Vinyl acetate copolymerization with ethylene

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). 

R. Reed, Moldable Ethylene/Vinyl Acetate Copolymer , USP 4090894 (1978) CA 39, 148908 (1978) [Vinyl acetate copolymerized with ethylene is used as a desensitizer and binder for moldable expl compns of cyclic nitramines such as RDX. From 82 to 98 wt % of binder is used, and various ratios of ethylene to vinyl acetate moieties in the resin are utilized to modify molding and extrusion properties. Prepn of typical compns consists of dissolving the copolymer in benz and addition with stirring to an RDX/w slurry, which is stirred until mixt is complete, followed by filtration and drying. Table 1 presents properties of sample compns with and without the ethylene/vinyl acetate copolymer (EVA). The inventor also states that the EVA, unlike other polymeric binders, endothermically breaks down at high temps and acts as a heat sink for the expl content]... 

Ethylene can be free radically copolymerized with vinyl acetate. Copolymerization with 0%-35% vinyl acetate is carried out in bulk at 1000-2000 bar, that of 35%-100%at 100-400 bar in /-butanol, and that of 60%-100%at 1-200 bar in emulsion. Products with vinyl acetate contents of over 10% give shrinkable films those with up to 30% vinyl acetate give thermoplastic films, and those with over 40% vinyl acetate give clear films. Products of still higher vinyl acetate content are elastomers, fusion, and solvent adhesives or modifiers for PVC. The products can be cross-linked with lauroyl peroxide on the addition of, for example, triallyl cyanurate. Copolymers of ethylene and ethyl acrylate have similar properties. 

High molecular weight and essentially linear polymers, controlled particle size in the case of emulsions, and even polymers with spatially regulated structures are available. Vinyl acetate copolymerizes with many other vinyl monomers. Acrylate esters vinyl chloride and vi-nylidene chloride dibutyl and other dialkyl maleates and fiimarates crotonic, acrylic, methacrylic and itaconic acids vinyl pyrroli-done and ethylene are commercially important comonomers. A monomer that does not combine with vinyl acetate alone may be combined by use of a third monomer. Grafting can be used with monomers such as styrene that do not copolymerize with vinyl acetate. 

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).

The simplest monomer, ethylenesulfonic acid, is made by elimination from sodium hydroxyethyl sulfonate and polyphosphoric acid. Ethylenesulfonic acid is readily polymerized alone or can be incorporated as a copolymer using such monomers as acrylamide, aHyl acrylamide, sodium acrylate, acrylonitrile, methylacrylic acid, and vinyl acetate (222). Styrene and isobutene fail to copolymerize with ethylene sulfonic acid. 

Some data recently obtained on high pressure ethylene copolymerizations illustrate the quantitative aspects of an ethylene-based Q-e scheme (6). In Figures 3 and 4 copolymer composition curves for the ethylene-vinyl chloride and the ethylene-vinyl acetate copolymerizations are given. The monomer reactivity ratios for these two systems are tabulated in Table III along with Q values and e values for vinyl chloride and vinyl acetate calculated using ethylene as the standard (Q = 1.0 and g = 0). These Q and e values may be compared with those obtained using styrene as the standard. 

The less nucleophilic acetals copolymerize with vinyl compounds more readily. Perhaps, in these systems the alkoxycarbenium ions (... —OCH ) that coexist in equilibrium with oxonium ions facilitate copolymerization with vinyl compounds. Styrene copolymerizes with trioxane 51,52) and tetraoxane53). The latter system yields polytrioxane and trioxane-styrene copolymer together with 1,4-phenyl-1,3-dioxane. It was formed in 25% yield in ethylene dichloride at 30 °C after 1 hr using [BF3 OEtj] = 10-2 mol l-1, [styrene], = [tetraoxane = 0.5 mol l-1. The proposed mechanism of 4-phenyl- 1,3-dioxane formation is shown below (cf. also Chap. 7) ... 

Different types of water-based emulsions are used in EPI adhesives. The most common are poly(vinyl acetate) (PVAc) emulsion, ethylene vinyl acetate (EVAc) emulsion, vinyl acetate-acrylate copolymerized (VAAC) emulsion, acrylic-styrene (AcSt) emulsion or styrene-butadiene rubber (SBR) latex or modified versions of these emulsion types [1, 8, 9], It has also been reported that tri- or ter-polymer emulsions like vinyl acetate-butyl acrylate-hydroxypropyl methacrylate or emulsions with different combinations of block copolymers can be used [4], Emulsion polymers containing cross-linking functional groups are especially well suited [4,6, 9]. The choice of emulsion(s) will, to a large extent, influence the adhesive properties such as setting time, bond quality, heat resistance, and moisture resistance. EPI adhesive systems are, however, very complex and the total composition (including the choice of cross-linker) and the interaction between the different components will determine the properties of the adhesive. Due to this it is difficult to describe in detail the effect of choosing one type of emulsion over the other. 

Emulsions can be formulated with only hard monomer and plasticized at a later stage, but it is normal to internally plasticize the emulsion by copolymerizing some soft monomer. Vinyl acetate plasticized with an acrylate such as butyl or ethylhexyl acrylate, or a dialkyl maleate, are common combinations. Other hard (high Tg) monomers include methyl methacrylate, styrene, and vinyl chloride. Soft monomers include Vinyl Versatate (Shell Chemicals), ethylene, and vinylidene chloride (Figure 1). 

PBT is also blended with PMMA, PET/PC, and polybntadiene. Another development involving the use of PBT is coextrusion of PBT and copolyester thermoplastic elastomer. This can then be blow molded into under-hood automotive applications, which minimize noise vibration. PBT is suitable for applications requiring dimensional stability. It is particnlarly good in water, and it is also resistant to hydrocarbons oils without stress cracking. To improve PBT s poor notch impact strength, copolymerization with ethylene and vinyl acetate will improve toughness. 

As mentioned previously, the Alfrey Priee Q and e values for vinyl acetate are 0.026 and —0.22, respectively [226]. Thus vinyl acetate is rather sluggish in its free-radical copolymerization, with most monomers, particularly olefinic monomers, bearing electron-donating subtitutents. The copolymerization reactivity ratios reflect the reluctance of vinyl acetate to enter into copolymerization with other monomers [270]. Nevertheless, vinyl acetate copolymers with a great many electron-rich as well as electron-poor olefins have been prepared. Especially significant from a commercial point of view are copolymers with ethylene, vinyl chloride, acrylates, methacrylates, fumarates, and maleates. Often, mixtures of three and more comonomers are used in these copolymerizations. 

Additionally to the procedures described earlier, improvements for thermostabilization is copolymerisation of vinyl chloride with suitable monomers. A great number of monomers were investigated to optimize the properties of resins. But only vinyl acetate, vinylidene chloride, ethylene, propylene, acrylonitrile, acrylic acid esters, and maleic acid esters, respectively, are of interest commercially [305,436,437]. The copolymerization was carried out in emulsion, suspension, and solution in connection with water- or oil-soluble initiators, as mentioned elsewhere. Another possibility for modifying PVC is grafting of VC on suitable polymers [305,438], blends of PVC with butadiene/styrene and butadiene/ methacryl acid esters copolymers [433], and polymer-analogous reactions on the macromolecule [439,440] (e.g., chlorination of PVC). 

Polyethylene has limited adhesion to paints and inks. This is because it is a non-polar hydrocarbon incapable of forming hydrogen bonds. Adhesion can be improved by copolymerizing ethylene with polar monomers such as ethyl acrylate or vinyl acetate to give ethylene ethyl acrylate (EEA) copolymers or ethylene vinyl acetate (EVA) copolymers. EVA is often used for shoe soles. 

Ethylene copolymerized with other olefins has already been covered above. Ethylene copolymers with polar comonomers are made by the high-pressure route the favoured monomer is vinyl acetate (VAC) which, under the usual reaction conditions, copolymerizes with ethylene ideally. Small amounts of VAC reduce crystallinity and melting point, but increase toughness and flexibility such copolymers (EVAC) are used for tough film, although the moisture permeability is increased by the inclusion of the polar groups. 

Each of these reactions is characterized by its specific rate constant kg. The composition of the polymer is determined by the copolymerization parameters ri = feii/ki2andr2 = 22/ 21- Ifti = t2 = 1, the comonomer is randomly distributed in the polymer chain. This is largely the case when vinyl acetate is copolymerized with ethylene. 

Vinyl Acetate-Based Copolymers and Derived Polymers. Vinyl acetate units transmit their intrinsic adhesivity to all VA-containing polymers. Thus, vinyl acetate is copolymerized with ethylene, acrylic monomers, and so on. Its reaction behavior can be predicted through parameters Q = 0.026 and e = 0.22 (see Section 8.5.11). 

Hydrocarbon resins (qv) are prepared by copolymerization of vinyltoluene, styrene, and a-methylstyrene in the presence of a Eriedel-Crafts catalyst (AlCl ). These resins are compatible with wax and ethylene—vinyl acetate copolymer (197). 

In order to increase the solubiUty parameter of CPD-based resins, vinyl aromatic compounds, as well as other polar monomers, have been copolymerized with CPD. Indene and styrene are two common aromatic streams used to modify cyclodiene-based resins. They may be used as pure monomers or contained in aromatic steam cracked petroleum fractions. Addition of indene at the expense of DCPD in a thermal polymerization has been found to lower the yield and softening point of the resin (55). CompatibiUty of a resin with ethylene—vinyl acetate (EVA) copolymers, which are used in hot melt adhesive appHcations, may be improved by the copolymerization of aromatic monomers with CPD. As with other thermally polymerized CPD-based resins, aromatic modified thermal resins may be hydrogenated. 

During this early period, a very ingenious free-radical route to polyesters was used to introduce weak linkages into the backbones of hydrocarbon polymers and render them susceptible to bio degradabihty (128—131). Copolymerization of ketene acetals with vinyl monomers incorporates an ester linkage into the polymer backbone by rearrangement of the ketene acetal radical as illustrated in equation 13. The ester is a potential site for biological attack. The chemistry has been demonstrated with ethylene (128—131), acryhc acid (132), and styrene (133). 

Small amounts of TAIC together with DAP have been used to cure unsaturated polyesters in glass-reinforced thermo sets (131). It has been used with polyfunctional methacrylate esters in anaerobic adhesives (132). TAIC and vinyl acetate are copolymerized in aqueous suspension, and vinyl alcohol copolymer gels are made from the products (133). Electron cure of poly(ethylene terephthalate) moldings containing TAIC improves heat resistance and transparency (134). 

Continuous polymerization systems offer the possibiUty of several advantages including better heat transfer and cooling capacity, reduction in downtime, more uniform products, and less raw material handling (59,60). In some continuous emulsion homopolymerization processes, materials are added continuously to a first ketde and partially polymerized, then passed into a second reactor where, with additional initiator, the reaction is concluded. Continuous emulsion copolymerizations of vinyl acetate with ethylene have been described (61—64). Recirculating loop reactors which have high heat-transfer rates have found use for the manufacture of latexes for paint appHcations (59). 

Suspension Polymerization. At very low levels of stabilizer, eg, 0.1 wt %, the polymer does not form a creamy dispersion that stays indefinitely suspended in the aqueous phase but forms small beads that setde and may be easily separated by filtration (qv) (69). This suspension or pearl polymerization process has been used to prepare polymers for adhesive and coating appHcations and for conversion to poly(vinyl alcohol). Products in bead form are available from several commercial suppHers of PVAc resins. Suspension polymerizations are carried out with monomer-soluble initiators predominantly, with low levels of stabilizers. Suspension copolymerization processes for the production of vinyl acetate—ethylene bead products have been described and the properties of the copolymers determined (70). Continuous tubular polymerization of vinyl acetate in suspension (71,72) yields stable dispersions of beads with narrow particle size distributions at high yields. 

Vinyl chloride can be copolymerized with many other monomers to improve its properties. Examples of monomers used commercially are vinyl acetate, propylene, ethylene, and vinylidine chloride. The copolymer with ethylene or propylene (Tg = 80°C), which is rigid, is used for... 

The monomers used to make an addition polymer need not be identical. When two or more different monomers are polymerized into the same chain, the product is a copolymer. For instance, we routinely copolymerize ethylene with small percentages of other monomers such as a-olefins (e.g., 1-butene and 1-hexene) and vinyl acetate. We call the products of these reactions linear low density polyethylenes and ethylene-vinyl acetate copolymer, respectively. We encounter these copolymers in such diverse applications as cling film, food storage containers, natural gas distribution pipes, and shoe insoles. 

In contrast, commercial processes for the copolymerization of ethylene with polar monomers such as acrylate and vinyl acetate still exclusively employ free radical processes [13]. The use of free radical initiators across the entire acrylic polymer... 

---