DE1239856B - Process for the polymerization of vinyl chloride or a mixture of vinyl chloride and a monoolefin having 2 to 4 carbon atoms - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Int. Cl .:

C08f

GERMAN

PATENT OFFICE

PATENT LETTERING

German KL: 39 c - 25/01

Number:

File number:

Registration dates:

St20019IVd / 39c

November 29, 1962

May 3, 1967

November 16, 1967

Display day:
Issue date:
The patent specification corresponds to the patent specification

The polymerization of vinyl chloride has been known for several decades and is a major one Scale executed process. With the usual radical catalysts of the peroxide and azonitrile types the polymerization is carried out at 45 to 80 ° C, since these catalysts at one temperature are not sufficiently effective below 45 ° C. However, efforts were made to polymerize at lower temperatures to be able to, because one thereby new properties in the polymers and a simplification of the process expected.

In the case of polymerization at lower temperatures, a new type of catalyst has been proposed, namely alkyl boron compounds such as triethyl boron and tri-n-butyl boron. Originally it was believed that alkyl boron _{compounds (BR 3} ) would initiate the polymerization like other organometallic compounds according to an anionic reaction mechanism. However, it later turned out that alkyl boron compounds belong to the group of free-radical catalysts. It has also been found that the polymerization cannot be catalyzed by the boron alkyls alone, but the presence of an activator, e.g. B. oxygen (air), hydrogen peroxide, organic hydroperoxides, organic peresters, is necessary. This was not mentioned in earlier publications on alkyl boron catalysts because these tests were not carried out under strictly defined conditions (ie with complete exclusion of air). In general, it can be said that the yields achieved when using the catalyst system in question (alkyl boron + activator) were too low to give the method any practical significance.

Vinyl chloride was then polymerized with boron trialkylene with the addition of organic peresters of basically different structure, namely with the addition of tertiary butyl peracetate (with an aliphatic acid residue), tertiary butyl perbenzoate (with an aromatic acid residue) and mono-tert.-butylpermaleate (with an unsaturated aliphatic dicarboxylic acid residue). The residual alcohol was the same in all cases. It has now been found that the polymerization results when using mono-tert-butylpermaleate differ significantly from the results obtained with the other organic peresters. After 10 hours of polymerization at + 20 ° C., the degree of conversion was 65 to 75%, ie 3 to 16 times higher when using the permaleate mentioned than when using peracetate and perbenzoate. With this polymerization system he processes for the polymerization of vinyl chloride
or a mixture of vinyl chloride and one
Monoolefin with 2 to 4 carbon atoms

Patented for:

Stockholm's Superfosfat Fabriks Aktiebolag,
Stockholm

Representative:

Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Named as inventor:

Dipl.-Ing. Ludwig Binder, Ljungaverk

(Sweden)

Claimed priority:

Sweden December 1, 1961 (12 005)

a polymerization yield that enables a practical evaluation was thus obtained.

The catalyst system has also been found to be trialkylboron plus mono-tert-butylpermaleate the corresponding catalyst systems, which contain other peresters, is far superior in the Polymerization of vinyl chloride with lower monoolefins having 2 to 4 carbon atoms, in particular Athens, propene and isobutene. The yields when using mono-tert-butylpermaleate in this combination were 3 to 10 times higher. From examinations of the various peresters (in the absence of alkyl boron) as catalysts in the polymerization of vinyl chloride and copolymers this shows that peresters alone as catalysts have approximately the same degree of conversion result. The present results therefore indicate that mono-tert-butylpermaleate between the peresters in combination with trialkyl boron occupies a special position.

709 716/333

The invention relates to a process for the polymerization of vinyl chloride or a mixture from vinyl chloride and a monoolefin having 2 to 4 carbon atoms using a catalyst system from a trialkyl boron and an organic perester. This procedure is thereby characterized in that the catalyst used is a mixture of a trialkyl boron and mono-tert-butylpermaleate is used.

The ethene content in copolymers is determined first hand by the amount of Athens that the Reaction system is fed, regulated. During the polymerization, the amount of ethene (the monomer composition) can be easily controlled and regulated with the help of the pressure. Correction happens by adding fresh Athens and / or vinyl chloride or by blowing off the reaction vessel. In the latter case, the monomer mixture which has been blown off is left, possibly after adding fresh Recirculate monomers so that the quantitative ratio is brought to the desired value. Due to the significantly higher compressibility of the Athens and the solubility in According to the invention, vinyl chloride at lower temperatures can give the copolymers high Ethylene quantities are supplied without particularly high pressure (not more than 150 atmospheres overpressure) must be applied. The most suitable polymerization temperature with regard to the product properties is 0 to 50 ° C, although these limits can be exceeded or not reached. It has also been shown that the catalyst system mono-tert-butylpermaleate-trialkylboron (such as triethyl boron, tri-n-butyl boron or triisobutyl boron) for changes in the relative molar ratio of the Components is relatively insensitive. The boron alkyl to active oxygen molar ratio of said permaleinate can vary between 13: 1 and 0.8: 1 without the degree of conversion being significant being affected. Also a change in

ίο absolute amount of alkyl boron within the for that Polymerization in the normal concentration range has no effect on the polymerization results. Triethyl boron, tri-n-butyl boron and triisobutyl boron give approximately the same yields. There is a difference between them the individual boron trialkyls cannot therefore be determined.

example 1

The polymerization was carried out at + 2O ⁰ C in a pressure vessel ao .2V2-1 performed with stirrer (400 rpm) to obtain 0.5 kg of vinyl chloride, 1.21 bidistilled water and 1.5 g of a water-soluble suspension stabilizer was added.

Trialkyl boron and organic peresters were also added according to the following table. The addition of Trialkylboron happened with strict exclusion of oxygen. The polymerization lasted 10 hours.

A series of polymerizations was carried out with 3.14 g of tri-n-butyl boron (0.216 mole percent of the added Monomers) and varying amounts of organic peresters.

Organic perester mole percent active 02
in the perester

Mole percent trialkyl boron

mol% active O ₂

in the perester

sales volume

Tert-butyl peracetate
(Comparison test)

1.0g

2.0g

4.0g

8.0 g

Tert-butyl perbenzoate
(Comparison test)

1.0g

2.0g

4.0g, ... '

8.0g

Mono-tert-butyl permaleate

1, Qg

2.0g

4, above ..;

8.0 g

0.024
0.047
0.094
0.188

0.016
0.032
0.064
0.128

0.017
0.033
0.066
0.132

9.: 1 4.5: 1 2.25: 1 .1,13: 1 13.4: 1 6.7: 1 3.35: 1 1.68: 1 13: 1 6.5: 1 3.26: 1 1.63: 1

9.6

12.8 14.6 20.8

8.2 4.0 4.6 4.6

69.6 64.6

75.6 71.4

It can be seen that the conversion when using 1.70 g of triethyl boron (0.216 mol percent of the added

des Permaleinats was many times greater than 65 monomers) and varying amounts of in the

with the rest of the peresters. Table indicated organic peroxides and

In the same way as stated above, hydroperoxides were carried out as comparative tests

leads a series of polymerizations with the addition of. The following values were obtained:

Organic peroxides and hydroperoxides

Mole percent active O2

in
Peroxide - hydroperoxide

Mole percent alkyl boron
mol% active O ₂

in
Peroxide - hydroperoxide

sales volume

Di-tert-butyl peroxide

0.8 g ...

1.6 g

3.2 g

6.4 g

Lauroyl peroxide

6.0g

12.0g

Benzoyl peroxide

5, above:

10.0g ......

Dichlorobenzoyl peroxide

4g

8g

16 g

32g

Cyclohexanone peroxide

1.0 g

2.0g

4.0 g

8.0g

Tert-butyl hydroperoxide

0.5 g

1.0 g.

2.0g

4.0 g

Cumene hydroperoxide

1.0 g

2.0 g

4.0 g

8.0 g

0.036 0.072 0.144 0.288

0.092 0.184

0.124 0.248

0.034 0.068 0.136 0.272

0.045 0.090 0.180 0.360

0.026 0.052 0.104 0.208

0.028 0.056 0.112 0.224

6th
3

1.5
0.7

2.34:
1.17:

1.74:
0.87:

6.5
3.25
1.63
0.81

2.5
1.25
0.62

8th
4th
■ 2
1

4th 2

3.6 3.4 4.0 8.8

"6.8 11.8

7.4

7.0 10.2 16.4 16.2

25.6

36.0

7.6

12.2

22.6 47.0 22.4 19.4

8.0 26.6 31.8

24.2

These experiments show that the conversions in comparison with those with the combination used according to the invention Trialkylboron + mono-tert-butylpermaleate achievable are essentially lower.

Example 2

On the same. Way, as indicated in Example 1, was a series of polymerizations with the addition of 1.70 g of triethyl boron (0.216 mol percent of the added monomer) were carried out instead of tri-n-butyl boron. The following values were obtained: -

Organic perester

Mole percent active O ₂ in the perester

Mole percent alkyl boron

_{O 2} active to molprocerite

in the perester

sales volume

Vc

Tert-butyl peracetate (comparative experiment)

2.0g

4.0 g ..

Tert-butyl perbenzoate (comparative experiment)

4.0 g

Mono-tert-butyl permaleate 4.0 g

0.047 0.094

0.064 0.066

4.5: 1
2.25: 1

3.35: 1
3.26: 1

11.4 11.8

10.2 78.2

Example 3

In the same manner as indicated in Example 1, a series of polymerizations with half Amount of trialkyl boron, d. H. 0.108 mole percent carried out in the presence of various peresters. The following values were obtained:

Mole percent active O ₂ in the perester

Mole percent alkyl boron

mol% active O ₂

in the perester

sales volume

a) triethyl boron

Tert.-butyl peracetate (comparison test) 2.0g ...:

Tert-butyl perbenzoate (comparative test) 2.0 g ... '....,

Mono-tert-butyl permaleate

2.0 g

b) tri-n-butyl boron

Tert-butyl peracetate (comparative experiment) 2.0 g

Tert-butyl perbenzoate (comparative experiment) 2.0 g

Mono-terL ^ butylpermaleate

2.0g

8.0g

Example 4

The peresters used in the previous experiments were in the form of 50% solutions in dimethyl phthalate. In order to check whether the phthalic acid esters influence the course of the polymerization and thus the conversion, a series of tests was carried out according to Example 1, in some cases using 0.047
0.032
0.033

0.047
0.032

0.033
0.132

2.25: 1 3.35: 1.

3.26: 1

2.25: 1 3.35: 1

3.26: 1 0.8: 1

16.4 13.6 66.8

22.6 11.2

68.2 66.6

a 50% solution of the mono-tert-butylpermaleate, partly with loo-like crystalline mono-tert.-butylpermaleate. The concentration of triethyl boron was 0.108 mol percent, which corresponds to the amount of permaleinate 0.033 mol percent active oxygen, calculated on the added monomer (molar ratio Triethylboron to active oxygen = 3.26: 1).

The following values were obtained:

2.0 g of 50% mono-tert-butylpermaleate, 66.8% conversion

1.0 g 100% mono-tert-butylpermaleate, 68.2% conversion

Example 5

In the same manner as indicated in Example 1, a series of polymerizations were used varying amounts of different peresters with no alkyl boron and with alkyl boron alone for comparison made with the combination of mono-tert-butylpermaleate and trialkylboron.

Comparative experiments

Organic perester

Mole percent active O2 Polymerization temperature UmsE in the perester ⁰ C % 0.033 20th 0 0.066 20th 0 0.033 50 0 0.066 50 0 0.033 70 1.7 0.066 70 1.3 0.047 20th 0 0.094 20th 0 0.047 50 0 0.094 50 0 0.032 20th 0 0.064 20th 0 0.032 50 0 0.064 50 0

Mono-tert-butyl permaleate

2.0g

4.0 g

2.0g

4.0g

2.0g

4.0g

Tert-butyl peracetate

2.0 g

4.0 g

2.0 g

4.0 g

Tert-butyl perbenzoate

2.0g

4.0 g

2.0g

4.0g

Comparative experiments

10

Mole percent alkyl boron

Polymerization temperature

sales volume

Triethyl boron
2.5 ml ...
2.5 ml ...

Tri-n-butyl boron
4.0 ml ...
4.0 ml ...

0.235
0.235

0.223
0.223

20th
50

20th
50

11.0

4.2

5.5
6.1

Experiments according to the invention

Organic perester

Mole percent active O2 in the perester;

Mole percent

Tri-n-butylboron too

Mole percent active O ₂

in the perester polymerization temperature

⁰ C

sales volume

Mono-tert-butylpermaleate

0.033
0.066

6.7: 1
3.35: 1

20th
20th

76.0
78.3

From this it follows that the conversion which is achieved with perester alone was very low and that the individual peresters do not differ from one another in this respect. It was because of that surprising to find that mono-tert-butylpermaleate in combination with trialkylboron resulted in such a high conversion.

Example 6

In an acid-proof 2V2-1 pressure vessel with a stirrer, 1.11 of distilled water, 1.25 g Polyvinyl alcohol and a perester in the amount • which corresponds to 0.10 mol percent active oxygen, calculated on the intended amount of vinyl chloride, filled. After repeated venting with compressed nitrogen was added 550 grams of vinyl chloride, followed by Athens to total pressure of 16 atmospheres (about 60 g Athens) was injected. Then it became 0.15 mole percent distilled tributyl boron is added to the reaction system.

No polymerization was achieved with perester alone or with trialkyl boron alone. Using of the combination of the two components were the yields after 5 hours of polymerization as follows:

Peroxide

Tert-butyl perbenzoate

(Comparison test)

Tert-butyl peracetate

(Comparison test)

Mono-tert-butylpermaleate ...

Yield,

Vo of vinyl chloride, with tributyl boron

60

8th
51

The copolymers obtained contained 6 to 8 mole percent Athens. Of the investigated catalyst combinations only those with monotert.-butylpermaleate gave technically interesting copolymer yields.

Example 7

A 0.2-1 pressure vessel was cooled with liquid nitrogen and in a pure nitrogen atmosphere With

80 ml of acid-free distilled water,
0.1% polyvinyl alcohol,
0.41 g mono-tert-butylpermaleate,
0.40 g tributyl boron,

40 g vinyl chloride,

20 g Athens

filled and then rotated in a water bath at 20 ° C. A was obtained after 15 hours Mixed polymer which, according to chlorine analysis, contained 28 mol percent Athens. The pressure in that The pressure vessel was never higher than 40 atmospheres. The experiment shows that copolymers with high Ethene content can be prepared without the polymerization under high pressure or at high Temperatures must be run.

Example 8

Vinyl chloride was with propene in principle in the same way as in Example 1 is indicated with Mono-tert-butylpermaleate and trialkyl boron copolymerized as a catalyst. The pressure vessel was with

100 ml of acid-free distilled water,
0.1 ⁰ Zo polyvinyl alcohol,
0.41 g mono-tert-butylpermaleate,
0.40 g tributyl boron,
50 g vinyl chloride,
0 or 12 g propene

709 716/333

filled. After lSstündiger polymerization at 20 ⁰ C. The following results received:

yield
% Propene content
Mole percent Relative viscosity
in l%
Cyclohexanone solution 19th
52 0
3 3.72
2.11

Claims (4)

Patent claims: 1. Process for the polymerization of vinyl chloride or a mixture of vinyl chloride and a monoolefin having 2 to 4 carbon atoms using a catalyst system from a trialkyl boron and an organic perester, characterized in that that as a catalyst a mixture of one Trialkyl boron and mono-tert-butylpermaleate is used. 2. The method according to claim 1, characterized in that a catalyst is used which contains triethyl boron, tri-n-butyl boron or triisobutyl boron as a component. 3. The method according to claim 1, characterized in that a catalyst is used in which the molar ratio of trialkyl boron to active oxygen in the mono-tert.-butylpermaleate is between 13: 1 and 0.8: 1. 4. The method according to claim 1, characterized in that the polymerization at -30 to + 80 ° C and preferably 0 to 50 ° C is carried out. Considered publications:
British Patent Nos. 851 850, 865 651. 709 578/337 4. 61 © Bundesdruckerei Berlin