Document O1QE6kmv9BrvZEY9VRQKnamkK

ucc 070010 UNION CARBIDE CORPORATION PLASTICS DIVISION To: Mr. D. E. Richardson Chemicals Division Texas City, Texas cc: Dr. F. E. Bailey Mr. J. F. Erdmann Mr. J. C. Schlichter^ Mr. R. N. Wheeler/ A copy of the article 1 use of certain additives as HC1 epoxy compounds are noted as you may be interested in a note ''PANTASOTE - Picked up from sells surfactants to Pantasote. (an epoxidized soybean oil) in th particle more porous. This acc G-62 seen at Pantasote some tir. fK 270 Park Avenue, New York 10017 October 14, 1966 I ski notes the nerization; is connection, ence files, salesman who Haas G-62 >54 to make the ber of drums of FDD/lr ucc 070011 0 VC '4B-2 INTERNAL. COKRE3POM3CMCE ,, 3 PLASTICS DIVISION fo (Nam*) DlvUfon loco lien Mr, B. Z. n.icbardson'^^ UCC - Plastics division Texas City, Tc..as Copf to RIVER ROAD, BOUND BROOK, NrW JERSEY 0R30S Oo`* Odder 11, IBCd OtlQtnolinQ Dipt. Applications - F. w Z Aftnr#rfji0 dole s,bi> Polymerization Procecbus Attache! for your reference is an article entitled *Vass Polymerization of Vinyl Chloride in the Presence of Acceptors of fjydroijwu Chlorluo" from Soviet Plastics of June dd. They conduce that the introduction of IIC1 acceptors into tile reaction medium will accelerate polymerization. Also the audition of stabilizing aeaitivcs in the reaction vill increase the stability an! reduce decree of branching. This itay bo of value in our non-solvent process or contemplated Pechiney-St. Gobain Process. Could our intermittent problems on the thermal stability of suspension resins be related to HC1 in the monomer? HJP:er Att. UCC 070012 natc indicate that the addition of 0-1 % benzoyl peroxide gives a slight increase in the time of gel formation. Cobult niiplithciKiic, Co-% fig. /^--Dependence of the gel formation time on the competition of the initiating systems: 1--0-2% methylethylkctone peroxide; 2--0-2% mcthylcthylketonc peroxide -i- 01% benzoyl peroxide; 3--0-2% methyl ethylkctone peroxide + 0-2% benzoyl peroxide; 4-0-2% methylethylketone peroxide + 0-S% benzoyl peroxide; S--0-2% methylethylkctone peroxide + 0-8% benzoyl peroxide; 6--0-2% methylethylkctone peroxide + 1-0% benzoyl peroxide. On increasing the amount of benzoyl peroxide to 0-2-Q-5% we observe a reduction in the gel formation time, but a further increase to 0-8-1 % gives an increase in this time (Fig. 6). The degree of hardening in this case cither remains at the same level or increases some what; the mechanical properties basically remain without change. This discrepancy with the data in the literature may be a result of the use of peroxides of different grades or of different methods of hardening. It is well known that the gel formation time may be considerably reduced by adding a tertiary amine to an initiator system consisting of a peroxide or hydro peroxide initiator and a cobalt hardener. We investigated the influence of the co-accelerator dicthylaniline on the gel formation time and the degree of hardening of PNA-ED-2 polyester rcsir. when using the following initiating systems: isopropyi benzene hydroperoxide--cobalt naphthenate; methylethylkctone peroxide--cobait naphthenate. It was found that the addition even of small amounts of dicthylaniline (0-02%) leads to a marked reduction in the gel formation time (to 10 min). A further increase in the amount of coaccelerator has little elTect on the rate of gel formation of PNA-ED-2 resin. The mechanical properties remain on the same level as when using systems with one accelerator, while the degree of hardening is reduced in many cases. Since acceleration of gel formation is possible when using systems with one accelerator, the addition of a co-accelerator is desirable only where the hardening of the resins has to be carried out at temperature below 20C. Conclusions 1. For the cold hardening of PNA-ED-2 resin the most suitable are two-component systems based on methyi- cthylkctonc and cyclohexanone peroxides with a cobalt accelerator. 2. Three-component systems (methylethylkctone per oxide--benzoyl peroxide--cobalt naphthenate and cyclo hexanone peroxide--isopropylbenzene hydroperoxide-- cobalt naphthenate) have no advantages over twocomponent systems. 3. The use of diethyianiline as a supplementary accelerator in the systems isopropylbenzene hydro peroxide-cobalt naphthenate and methylethylkctone peroxide--cobalt naphthenate gives a marked reduction in the gel formation time without changing the mechan ical properties. Bibliography 1. Z. V. Mikhailova and P. Z. Li. Soviet Plast. N'o. i, 1964 (translation of Plast. Massy, No. 1, 1963), p. 13. 2. I. W. Cywinski, Appl. Plast., 3, 2, 1960, p, 56 (sic). 3. I. W. Cywinski, Rcinf. Plast., 4, 8, 1960, p. 8. 4. P. Z. Li el a/.. Plast Massy, No. .2, 1959, p. 19. 5. 1. W. Cywinski and P. Stopp. Kunsut. Rundschau, 8,12, 1961, p. 593. 6. S. I. Omel'chenko el al,, Soviet Plast., No. 2, 1963 (translation of Plast. Massy, No. 2, 1964), p. 20. Mass polymerisation of vinyl ch!onde in the presence of acceptors of hydrogen chloride V. I. Tomashchuk, I. B. Kotlyar, A. M. SharetsklT and E. N. Zii'berman Translated by R. J. A. Hendry THE production of PVC by polymerisation of vinyl of the polymer. Therefore the PVC produced by poly chloride in the mass is of interest because of the merisation of vinyl chloride in the mass usually has low brevity of the process. There is no need for an aqueousheat-resistance, a wide molecular weight distribution and dispersion medium, emulsifiers or emulsion stabilisers, probably a more branched structure. When the degree and the stages of filtration of the suspension and drying of conversion exceeds 60-65% the quality of the polymer of the polymer, occurring in the usual emulsion and is reduced still further1, and the heat removal is greatly suspension methods will also be obviated. impaired because of the virtual absence of a liquid The major obstacle preventing the widespread indus phase. trial use of this method arises out of difficulties in To improve the quality of the polymer, additives which uniform removal of the polymerisation heat with combine with hydrogen chloride3 are added to the consequent local -overheating, and dehydrochlorination monomer. 11 ucc 070013 p-v-sent authors studied the effect of certain ,v.v: u-s used generally as stabilisers of PVC (stearates of lead, barium, cadmium, calcium anti also epoxy com* pounds) on the polymerisation of vinyl chloride in the mass, and investigated certain properties of the polymer. Experimental method The vinyl chloride was polymerised in a horizontal rotating cylindrical 101. reactor of Kh 18 N steel. Mixing was effected by means of a roller which rolled around the cylinder wall as the reactor rotated. To 100 parts (by weight) of the monomer 0-2 parts of a,a'*azobisisobutyronitrile were taken (or 0-25 parts of lauryl peroxide), and also 6-5 x 10*4 mol of the metal stearates (or 0-625 g of an epoxy compound). The reagents were added to the reactor immediately before the vinyl chloride. The amount of the additives was determined as follows. An empirical method was used (with lead stearate as an example) to determine the least amount of the stabiliser (6-5 X 10_s mol ph parts of the monomer) which would ensure the highest yield of the polymer in a certain time. However, on investigation of the properties of the PVC it was difficult to determine the very small amount of metal stearate remaining in the polymer after several reprecipitations from a 1 % solution in cyclohexanone. It was therefore necessary to increase the content of metal stearates to 6-5 x KH mol. The Huggins constant (k1) was calculated from the data obtained. The PVC was reprecipitated from 1 % solution in cyclohexanone with cooled methanol. The kinetics of the decomposition of a,a'-azobisisobutyronitrilc in the presence of lead stearate were determined in toluene by the amount of nitrogen evol* vcd*-4. The rate of polymerisation of vinyl chloride in the presence of HC1 was determined in ampoules, the polymer formed being weighed a certain time after the umpoules had been opened. It will be seen that the rate of polymerisation of vinyl chloride increases in the presence of certain additives, but not to the same extent in each case. Certain epoxy compounds4-'-* are effective stabilisers of PVC. Fig. 1 shows that ED-5 resin has an inhibiting effect on the polymerisation of vinyl chloride, which is probably due to the presence of phenolic residues in the ED-5. On the other hand the addition of an aliphatic epoxy compound (a product of the condensation of epichlorohydrin and ethylene glycol) noticeably in creases the rate of polymerisation of vinyl chloride. Fi[. 2--Kinetics of polymerisation of vinyl chloride in the moss ot S0C (initiator; louryl peroxide): I--without HCI acceptor; 2~in presence of lead stearate. Fig. 2 shows the kinetics of the polymerisation of vinyl chloride in the mass with lauryl peroxide ns_ initiator. In this case also the rate of polymerisatiorrrvf vinyl chloride is appreciably increased in the presd. V of lead stearate. ,Jr^ The increase in the rate of polymerisation of vinyl chloride may be due to the combination of the HCI, which is probably capable of inhibiting polymerisation. Discussion of results The kinetics of the polymerisation of vinyl chloride in the mass in the presence of HCI acceptors are shown in Fig. I. Fig. 3--Kinetics of polymerisation of vinyl chloride in the mass at SCfC (initiotor: a,a'-oiobisisobutyronitrile); I--in absence of HCI; 2-- in presence of HCI (0-8% on weight of monomer). Fig. I--Kinetics of polymerisation of vinyl chloride In the moss ot S0C in the pretence of acceptors of HCI {initiotor; oM'oiobisisobutyroni. trile). HCI acceptor: I--none; 2--colcium stearate; 2^-olibhoticjiggy compound; 4--barium sttorote or cadmium stearate; b--ieoo stearate; &--E&-5 epoxy resin. To verify this a study was made of the rate of poly merisation of vinyl chloride in the presence of HCI. Fig. 3 shows that the rate is noticeably reduced by the presence of 0-8 % of HCI on the weight of the monomer. Moreover in view of the increased rate of polymerisation of vinyl chloride in the presence of stabilising additives, there is a suggestion of their accelerating effect in the decomposition of the o,a'-azobisisobutyronitrile. The rate constant of decomposition of a,a'*azobisisobulvronitrile in the presence of lead stearate was therefore determined (Table 1). 12 ucc 070014 iuc.e 1 sh.nvs ih.it the constant of the rate of de composition does not increase in the presence of lead stearate. TABLE 1 Rate of breakdown of a. a'-azobisisobutyronitrile in presence of lead stearate in toluene_______ Amount of lead Morale, mol per mo1 of initiator Temperature, *C k x JO\sec-1 0 7.74 x 10-4 7*74 x 107*74 x 10 ' 84 84*10 83*8 84 3*0 3*6 2*8 3*1 The values of k given in the Table agree well with the published data0 obtained in a study of the decompo sition of a.ci'-azobisisobutyronitriic without additives; consequently, the lead stearate present in the poly merisation medium has no effect on the rate of de composition of the initiator. The combination of the hydrogen chloride evolved during polymerisation of vinyl chloride may affect not only the rate of the reaction but also the properties of the polymer. It was shown in * that even a low degree of dehydro chlorination of the polymer further increases its sensitiv ity to various factors, particularly that of temperature. Therefore the suppression of dchydrochlorination in the polymerisation of vinyl chloride should improve the heat stability of the polymer, which is confirmed by Table 2. TABLE 2 Heat stability and decompostion temperature of PVC produced in presence of lead stearate (0*59 % on weight of polymer) Mo. of repre- eipitation Characteristics PVC pro- duced in PVC mixed PVC with presence with a out a of a sta stabiliser stabiliser biliser 0 Decomposition temperature, *C 170 171*5 125 Heat stability, min 10 12 1*5 Lead content, % 0*155 0*16 -- 167 165 144 1 Ditto 20 3-8 1*5 0*07 012 173 167*5 142 2 Di(tto 17*5 0*04 4*0 0*033 1*6 -- 166*5 164 140 3 Ditto 10-5 1*75 * 1-5 Nil Nil -- 166 -- 4 Ditto 10 -- -- Nil ____ -- 166 ____ -- 5 Ditto 10 -- ------ The PVC produced in the presence of lead stearate and with subsequent complete removal of the latter by means of repeated reprecipitation from cyclohexanone retains its high decomposition temperature and heat stability. At the same time PVC produced in the absence of lead stearate but mixed with it in the mixer, after rcprccipitation under the same conditions loses the high heat stability of the mixture. Thus Table 2 shows that PVC produced in the presence of an HC1 acceptor acquires higher intrinsic heat stability. The higher decomposition temperature of the PVC mixed with the stabiliser and then rcprecipitatcd, compared with the decomposition temperature of the initial PVC, is probably due to partial washing out of low-molecular fractions of the polymer during reprecipitation. TABLE 3 Intrinsic viscosity anil Huggins' constants of F VC produced without additives, and with lend stearate added to polymerisation medium No, of Content of lead stearate Degree of con version Intrinsic vis- | Huggins' experiment in PVC, % ofmono cosilj, fa] j constant, k mer, y. i0 60 0*855 ! 0*62 20 60 0*86 0*61 30 70 0*8S 1 0*55 4 1*48 60 1*12 0*32 5 0*785 85 1*06 j 0*36 6 1*00 83 0*94 | 0*40 Table 3 gives the data on the intrinsic viscosity of PVC produced without additives, and alsc with the addition of lead stearate; also the calculated Huggins' constants, indicating the relative branching of the polymer1. It shows that PVC produced without HCl acceptors has macromolecular structure with a consider ably higher degree of branching. At the same time relatively greater linearity of the structure is obtained even with a conversion adjusted to 83-85 % (experiments 5,6) when considerable overheating should occur in places on account of poor heat transfer. Conclusions 1. In view of the inhibiting action of HCl on the poly merisation of vinyl chloride, the introduction of HCl acceptors into the reaction medium accelerates the polymerisation. 2. The introduction of stabilising additives in the polymerisation of vinyl chloride in the mass increases the intrinsic stability of the polymer, and reduces the degree of branching. Bibliography 1. I. B. Kotlyar and A. M. Sharetskil, Soviet Plast., No. 2,1966 (translation of Plast. Massy, No. 2, 1965). Z K. Bik, Polimery, No. 7-3, 1962, p. 244. 3. M. Imoto, J. Soc. Organic Chem. (Japan), 14, No. 1, 1956, p. 10-19. 4. G. Ya. Gordon, " Stabilisation of synthetic high polymers ", 1963, translation in English, 1964. 5. C. G. Overberger el al,, J. Am. Chem. Soc., 71, 19*19, p. 2661. 6. C. H. Bamford, W. G. Barb, A. D. Jenkins and P. F. Onyon, '.`Kinetics of vinyl polymerisation by radical mechanisms ", 1958, (Russian version, 1963), p. 248. 7. E. N. Zil'bcrman, " Progress in polymer chemistry and tech nology ", No. 3.1960. p. 83. 8* ``n^scin* ?nd stabilisationpolymers ", ed. M. B. Nelman, ucc 070015 13