Vinyl chloride polymers polymerisation

Slush powders were prepared from mass polymerised and suspension polymerised vinyl chloride polymers and the absorption of plasticisers into the polymers was investigated using the Haake rheomix procedure. The fusion behaviour of the powders was also investigated and the morphology of the particles analysed by scanning electron microscopy. The properties of the two different powders are compared. 6 refs. 

The third assumption results from the known reactivity difference between vinyl chloride and vinylidene chloride monomers in the copolymerisation process. In the polymer molecules formed at the beginning of polymerisation, vinyl chloride exists in the polymer chain as a single unit among many vinylidene chloride units. In the polymer molecules formed in the latter part of polymerisation, vinylidene chloride exists in the polymerisation chain as a single unit among many vinyl chloride units. Because of the relative reactivity ratio (rl, r2) of vinylidene chloride and vinyl chloride monomers, the probability of forming an alternating monomeric unit in the copolymer molecules is minimal. With this assumption, the polymer molecules have a vinylidene chloride/vinyl chloride distribution as follows ... 

The principal use of the peroxodisulfate salts is as initiators (qv) for olefin polymerisation in aqueous systems, particularly for the manufacture of polyacrylonitrile and its copolymers (see Acrylonitrile polymers). These salts are used in the emulsion polymerisation of vinyl chloride, styrene—butadiene, vinyl acetate, neoprene, and acryhc esters (see Acrylic ester polymers Styrene Vinyl polymers). 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

PVC. Poly(vinyl chloride) (PVC), a very versatile polymer, is manufactured by the polymerisation of vinyl chloride monomer, a gaseous substance obtained from the reaction of ethylene with oxygen and hydrochloric acid. In its most basic form, the resin is a relatively hard material that requites the addition of other compounds, commonly plasticisers and stabilisers as well as certain other ingredients, to produce the desired physical properties for roofing use. The membranes come in both reinforced and nonreinforced constmctions, but since the 1980s the direction has been toward offering only reinforced membranes. The membrane thickness typically mns from 0.8—1.5 mm and widths typically in the range of 1.5—4.6 m. 

Another important use of BCl is as a Ftiedel-Crafts catalyst ia various polymerisation, alkylation, and acylation reactions, and ia other organic syntheses (see Friedel-Crafts reaction). Examples include conversion of cyclophosphasenes to polymers (81,82) polymerisation of olefins such as ethylene (75,83—88) graft polymerisation of vinyl chloride and isobutylene (89) stereospecific polymerisation of propylene (90) copolymerisation of isobutylene and styrene (91,92), and other unsaturated aromatics with maleic anhydride (93) polymerisation of norhornene (94), butadiene (95) preparation of electrically conducting epoxy resins (96), and polymers containing B and N (97) and selective demethylation of methoxy groups ortho to OH groups (98). 

The thermoplastic or thermoset nature of the resin in the colorant—resin matrix is also important. For thermoplastics, the polymerisation reaction is completed, the materials are processed at or close to their melting points, and scrap may be reground and remolded, eg, polyethylene, propjiene, poly(vinyl chloride), acetal resins (qv), acryhcs, ABS, nylons, ceUulosics, and polystyrene (see Olefin polymers Vinyl polymers Acrylic ester polymers Polyamides Cellulose ESTERS Styrene polymers). In the case of thermoset resins, the chemical reaction is only partially complete when the colorants are added and is concluded when the resin is molded. The result is a nonmeltable cross-linked resin that caimot be reworked, eg, epoxy resins (qv), urea—formaldehyde, melamine—formaldehyde, phenoHcs, and thermoset polyesters (qv) (see Amino resins and plastics Phenolic resins). 

There is much evidence that weak links are present in the chains of most polymer species. These weak points may be at a terminal position and arise from the specific mechanism of chain termination or may be non-terminal and arise from a momentary aberration in the modus operandi of the polymerisation reaction. Because of these weak points it is found that polyethylene, polytetrafluoroethylene and poly(vinyl chloride), to take just three well-known examples, have a much lower resistance to thermal degradation than low molecular weight analogues. For similar reasons polyacrylonitrile and natural rubber may degrade whilst being dissolved in suitable solvents. 

Bulk polymerisation is heterogeneous since the polymer is insoluble in the monomer. The reaction is autocatalysed by the presence of solid polymer whilst the concentration of initiator has little effect on the molecular weight. This is believed to be due to the overriding effect of monomer transfer reactions on the chain length. As in all vinyl chloride polymerisation oxygen has a profound inhibiting effect. 

Over the past years considerable attention has been paid to the dispersing system since this controls the porosity of the particle. This is important both to ensure quick removal of vinyl chloride monomer after polymerisation and also to achieve easy processing and dry blendable polymers. Amongst materials quoted as protective colloids are vinyl acetate-maleic anhydride copolymers, fatty acid esters of glycerol, ethylene glycol and pentaerythritol, and, more recently, mixed cellulose ethers and partially hydrolysed polyfvinyl acetate). Much recent emphasis has been on mixed systems. 

The polymer may be prepared readily in bulk, emulsion and suspension, the latter technique apparently being preferred on an industrial scale. The monomer must be free from oxygen and metallic impurities. Peroxide such as benzoyl peroxide are used in suspension polymerisations which may be carried out at room temperature or at slightly elevated temperatures. Persulphate initiators and the conventional emulsifying soaps may be used in emulsion polymerisation. The polymerisation rate for vinylidene chloride-vinyl chloride copolymers is markedly less than for either monomer polymerised alone. 

The molecules join together to form a long chain-like molecule which may contain many thousands of ethylene units. Such a molecule is referred to as a polymer, in this case polyethylene, whilst in this context ethylene is referred to as a monomer. Styrene, propylene, vinyl chloride, vinyl acetate and methyl methacrylate are other examples of monomers which can polymerise in this way. Sometimes two monomers may be reacted together so that residues of both are to be found in the same chain. Such materials are known as copolymers and are exemplified by ethylene-vinyl acetate copolymers and styrene-acrylonitrile copolymers. 

By contrast, addition polymers are those formed by the addition reaction of an unsaturated monomer, such as takes place in the polymerisation of vinyl chloride (Reaction 1.2). 

Chain reactions carried out on one type of monomer give rise to homopolymers when using two types of monomer the situation is more complicated. For example, polymerising mixtures of vinyl chloride with acrylate esters gives rise to a range of molecules, the first of which are relatively rich in acrylate molecules formed later, when the amount of acrylate monomer is relatively depleted, are richer in vinyl chloride. In a number of instances, reactions of this kind can be used to prepare polymers containing monomers which will not homopolymerise, e.g. maleic anhydride and stil-bene (vinylbenzene). 

Propane was selected as solvent for the isobutene for experiments down to -145° the aluminium chloride was dissolved in ethyl chloride, for the work at lower temperatures a mixture of ethyl chloride and vinyl chloride was used. Although these catalyst solutions were made up at -78° they were yellow, and as stated above, they probably contained some hydrogen chloride and other catalytically active decomposition products. The polymerisations were carried out by running the cooled catalyst solution into the monomer solution. Polymer was formed, and came out of solution, almost immediately, and the reaction was very fast even at the lowest temperature (-185°) and lowest monomer concentration (0.6 mole/1). After the reaction was over, propanol at the reaction temperature was added to the reaction mixture to deactivate the catalyst. 

For instance, poly(vinyl chloride), derived from the polymerisation of vinyl chloride (chloroethene), CH2=CHC1, contains repeating units -CH2-CHCI-. However, long-chain molecules are of various lengths and the units are not necessarily all uniquely oriented and joined in a regular fashion, which would result in the polymer formulated -(CH2-CHC1)h. ... 

Materials that are constructed from organic polymers such as polyethylene, polystyrene, polyisoprene (natural rubber and a synthetic elastomer) and poly(vinyl chloride) are common features of our daily lives. Most of these and related organic polymers are generated from acyclic precursors by free radical, anionic, cationic or organometallic polymerisation processes or by condensation reactions. Cyclic precursors are rarely used for the production of organic polymers. 

The most common molecules from which polymers are made are ethylene (chemical formula CH2=CH2) and its derivatives. The key to its polymerisation is the double bond, which opens to form bonds to other ethylenes and the end result is a chain of CH2 groups, -CH2-CH2-CH2-CH2-CH2- which can be millions of carbons long. This is polyethylene. Another common polymer is poly(vinyl chloride) which is made from vinyl chloride (chemical formula CH2=CHCl) and is better known as PVC. See also PPMA and HEMA. The following table lists various common polymers headed by those based on ethylene and its derivatives ... 

Xie, T.Y, Hamielec, A.E., Wood P.E., Woods, D.R., Experimental investigation of vinyl chloride polymerisation at high conversion mechanism, kinetics and modeling, Polymer, 1991, 32(6), 537-557... 

Very little significant advance was then made until 1912-1916 when Fritz Klatte discovered the basis for the production of PVC. Patents were granted for the manufacture of vinyl chloride by reacting hydrogen chloride gas with acetylene at 180 °C in the presence of metal chlorides as the catalysts. They also referred to polymerisation by sunlight and suggested some uses for the polymer. 

Dechlorination of poly (vinyl chloride) (PVC) prepared by polymerisation of vinyl chloride (VC) with butyllithium (BuLi) was investigated under the conditions of high pressure and high temperature water. Dechlorination was induced completely and polyene product was formed from PVC under high pressure and high temperature. The polymers obtained from polymerisation of VC with the BuLi revealed different decomposition behaviour from that obtained with radical initiator such as lauryl peroxide. This was attributed to the different chemical structure of the sample PVC. Complete dechlorination of PVC could be achieved in hot water under the conditions of 19.3 MPa and 300 deg.C. 3 refs. 

The absorption of vinyl chloride(VC) on surface-treated light-grade and nanoscale calcium carbonate was shown to obey the Langmuir isothermal equation in VC/calcium carbonate/water system. The absorption of VC on calcium carbonate was shown to increase with increase of the partial pressure of VC up to the saturation absorption and the absorption of VC on nanoscale calcium carbonate was greater than that of light-grade calcium carbonate at the same temp, and partial pressure of VC. The presence of calcium carbonate in VC suspension polymerisation system was found to influence the pressure/temp./ conversion(PTC) relationship of the reaction system. Based on the absorption of VC on calcium carbonate and VC distribution in vapour, water and polymer phases, a modified model to represent the PTC relationship of VC suspension polymerisation in the presence of calcium carbonate was proposed. 10 refs. 

Polystyrene supported nickel(II) carborane complexes 44a and 44b have been tested in the polymerisation of ethylene, styrene and vinyl chloride in [C4Ciim][BF4], The compounds were active for all three substrates, even in the absence of a co-catalyst. Increased catalytic activity was observed relative to THF, affording polymers with higher molecular weight and, in most cases, lower polydispcrsity.1671... 

In situ polymerisation does not however guarantee homogeneous blends as two phase regions can exist within the polymer/polymer/monomer three component phase diagram. In the case of vinyl chloride polymerisation with solution chlorinated polyethylene, the vinyl chloride has limited solubility in both poly(vinyl chloride) and chlorinated polyethylene. The phase diagram has the form shown in Fig. 3 The limit of swelling of vinyl chloride in the chlorinated polyethylene is A and the highest concentration of PVC prepared by a one-shot polymerisation is B. 

In the case of vinyl chloride polymerisation in polyfbutyl acrylate) these materials are completely miscible but a two phase region exists within the phase diagram as shown in Fig. 4 Polymerisation from A to B produces a homogeneous blend whereas from E to F produces a two phase structure. Composition B can be reswollen to C with vinyl chloride which can then be polymerised to D to producea homogeneous blend. This route avoids the two phase region in the phase diagram and in principle all compositions of polymer blend can be prepared in a series of steps. 

Vinyl chloride can be polymerised to form polyvinyl chloride (PVC) which is fairly brittle and unsuitable for food contact applications, so it is mixed with plasticisers to soften the polymer and impart flexibility. Plasticised PVC may contain about 30% of plasticisers and is used to make stretch films and flexible PVC. Flexible PVC used for tubing and gaskets may contain di(2-ethylhexyl)phthalate, and stretch films will probably contain di(2-ethylhexyl)adipate and a polymeric adipate plasticiser. Rigid PVC may... 

The most important industrial applications of radical reaction to date are used for the manufacture of polymers. Around 108 tonnes (or 75%) of all polymers are prepared using radical processes. These are chain reactions in which an initial radical adds to the double bond of an alkene monomer and the resulting radical adds to another alkene monomer and so on. This addition polymerisation is used to make a number of important polymers, including poly(vinyl chloride) (PVC), polystyrene, polyethylene and poly(methyl methacrylate). Copolymers can also be easily prepared starting from a mixture of two or more monomers. These polymers have found widespread use as they possess a range of chemical and mechanical properties (such as strength and toughness). 

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