DE891025C - Process for the polymerization of vinyl compounds or 1,3-diene hydrocarbons - Google Patents

Description

(WiGBl. P. 175)

ISSUED SEPTEMBER 24, 1953

F 2754 IVc j 3g c

(Ges. Of 15 7.51)

The polymerization of unsaturated compounds in aqueous emulsion, d. H. in the presence of water and emulsifiers, in most cases by adding oxygen-releasing agents such as Hydrogen peroxide, benzoyl peroxide or potassium persulfate, stimulated or accelerated. Such unsaturated compounds include vinyl compounds, such as vinyl esters, acrylic acid esters, styrene and unsaturated ketones and most 1,3-diene hydrocarbons such as butadiene, isoprene or dimethylbutadiene, and also mixtures of such compounds with one another.

It has now been made the surprising discovery that in the emulsion polymerization compounds defined above in the presence of oxygen-releasing agents a further acceleration can be achieved if reducing agents and the working conditions are added at the same time selects so that molecular oxygen is at least largely excluded, but on the other hand the den active oxygen-forming compounds are not completely destroyed. Technical information from production 2-chlorobutadiene-i, 3 which already contains peroxides does not, however, require the additional

Excitation by active oxygen, but also experiences according to the invention by reducing agents a further acceleration of the polymerization because the redox system has now been formed. Suitable Reducing agents are the known reducing agents. Connections, e.g. B. sodium thiosulphate, sodium hydrosulphite, Hydroxylamine, hydrazine, ascorbic acid and dioxymaleic acid. Unsuitable, however, are of course those from which polymerisation-inhibiting substances, such as quinones in particular, arise. The requirement that molecular oxygen should be excluded as far as possible can be added can be met by removing the air from the emulsion by introducing inert gases removed and otherwise avoids contact with air or oxygen.

The new way of working allows unwanted

To avoid delays in the start of the polymerization, to lower the polymerization temperature or to shorten the polymerization time.

The new way of working is on both working

Applicable in acidic as well as in neutral or alkaline medium. In the latter case come as Emulsifiers soaps or alkylated naphthalene sulfonic acids, for the neutral medium higher paraffin sulfonic acids and for the acidic medium, mineral acid salts of higher fatty amines or of aminoethanol esters higher fatty acids in question.

' Example 1

100 parts by weight of styrene are emulsified with 200 parts by weight io ° / ₀ hydrochloric Natnumoleatlösung and 10 parts by weight of IO7 ₀ solution of ammonium persulfate. The approach remains quiet while slowly over the surface of a current 9g, 8 ° / _o sodium Nitrogen is passed (batch A) in a water bath of 30 ^0th In a corresponding recognition B are subsequently 6.6 parts by weight of a 5 ° / _o solution of Natriumhydrosulftt, in another approach, 13.5 parts by weight of C added 5% Natriumhydrosulntlösung.

20 7ο-

A. without addition after 0.95

B. with hydroxylamine after 0.1

C. - hydrazine after 0.3

D. - Potassium bisuhitol after 0.4

E. - Chromium chloride after 0.05

Example 4

100 parts by weight of styrene are combined with 300 parts

a 3% acetic acid solution of dodecylamine (0.9 mol. acetic acid to 1 mol. amine) and 10 parts a 10% solution of ammonium persulphate

40 7o yield 60 o / o 70% 80 0/0 3.6 50% 6.3 8.1 10.7 hours A. After o, 3 4-7 o, 5 1.0 3.5 B. - o, 3 o, 4 o, 5 1.0 3.5 C. - o, 4

Example 2

100 parts by weight of styrene are emulsified with 300 parts by weight of a 3% acetic acid solution of dodecylamine (0.9 mol. Of acetic acid to 1 mol. Of amine) and 10 parts by weight of 3 ° / ₀ solution of hydrogen peroxide and, as in Example 1-treated (Run A ). In a corresponding mixture B 11.3 parts by weight of a 5 ° / _o solution of sodium hydrosulfite are appended subsequently.

Example 3

100 parts by weight of styrene are emulsified with 300 parts io ° / ₀ hydrochloric sodium oleate solution with addition of 10 parts of a io ° / ₀ solution of ammonium persulfate and treated as in Example 1 (Batch A). To corresponding lugs are added after the emulsification: at Approach B: 8.4 parts of 5 ° / _o by weight solution of hydroxylamine hydrochloride in approach C: 5% solution at 8.7 parts by Hydrazinsulf in batch D: 7.4 parts 5% solution of potassium bisulfite, for batch E: 20 parts

- Chromium chloride solution.

yield B. with 'A. without sodium Sodium- hydrosulfite hydrosulfite 25% I 40 ' 0% 40 7o I ^h 25 ' 0% 53% 2 ^h 40 ' a ° / o 78 7o - 6 ^h 40 ' 26% 88% - io ^h 4o ' 90 7o

yield 40 7o 50% 60% 70 7o 80 o / o 30% 1.65 2.1 2.65 3.35 4.35 1.28 0.25 0.33 0.4 0.48 0.72 0.22 0.45 0.5 0.55 0.68 1.2 o, 45 0.55 0.65 0.75 1.3 2.4 o, 55 0.17 0.25 0.4 0.6 o, 95 0.10

hours

emulsified and treated as in Example 1 (approach A). ¹¹ S to corresponding projections to be added after the emulsification: at Approach B: 4.7 parts of 5 ^o / _o solution of sodium Hydroxylanimhydrochlorid in approach C: 17 Teüe 5 ° / _o by weight solution of sodium thiosulfate.

A. without addition after

B. after with hydroxylamine

C. - Sodium thiosulphate according to ...

yield 40% 50% 60% 70% 20 o / o 30 7o 2.0 2.3 2.65 3.95 hours 1.35 i, 75 0.2 0.3 o, 4 0.8 0.05 0.15 0.2 o, 3 o, 4 0.7 0.05 0.15

Example 5

100 parts of vinyl chloride in 200 parts of water with the aid of 5 parts of is obtained by treating a petroleum fraction of boiling points 200 to 250 ⁰ with sulfur dioxide and chlorine and subsequent alkaline hydrolysis of an emulsifier, emulsified. In the case of a polymerization in the presence of ¹ part of ammonium persulfate at 30 °, the yield was 0% after 20 hours without further addition, 100% with 10 parts of a 5% solution of sodium hydrosulfite, and 94 with 10 parts of a 2.2% solution of hydroxylamine hydrochloride %. Parallel tests in the presence of 5 parts of 2% borax solution give 0.94.90% yield in the corresponding order; in the presence of 10 parts of a 10% solution of primary potassium phosphate 0.92.76%, in the presence of 5 parts of simple normal acetic acid without addition 0%, with hydroxylamine hydrochloride 96%, in the presence of 5 parts of simple normal hydrochloric acid without addition 0%. ^with hydroxylamine hydrochloride 66% yield.

In a further series of tests, 5 parts of the same emulsifier and 1 part of ammonium persulfate were dissolved in 200 parts of water and 100 parts of vinyl chloride were added. It was the polymerization at 30 ⁰ reaction temperature without further addition after 15 hours .0%, after 20 hours of 5%, on the other hand, after the addition of 10 parts of i, 6% solution of hydrazine hydrate, which was neutralized with hydrochloric acid, after 15 hours 48 %, after 20 hours 76%.

In a further series of tests, 10 parts of the same emulsifier, 0.5 parts of ammonium persulfate and 2 parts of simple normal formic acid were dissolved in 100, 200 or 300 parts of water, the air above the emulsifier was displaced by nitrogen, as is the case with the procedure according to the Paragraphs 1 and 2 are done, after cooling in ice-common salt cold mixture, 100 parts of liquefied vinyl chloride and 5 parts of 5% sodium hydrosulfite solution are added. Upon heating to 20 ⁰ a very violent reaction occurred; the yield after just 4 hours from the start of heating when using 100 parts of water was 100% or 90% for 200 parts of water and 70% for 300 parts of water, a considerable increase in temperature and pressure being obtained due to the exothermicity the greater the less water was available to absorb the heat of reaction.

Example 6

25 parts of styrene and 75 parts of butadiene are in the sulfuric acid solution of 4 parts of an emul-

Claims (1)

PATENT CLAIM: gators, which is obtained by esterification of fatty acid soap with diethylaminoethanol, polymerized in 180 parts water with the addition of 0.5 part of ammonium persulfate at 30 ⁰ among the molecular oxygen, at least substantial off. The yield was without further addition after 24 32 40 48 hours. 18 25 33 36%,
with the addition of 0.35 parts sodium ascorbate. 25 36 43 51%. Were 25 parts of styrene and 75 parts of butadiene in 200 parts of water with the aid of 4 parts of diisobutylnaphthalenesulfonic acid Sodium emulsified and with the addition of 0.3 part of sodium hydroxide solution and 0.5 part of ammonium persulfate polymerized at 30 °, so without further addition 53%, with 0.15 parts of ascorbic acid Sodium 66% yield obtained n. Example 7 25 parts of styrene and 75 parts of butadiene were after at least largely eliminated the molecular Oxygen in the hydrochloric acid solution of 4 parts of an emulsifier produced by esterification of diethylaminoethanol with soap fatty acid is obtained in 180 parts of water with the addition of 0.5 part of ammonium persulfate polymerized. The yield was 45% after 17 hours without further addition, 68% with the addition of 0.6 parts of glucose Addition of 0.3 parts of dioxymaleic acid 71%. Process for the polymerization of vinyl compounds or i, 3-diene hydrocarbons or Mixtures of the same in the presence of water, emulsifiers and oxygen-releasing agents, characterized in that it is carried out in the presence of reducing agents, wherein the working conditions are to be chosen so that the compounds supplying the active oxygen are not completely destroyed and molecular oxygen is at least largely excluded and the reducing agent does not contain any polymerization-inhibiting substances, in particular quinones, develop. Referred publications: Reports of the German Chemical Society Vol. 71, 1938, pp. 1438 to 1440. @ 5427 9.53