DE1720481A1 - Process for the polymerization and copolymerization of vinyl chloride - Google Patents

Description

67 ο 41

DYIIAMIO? NOBEL AKTIENGESELLSCHAFT Troisdori, Cologne district

Process for the polymerization and copolymerization of vinyl chloride Addition to D 42 155 IVd / 39c (DAS 1 213 119)

Patent specification (D 42 155 IVd / 39e «DAS 1 213 119) describes a process for the polymerization and copolymerization of vinyl chloride at temporary temperatures zv / isehen -OC and -2O ⁰ C using AeeorbincUure, Cohv / erraotallsalzen and peroxides as ileäoxsystem . Meoe's process is carried out as a bulk polymerization in the presence of 0-20% by weight of a lower alcohol and is characterized by the use of cyclohexanesulfonylacotyl peroxide as the peroxide.,.

Furthermore, the polymerisation and mixed polymerisation of vinyl chloride;) using Rodoxeyofceraen aua ascorbic acid, Schwermetullfliilsjön and H ₂ Oj, al o peroxide is known (French patent specification 1 430 017). When using K ₂ O ₂ or cyclohexanesulfonylacetylporoxide alone, however, moderately high reaction rates are achieved and at temperatures below -20 ⁰ O the rate of reaction increases with decreasing i, f}. "]: Tloni; t (>r; iporatur die Ganchv / indigkoit the polymerisation decreases so much that it is insufficient for practical purposes. It is admittedly acceptable to increase the polymerisation ability by using more nin 20; fc urine sy, \ thoivio unstable on polypierinates, the preparation of which- Qir, <! iwoh; j: icn nacholll, -; influences oiud

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The syndiotactic PVC grades produced is, however, thernostability especially important because their increased tactility requires increased processing temperatures.

In various training of the process according to D 42 155 IVd / 39c (DAS 1 213 119) it was found that polymers with good processing properties can be obtained using a combination of HgOg xind cyclohexanaulfonylacetyl peroxide at temperatures from -8 to -50 ⁰ O. and achieved increased rates of polymerization compared to the individual use of each of the two peroxides alone. In Polynerisationstempsraturen below -20 bit -50 ⁰ C by applying the Peroxidkombination syndiotaktieehe polymers with good PolymerisationEgeBchwindigkelt obtained while using each of the peroxides alone provides no or unsatisfactory sales. Furthermore, by using the combination of peroxides, a K-value regulating influence becomes effective, which can be further intensified by the addition of regulators.

Products with K values below 90 down to 50, especially between 75 and 55 »are technically interesting, and it is possible to obtain both low and high K-Y / erto su. As a regulator can chlorinated hydrocarbons such as chloroform or trichlorethylene, Tetrahydrofuran, acetone etc. used in Hengen from 1 to 10V *.

The two peroxides are iltni8 * in a molar Ver2i van ¹ '5 bie ^c -. · 1 is used.

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Iiacli cleni er.finilungogen? .know ancestors and Cc'polyirierisate of vinyl chloride3 horgustell verden, v / obsi alß comoners, e.g. vinyl ether, vinyl acetate, vinyl propionate, vinyl cetyl ether, acrylic acid ester, acrylonitrile, diehloroethylene, ethylene, falenaic acid ester, propionate, etc. beoondero can be used in amounts of 2 to 20% by weight, based on vinyl chloride.

Sulphates, chlorides, IJl, for example, can be used as heavy metal salts and acetates of iron, cobalt, nickel, etc. can be used.

A preferred embodiment of the process is polymerization in vessels with shearing agitators or rotating cylindrical vessels containing bald bodies.

The use of UV light or short-wave visible light not necessary.

In the following examples, polymerizations according to the same method are compared with comparative examples. The yield was determined after 21 hours in each case. The KV / crte was determined according to Fickentscher (Sin 53 726). The tacticities were best imnt according to H.Germs.r et al. (Makromolekulare Chera.60 (1963) 106-119).

1. Comparative bite game!

8 spheres of V '2 A are placed in a cylindrical vessel with a diameter of 110 minutes and a volume of 2 liters

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nit oinotn Hurohmonear of 35 mn », 500 β vinyl chloride, 50 g ₁ methanol, 1.5 g ascorbic acid, 1.5 ocm HgOg (35 ^ ifi) and 0.75 ocn Fe« (SO *) »solution in HgO (l fiß) given at a temperature of -25 ° C. The vessel is on rollers at 50 rpm godreht lind through a brine bath to -25 ⁰ C. Yield 51 # (powder), tactic 69.9 $ _t K-value 98.

2. Comparative example

Example 1 is repeated, but instead of 1.5 ecm ^H 2 ° 2 ^ ^^ equimolecular 4.9 g of cyclohexane sulfonylacetyl peroxide is used. The yield is only $ 6, an auobcute that is technically uninteresting

3. Example 1 is repeated, except that instead of 1.5 ocm H ₂ Og (35 ig) 0.75 ecm HgO ₂ plus 2.45 g cyclohexane sulfonyl. acetyl peroxide is used. The yield after 21 hours is 88 #, activity 69.8 #, K value 79.

4 * Example 3 is repeated with the additional use of 6 £ trichlorethylene, yield 715 », K value 69, instead of 79 in example 3.

5. Comparative examples

Example 1 is repeated at a polymerization temperature of -38 ⁰ C. Yield 35 # .- K value 104th

6. Verßleichobelspiel:

Example 2 is repeated C. at a polymerization temperature of -30 ⁰ yield

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7. '3ΰ.1σρίΘΐ 3 v / lrd repeated; at a polymerization duration of -35 ⁰ C, Auebeut ο 75 #, KY / crt 88.

O. Eoiapiel 3 v / ird v / Iodorholt ·, with anotelle of 500 g of VC /! 50 f ·; VC and 50 g vinyl acetate are used. Prey on Copolymer £ 86. K-V / ort 68.

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Claims (2)

1720A81 claims 1. Further development of the process according to patent application D 42 155 XVd / 39c (DAS 1 213 119) for the polymerization or copolymerization of vinyl chloride using ascorbic acid, heavy metal salts and peroxides as a redox system in the presence of 8 to 20 yes one lower alcohol, thereby characterized in that use is additionally hydrogen peroxide and at temperatures of -8 ° C to -50 ⁰ C, preferably below -2O ⁰ C and -50 ⁰ C, operates. 2. The method according to claim 1, characterized in that the polymerization in vessels with shear Agitators or in rotating cylindrical bare bodies. Vessels, carried out. Pat.Abt.
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