Acetal Polymerization

Cyclic ether and acetal polymerizations are also important commercially. Polymerization of tetrahydrofuran is used to produce polyether diol, and polyoxymethylene, an excellent engineering plastic, is obtained by the ring-opening polymerization of trioxane with a small amount of cycHc ether or acetal comonomer to prevent depolymerization (see Acetal resins Polyethers, tetrahydrofuran). 

Often a chain-transfer agent is added to vinyl acetate polymerizations, whether emulsion, suspension, solution, or bulk, to control the polymer molecular weight. Aldehydes, thiols, carbon tetrachloride, etc, have been added. Some emulsion procedures call for the recipe to include a quantity of preformed PVAc emulsion and sometimes antifoamers must be added (see Foams). 

Solution Polymerization. Solution polymerization of vinyl acetate is carried out mainly as an intermediate step to the manufacture of poly(vinyl alcohol). A small amount of solution-polymerized vinyl acetate is prepared for the merchant market. When solution polymerization is carried out, the solvent acts as a chain-transfer agent, and depending on its transfer constant, has an effect on the molecular weight of the product. The rate of polymerization is also affected by the solvent but not in the same way as the degree of polymerization. The reactivity of the solvent-derived radical plays an important part. Chain-transfer constants for solvents in vinyl acetate polymerizations have been tabulated (13). Continuous solution polymers of poly(vinyl acetate) in tubular reactors have been prepared at high yield and throughput (73,74). 

One of the most dramatic examples of a solvent effect on propagation taken from the early literature is for vinyl acetate polymerization.78,79 Kamachi el al.n reported a ca. 80-fold reduction in kp (30aC) on shifting from ethyl acetate to benzonilrile solvent (Table 8.1). Effects on polymer structure were also reported. Hatada ef a m conducted a H NMR study on the structure of the PVAc formed in various solvents. They found that PVAc (M n 20000) produced in ethyl acetate solvent has 0.7 branches/chain while that formed in aromatic solvents is essentially unbranched. 

A typical mixture for vinyl acetate polymerization can be seen below [94] ... 

The density change on polymerization is typically about 20%, and this density gradient can cause significant secondary flows and natural convection effects. The experiments cited above for vinyl acetate polymerization were performed in a helical reactor. The centrifugal force in helical reactors induces secondary flows as well. The effects of helical flow have been analyzed, but were found to be less significant than the effects of natural convection [14]. 

SOLUTION OF KINETIC EQUATIONS FOR LONG CHAIN BRANCHING IN BULK VINYL ACETATE POLYMERIZATION ... 

Loop A continuous process for polymerizing aqueous emulsions of olefinic compounds such as vinyl acetate. Polymerization takes place in a tubular reactor (the loop) with recycle. Invented by Gulf Oil Canada in 1971 and further developed by several United Kingdom paint companies. It is now used for making copolymers of vinyl acetate with ethylene, used in solvent-free paints and adhesives. 

Acetal formation, microwaves in, 76 557 Acetalization, of PVA, 25 602-603 Acetal polymerization, 74 271 Acetal resins, 70 183-185 Acetal resins, formaldehyde in, 72 122 Acetals, 2 64 70 529 aroma chemicals, 3 253 inorganic pigment applications, 7 372t organic pigment applications, 7 368t typical soluble dye applications, 7 376t Acetaminophen, 4 701. See also AT-Acetyl-p-aminophenol (acetaminophen)... 

Gustin, J. L., and F. Laganier (1998). "Understanding Vinyl Acetate Polymerization Accidents." IChemE Symposium Series 144, 387-403. 

An especially interesting case of inhibition is the internal or autoinhibition of allylic monomers (CH2=CH—CH2Y). Allylic monomers such as allyl acetate polymerize at abnormally low rates with the unexpected dependence of the rate on the first power of the initiator concentration. Further, the degree of polymerization, which is independent of the polymerization rate, is very low—only 14 for allyl acetate. These effects are the consequence of degradative chain transfer (case 4 in Table 3-3). The propagating radical in such a polymerization is very reactive, while the allylic C—H (the C—H bond alpha to the double bond) in the monomer is quite weak—resulting in facile chain transfer to monomer... 

Transfer and termination occur by the modes described previously for cyclic ether polymerizations. Chain transfer to polymer (both inter- and intramolecular) is facilitated in cyclic acetal polymerizations compared to cyclic ethers because acetal oxygens in the polymer chain are more basic than the corresponding ether oxygens [Penczek and Kubisa, 1989a,b]. Working at high monomer concentrations, especially bulk polymerizations, is used to depress cyclic oligomer formation. 

Another mechanism, conceivable with most monomers, and believed to occur in vinyl acetate polymerization (see Section 10), is transfer with the monomer forming a polymer with an unsaturated end-group capable of copolymerizing, e.g. ... 

Graessley and his co-workers have made calculations of the effects of branching in batch polymerizations, with particular reference to vinyl acetate polymerization, and have considered the influence of reactor type on the breadth of the MWD (89, 91, 95, 96). Use was made of the Bamford and Tompa (93) method of moments to obtain the ratio MJMn, and in some cases the MWD by the Laguerre function procedure. It was found (89,91) that narrower distributions are produced in batch (or the equivalent plug-flow) systems than in continuous systems with mixing, a result referrable to the wide distribution of residence times in the latter. 

In another variant of the kinetic method, the shapes of curves of Mn, Mw, or [ /], versus conversion in batch polymerization may be used to obtain transfer coefficients, both with monomer and with polymer this procedure has been used by Wheeler (142), Graessley (143), and others, to obtain transfer coefficients for vinyl acetate polymerization (Section 11). 

Base fluids (BFs) represent the major ingredient of nonaqueous drilling mud systems. They act as the continuous phase in OBMs and SBMs. Oil-based fluids (OBFs) such as diesel and mineral oils have been replaced with synthetic-based fluids (SBFs) because of the deleterious environmental hazards of OBMs. The SBFs contain fatty adds which are usually derived from vegetable oil (e.g., palm oil) or fish oil. SBFs usually constitute about 50-90% by volume of the fluid portion of the SBM [27] and about 20-40 % of the mass of the mud [35]. Ethers, esters, acetals, polymerized olefins (poly-a-olefins, linear a-oleftns, and internal olefins), enhanced mineral oils, and paraffins are used most frequently as SBFs (Table 11.2) in mud formulations [8, 36, 37]. 

The initiators used m vinyl acetate polymerizations are the familiar free-radical types, Buffers are frequently added to emulsion recipes. Vinyl acetate emulsion polymerization recipes are usually buffered to pH 4-5. The pH of most commercially available emulsions is 4-6. 

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