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POLYMERISATION of SOME CYCLIC ETHERS and ALLYL COMPOUNDS at Higf PRESSURES

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POLYMERISATION of SOME CYCLIC ETHERS and ALLYL COMPOUNDS at Higf PRESSURES POLYMERISATION OF SOME CYCLIC ETHERS AND ALLYL COMPOUNDS AT HIGf PRESSURES. THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN THE FACULTY OF SCIENCE UNIVERSITY OF LONDON BY MUSTAFIZUR RAHMAN. DEPARTMENT OF CHEMICAL ENGINEERING AND CHEMICAL TECHNOLOGY, IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, LONDON, S.W.7. SEPTEMBER, 1967. ABSTRACT. The polymerizations of seven cyclic ethers and two allyl compounds have been studied at high pressures (up to 12,000 atm.). BF3.(C2H5)20 was usually used as catalyst to polymerize the ethers, except for 1,4-epoxycyclohexane with wilich the co-catalyst epichlorohydrin was employed. Benzoyl peroxide and azo-isobutyronitrile were used to polymerize the allyl compounds. The polymerizations of 1,4-epoxycyclohexane and tetrahydrofuran (THF) have been studied most extensively. From the lag rate vs. pressure graphs, "overall volumes of activation" Air*pol were calculated and compared with those for vinyl compounds. Conductances of solutions of BP3.(C2H5)20 in tetrahydropyran were measured and the results discussed in relation to the kinetic measurements. The variation of the polymerization ceiling temperature of THF with pressure was determined between 1 and 2500 atm. The polymerizations of cyclohexene oxide, styrene cxide, cyclooctene oxide, tetrahydropyran, triallyl phosphate, triallyl phosphite and the co-polymerization of triallyl phosphate and styrene, have been studied briefly. The results, wherever possible, have been explained in terms of existing ideas. 3. Polymers from viscous liquid to insoluble solids were obtained during this investigation and the molecular weights were determined, where possible. 4 ACKNOWLEDGEBENTS. The author wishes to express his gratitude to Dr. K.E.Weale for his kind supervision, valuane guidance and constant encouragement during the course of this study. The author would also like to thank Pakistan Council of Scientific and Industrial Research (Karachi) and Valika Trust (Karachi) for the financial support during the period of this investigation. Thanks are also due to the Departmental Workshop staff for their help in maintaining the high pressure equipment and especially for making a new steel reaction tube. 5. COITIENTS. Page Section I. INTRODUCTION. 8 1, General Theory of Polymerization. 8 A. Free Radical polymerization. 8 B. Kinetics of free radical polymerisation. 10 C. Chain Transfer Reaction. 12 D. Inhibitors and Retarders. 13 E. Determination of Velocity Constants of the Component Remotions. 14 F. Cationic Polymerization. 15 G. Anionic Polymerization. 18 H. Living Polymers. 20 I. Co-ordination Polymerization. 21 J. Polymerization-Depolymerization Equilibrium. 22 2(1) Theory of Chemical Reaction. 23 A. Collision Theory. 23 B. Transition Rate Theory. 24 C.Effects of pressure on Rates of Polymerization. 31 2(2) Polymerization at High Pressure. 31 2(3) Effects of Pressure on Ceiling Temperature. 34 2(4) Effect of Pressure on Ionic Equilibrium. 35 3. Review of Polymerization of Cyclic Ethers. 36 A. At Atmospheric Pressure. 36 B. At High Pressures. 39 C. Review of Polymerization of Triallyl Phosphate. 41 4. Scope of this work. 41 6. Page Section II. EQUIPMENT, MATERIALS AND PROCEDURE. 43 1. Equipment. 43 A. High Pressure Equipment. 43 B. Reaction Tubes and Holders. 48 C. Atmospheric Pressure Equipment. 51 D. Equipment for Conductivity Measurement at High Pressure. 51 2. Materials. 55 A. Monomers. 55 Be Catalysts and co-catalysts. 57 C. Solvents. 58 3. Procedure. 59 A. PrepataTion of Reaction Mixture. 59 B. Technique of Polymerization. 59 C. Separation of the Polymers. 60 D. Molecular Weight Determination. 61 Section III. RESULTS AND DISCUSSION. 64 1. The Polymerization of 1,4-epoxycyclohexane. 64 2. The Polymerization of Tetrahydrofuran. 79 3. The Variation of Polymerization Ceiling Temperature of Tetrahydrofuran with Pressure. 100. r, • Page 4. The polymerization of cylcohexene oxide. 109 5. The polymerization of styrene oxide. 114 6. The polymerisation of cyclooctene oxide. 116 7. The polymerization of tetrahydropyran. 118 8. The polymerization of triallyl phosphate and triallyi phosphite. 119. Section IV. GENERAL DISCUSSION. 26 REFERENCES. 130 SECTION I. INTRODUCTION. 1.1. General Theory of Polymerization. Staudinger 1 proposed first in 1920 that addition polymerizations are chain reactions which show the stages of initiation, propagation and of termination in which polymer chain-carriers are either destroyed or rendered inactive. Depending on whether the chain-carrier is a free radical, cation or an anion, addition polymerization reactions are classified into three main types : (a) Free radical polymerizations; (b) Cationic polymerizations; and (c) anionic polymerizations. A. Free Radical Polymerization. The first step in radical polymerization is usually the decomposition of the initiators such as organic peroxides, azo- and diazo-compounds, under photochemical or thermal influence to give radicals. Two reactions often used to produce free radicals in addition polymerization are the decomposition of benzoyl peroxide (Bz202) e + 2C0 (C6H3C00)2 206H5COO' = 2C65H 2 and of azobisisobutyronitrile (AIBN) 0 = 2(0113) -C + N (CH3)2 - C - N = N - C - (CH3)2 2 2 CN CN CN 0 Such reactions can be represented generally by l = 2 X* The addition of a free radical to the double bond of an ethylenic compound; with regeneration of a free radical, leads to propagation of a growing polymer chain CH2 = X* + CH2 = C'= X - CH2 - R, X - CH2 - C(RR')-CH2-d(RR) R' R' etc. At each addition, one electron of the double bond pairs with that of the free radical, and the second electron of the double bond regenerates a radical which repeats the process. The chain can thus be propagated by the addition of a large number of monomers. Evidence for this mechanism comes not only from the acceleration of such polymerization by free radicals but also from the fact that polymers formed have been shown to contain fragments of the initiating radicals. The growing polymer chains can be terminated in at least two ways. Two growing chains may combine, the activity of the two free radicals being mutually satisfied (Termination by coupling or combination) : X - [CH2-C(RRI)]m, + X - [CH2-C(RR')]n = X - [CH2-C(RR')]mill - X. Alternatively, two growing chains may undergo a procass of disproportionation; this involves the transfer of a hydrogen atom from one growing chain to the other with the formation of an unsaturated end group on the chain which 1c-es the 10. hydrogen atom : R "00H2-C(RR, ) +-w,C1-12-C(RR') =e-CFI2 - CH + (RR') Jr.= CHP40 R' The wavy lines denote the bulk of polymer chains. Each type of termination is known: polystyrene chains terminate mainly by combination, polymethyl methacrylate chains terminate entirely by disproportionation at temperature: above 6000. B. Kinetics of Free Radical Polymerization. The initiation of free radical chains may be regarded as occurring in two steps; (a) the decomposition of the initiator, I, with a velocity constant kd kd I la: 2 X' and (b) addition of monomer, denoted by M, to form a radical, M.1 ' with a velocity constant ka : ka X' + M Mi The propagation steps, M' + M = Id' ; M' + M = M' 1 2 2 3 etc. can be represented generally by M' + M = M'2+1 and are assumed to have the same velocity constant k , i.e. the radical reactivity is assumed to be independent of the chain length. The termination step may occur by either 11. combination or disproportionation. A single velocity constant kt can be assumed to cover both mechanisms. The rates of the three steps can be expressed in terms of the molar concentration (C) of the substances involved and the appropriate velocity constants. The rate of initiation Vi is given by Vi = (dCm(dt) = 2f kd CI (1) where f is the efficiency of the initiator i.e. the fraction of the radicals formed from I which initiate chains. The value of f is usually less than unity because a fraction of the radicals (X) formed in pair from the initiator recombine by a "cage effect" before escaping from each other's proximity. The rate of termination Vt is given by Vt = (-dCm/dt) = 2kt Cm2 (2) It is assumed that in the process of polymerization, 0 will become constant very eazly in the reaction, as radicals are formed and destroyed at identical rates. In such a steady-state condition Vi = Vt and ,? 2f kd CI = 2ktCm (3) from which 0 = (fkdykt)2 (4) The rate of propagation V is essentially the same as the overall rate of disappearance of the monomer, that is, of polymerization, since if the chains are long the number 12. of monomers concerned in the reaction X' = M°1 must be small compared with those used in propagation, Hence, Vp = (—dCH/dt) = ki)C14Cm = yfkd Cl/lied' Cm (5) The overall rate of polymerization in the early stages of the reaction should thus be proportional to the square root of the initiator concentration, and if f is independent of Cm, to the first power of monomer concentration. This is true if initiator efficiency is high. With very low efficiencies f may be proportional to Cm, making Vp 3/2 proportional to 0,.7 • The proportionality of the overall rate to the square root of initiator concentration has been confirmed experimentally in a large number of cases. C. Chain Transfer Reaction. The kinetic chRin lengthli is defined as the number of monomer units eonsumee7, per active centre. If no reaction takes place other t:lan those already discussed * the kinetic chain. length should he related to the number average degree of polymerization Y : for termination by combination fn = 2`ti and for disproportionation n=1) . This is found to be precisely true for some systems, but for others wide deviations are noted in. the direction of more polymer molecules than active centres. The deviations are the results of chain transfer reactions, as pointed out by Flory 2 in 1937.
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