Vinyl methacrylate random copolymers

The toughness of interfaces between immiscible amorphous polymers without any coupling agent has been the subject of a number of recent studies [15-18]. The width of a polymer/polymer interface is known to be controlled by the Flory-Huggins interaction parameter x between the two polymers. The value of x between a random copolymer and a homopolymer can be adjusted by changing the copolymer composition, so the main experimental protocol has been to measure the interface toughness between a copolymer and a homopolymer as a function of copolymer composition. In addition, the interface width has been measured by neutron reflection. Four different experimental systems have been used, all containing styrene. Schnell et al. studied PS joined to random copolymers of styrene with bromostyrene and styrene with paramethyl styrene [17,18]. Benkoski et al. joined polystyrene to a random copolymer of styrene with vinyl pyridine (PS/PS-r-PVP) [16], whilst Brown joined PMMA to a random copolymer of styrene with methacrylate (PMMA/PS-r-PMMA) [15]. The results of the latter study are shown in Fig. 9. 

Radical copolymerization is used in the manufacturing of random copolymers of acrylamide with vinyl monomers. Anionic copolymers are obtained by copolymerization of acrylamide with acrylic, methacrylic, maleic, fu-maric, styrenesulfonic, 2-acrylamide-2-methylpro-panesulfonic acids and its salts, etc., as well as by hydrolysis and sulfomethylation of polyacrylamide Cationic copolymers are obtained by copolymerization of acrylamide with jV-dialkylaminoalkyl acrylates and methacrylates, l,2-dimethyl-5-vinylpyridinum sulfate, etc. or by postreactions of polyacrylamide (the Mannich reaction and Hofmann degradation). Nonionic copolymers are obtained by copolymerization of acrylamide with acrylates, methacrylates, styrene derivatives, acrylonitrile, etc. Copolymerization methods are the same as the polymerization of acrylamide. 

Most dispersion polymerizations in C02, including the monomers methyl methacrylate, styrene, and vinyl acetate, have been summarized elsewhere (Canelas and DeSimone, 1997b Kendall et al., 1999) and will not be covered in this chapter. In a dispersion polymerization, the insoluble polymer is sterically stabilized as colloidal polymer particles by the surfactant that is adsorbed or chemically grafted to the particles. Effective surfactants in the dispersion polymerizations include C02-soluble homopolymers, block and random copolymers, and reactive macromonomers. Polymeric surfactants for C02 have been designed by combining C02-soluble (C02-philic) polymers, such as polydimethylsiloxane (PDMS) or PFOA, with C02-insoluble (C02-phobic) polymers, such as hydrophilic or lipophilic polymers (Betts et al., 1996, 1998 Guan and DeSimone, 1994). Several advances in C02-based dispersion polymerizations will be reviewed in the following section. 

Aldol group transfer polymerization of ferf-butyldimethylsilyl vinyl ether [62] was initiated by pendant aldehyde functions incorporated along a poly(methyl methacrylate) (PMMA) backbone [63]. This backbone was a random copolymer prepared by group transfer polymerization of methyl methacrylate (MMA) and acetal protected 5-methacryloxy valeraldehyde. After deprotection of the aldehyde initiating group, polymerization proceeded by activation with zinc halide in THF at room temperature. The reaction led to a graft copolymer with PMMA backbone and poly(silyl vinyl ether) or, upon hydrolysis of the ferf-butyldimethylsilyl groups, poly(vinyl alcohol) branches. 

The polymeric dispersants included random copolymers of long chain alpha olefins or long chain methacrylates with acidic or basic co-monomers such as vinyl acetate, vinyl alcohol, vinyl pyridine, vinyl pyrollidone, hydroxyethyl methacrylate, etc. The alpha-olefin vinyl acetate copolymers had molecular weights in the 1-25,000 range and the methacrylates were in the 100,000 + range. All were oil soluble and reduced the oil-water interfacial tension appreciably. 

Dispersancy Solution copolymers are comparatively easy to produce in dispersant form as copolymerization with an appropriate polar monomer is relatively straightforward. If the polar monomer is also a methacrylate, reactivity ratios are essentially the same and no special procedures are required to produce random copolymers. Commercial examples have included dimethyl (or diethyl)aminoethyl methacrylate [11], hydroxyethyl methacrylate [12] and dimethylamino-ethyl methacrylamide [13]. 2-Methyl-5-vinyl pyridine [14] has also been used commercially, reactivity ratios are such that it copolymerizes slightly faster than alkyl methacrylates. Although composition drift is not severe, it should be added in a programmed fashion if a uniform distribution is desired. V-vinyl pyrrolidinone, in contrast, copolymerizes very sluggishly with methacrylates and is best incorporated via a graft reaction [15], sometimes also grafted in combination with V-vinyl imidazole [16]. Since solution chemistry is used to produce dispersant polymethacrylates, like preparation of the base polymer, only relatively simple process modifications are necessary to produce dispersants commercially. 

It is possible to prepare block copolymers by free-radical initiation, as R. B. Seymour, G. A. Stahl, D. R. Owent, and H. Wood discuss in their chapter. Methyl methacrylate macroradicals were made with peroxide and azo initiators in diluents, and different vinyl monomers were polymerized onto them. Block copolymers of two ethylene imines, one having a long (lauroyl) side chain and one with a short (propionyl) side chain were synthesized by M. H. Litt and T. Matsuda in a two-step cationic polymerization process. Block and random copolymers of episulfides were prepared by E. Cernia, A. Roggero, A. Mazzei, and M. Bruzzone using anionic catalysts of metalated sulfoxides and sulfones. 

Gao and co-workers investigated the random copolymers of acrylamide and vinyl pyridine, of varying MW and pyridine content, which were subsequently quaternised with dimethyl sulfate [22], Investigations proved that polymers with higher cationic functionality showed stronger antibacterial activity. In addition, depending on their alkyl chain length, methacrylate-based polymers with pendent pyridinium moieties were found to exhibit antibacterial activity [23]. 

The experimental results that will be examined consist of studies that look at the ability of a random copolymer to improve the properties of mixtures of the two homopolymers relative to the ability of a block copolymer. The three different systems that are examined include copolymers of poly(styrene-co-methyl methacrylate) (S/MMA), poly(styrene-co-2-vinyl pyridine) (S/2VP), and poly(styrene-co-ethylene) (S/E) in mixtures of the two homopolymers. The experiments that have been utilized to examine the ability of the copolymer to strengthen a polymer blend include the examination of the tensile properties of the compatibilized blend and the determination of the interfacial strength between the two homopolymers using asymmetric double cantilever beam (ADCB) experiments. 

The components of the copolymers are cycloaliphatic monomers (norbor-nene), and vinyl ether, maleic anhydride, acrylate, and methacrylate. In addition, vinyl sulfonamides have been used as co-monomers in the synthesis of random copolymers capable of functioning as acid-amplified resists. An example is presented in Chart 9.5. A high sensitivity, S = 2mJ cm, was measured for a copolymer (Chart 9.5) with n=0.4 and m=0.6 (resist thickness d=220nm, developer aqueous tetramethylammonium hydroxide solution). Triphenylsulfonium perfluoro-1-butane sulfonate served as acid generator [33]. 

Figure 9-19. A universal gel-permeation chromatography calibration curve obtained from measurements on linear poly(styrene) (O), comb-branched poly(styrene) (O ), star-branched poly(styrene) ( ), poly(methyl methacrylate) ( ), poly(vinyl chloride) (a) c -l,4-poly-(butadiene) (A), poly(styrene)-poly(methyl methacrylate) block copolymer (Qj ), random copolymer from styrene and methyl methacrylate O), and ladder polymers of poly(phenyl siloxanes) ( ) (according to Z. Grubisic, P. Rempp, and H. Benoit).

Group-transfer polymerizations yield very narrow molecular weight distribution polymers. When mixtures of monomers are used, random copolymers form. The polymerization reaction is very tolerant of other functional groups in the monomer. Thus, for instance, p-vinylbenzyl methacrylate is converted to poly(p-vinylbenzyl methacrylate) without the polymerization of the vinyl... 

Poly(vinyl chloride) (PVC) homopolymer is a stiff, rather brittle plastic with a glass temperature of about 80°C. While somewhat more ductile than polystyrene homopolymer, it is still important to blend PVC with elastomer systems to improve toughness. For example, methyl methacrylate-butadiene-styrene (MBS) elastomers can impart impact resistance and also optical clarity (see Section 3.3). ABS resins (see Section 3.1.2) are also frequently employed for this purpose. Another of the more important mechanical blends of elastomeric with plastic resins is based on poly(vinyl chloride) as the plastic component, and random copolymers of butadiene and acrylonitrile (AN) as the elastomer (Matsuo, 1968). On incorporation of this elastomeric phase, PVC, which is ordinarily a stiff, brittle plastic, can be toughened greatly. A nonpolar homopolymer rubber such as polybutadiene (PB) is incompatible with the polar PVC. Indeed, electron microscopy shows... 

The viscosity and coil size of weakly hydrophobic polyampholytes have minima at the isodectric pH, " and a negative second virial coeffident (see globule regime in Figure 48). The minimum in viscosity is seen in Figure 49, for a random copolymer of 62% 2-vinyl pyridine and 38% methacrylic add in a solvent that is 90% methanol and 10% water. ... 

Random copolymers of 3-methylthiophene with methyl methacrylate are readily prepared by initiating the polymerization of MMA with the Grignard of 2,5-diiodo-3-methylthiophene. During the oxidation of 3-methylthiophene, certain vinyl monomers copolymerize directly with the thiophene. But this random insertion of vinyl units disrupts the conjugation and there is a drastic decrease in electrical conductivity. There is no evidence that the doped copolymers are processable. 

While most copolymers of vinyl acetate are random copolymers, alternating copolymers are formed when the reactivity ratios for the two monomers are suitable. This occurs spontaneously when vinyl acetate is polymerized with electron-poor monomers such as maleic anhydride [273]. Alternatively, it has been reported that acrylonitrile which has been precomplexed with zinc chloride gives alternating polymers with vinyl acetate [274]. Block polymers of vinyl acetate with methyl methacrylate, acrylonitrile, acrylic acid, and n-vinyl pyrrolidone have been prepared by the strategy of preparing poly(vinyl acetate) macroradicals in poor solvents in which the macroradicals are occluded. Addition of a second monomer swells the polymer coils, and polymerization continues with the addition of the new monomer [275]. 

Introduction of other functionality is possible by copolymerization with, for example, vinyl methacrylate. Addition of a mixture of nBMA, GMA, MMA, and VMA monomers to the initiator fragment was calculated to give a random copolymer of composition n with Mn 5711. 

TLC has been used in the study of many homopolymers polystyrene, poly(methyl methacrylate), poly(ethylene oxide), polyisoprene, poly(vinyl acetate), poly(vinyl chloride) and polybutadiene. Their molecular weight, molecular-weight distributions, microstructure (stereo-regularity, isomerism and the content of polar end groups), isotope composition and branching have been studied. For copolymer characterisation (e.g. purity and compositional inhomogeneity), random copolymers such as styrene-methacrylate, and block copolymers such as styrene-butadiene, styrene-methyl methacrylate and styrene-ethylene oxide have been separated. A good review article on polymers... 

Random copolymer addition to binary blends involving copolymers with structural units equal or similar to the blend components or with specific interacting groups capable of non-reactive interaction with one of both the blend components comprises another ternary polymer addition approach. An early example involved EPR (ethylene-propylene rubber) addition to HDPE/PP blends, where synergistic impact strength was observed. In some cases, the random copolymers have been compared to block copolymers comprised of the same units. The compatibihzation of LLDPE/PMMA and LLDPE/poly(MMA-co-4-vinyl pyri-dine(4VP)) blends with poly(ethylene-co-methacrylic acid) (EMAA) addition were compared [47]. Modest improvements in LLDPE/PMMA dispersion and strength were observed. The specific acid-base interaction allowed for much larger improvements with EMAA addition to LLDPE/PMMA-CO-4VP blends. 

Vinyhdene chloride copolymerizes randomly with methyl acrylate and nearly so with other acrylates. Very severe composition drift occurs, however, in copolymerizations with vinyl chloride or methacrylates. Several methods have been developed to produce homogeneous copolymers regardless of the reactivity ratio (43). These methods are appHcable mainly to emulsion and suspension processes where adequate stirring can be maintained. Copolymerization rates of VDC with small amounts of a second monomer are normally lower than its rate of homopolymerization. The kinetics of the copolymerization of VDC and VC have been studied (45—48). 

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