Functional comonomer

The water solubilities of the functional comonomers are reasonably high since they are usually polar compounds. Therefore, the initiation in the water phase may be too rapid when the initiator or the comonomer concentration is high. In such a case, the particle growth stage cannot be suppressed by the diffusion capture mechanism and the solution or dispersion polymerization of the functional comonomer within water phase may accompany the emulsion copolymerization reaction. This leads to the formation of polymeric products in the form of particle, aggregate, or soluble polymer with different compositions and molecular weights. The yield for the incorporation of functional comonomer into the uniform polymeric particles may be low since some of the functional comonomer may polymerize by an undesired mechanism. 

Soapless seeded emulsion copolymerization has been proposed as an alternative method for the preparation of uniform copolymer microspheres in the submicron-size range [115-117]. In this process, a small part of the total monomer-comonomer mixture is added into the water phase to start the copolymerization with a lower monomer phase-water ratio relative to the conventional direct process to prevent the coagulation and monodispersity defects. The functional comonomer concentration in the monomer-comonomer mixture is also kept below 10% (by mole). The water phase including the initiator is kept at the polymerization temperature during and after the addition of initial monomer mixture. The nucleation takes place by the precipitation of copolymer macromolecules, and initially formed copolymer nuclei collide and form larger particles. After particle formation with the initial lower organic phase-water ratio, an oligomer initiated in the continuous phase is... 

The uniform polymeric microspheres in submicron-or micron-size range can also be prepared as seed particles by the soapless emulsion or dispersion polymerization of a hydrophobic monomer like styrene. The uniform seed particles are swollen with the organic phase including functional comonomer, monomer, and oil-soluble initiator at a low temperature in an aqueous... 

The cationic Pd(II) catalysts exhibit effective copolymerizations of ethylene and other a-olefins with polar-functionalized comonomers, with the majority of insertions occurring at the ends of branches. Among the best tolerated monomers are those bearing fluorine or oxygen-containing functionalities, such as esters, ketones, and ethers. The copolymerization of ethylene and acrylates, attractive because the monomers are inexpensive and the copolymers exhibit unique physical properties, has been well-studied mechanistically [27,69], Examples of copolymerizations of ethylene and a-olefins with methyl acrylate are shown in Table 4. In general, the amount of comonomer incorporation varies linearly with its reaction concentration and... 

For this reaction, soluble monomers are needed, e.g. a mixture of N AT-methylene bisacrylamide as crosslinker, methacrylamide as an inert comonomer, methacrylic acid as ionic comonomer for stabilization [309] and methacryl ami-do-AT-acetaldehyde-dimethylacetal as functional comonomer. The coupling with proteins is only possible if the free aldehyde groups are accessible, i.e. if they are not located in the interior of the microgel. This condition can only be fulfilled by a careful choice of the comonomer composition in the reaction mixture [291]. 

Since PTFE was first synthesized more than 50 years ago, fluoropolymers have been produced by radical polymerization and copolymerizaton processes, but without any functional groups, for several reasons. First, the synthesis of functional vinyl compounds suitable for radical polymerization is much more complicated and expensive in comparison with common fluoroolefins. In radical polymerization of one of the simplest possible candidates—perfluorovinyl sulfonic acid (or sulfonyl fluoride—there was not enough reactivity to provide high-molecular-weight polymers or even perfluorinated copolymers with considerable functional comonomer content. Several methods for the synthesis of the other simplest monomer—trifluoroacrylic acid or its esters—were reported,1 but convenient improved synthesis of these compounds as well as radical copolymerization with TFE induced by y-irradiation were not described until 1980.2... 

Polyols. Typical polyols used in automotive topcoats Include acrylic copolymers and polyesters which have varied number of hydroxyl groups. Acrylic copolymers ranging in number average molecular weight from 1,000 to 10,000 and containing 15-40% by weight of a hydroxy functional comonomer such as hydroxyethyl acrylate have been studied. The acrylic copolymers were prepared by conventional free radical solution polymerization. 

A new class of functional comonomers exemplified by acrylamidobutyraldehyde dialkyl acetals 1 and their Interconvertible cyclic hemlamidal derivatives 2 were prepared and their chemistry was Investigated for use In polymers requiring post-crosslInking capability. These monomers do not possess volatile or extractable aldehyde components and exhibit additional crosslinking modes not found with conventional am1de/forma1dehyde condensates, eg, loss of ROH to form enamides 9 or TO and facile thermodynamically favored reaction with diols to form cyclic acetals. 

Vinyl substituted cyclic hemlamidals 2 and their Interconvertible acetal precursors (eg. acrylamldo-butyraldehyde dimethyl acetal 1) were Incorporated as latent crosslinkers and substrate reactive functional comonomers In solution and emulsion copolymers. Some use and applications data for copolymers prepared with these new monomers are presented. They show low energy cure potential, long shelf life and high catalyzed pot stability In solvent and aqueous media, good substrate reactivity and adhesion, and good product water and solvent resistance. They lack volatile or extractable aldehyde (eg. formaldehyde) components and show enhanced reactivity and hydrolytic stability with amines and diol functional substrates. 

Incorporation of more than 5% of a functionalized comonomer into EVA is difficult in emulsion polymerization because of several issues (11) ... 

The use of a reactive di- or poly-functional comonomer (non-antioxidant) which can co-graft with a monofunctional polymerisable antioxidant on polymers can improve the grafting efficiency from as low as 10-40% to an excess of 80-90%. This strategy, however, presents immense challenges due to the presence of more than one polymerisable group in the comonomer which could lead to additional undesirable (competing) side reactions com-... 

The inner porous morphology of these resins is distinguished by interconnected channels that form a porous network, which pervades the rigid, significantly cross-linked polymer matrix [205], These materials are often synthesized by suspension polymerization [206], where a polymerization mixture which includes a cross-linking monomer, a functional comonomer or comonomer, an initiator, and a porogenic agent is polymerized. 

For the encapsulation of pigments by miniemulsification, two different approaches can be used. In both cases, the pigment/polymer interface as well as the polymer/water interface have to be carefully chemically adjusted in order to obtain encapsulation as a thermodynamically favored system. The design of the interfaces is mainly dictated by the use of two surfactant systems, which govern the interfacial tensions, as well as by employment of appropriate functional comonomers, initiators, or termination agents. The sum of all the interface energies has to be minimized. 

FIGURE 27.26 Typical functional comonomer stmctures for each ionomer system. (Reproduced from Doyle, M. and Rajendran, G., in W. Vielstich, H.A. Gasteiger, and A. Lamm (Eds.), Handbook of Fuel Cells Fundamentals, Technology and Applications, Vol. 3, J. Wiley Sons, Chichester, 2003. With permission.)... 

Although the telechelic functional polymers are very attractive from a fundamental point of view, their synthesis is often impossible. Much more commonly, the active groups are incorporated in the chain either by a free-radical copolymerization with a small amount of functionalized comonomer or by functionalization of the chain after polymerization in the presence of free radicals (typical of the functionalization of the polyolefins). Either method generally produces several reactive sites per chain. 

Copolymers having high molecular weight of more than 3 x 10 can be obtained by adopting bulk or emulsion system with extremely purified functional comonomers. 

A series of patents were issued to DuPont in the mid-1970s that covered the terpolymerization of ethylene, propylene, and functional monomers. The catalyst employed was a soluble VCl4/AlEt2Cl in combination with hexachloropropene as a catalyst activator. The functional comonomers studied included 2-hydroxy-5-norbornene, 2-hydroxymethyl-5-norbornene, allylsulfonyl chloride, 2-allylphenol, and... 

Besides the synthesis of bulk polymers, microreactor technology is also used for more specialized polymerization applications such as the formation of polymer membranes or particles [119, 141-146] Bouqey et al. [142] synthesized monodisperse and size-controlled polymer particles from emulsions polymerization under UV irradiation in a microfluidic system. By incorporating a functional comonomer, polymer microparticles bearing reactive groups on their surface were obtained, which could be linked together to form polymer beads necklaces. The ability to confine and position the boundary between immiscible liquids inside microchannels was utilized by Beebe and coworkers [145] and Kitamori and coworkers [146] for the fabrication of semipermeable polyamide membranes in a microfluidic chip via interfacial polycondensation. 

Table 15.8 Functional Comonomers Used with Acrylates...

Carboxy- and amino-functionaUzed polystyrene nanoparticles have been synthesized by the miniemulsion process using styrene and the functional monomers acrylic acid (AA) or 2-aminoethyl methacrylate hydrochloride (AEMH) as functional comonomers [30,31]. By changing the amount of the comonomer, different surface densities of the charged groups could be realized. Since a fluorescent dye was incorporated inside the nanoparticles, the uptake behavior of different cell Unes could be determined as a function of the surface functionalization [30,31]. It was found that, in general, the uptake of the nanoparticles into the cells increases with increasing functionality on the particle s surface. For HeLa cells, for example, the internalized particle amount was up to sixfold better for carboxy-functionaUzed polystyrene (PS) nanoparticles than for non-functionalized PS particles. For amino functionalized PS nanoparticles, an up to 50-fold enhanced uptake could be detected. In order to investigate the actual uptake pathway into HeLa cells, positively... 

Initially developed for carbon black [75], this technique was also successfully applied for other organic pigments (see Fig. 12) [74]. Surface functionalization for the adhesion process to different substrates was either obtained by physically adsorbed surfactants, as the anionic SDS, the cationic cetyltrimethylammonium chloride (CTMA-Cl), or the non-ionic Lutensol AT50, or by copolymerizing styrene or acrylates with functional comonomers. 

These authors concluded that the differences in the hydrophobicity of the oil and the polymer turned out to be the driving force for the formation of nanocapsules. Due to the pronounced difference of polarity of PMMA and hexadecane, the system was very well suited for the formation of nanocapsules. With more hydrophobic monomers such as styrene, however, it was more difQcult to create nanocapsules as the cohesion energy density of the polymer phase was close to that of the oil, and adjustment of parameters to influence the interfacial tensions and spreading coefficients became critical in order to form nanocapsules. The parameters studied were monomer concentration, type and amount of surfactant and initiators, and the addition of functional comonomers. For example, addition of 10 wt% acrylic acid as a comonomer in the miniemulsion leads to an increase in the number of close-to-perfect nanocapsules. 

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