Document Qkp6EjgEMoLeEvvoGRzQ0EvG5

3217 Chemical Abstracts Vol. 68, 1968 */ Pe teriostatic properties and were resistant to aging under uv light. azelaic acid, crotonic acid, adipic acid, and succinic acid show t CPJR the acids accelerate the rate of degradation. Phenols stud 32l7r Copolymerization of divinyl adipate with methyl acrylate Temp, Pressure, mm. M Studied by polarography. A. M. Shur, M. M. Filimonova, and 175* 60 1.4 0.6 9.1 x 10-* B, F. Filimonov (Kishinevsk. Gos. Untv,, Kishinev). Vysokomol. Soedin., Ser. A 9(10), 2l93-7(1907)(Russ). In 0.05J/ EttXOH, as base electrolyte, divinyl adipate (I) (Mi) is hydrolyzed 180* 105 1.4 655 1.4 46$ 76 1.6 1.4 0.9 l.i x 10-< to AclI. The height of the polarographic wave (X) due to AcH is proportional to 1 concn. In 0.00:1/ Et,NOH, Me acrylate (II) (M,) has a polarographic halfwave potential of --1.88 v.; X 185 146 1.6 416 1.5 646 1.4 65 1.4 0.8 1.# X lO-i height gradually decreases (Brdicka and Wicsnor, CA 41: 5403d). However, in 0.05.1/ Et<Nl II has a const. X, which depends only on II concn. This difference in polarographic ISO* 106 1.6 310 1.6 606 1.5 06 1.6 0.9 3.0 X 10-' behavior of 1 and II was used to develop a sensitive anal, proce dure for their detn. in the presence of each other. Copolymn. of I and II in sealed glass ampuls at 00 was carried out as described earlier (CA 56: 10385h). Samples were withdrawn and their 1 and II contents were detd. by polarography of ali quots in 0.05.1/ EttN'OH (for I) and 0.05.1/ EL.N1 (for II). Kinetic curves were constructed and monomer reactivity ratios were found: r, = 0.1 0.1, rj = 4 1; on the basis of reac tivity per double bond, rt' = 0.05 0.05, r,' - 8 2. CPJR 3218s Free-radical polymerization of ethylene. VII. Effect of pressure on copolymerization of ethylene with vinyl chloride. F. 1. Duntov, A. L. Gol'dcnbcrg, M. A. Litvinova, and B. L. Erusalimskii. Vysokomol. Soedin., Her. -si 9(9), 1920-3(1907) (Russ); cf. CA 63: 10070b. The influence of the pressure on 90S 1.4 365 1.6 670 1.5 show that the accelerating rates decrease in the order phei >2,4-di-ter/-butyIphenol >2,4,6-tri-/er/-butylphenol. The met anism of the degradation was studied. The HCI attacks vicii H and Cl to form double bonds and the ales, and phenols atta labile Cl atoms. BRJR 3222p Styrene derivatives. VII. Polymerization of sor substituted 4-vinylphthalans. G. M. Pogosyan, A. A. Choi kyan, Al'b. A. Saakyan, and S. G. Matsoyan. Vysokom Soedin., Ser, B 9(5), 305-8(1967)(Russ). 1,3-Dimcthyl vinylphthalan (I), l,l,3,3-tetramethyl-4-vinylphthalan (L l,3-dimethyl-l,3-diethy1-4-vinylphthalan(III), and l,3-bis(cyci reaction rate and the monomer relative reactivities in the co HJDCH polymn. of ethylene and vinyl chloride in the presence of azoisobutyronitriic at 300-1500 atm. was studied. The study used 2 compns.: 13-17% and 43-61 mole % vinyl chloride. In both M* ,, eBt m cases, the copolymn. rate increases with increasing pressure, and the increase is more pronounced at higher ethylene content. Curves showing the dependence of copolymn. rate on pressure and on compn. are given, and reactivity ratios are 0.10 and 1.85 for ethylene and vinyl chloride at 300 atm., and 0.2 and 1.85 at 1500 atm., resp, Ir spectra are given for the copolymers, and bands are present at 833, 770, 752, 726, and 722 cm.-* Approx. 20% -CHiCHC1(CHj),CHCICHi- is present in the copolymer. pentamethylene)-4-vinylphthalan (IV) were polymd. in bu or in a C*H soln. in the presence of Bz-Oi or azobisisobutyr nitrile. The polymn. rate increased with initiator concn. ai with an increase of temp, from 80 to 100. All the polyrnc formed were powderlike and sol. After 2 hrs. polymn., tyields were 13-19.5, 32-95, and 79-89% and the polymer solte J BRJR 3219t The crystallization of ethyl- and methyl-branched co polymers of polyethylene from dilute solution. P. J, Holdsworth and A. Keller (L'niv, Bristol, Engl,). J. Polvm, Set., Part B 5(8), G05-12(19G7)(Eng). The morphology of crystals was studied for both ethylene-propylene (I) and ethylene-1butenc (II) copolymers grown from 0.1% soln. I contained 8.4 and 27.9 Mc-braiiches/1000 C-atoms and II had 11 and 31.4 Et-branches/1000 C-atoms. Mats of the crystals were annealed and their crystallinity was deld. by heat of fusion. Varying lamellar thickness with appropriate crystn. and an nealing conditions caused no tendency for the branches to be ejected from the lattice. Both 1 and II were crystd. as chainfolded lamellae, within which the branches were accommodated, producing less regular crystal habits and less perfect chain pack ing than for the liomopolymer. When allowance was made for ing temps, were 220-40, 300-20, and 270-95 for polymers of II, and III, resp. The yield of IV polymer (softening temp, 3CJ 90) was 68-82% within 9.5-32 hrs. Cf. CA 67:116671g. BMJR 3223q Ultrasonic absorption in polymer solutions. Polystyrene in toluene. Hiroyasu Nomura and Yutaka Miy; hara (Nagoya Univ., Nagoya, Japan). Nippon Kagaku Zassi 88(5), 502-4(1967)(Japan). The ultrasonic absorption in solnof polystyrene in toluene was measured by a pulse-echo metho at 20 Me./see. In the plot of a/P (a is the amplitude absorptiu coeff. and/ the frequency) vs. polymer concn., a break point wa observed which was shifted toward low concns. with incrcasin mol. wt. of the polystyrene. For concns. above the break point the a/p vs. concn. curve was independent of the mol. wt. Th break point was ascribed to the onset of entanglement in th differences in nt.p., the variations of lamellar thickness with polymer soln. Yutaka Miyahara crystn. and annealing temps, and with solvent followed the 3224r Radiation-induced solid-state polymerization of butane trends established for linear polyethylene. BZJN diol dimethacrylate. 1. G. Gusakovskaya and Y. I. Gol'dan 3220m Polymerization in an electric field. Norio Ise (Kyoto skit. Vysokomol. Soedin., Ser, B 9t5), 390-2(1907)(Russ Univ., Kyoto, Japan). Kyoto Oaitnku Nippon Kagakuseni Within the exptl. error range, butaneh.ol dimethacrylate (1 Kenkyusho Kocnshti 1966(23), 47-56( Japan), Styrene (I), a- did not polymerize at --196 under the edict of 7-irradn. Th; methylstyrenc (II), iso-Bu vinyl ether (III), or p-methoxystyrene was observed to be independent of the freezing rate of I. When oo (IV) was polymd. by Is in 1,2-CliCjH, in an elec, field to give prior to the irradn., I was frozen at l'/min., the monomt the following results (monomer, Rpe/Rpo. and Pg/Po given): I, polymd, on subsequent melting in the m.p. region. At 1.0, 1.0; 11,1.25; 1.05,111,1.28, 1.04; IV, 1.34, 1.8; where cooling rate of 600/min., the polymn. occurred in 2 temp, rt Rpt and (or) Ft are polymerization rate and d.p., resp., in an elec, gions: at --107 to --85 (crystn. temp.) and at the m.p. field (1 kv./cm.) and Rpo and P0 are polymn. rate and d.p., BMJR resp., under standard conditions. The elcc. field did not affect 3225s Preparation and electrical properties of po!y(tetra the rate and degree of radical polymn. with Bz-Os as catalyst. cyanoethylene copper chelate) film. Tunezo Xaraba, Yoshiiiik Rpi/Rpo is const, with varied elec, field. The author suggests Mizushima, Haruo Xoake, Atsuo Xishioka, Yoshitaka Igarask: that the initial step is formation of an ion pair of monomer, Akira Jmamura, and Yoshikazu Torihashi. Rex. Elec. Comnmn and catalyst and that the ion pair is equilibrated with free ions. Lab. (Tokyo) 15(7-8), 551-62(1907)(Ero). Poly(tetracyanc The mechanism is discussed. I. Tabushi ethylene Cu chelate) films were prepd. by heating tetracyam. 322In Autoeatalytie character of the thermal degradation of ethylene and a Cu plate in a sealed, evacuated glass tube. Th poly(vinyl chloride). L. S. Troitskaya, V. X, Myakov, B. B. max. yield of chelate was obtained at 400. Yield increase Troitskii, and G. A. Razuvaev. Vysokomol. Soedin., Ser. A rapidly with reaction time up to about 50 min., and then increase 9(10), 2119-25(1967)(Russ), Po|y(vinyl chloride) thermal deg more slowly. The yield during the second stage of the rcactio radation dependence on pressure of HCI and the catalyst includ was linearly dependent on the sq. root of the time. The film ing org. acids, ales., and phenols was studied. The HC! pres formed on plates pretreated by high-frequency heating wit sure at 179 and pressures of iWi-ielo mm. >v.is stud'VI, .md the thinner than thrive formed mi plates treated only by c-ketr- effect is given by the re-labor. dx,dt - u'ev,. Jt - kx^'-p'1 where polishing, but films were obtained even on plates witn a suri.e. dx/dt is the sum of the e.it'ytic and noucaulytie rates, cx^/dt is oxide layer. The film contained 24-8 wt. % Cu. Eh.giro the rate of thermal degradation at 10"ram., p is the HC1 probe microanalysis showed the Cu concn. to be 30-0/7 at th. pressure, x is the amt. of HCI, x,, is the amt. of HC1 at 10-1- base layer and 20% on the upper surface. The films showc 10~* mm., m and n are reaction order coasts., and k is the reaction p-type cond., with the activation energy for cond. varying frm rate const. The consts. arc given in the table. The uncatalyzed 0.1 to 0.5 ev. Resistivity showed a marked anisotropy, wit energy of activation for thermal degradation is 28 1 keal./ space-charge-limited characteristics in the perpendicular dim mote, and the catalyzed energy of activation is 21 1 kcal./roole. tion. Heat treatment decreased the resistivity and space-churf. Curves showing the effect of org. acids at 180 including maleic cond. The dielec, const, and loss factor decreased with increU' unhydride, sebacic acid, ClCHjCOjH, stearic acid, (auric acid, ing frequency. Other metals with electronegativity <1.9 a"