by the complexation of two polymer latices with chemically complementary structures

In this study, water‐based polymer coating materials used for the surface coating of substrates with lower surface energies were prepared by the complexation of two‐component polymer latices containing polydimethylsiloxane (PDMS) and having chemically complementary structures. The film‐forming performance of the polymer latices and the surface structures and properties of the coatings formed by the polymer latices were studied by means of scanning electron microscopy and by the measurement of mechanical strength, thermal performance, water absorbability, and contact angle. When the two‐component polymer latices [the poly(methyl methacrylate‐co‐butyl acrylate‐co‐methyl acrylic acid)/polydimethylsiloxane system (PA latex) and the poly(methyl methacrylate‐co‐butyl acrylate‐co‐pyrrolidone)/polydimethylsiloxane system (PB latex)] were compared, the complex polymer latex formed by the complexation of the PA latex with the PB latex had the best film‐forming performance, with formed coatings that were more smooth and had fewer less cracks. Also, compared to the two coatings formed by the two‐component polymer latices, the coatings formed by the complex polymer latex had a unique structure, a higher mechanical strength and elongation, a higher decomposing temperature, and better water resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1748–1754, 2003     

Preparation of core‐shell latexes for paper coatings

Novel core‐shell latices with a partially crosslinked hydrophilic polymer core and a hard hydrophobic shell of polystyrene were prepared to improve optical properties of coated paper such as gloss and brightness. These core‐shell latices were prepared by sequential addition of a monomer mixture of styrene, n‐butylacrylate and methacrylic acid. Different crosslinkers were used to form the polymer core and in the second stage styrene to form the hard shell component. In addition, attempts were made to further improve optical properties by introducing a new polymerizable optical brightener, i.e., 1‐[(4‐vinylphenoxy)methyl]‐4‐(2‐phenylethylenyl)benzene during polymerization either into the core or into the shell. The prepared core‐shell latex particles were used as specialty plastic pigments for paper coating together with kaolin as the primary pigment. The runability of paper coating formulation by either using a laboratory scale Helicoater or pilot scale JET‐coating machine was very good. The produced coated papers were printed on both sides employing a heat set web offset (HSWO) printer to study the quality of image reproduction in terms of print gloss, print mottle, print through, etc. The core‐shell latices improved the overall print quality. Furthermore, the results demonstrated that by optimizing polymer composition one can significantly enhance the optical properties and surface smoothness of coated paper. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

水性聚氨酯与丙烯酸酯乳液交联反应的研究

将由双丙酮丙烯酰胺（DAAM）参与共聚的丙烯酸酯乳液与含有肼基的聚 氨酯水分散体混合后，得到了交联型聚氨酯／丙烯酸酯复合乳液，利用红外光谱和透射电镜技术证实了酮羰基与肼基之间的交联反应的发生。对乳液膜性能的研究结果表明，交联反应极大地提高了乳液膜的耐水性，耐溶性，断裂强度，断裂伸长率。     

水性丙烯酸酯乳液的合成及性能研究

以双丙酮丙烯酰胺（DAAM）为功能性单体,采用预乳化半连续种子乳液聚合法合成水性丙烯酸酯乳液,添加己二酸二酰肼（ADH）为交联剂,构成室温自交联体系。考察了DAAM、ADH用量对乳液及其乳胶膜性能的影响。用傅里叶红外光谱仪（FT-IR）对交联反应进行了表征。通过差示扫描量热法、力学性能和耐溶剂性能的测试等方法研究了乳液和乳胶膜的性能。结果表明,当DAAM用量为2.4%~3.5%,ADH与DAAM的当量比为1~1.2时,乳液和乳胶膜的综合性能较好。     

Self film‐forming and opaque hollow latexes fabricated via seeded emulsion polymerization followed by alkali post‐treatment

In order to obtain novel hollow latexes with both opaque and self film‐forming properties, the four‐layer core/shell latex particles—sequentially consisting of a high carboxyl‐containing soft core, a transition layer, a rigid supporting layer, and an outermost film‐forming layer—are first designed and prepared by emulsion polymerization, and then treated with alkali to fabricate self film‐forming hollow latexes. On the basis of the previous research on the three‐layer core/shell latex, influences of the composition and thickness of the film‐forming layer on the properties and morphologies of the four‐layer core/shell and the final hollow latexes are investigated. Results show that under optimized conditions with butyl acrylate/styrene (BA/St) mass ratio of 2/1, divinyl benzene (DVB) content of 1 wt %, and core/film‐forming layer mass ratio of 1/6 in the film‐forming layer preparation, the final hollow latex particles exhibit best morphology considering both light scattering efficiency and film‐forming capability at room temperature. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42541.     

Investigation of fluorinated polyacrylate latex with core–shell structure

Fluorinated polyacrylate latices with core–shell structure were prepared by semi‐continuous emulsion polymerization, using a mixed emulsifier system composed of a reactive emulsifier and a small amount of anionic emulsifier. The conversion and chemical components of the final latices were studied by gravimetric methods and Fourier‐transform infrared (FTIR) spectrometry, respectively. The structure of the latex particles was determined by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and particle size analysis. The latex films exhibited a low surface energy and high water‐contact angles. The surface analysis from X‐ray photoelectron spectroscopy (XPS) revealed that the fluorinated components preferentially self‐organized at the film–air interface. From XPS depth profiling of the film, it was found that a gradient concentration of fluorine existed in the structure of the latex film from the film–air interface to the film–glass interface. Compared with the core–shell structure with a fluorinated core, the core–shell structure with a fluorinated shell was more effective for modifying the properties of the latex films. Copyright © 2005 Society of Chemical Industry     

Control of adhesive properties through structured particle design of water-borne pressure-sensitive adhesives

The concept of using structured particles and the mechanism of film formation from latexes to produce pressure-sensitive adhesive (PSA) films with controlled sub-micron and nanometre scale morphology has been investigated with the objective of enhancing adhesive performance. Structured particle acrylate-based latexes were synthesised by seeded semi-continuous emulsion polymerisation procedures. Aliquots removed at intervals during the polymerisations were analysed for conversion and z-average particle diameter; the results confirm that the particles grew without secondary nucleation or coagulation. Three-layer particles were studied first and comprised a core whose composition was the same for all particles, an interlayer between core and shell which was crosslinked during synthesis (using 1,6-hexanediol diacrylate, HDDA) and a shell which contained diacetone acrylamide (DAAM) repeat units that provided for interfacial crosslinking between particles during film formation by reaction with post-added adipic acid dihydrazide (ADH). The three-layer latexes produced adhesive films with high shear resistance when ADH was added, but peel adhesion was generally low and further reduced by increasing either the thickness or HDDA concentration of the interlayer. Thus two-layer latexes with shell layers containing DAAM but no pre-crosslinked interlayer were the main focus of the study. The effects of core:shell ratio and amount of DAAM on adhesive performance were optimum with a core:shell ratio of 80:20 and 2 wt% DAAM in the shell copolymer, for which interfacial crosslinking using the stoichiometric amount of ADH led to a marked increase in shear resistance with only a slight reduction in peel adhesion. Increasing the level of n-dodecylmercaptan (DDM) chain transfer agent used in synthesis of the core increases peel adhesion and reduces shear resistance in the absence of ADH, but high shear resistance can be recovered through interfacial crosslinking with ADH. Adhesive performance can be optimised by using a high DDM level in the core and a low DDM level in the shell, a combination that enables both high peel adhesion and shear resistance to be achieved with the addition of ADH. The results from this study define guiding principles for development of commercial water-borne PSAs that can compete with solvent-borne PSAs in high-performance applications.     

Formation of transparent conducting films based on core‐shell latices: Influence of the polypyrrole shell thickness

Transparent conducting latex films have been prepared from core‐shell latices. The latex particles have a poly(butyl methacrylate) (PBMA) core of about 700 nm and a very thin polypyrrole (PPy) shell. We have studied the film formation of latices with 1, 2, and 4 wt % PPy and compared this with the film formation of the pure PBMA latex. The film formation process was studied by transparency measurements, atomic force microscopy surface flattening, and transmission electron microscopy on ultrathin sections of films after various annealing times at 120°C. It is demonstrated that highly transparent (>90%) and antistatic films can be produced using these latices. The presence of a polypyrrole shell around the PBMA latex particle seriously hinders the deformation of the particles. The amount of polypyrrole, and thus the shell thickness, is the determining factor for the speed of film formation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 900–909, 2001     

Evaluation of the shrinking‐core model for examining the kinetics of film formation in a reactive latex blend

We prepared reactive latex blends from two copolymer latices comprised of n‐butyl methacrylate (n‐BMA) with acetoacetoxyethyl methacrylate and n‐BMA/dimethylaminoethyl methacrylate to study the kinetics of film formation. We generated thin films by blending equal weights of the two latices. The films were then cured at temperatures ranging from 50 to 90°C. The extent of the crosslinking reaction was calculated from the crosslink density, which was determined from swelling measurements of the films in toluene. The shrinking‐core model, a diffusion/reaction model, which was originally derived for combustion reactions of coal particles, was adopted to calculate the diffusion coefficient (D_e) and reaction rate constants from the extent of the reaction with time data. This model system exhibited a diffusion‐controlled regime above 70°C and a reaction‐controlled regime at temperatures below 70°C. In the reaction‐controlled regime, the shrinking‐core model predicted D_e for the system, which was in agreement with literature values for n‐BMA. In the diffusion‐controlled regime, the model predicted a lower apparent value for D_e but with an activation energy that was close to that obtained for n‐BMA. The model was also used to examine the kinetics of the crosslinking reaction. The kinetic rate constants for the crosslinking reaction were also determined. The activation energy for the crosslinking reaction was 18.8 kcal/mol, which compared reasonably with the activation energy of 22.8 kcal/mol determined for the reaction between the functional monomers as small molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3659–3665, 2006     

Role of acrylic acid in the synthesis of core‐shell fluorine‐containing polyacrylate latex with spherical and plum blossom‐like morphology

The core‐shell fluorine‐containing polyacrylate latex was successfully synthesized by two‐stage semicontinuous emulsion copolymerization of methyl methacrylate (MMA), butylacrylate (BA), acrylic acid (AA), and dodecafluoroheptyl methacrylate (DFMA). The fluorine‐containing polyacrylate latex was characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential, thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC). The effects of AA content on monomer conversion, polymerization stability, particle size, corsslinking degree, carboxyl groups distributions (latex surface, aqueous phase or buried in latex), as well as mechanical properties and water absorption rate of latex film were investigated. The obtained fluorine‐containing polyacrylate latex exhibited core‐shell structure with a particle size of 120–150 nm. The introduction of AA was beneficial for the increase of monomer conversion and the polymerization stability, and had little effects on the mechanical property of latex film. However, the hydrophilicity of AA made the water resistance of latex film get bad. With the increase of AA content, the carboxyl groups preferred to distribute on aqueous phase, and the possibility of homogeneous nucleation increased and more oligomers particles were formed. Moreover, the oligomers would distribute to the latex and continued to grow up, making the latex morphology changed from spherical to plum blossom‐like. The core‐shell latex had two T_g corresponding to the rubber polyacrylate core and hard fluorine‐containing polyacrylate shell, and the latex film possessed excellent thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42527.     

Photo‐crosslinking of poly[ethene‐stat‐(methacrylic acid)] functionalised with maleimide side groups

BACKGROUND: Photo‐crosslinkable polymers are well known and commercially applied as photoresists. But so far they have not been applied as membrane materials for separation processes. They would offer certain advantages in membrane fabrication over conventional crosslinked polymer materials. Therefore, in this work, a poly[ethene‐stat‐(methacrylic acid)] (PEMAA) which is a potential membrane polymer for different separation problems was functionalised with photo‐crosslinkable maleimide side groups. RESULTS: It has been shown that PEMAA can be used as basic polymer material and a conversion with 3‐hydroxypropylmaleimide is possible in order to obtain a photo‐crosslinkable polymer. Investigation of the crosslinking mechanism was performed using stationary infrared and UV‐visible spectroscopy as well as nanosecond transient spectroscopy absorption measurements of a rotating film. Intense transient absorption of the maleimide‐esterified PEMAA occurs at 250 nm in the film pointing to maleimide anion formation and crosslinking via an ionic dimerisation mechanism. CONCLUSION: It is found that crosslinking reactions can be observed spectroscopically in situ using a maleimide‐functionalised PEMAA. Furthermore, experiments can be performed in the liquid phase (polymer in solution) as well as in the solid phase (polymer film) using a rotating polymer film sample. Maleimide anion formation and crosslinking via an ionic dimerisation mechanism can be investigated by variation of the polymer structure as well as the structure of the maleimide side groups. Copyright © 2009 Society of Chemical Industry