Vinyl acetate block copolymers

Although an ethylene vinyl acetate copolymer was immiscible in NR blends, addition of a 6 phr ethylene vinyl acetate block copolymer enabled compatibilization of heterogeneous NR/acrylonitrile butadiene rubber blends. These blends increased the tensile strength, the elongation at break and tear strength due to an increase in the interfacial adhesion between the blended components by increasing the rigidity of the matrix in the presence of the ethylene vinyl acetate copolymers. ... 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

However, in a recent publication, Shirinyan, Mnatsalianov, et al. (20) find that differences between the rates of vinyl acetate emulsion polymerisation observed with samples of similar polyvinyl alcohols manufactured by the same process In three different factories could be attributed to a condensation product of acetaldehyde derived from hydrolysis of residual vinyl acetate this gave rise to a conjugated ketone type ultra-violet spectrum and could be extracted from the polyvinyl alcohol under suitable conditions. This could be the uncontrolled factor which appears to have confounded nmuiy of the experiments reported here. Even more recently the same laboratory ( ) has reported that there Is an optimum sequence length of hydroxyl groups in the polyvinyl cdcohol-acetate block copolymer for polymerisation rate and dispersion stability. 

Tuzar and Kratochvil (23) have reported that styrene-butadiene block copolymers mlcellise in selective solvents for polystyrene and solubilise large amounts of polybutadiene homopolymer. Sinc.e the surface active grades of polyvinyl alcohol are polyvinyl alcohol-acetate block copolymers and water is a selective solvent for polyvinyl alcohol a similar effect may be expected which could affect the course of the vinyl acetate emulsion polymerisation. 

Melt adhesives are based on thermoplastics, but usually contain a number of other components. The most commonly used melt adhesives are based on ethylene-vinyl acetate (EVA) copolymers, but polyethylene, polyesters, polyamides, and thermoplastic rubbers (e.g., styrene-butadiene block copolymers) are also used (see Adhesive Bonding of Plastics in Chapter 2). 

Hydrolysis of the trialkyl silyl groups gives poly(vinyl alcohol). Block copolymers in which one block is poly( vinyl alcohol) can be synthesized if a telechehc with an aldehyde terminal group is used to initiate the aldol GTP structures such as polyfsty-rene-h/oc -vinyl alcohol) can be prepared in this way. Alternatively, as silyl ketene acetals can react with aldehydes, block structures can be formed by a coupling process. 

Tonnar, J. Pouget, E. Lacroix-Desmazes, P. Boutevin, B., Synthesis of Poly(vinyl acetate)-block-Poly(dimethylsiloxane)-Poly(vinyl acetate) Copolymers by Iodine Transfer Photopolymerization in Microemulsion. Macromol. Symp. 2009,281,20-30. 

The degree of blockiness in the structure of partially hydrolysed, poly(vinyl acetate) depends on the method of hydrolysis. Saponification with alkali gives vinyl acetate-alcohol copolymers with a highly blocked structure, transesterification with methanolic methoxides gives intermediate blockiness, and acid-catalysed equilibrium hydrolysis gives near-random copolymers. These structures respond differently in iodination analyses. ... 

IDestarac, M., Pees, B., and Boutevin, B. (2000). Radical telomerization of vinyl acetate with chloroform. Application to the synthesis of poly(vinyl acetate)-block-polystyrene copolymers by consecutive telomerization and atom transfer radical polymerization. Macromol. Chem. Phys., 20/(11) 1189 1199. 

Similarly to double hydrophilic block polymers, double C02-philic copolymers are made of two chemically different blocks soluble in CO2. At high pressures, they behave as fully soluble block copolymers. Their amphiphilic behavior can be induced by a change in pressure or temperature which renders COj a selechve solvent for one of the blocks. The resulting amphiphUic copolymers with a C02-philic outer sheh and a CO2-phobic core can be expected to self-assemble into aggregates or polymer-somes. To date, the only example of double C02-phihc copolymers concerns block copolymers comprising fluorinated poly(acrylate) andpoly(vinyl acetate) blocks (see Figure 13.21). 

The above polymer (PVA) is a blocky copolymer (containing short vinyl acetate blocks) and hence it does not represent the case for adsorption of homopoly-... 

Poly( vinyl alcohol) [with poly( vinyl acetate) blocks - usually 4—12%], -(CH2-CH-OH),t-(CH2-CH(OCOCH3)-OH)y-(CH2-CH-OH)x-. Block copolymers of ethylene oxide-propylene oxide (ABA block of PEO-PPO-PEO), e.g. Plur-onics (BASF), Synperonic PE (ICI), H-(0-CH2-CH2) -(CH2-CH(CH3)-0) -(CH2-CH2-0) -H. Graft copolymers, e.g. poly(methyl methacrylate) (PMMA) backbone [with some poly(methacrylic acid)] with grafted PEO chains, e.g. Atlox 4913 Hypermer CG6(ICI). 

The two EVA copolymers with 17% and 28% of vinyl acetate blocks were oven-aged at 180 °C and samples analysed at different stages for hydroperoxide concentration. Figure 3.9 illustrates that the hydroperoxides form and decay in a typical auto-oxidative fashion [28] as found previously for polyolefins. Hydroperoxide growth... 

Polyolefin Polyester Block copolymers of styrene and butadiene or styrene and isoprene Block copolymers of styrene and ethylene or styrene and butylene Poly(vinyl chloride) and poly(vinyl acetate) ... 

A number of methods such as ultrasonics (137), radiation (138), and chemical techniques (139—141), including the use of polymer radicals, polymer ions, and organometaUic initiators, have been used to prepare acrylonitrile block copolymers (142). Block comonomers include styrene, methyl acrylate, methyl methacrylate, vinyl chloride, vinyl acetate, 4-vinylpyridine, acryUc acid, and -butyl isocyanate. 

Block copolymers of vinyl acetate with methyl methacrylate, acryflc acid, acrylonitrile, and vinyl pyrrohdinone have been prepared by copolymeriza tion in viscous conditions, with solvents that are poor solvents for the vinyl acetate macroradical (123). Similarly, the copolymeriza tion of vinyl acetate with methyl methacrylate is enhanced by the solvents acetonitrile and acetone and is decreased by propanol (124). Copolymers of vinyl acetate containing cycHc functional groups in the polymer chain have been prepared by copolymeriza tion of vinyl acetate with A/,A/-diaIlylcyanamide and W,W-diaIl5lamine (125,126). 

Pa.ints, Paints (qv) prepared from poly(vinyl acetate) and its copolymers form flexible, durable films with good adhesion to clean surfaces, including wood, plaster, concrete, stone, brick, cinder blocks, asbestos board, asphalt, tar paper, wahboards, aluminum, and galvani2ed iron (147). Adherence is also good on painted surfaces if the surfaces are free from dirt, grease, and mst. Developments in emulsion polymeri2ation for paint latices have been reviewed (148). 

Fig. 3. Influence of vinyl alcohol—vinyl acetate copolymer composition on melting temperature (56), where A represents block copolymers B, blocky...

Fig. 24.1. (a) A copolymer of vinyl chloride and vinyl acetate the "alloy" pocks less regularly, has a lower Tg, and is less brittle than simple polyvinylchloride (PVC). (b) A block copolymer the two different molecules in the alloy ore clustered into blocks along the chain. 

Among the different pressure sensitive adhesives, acrylates are unique because they are one of the few materials that can be synthesized to be inherently tacky. Indeed, polyvinylethers, some amorphous polyolefins, and some ethylene-vinyl acetate copolymers are the only other polymers that share this unique property. Because of the access to a wide range of commercial monomers, their relatively low cost, and their ease of polymerization, acrylates have become the dominant single component pressure sensitive adhesive materials used in the industry. Other PSAs, such as those based on natural rubber or synthetic block copolymers with rubbery midblock require compounding of the elastomer with low molecular weight additives such as tackifiers, oils, and/or plasticizers. The absence of these low molecular weight additives can have some desirable advantages, such as ... 

MAIs may also be formed free radically when all azo sites are identical and have, therefore, the same reactivity. In this case the reaction with monomer A will be interrupted prior to the complete decomposition of all azo groups. So, Dicke and Heitz [49] partially decomposed poly(azoester)s in the presence of acrylamide. The reaction time was adjusted to a 37% decomposition of the azo groups. Surface active MAIs (M, > 10 ) consisting of hydrophobic poly(azoester) and hydrophilic poly(acrylamide) blocks were obtained (see Scheme 22) These were used for emulsion polymerization of vinyl acetate—in the polymerization they act simultaneously as emulsifiers (surface activity) and initiators (azo groups). Thus, a ternary block copolymer was synthesized fairly elegantly. 

Hot melt adhesives based on poly(3HB-co-3HV) have also been described [119]. Hot melts are commonly used in bookbinding, bag ending and case and carton sealing and are mostly based on synthetic materials such as polyethylene, polypropylene ethylene-vinyl acetate and styrene block copolymers [119]. Hot melts based on PHAs alleviate the dependence on petroleum based materials and allow the development of biodegradable alternatives based on natural raw materials. 

A product is only considered to be totally biodegradable if all its single components can be degraded naturally. Currently, pressure sensitive adhesives (PSA) are mostly based on non-biodegradable synthetic polymers such as polyacrylates, ethylene-vinyl acetate copolymers and styrene block copolymers [124]. Therefore there is a growing demand for the application of biodegradable PSAs on naturally degradable products like paper and cardboard. 

In a previous paper (15) the segment density of PVA adsorbed on PS latex in water was presented and it was noted that H Cgans was at the extremity of the s.a.n.s. profile. Calculating <5 assuming a value of a of 0.5 nm gives 13 nm in contrast to the experimental value of 18 nm. The discrepancy here is much smaller than in the case of PE0. This effect is difficult to interpret without further theoretical work but may be attributable to the fact that the PVA chain is less flexible than PEO and that the block structure (PVA is a random block copolymer of vinyl acetate. 12%, and vinyl alcohol) makes the formation of tails less likely. 

Much work on the preparation of nonaqueous polymer dispersions has involved the radical polymerization of acrylic monomers in the presence of copolymers having the A block the same as the acrylic polymer in the particle core 2). The preparation of polymer dispersions other than polystyrene in the presence of a PS-PDMS diblock copolymer is of interest because effective anchoring of the copolymer may be influenced by the degree of compatibility between the PS anchor block and the polymer molecules in the particle core. The present paper describes the interpretation of experimental studies performed with the aim of determining the mode of anchoring of PS blocks to polystyrene, poly(methyl methacrylate), and poly(vinyl acetate) (PVA) particles. 

PVA Particles. Dispersions were prepared in order to examine stabilization for a core polymer having a glass transition temperature below the dispersion polymerization temperature. PVA particles prepared with a block copolymer having M PS) x 10000 showed a tendency to flocculate at ambient temperature during redispersion cycles to remove excess block copolymer, particularly if the dispersion polymerization had not proceeded to 100 conversion of monomer. It is well documented that on mixing solutions of polystyrene and poly(vinyl acetate) homopolymers phase separation tends to occur (10,11), and solubility studies (12) of PS in n-heptane suggest that PS blocks with Mn(PS) 10000 will be close to dissolution when dispersion polymerizations are performed at 3 +3 K. Consequently, we may postulate that for soft polymer particles the block copolymer is rejected from the particle because of an incompatibility effect and is adsorbed at the particle surface. If the block copolymer desorbs from the particle surface, then particle agglomeration will occur unless rapid adsorption of other copolymer molecules occurs from a reservoir of excess block copolymer. 

PVA in, 25 617 setting speed of, 25 579-580 smectites application, 6 697t solution, 1 532-534 structural, 1 534-545 styrenic block copolymers in, 24 714 use of latex in, 14 711-712 vinyl acetate polymers in, 25 578-583 viscosity of, 25 581 water-borne, 25 475 Adhesive systems, microencapsules in, 16 460... 

Uses Copolymerized with methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, or 1,1-dichloroethylene to produce acrylic and modacrylic fibers and high-strength fibers ABS (acrylonitrile-butadiene-styrene) and acrylonitrile-styrene copolymers nitrile rubber cyano-ethylation of cotton synthetic soil block (acrylonitrile polymerized in wood pulp) manufacture of adhesives organic synthesis grain fumigant pesticide monomer for a semi-conductive polymer that can be used similar to inorganic oxide catalysts in dehydrogenation of tert-butyl alcohol to isobutylene and water pharmaceuticals antioxidants dyes and surfactants. 

This comprises a copolymer containing 72 to 95 wt.% of ethylene and 28 to 5 wt.% of vinyl acetate and a small amount of organic composite having a bactericidal action contained therein, which is composed mainly of N,N-dimethyl-N -phenyl-N -(fluorodichloromethylthio)sulphamide, 1,2-benzisothiazoline-3-on, diiodomethyl-p-tolylsulphone and methyl(benzimidazol-2-yl)carbamate. It is suitable as cushioning material for floors and walls and as a material for building blocks and babies toys. 

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