Vinyl halide copolymers

This section deals with paints based on vinyl resins (including vinyl copolymers) which are synthesized by polymerization of monomers containing terminal CH2 = CH groups. Polyolefins, poly(vinyl halides) and vinyl halide copolymers, poly(vinyl esters), poly(vinyl alcohol), poly(vinyl acetals), poly(vinyl ethers), and polystyrene are discussed. Polyacrylates (acrylic resins) are treated in Section 2.5. 

Poly(Vinyl Halides) and Vinyl Halide Copolymers... 

N.W. Johnston and H.J. Harwood, Intersequence cyclization reaction in methyl methacrylate - vinyl halide copolymers and terpolymers, Polym. Sci., Part C, No. 22 591 (1969). 

The presence of halogen atoms appears to exert little, if any, effect on catalyst activity, but it can influence the course of the metathesis reaction. Vinylic halides are unreactive, as exemplified by the ring-opening polymerization of l-chloro-l,5-cyclooctadiene, which afforded a perfectly alternating copolymer of butadiene and chloroprene (7/2) via polymerization exclusively through the unsubstituted double bond. 

Koshechko, V.G., Titov, V.E. and Sednev, D.V. (1994) New route for producing acrylic add copolymers, based on electrochemical carboxylation of poly(vinyl halide)s and polybutadiene. Polymer 35, 1787-1788. 

With regard to carbon fiber stabilization. Table 1 and Figure 3 clearly show that the vinyl halides depress the melting point considerably less than more voluminous monomers such as methyl acrylate, methyl methacrylate or vinyl acetate, at comparable molar level. It can be concluded that fiber fusion will be less of a problem with the former, as compared with the latter. Figure 4 illustrates this point for copolymers AN/VBr as compared to AN/VA. The melting points are calculated using Eq. (2),... 

Poly(vinyl halides) (PVC etc.) and PoIy(vinyl alcohol) (PVA).—A series of papers has appeared concerned with the photo-dehydrochlorination, discoloration, and sensitized photolysis of model compounds of PVC,819 and its copolymers.220 The photolysis of poly(vinyl bromide)221 and a trifluorochloroethylene-vinylidene fluoride copolymer228 has been described. The photo-oxidative destruction of PVA has been reported in a series of papers.223... 

Some vinylphosphonates and allylphosphonates are slow to form homopolymers although they copolymerise well with vinyl halides, acrylonitrile, CH2=CH CN and acrylates CH2=CH COOH. A simple alternating polymer (A B A B -type) is indicated in (12.168). As in all copolymers however, there also arises the possibility of a block-type polymer - (A) (B) , (A) (B) - being formed. 

Bis(2-chloroethyl)vinylphosphonate, CH CH P(0)(0CH2CH2C1)2 can be used to form emulsion copolymers with vinyl halides, or it may be used on its own and mechanically incorporated into textile fibres. Compound (12.212a) when dispersed in rayon is an effective retardant additive [44], while (12.212b), when copolymerised with a suitable monomer, will act as an intumescent flame retardant. 

This study was followed by a series of papers that examined the effect of the distance between the pendant fluorine [96], chlorine [97], or bromine [98] atoms. Later, a series of ethylene/vinyl halide polymers containing fluorine, chlorine, and bromine were created via ADMET copolymerization of a halogen-containing (x,K)-diene and 1,9-decadiene [99]. Thermal analysis of these statistically random copolymers showed a distinct difference between their crystallization behavior and that of their compositionally matched precise analogs. The sharp melting... 

Monomers with electron-rich double bonds produce one-to-one copolymers with monomers having electron-poor double bonds in reaction systems that also contain certain Lewis acids. These latter are halides or alkyl halides of nontransition metal elements, including AlCb, ZnCh, SnCL, BF3, AI(CH2CH3)Cl2, alkyl boron halides, and other compounds. The acceptor monomer generally has a cyano or carbonyl group conjugated to a vinyl double bond. Examples are acrylic and methacrylic acids and their esters, acrylonitrile, vinyl ketones, maleic anydride, fumaric esters, vinylidene cyanide, sulfur dioxide, and carbon monoxide. The variety of donor molecules is large and includes various olefins, styrene, isoprene, vinyl halides and esters, vinylidene halides, and allyl monomers [30]. 

Boz, E., Ghiviriga, I., Nemeth, A.J. et al. (2008a) Random, defect-free ethylene/vinyl halide model copolymers via condensation polymerization. Macromolecules, 41,25-30. 

Bush, C. N. Mikofalvy, K. M. B. F. Goodrich Co. "Process for Producing Horaopolymers or Copolymers of Vinyl or Vinylidene Halides by Emulsion Polymerization", U. S. Patent 4186259, January 29, 1980. 

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. 

In later communications (27, 28) Hirooka reported that in addition to acrylonitrile, other conjugated monomers such as methyl acrylate and methyl methacrylate formed active complexes with organoaluminum halides, and the latter yielded high molecular weight 1 1 alternating copolymers with styrene and ethylene. However, an unconjugated monomer such as vinyl acetate failed to copolymerize with olefins by this technique. 

Controlled/ Living radical polymerization (CRP) of vinyl acetate (VAc) via nitroxide-mediated polymerization (NMP), organocobalt-mediated polymerization, iodine degenerative transfer polymerization (DT), reversible radical addition-fragmentation chain transfer polymerization (RAFT), and atom transfer radical polymerization (ATRP) is summarized and compared with the ATRP of VAc catalyzed by copper halide/2,2 6 ,2 -terpyridine. The new copper catalyst provides the first example of ATRP of VAc with clear mechanism and the facile synthesis of poly(vinyl acetate) and its block copolymers. 

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