DE1245127B - Process for the production of polyvinyl chloride or copolymers containing vinyl chloride - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08f

German class: 39 c - 25/01

Number: 1 245 127

File number: C 20637 IV d / 39 c

Filing Date: January 26, 1960

Opened on: July 20, 1967

The production of a polyvinyl chloride with a certain average molecular weight requires the maintenance of a certain temperature, which becomes lower with increasing molecular weight. The molecular weight is expressed by the K value introduced by Fikentscher in the polymerisation terminology. The production of polyvinyl chloride with a K value above 70 requires, because in this case ^{polymerisation has to take place at temperatures below 50 °} C., long polymerisation times, which is uneconomical.

For the production of polyvinyl chloride and containing vinyl chloride Copolymers by polymerizing vinyl chloride or mixtures of vinyl chloride and polymerizable vinyl compounds in aqueous suspension using oil-soluble Catalysts are already used as suspending agents as mixtures of water-soluble colloids and partial esters of aliphatic polyalcohols with a higher fatty acid used, with one in place the partial esters of aliphatic polyalcohols with a higher fatty acid also mixed esters of aliphatic polycarboxylic acids with 2 to 12 carbon atoms, in which an acid group with an aliphatic polyhydric alcohol and the remaining acid groups with aliphatic monohydric alcohols having 1 to 20 carbon atoms are esterified.

Furthermore, one has already used the preparation of polymers or copolymers of vinyl chloride by suspension polymerization in the presence of Na salts of copolymers of styrene and Maleic anhydride as a suspension stabilizer and of cyclohexylsulfonyl peroxide as a catalyst, also worked in combination with azodiisobutyronitrile (German patents 1011623 and 1 032 542). However, when using such procedures on a technically advantageous scale either no meaningful polymerization is carried out at all, or polymerization times that are too long are still required or receives relatively low yields.

Like Tables II and III, in which the results Test series carried out on a technical scale are recorded, show, can be at Use of the procedure according to the invention increases the yields visibly and at the same time more noticeably Reduction of response times. With the abundance of suspension polymerization processes available for vinyl chloride an inventive selection was required, especially such Finding out conditions by which an industrially advantageous process can be made possible.

Process for the production of polyvinyl chloride
or copolymers containing vinyl chloride

Applicant:

Chemical works Hüls Aktiengesellschaft, Mari

Named as inventor:
Dr. Kurt Hoffmann,

Dr. Paul Kränzlein, Mari

It has been found that polyvinyl chloride and copolymers containing vinyl chloride can be obtained by polymerization of vinyl chloride or of mixtures of vinyl chloride and polymerizable vinyl compounds in aqueous suspension using oil-soluble catalysts in the presence of mixtures from water-soluble colloids and partial esters of aliphatic polyalcohols with a higher Fatty acid or mixed esters of aliphatic polycarboxylic acids with 2 to 12 carbon atoms, in which an acid group with an aliphatic polyhydric alcohol and the remaining acid groups are esterified with aliphatic monohydric alcohols having 1 to 20 carbon atoms, as Suspending agent can advantageously be produced if one is used as a catalyst in a manner known per se Acetylcyclohexylsulfonylperoxid or its mixtures with other oil-soluble catalysts are used. Suitable catalyst mixtures consist of acetylcyclohexylsulfonyl peroxide and 5 to 90 percent by weight, based on the total weight, of other oil-soluble catalysts, e.g. B. organic Peroxides, such as benzoyl, lauroyl, cumene peroxide, and also aliphatic azo compounds, e.g. B. azodiisobutyric acid nitrile. The total amount of catalyst required is generally 0.05 to 5 percent by weight, in particular 0.1 to 2 percent by weight, based on the monomers used. By using acetylcyclohexylsulfonyl peroxide as a catalyst, the polymerization time can be substantial at the same polymerization temperature shortened or reduced with the same polymerization time.

For the polymerization of vinyl chloride alone, it is advisable to use mixtures of acetylcyclohexylsulfonyl peroxide to use with other oil-soluble catalysts, while the production of copolymers of vinyl chloride with more than

709 617/552

10 percent by weight of monomers that reduce the molecular weight of the polymer, such as. B. when using maleic acid esters, advantageously only in the presence of acetylcyclohexylsulfonyl peroxide he follows. Copolymers of vinyl chloride with monomers that have the molecular weight of the Polymerisates not reduce, both in the presence of Acetylcyclohexylsulfonylperoxid alone as well as in the presence of mixtures of this peroxide with others. Oil-soluble catalysts produced will.

For example, in order to produce a vinyl chloride copolymer with 15 ° / ₀ dioctyl maleic ester with a K value of 70, a polymerization temperature of 35 ° C must be selected. At this temperature, however, the half-life of the usual catalysts, such as lauroyl peroxide or azodiisobutyronitrile, is very short. Although one ^one can increase the catalyst concentration; but this possibility is limited. If, however, acetylcyclohexylsulfonyl peroxide is used as the catalyst, copolymers with a high proportion of plasticizing component and a relatively high K value, which has hitherto been practically impossible to achieve with conventional catalysts, can be obtained in a short time with very low catalyst concentrations at low polymerization temperatures. Similar conditions exist in the production of copolymers from vinyl chloride and acrylic acid esters.

For example

a) (comparison test)

In a stainless steel autoclave, 100 parts by weight of vinyl chloride and 0.2 part by weight of lauroyl peroxide in 183.5 parts by weight of water containing 0.1 part by weight of triglycerol monostearate and 0.27 part by weight of polyvinyl alcohol are polymerized ^{at a temperature of 50 ° C. with vigorous stirring.} The polymerization time until the pressure drops is 26 hours. After the pressure in the autoclave has been released, the aqueous phase of the suspension is spun off. After drying, a pure polyvinyl chloride is obtained which has the values shown in the table.

ao b) The polymerization is carried out under otherwise identical conditions, but 0.07 part by weight is used as the catalyst Lauroyl peroxide and 0.03 part by weight of acetylcyclohexylsulfonyl peroxide, the pressure drop occurs already after 16 hours. The properties of the polyvinyl chloride are as follows Table summarized.

Vibration volume
cm ^3/100

g ^; '■' ■

WA ¹ )

K value

<60 60

100

Sieve analysis in μ

I 150 I.
Weight percent

200

236
251

5.9
6.2

73.0

74.5

2.4 12.6 28.3
28.2

59.4
35.3

9.4

23.4

0.6

WA = plasticizer uptake cubic centimeters of dioctyl phthalate on 5 g of polyvinyl chloride.

From the example it can be seen that the polymerization time when using the catalyst mixture decreases about 38% ....

·.: ■: ■■. Example 2-

Under the conditions given in Example 1, the copolymerization of vinyl chloride is obtained with dioctyl maleic ester the following values:

Vinyl chloride
Weight percent Maleic acid octyl ester
Weight percent Acetylcyclohexyl
sulfonyl peroxide
Weight percent Tempe
rature
⁰ C Polymerization time
in hours to print
waste yield
Weight percent
on deployed
Monomers 90
85
75 ■ 10
,, 15
25th 0.3
0.3
0.3 30th
36
30th 12.5
5.5
13.5 79
73
74

Example3

Under the conditions given in Example 1, the copolymerization of vinyl chloride is obtained with octyl acrylate the following values:

Vinyl chloride
Weight percent Acrylic acid octyl ester
Weight percent Acetylcyclohexyl
sulf onyl peroxide
Weight percent Tempe
rature
⁰ C Polymerization time
in hours
until pressure drop yield
Weight percent,
based on a
set monomers K value 80
75
80 to to to
O Ui O 0.35
0.35
0.20 32
32
30th . 10
9
9 74
76
71 87.5
88.5
87.8

Example 4 Table I.

1*)

2 *)

3 *) Experiment no.
4 *)

Boiler size, m ³

Completely desalinated water,
kg

Vinyl chloride, kg
Phase relationship

Suspending agent,
Art

/O

Art

O/ / o ·· ■ ·· ■

Catalyst,
Art

/O

Art

Additions,
Art ..

Polymerization time,
hours

sales

2600 2600 1: 1

NaMaSt. .- .. 0.5

Cat. 3 0.05

2600 2600 1: 1

NaMaSt. .0.5

Cat. 3 0.03

Cat. 1 0.05

Approaches had to be relaxed after or after 4 hours because of the increase in pressure

3500 2200 1.6: 1

NaMaSt. 0.5

Cat. 0.05

Explanation of symbols

NaMaSt. = Sodium maleic acid styrene copolymer. PVA = polyvinyl alcohol **). TGS = triglycerol monostearate. Lorol = lauryl alcohol.
Catalyst 1 = azodiisobutyronitrile.

3500
2200
1.6: 1

NaMaSt.
0.5

Cat. 3
0.03

Cat. 1
0.05

12th

78

3500
2200
1.6: 1

PVA

0.32

TGS

0.1

Cat. 3
0.05

Lorol
0.1

6.5

absolutely relaxed

88.7

3500 2200 1.6: 1

PVA

0.32

TGS

0.1

Cat. 3 0.03

Cat. 1 0.05

Lorol 0.1

91.8

3500 2200 1.6: 1

PVA

0.32

TGS

0.1

Cat. 0.03

Cat. 0.12

Lorol 0.1

10

91.5

Catalyst 2 = lauroyl peroxide.
Catalyst 3 = cyclohexylsulfonyl peroxide. *) Comparative tests.

**) (viscosity of 4 ° / ₀ aqueous solution, 20 C ⁰ = 25 cP; saponification value = 250).

Table II

1*)

2 *)

Attempt no.
4 *)

Boiler size, m ⁸

Completely desalinated water,

kg

Vinyl chloride, kg

Phase relationship

Suspending agent,
Art

° / o

Art

O/ /O

Catalyst,
Art

O/ /O

Art

Explanation of symbols at the end of the table.

2600 2600 1: 1

NaMaSt. 0.5

Cat. 3 0.05

2600 2600 1: 1

NaMaSt. 0.5

Cat. 0.03

Cat. 0.05

3500 2200 1.6: 1

NaMaSt. 0.5

Cat. 0.05 3500
2200
1.6: 1

NaMaSt.
0.5

Cat. 3
0.03

Cat. 1
0.05

3500
2200
1.6: 1

PVA
0.32

CDLGE
0.1

Cat. 3
0.05

3500 2200 1.6: 1

PVA 0.32

CDLGE 0.1

Cat.

0.03 cat.

0.05

3500 2200 1.6: 1

PVA 0.32

CDLGE 0.1

Cat.

0.03 cat.

0.12

Table II (continued)

1*)

2 *)

3 *) Experiment no
4 *)

Additions,

Art ..
O/
/ o · · ·

Polymerization time,
hours

sales

Approaches had to be relaxed after 3 or 4 hours because of the increase in pressure

12th

80 12

78

Lorol
0.1

91.0

Lorol 0.1

10

91.9

Lorol 0.1

11

92.2

Explanation of symbols

NaMaSt. = Sodium maleic acid styrene copolymer.

PVA = polyvinyl alcohol **). CDLGE = citric acid dilauryl glycerol ester.

Lorol = lauryl alcohol.
Catalyst 1 = azodiisobutyronitrile.

Claims (1)

Claim: Process for the production of polyvinyl chloride or copolymers containing vinyl chloride by polymerizing vinyl chloride or mixtures of vinyl chloride and polymerizable vinyl compounds in aqueous suspension using oil-soluble catalysts in the presence of mixtures of water-soluble colloids and partial esters of aliphatic polyalcohols with a higher fatty acid or mixed esters of aliphatic polycarboxylic acids with 2 to 12 carbon atoms, in which an acid group with an aliphatic multi-catalyst 2 = lauroyl peroxide.
Catalyst 3 = cyclohexylsulfonyl peroxide. *) Comparative tests. **) (viscosity of 4 ° / ₀ aqueous solution, 2O ⁰ C = 25 cP; saponification value = 250). valuable alcohol and the remaining acid groups with aliphatic monohydric alcohols with 1 to 20 carbon atoms are esterified, as a suspending agent, characterized by that in a manner known per se as a catalyst acetylcyclohexylsulfonyl peroxide or uses its mixtures with other oil-soluble catalysts. Documents considered: German Auslegeschrift No. 1 011 623; British Patent No. 755,796; U.S. Patent No. 2,528,469. 709 617/552 7. 67 © Bundesdruckerei Berlin