Copolymerization chloride

Isopropenyl acetate gives spinnable fibres on copolymerization with vinyl chloride. 

Copolymerization can be carried out with styrene, acetonitrile, vinyl chloride, methyl acrylate, vinylpyridines, 2-vinylfurans, and so forth. The addition of 2-substituted thiazoles to different dienes or mixtures of dienes with other vinyl compounds often increases the rate of polymeriza tion and improves the tensile strength and the rate of cure of the final polymers. This allows vulcanization at lower temperature, or with reduced amounts of accelerators and vulcanizing agents. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

Poly(vinyhdene chloride) (PVDC) film has exceUent barrier properties, among the best of the common films (see Barrier polymers). It is formulated and processed into a flexible film with cling and tacky properties that make it a useful wrap for leftovers and other household uses. As a component in coatings or laminates it provides barrier properties to other film stmctures. The vinyUdene chloride is copolymerized with vinyl chloride, alkyl acrylates, and acrylonitrile to get the optimum processibUity and end use properties (see Vinylidene chloride monomer and polymers). 

Poly(vinylidene chloride). Poly(viayHdene chloride) [9002-85-1] (PVDC), most of which is produced by Dow Chemical, is best known in its saran or PVC-copolymerized form (see Vinylidene chloride and poly(VINYLIDENE chloride)). As solvent or emulsion coating, PVDC imparts high oxygen, fat, aroma, and water-vapor resistance to substrates such as ceUophane, oriented polypropylene, polyester, and nylon. 

Internal Plasticizers. There has been much dedicated work on the possibiUty of internally plasticized PVC. However, in achieving this by copolymerization significant problems exist (/) the affinity of the growing polymer chain for vinyl chloride rather than a comonomer implies that the incorporation of a comonomer into the chain requites significant pressure (2) since the use of recovered monomer in PVC production is standard practice, contamination of vinyl chloride with comonomer in this respect creates additional problems and (J) the increasing complexity of the reaction can lead to longer reaction times and hence increased costs. Thus, since standard external plasticizers are relatively cheap they are normally preferred. 

Vinyl resins ie, copolymers of vinyl chloride and vinyl acetate which contain hydroxyl groups from the partial hydrolysis of vinyl acetate and/or carboxyl groups, eg, from copolymerized maleic anhydride, may be formulated with alkyd resins to improve their appHcation properties and adhesion. The blends are primarily used in making marine top-coat paints. 

Fig. 2. Relationship between relative rate and monomer composition in the copolymerization of DAP with vinyl monomers A, styrene or methyl methacrylate B, methyl acrylate or acrylonitrile C, vinyl chloride D, vinyl acetate, and E, ethylene (41).

A great number of other aHyl compounds have been prepared, especially aHyl ethers and aHyl ether derivatives of carbohydrates and other polymers. They are made by the reaction of hydroxyl groups with aHyl chloride in the presence of alkaU (1). Polymerizations and copolymerizations are generally slow and incomplete. Products have only limited use in coatings, inks, and specialties. Properties of a few aHyl ethers are given in Table 10. 

Polymerization and Spinning Solvent. Dimethyl sulfoxide is used as a solvent for the polymerization of acrylonitrile and other vinyl monomers, eg, methyl methacrylate and styrene (82,83). The low incidence of transfer from the growing chain to DMSO leads to high molecular weights. Copolymerization reactions of acrylonitrile with other vinyl monomers are also mn in DMSO. Monomer mixtures of acrylonitrile, styrene, vinyUdene chloride, methallylsulfonic acid, styrenesulfonic acid, etc, are polymerized in DMSO—water (84). In some cases, the fibers are spun from the reaction solutions into DMSO—water baths. 

Polymerization. The most important reaction of vinyl chloride is its polymerization and copolymerization in the presence of a radical-generating initiator. 

The principal solution to fabrication difficulties is copolymerization. Three types of comonomers are commercially important vinyl chloride acrylates, including alkyl acrylates and alkyimethacrylates and acrylonitrile. When extmsion is the method of fabrication, other solutions include formulation with plasticizers, stabilizers, and extmsion aids plus applying improved extmsion techniques. The Hterature on vinyHdene chloride copolymers through 1972 has been reviewed (1). 

GopolymeriZation. The importance of VDC as a monomer results from its abiHty to copolymerize with other vinyl monomers. Its Rvalue equals 0.22 and its e value equals 0.36. It most easily copolymerizes with acrylates, but it also reacts, more slowly, with other monomers, eg, styrene, that form highly resonance-stabiHzed radicals. Reactivity ratios (r and r, with various monomers are Hsted in Table 2. Many other copolymers have been prepared from monomers for which the reactivity ratios are not known. The commercially important copolymers include those with vinyl chloride (VC),... 

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). 

The properties of PVDC (Table 3) ate usually modified by copolymerization. Copolymers of high VDC content have lower melting temperatures than PVDC. Copolymers containing mote than mol % acrylate or methacrylate ate amorphous. Substantially mote acrylonitrile (25%) or vinyl chloride (45%) is required to destroy crystallinity completely. 

Although they lack commercial importance, many other poly(vinyl acetal)s have been synthesized. These include acetals made from vinyl acetate copolymerized with ethylene (43—46), propjiene (47), isobutjiene (47), acrylonitrile (48), acrolein (49), acrylates (50,47), aHyl ether (51), divinyl ether (52), maleates (53,54), vinyl chloride (55), diaHyl phthalate (56), and starch (graft copolymer) (47). 

Liquid trichloroethylene has been polymerized by irradiation with Co y-rays or 20-keV x-rays (9). Trichloroethylene has a chain-transfer constant of <1 when copolymerized with vinyl chloride (10) and is used extensively to control the molecular weight of poly(vinyl chloride) polymer. 

Vinyls. Vinyl resins are thermoplastic polymers made principally from vinyl chloride other monomers such as vinyl acetate or maleic anhydride are copolymerized to add solubUity, adhesion, or other desirable properties (see Maleic anhydride, maleic acid, and fumaric acid). Because of the high, from 4,000 to 35,000, molecular weights large proportions of strong solvents are needed to achieve appHcation viscosities. Whereas vinyls are one of the finest high performance systems for steel, many vinyl coatings do not conform to VOC requirements (see Vinyl polymers). 

O.JVI. Scott Sons. The O.M. Scott Sons Co. (Scotts) has developed a series of coated products which utilize copolymer blends of vinyHdene chloride copolymerized with methyl methacrylates, acrylonitriles, methyl acrylates, and/or vinyHdene—vinyl chloride monomers. 

Random copolymers of vinyl chloride and other monomers are important commercially. Most of these materials are produced by suspension or emulsion polymerization using free-radical initiators. Important producers for vinyl chloride—vinyUdene chloride copolymers include Borden, Inc. and Dow. These copolymers are used in specialized coatings appHcations because of their enhanced solubiUty and as extender resins in plastisols where rapid fusion is required (72). Another important class of materials are the vinyl chloride—vinyl acetate copolymers. Principal producers include Borden Chemicals Plastics, B. F. Goodrich Chemical, and Union Carbide. The copolymerization of vinyl chloride with vinyl acetate yields a material with improved processabihty compared with vinyl chloride homopolymer. However, the physical and chemical properties of the copolymers are different from those of the homopolymer PVC. Generally, as the vinyl acetate content increases, the resin solubiUty in ketone and ester solvents and its susceptibiUty to chemical attack increase, the resin viscosity and heat distortion temperature decrease, and the tensile strength and flexibiUty increase slightly. 

Liquid organic rubbers with reactive functionality can be prepared by several methods. End-functional oligomers are preferred. Chains attached to the network at only one end do not contribute as much strength to the network as those attached at both ends [34], Urethane chemistry is a handy route to such molecules. A hydroxy-terminated oligomer (commonly a polyester or a polyether) can be reacted with excess diisocyanate, and then with a hydroxy methacrylate to form a reactive toughener [35]. The methacrylate ends undergo copolymerization with the rest of the acrylic monomers. The resulting adhesive is especially effective on poIy(vinyl chloride) shown in Scheme 2. 

Group of plastics whose resins are derived from the polymerization of vinylidene chloride or the copolymerization of vinylidene chloride and other unsaturated compounds. 

Polyethylene can be chlorinated in solution in carbon tetrachloride or in suspension in the piescnce ot a catalyst. Below 55-60% chlorine, it is more stable and more compatible with many polymers, especially polyvinyl chloride, to which it gives increased impact strength. The low pressure process copolymerizes polyethylene with propylene and butylene to increase its resistance to stress cracking. Copolymerization with vinyl acetate at high pressure increases flexibility, resistance to stress cracking, and seal ability of value to the food industry. 

The reported values for the exponent of the dose-rate for the polymerization rate in gamma radiation-induced copolymerization of acrylamide with methyl chloride salt of A, A -dimethylaminoethyl methacrylate (DMAEM-MC) in aqueous solution was found to be 0.8 [16]. However, the dose-rate exponent of the polymerization rate at a lower dose-rate was found to be slightly higher than 0.5 for gamma radiation-induced polymerization of acrylamide in aqueous solution [45,62]. 

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