DE1645258C - Process for the production of vinyl chloride copolymers - Google Patents

Description

I 645 258

1 - 2

The invention relates to a process for the preparation of the French patent preferred comonomers,

new vinyl chloride copolymers. was determined, not achieved because the

It is known to obtain vinyl chloride polymers under such average degree of polymerization as η ProConditions to polymerize that high molecular weight products is only slightly higher than that of vinyl

Products with improved physical self-5 chloride homopolymers that are under the same

shafts are preserved. Reaction conditions are established. This too

For the production of high molecular weight vinyl chloride processes known so that the invention solves

It is known that polymers do not use vinyl chloride in the case of a ratio-based task,

to polymerize at moderately low temperatures or the object of the invention is not to use the

branched or crosslinked copolymers with disadvantages of known processes

Produce vinyl chloride by adding vinyl chloride to the production of new vinyl chloride copolymers

Presence of a polyallyl compound as crosslinking agent, with a high average degree of polymerization

such as diallyl phthalate and diallyl maleate. to make available the improved physical

In the low temperature polymerization, however, you must have properties such. B. regarding stiffness,

at a temperature of at most about 35 ° C 15 the brittleness temperature and the warmth.

work to produce polymers with high molecular weight. The invention thus provides a process

weight, d. H. with an average polymer for the production of vinyl chloride copolymers

degree of sation of z. B. to get more than 3000. Made by polymerizing vinyl chloride with at least

for this reason, the process requires expensive cata-

Sators or special devices around the poly ao is characterized by the fact that as an unsaturated mono-

dissipate merization heat. When the polymer is a glycol divinyl ether of the general formula

salion velocity to avoid this _n " _{n ΓΗ} _ _ΓΗ

parts is reduced, the space-time yield is just- H ₂ C = CH-U- C _n M _2n - υ en en ₂

if decreased. It is therefore polymerized in commercial terms, in which C _n H _2n an un-

very unfavorable, the polymerization rate as branched or branched saturated hydrocarbon

to reduce. Since the diallyl esters mentioned are two radicals, π is an integer with a value

polymerizable double bonds in the molecule ent- from 2 to 20 and the two vinyl ether groups

hold and are very reactive, are made of different carbon atoms,

these diallyl esters and vinyl chloride obtained. The process according to the invention can be

Mixed polymers are strongly cross-linked and contain conventional polymerisation methods

considerable amounts of gel that will be in solvents. The suspension polymer is preferably

is insoluble, in which ordinary vinyl chloride sation is applied,

homopolymers are soluble. Examples of those in the method according to the invention

Furthermore, these copolymers have the after- used glycol divinyl ethers are ethanediol divinyl

part of a poorer thermal flowability, and they 35 ethers, propyandiol divinyl ether, butanediol divinyl ether,

do not have good properties on the roller with octanediol divinyl ether, dodecanediol divinyl ether, hexa-

Processing temperatures from 150 to 170C, the decandiuldivinylether and octadecandio'divinylether

common processing temperatures for vinyl these saturated glycol divinyl ethers have despite

chloride homopolymers. of their two double bonds in the molecule a low one

From the USA.-Patent 3 025 280 it is known 40 reactivity when mixed with vinyl chloride

Vinyl chloride with a polyallyl ether that polymerizes two to three times. As a result, they cause

terminal olefinically unsaturated polymerizable no undesirably high crosslinking. For this

Groups, namely allyl or methylallyl residues, basically they have a great influence on the

to polymerize as a comonomer, which increases the average degree of polymerization,

even at higher temperatures of about 30 to 70 C 45 and it can be copolymers with high

Polymers with a relatively high degree of polymerization at a relatively high temperature

average degree of polymerization obtained. Also make this peratui *.

however, known method may not be satisfactory, Even if the. Glykoldivinyläther in the obtained

since the copolymers produced thereafter are polymerized too high, deteriorate

Have gel contents and the polymerization rate does not affect the properties of the resulting mixed poly-

and thus the space-time yield despite the merisats, since they are used as plasticizers or as lubricants

relatively high possible polymerization temperatures of the vinyl chloride polymers can act,

are not high enough. The glycol divinyl ethers are in the invention

Finally, the method according to the French patent is preferably in an amount of

801 462 a method known, according to which at 55 0.01 to 10 percent by weight, in particular 0.05 to

relatively high polymerization temperatures and with 1 percent by weight, based on the total weight

high space-time yield, vinyl chloride polymers of the monomers used, used. Vinyl chloride

with a high average degree of polymerization is the main component of the

should be let. adjustable copolymers, but still other

In this process, as comonomers βο olefinically unsaturated monomers, in an amount of Compounds with at least two olefinic less than about 50 percent by weight, based on the Double bonds are used, with the proviso that the weight of the vinyl chloride and the olefinically un-

the comonomers cannot contain any monomers which are saturated in the conjugation position. examples for

each other standing olefinic double bonds these olefinically unsaturated monomers are vinyl

and no conjugated and crossed double acetate, vinyl esters of higher aliphatic carboxylic acids,

May contain bonds in the molecule. Vinylidene chloride, acrylic acid ester, methacrylic acid ester However, the desired success will be, as with Ver and higher alkyl vinyl ethers.

search with divinyl ether, one according to the French

polymers using alkyl vinyl ethers or vinyl esters of aliphatic carboxylic acids, which When vinyl chloride polymers soften internally, their processability is significantly improved. The according to the invention The method for producing the copolymers is predominantly based on the suspension polymerization method carried out, but the process can also be carried out as solution polymerization or emulsion polymerization or by other known polymerization methods. To the suspension polymerization can be carried out in a similar manner to the process according to the invention become as with the homopolymerization of vinyl chloride. As suspension stabilizers, polyvinyl alcohol, Cellulose derivatives, sorbitan esters and the like can be used. As polymerization initiators are among others lauroyl peroxide, diisopropyl peroxydicarbonate, Benzoyl peroxide and azoisobutyric acid dinitrile

As well as for the homopolymerization of vinyl chloride the polymerization temperature in the process according to the invention can be in the range from 30 to 70 C. The copolymers obtained are identical in their appearance the polyvinyl chloride, and they can be dried in a similar way as thick turn. The copolymers of vinyl chloride which can be prepared according to the invention have a lower value V »firm strength and good processing properties,

Table I.

Ver Granted amount
1,12-octadecanediol divinyl Average search ether Pülymerisaiionsgi ..d Weight percent 1 0.00 1060 2 0.02 UOO 3 0.05 1150 4th 0.10 1370 5 0.20 1520

The average degree of polymerization is determined as follows:

0.4 g of polymer are dissolved in 100 ml of nitrobenzene. The small undissolved portions are filtered off and the specific viscosity of the filtrate is measured. The average degree of polymerization is determined from the viscosity: Average degree of polymerization P = 500.

The values given in the following examples for the average degree of polymerization are determined in a similar manner.

example

lined 0 Til Vi

A glass-lined 5 liter autoclave is filled with 100 parts vinyl chloride, 150 parts deionized water, 0.1 part polyvinyl alcohol, 0.1 part

The invention Verfahret ^r d wi further illustrated by the following examples. Parts are by weight unless otherwise

is specified. .

^b Example 1

100 parts of V.p.ylehiorid, 600 parts of deionized water, 0.3 parts are put into a 50 ml glass ampoule Polyvinyl alcohol, 0.2 parts lauroyl peroxide and the

Stickston verarangi. lw uwu ^ .. ....- .-

heated to 55 ° C and polymerized. Unreacted monomers are removed from the reaction mixture

separated, and the resulting copolymer is dehydrated and dried. There is obtained a white powdery copolymer having a similar appearance as polyvinyl chloride in 81 ° / _o yield. The particle size of the copolymer is dc

»_: .. j" α o "o / _ Hpr particles a sieve of the clear

Ston Verarangi. Lfailll wuu uic miifuuv 1.1I ₆ VnIIiUViO.,.

and in a ^{water bath kept constant at 55 0} C sats amounts to uw.

shaken. The physical properties of the mixed poly-

After 20 hours of polymerization, the ampoule 45 is merisats with polyvinyl chloride as follows

opened, unreacted monomers are compared.

. . 1 _·.-_. w: __ u— * i .. "- ..;," »u, irH Ipu / riU 100 parts of the resulting copolymer

Copolymer was so fine that more than

specified.

Table II

polymer

Copolymer of the invention polyvinyl chloride

Average

Polymerisation

gfad

1300
1300

Stiffness performance

72 67

Brittleness temperature

- 2 + 10

I 645

From tables it can be seen that the invention The copolymer produced has a higher stiffness temperature and a lower brittleness temperature has the same average degree of polymerization as the polyvinyl chloride.

Example 3

In a manner similar to Example 2 will be lOOTtile vinyl chloride with 0.3 part 1,12-octadecanediol divinylc iher in the presence of 150 parts of deionized water, 0.1 part of polyvinyl alcohol and 0.2 part Copolymerized with lauroyl peroxide at 50 ° C for 19 hours.

Unreacted monomers are separated from the reaction mixture and the resulting copolymer is dehydrated and dried. A white powdery copolymer is obtained in _a yield of 83%. More than 98 ° / _{6 of} the copolymer powder pass through a sieve with a mesh size of 0.351 mm. The average degree of polymerization of the copolymer obtained is 2280.

The physical properties of this copolymer! » are with polyvinyl chloride as follows compared.

In each case 100 parts of the mixed pole obtained; merisats or of polyvinyl chloride (1), produced under similar conditions as the copolymer and with an average degree of polymerization of 1400, as well as a polyvinyl chloride (2), which was produced at a lower polymerization temperature and has an average degree of polymerization of 2,300, are made with 40 parts of dioctyl phthalate , 4 parts of tribasic lead stearate and 1 part of barium stearate was added, milled for 10 minutes at 170 ⁰ C and pressed for 10 minutes at 170 ⁰ C. Plates of size 35 x 35 mm and a thickness of 2.0 ± 0.2 mm are made from the fur. Each of the plates is heated to a certain temperature and at this temperature is loaded with a weight of 2 kg for 15 minutes. Then the heat resistance is determined according to the following equation:

Heat resistance, ° / ₀ = /, - / _s * i · 100.

/, = Thickness of the plate before heat treatment, mm,

t _t = thickness of the plate after heat treatment, mm.

The results are shown in Table III.

Table III

polymer

Average Polymerization

Heat resistance, ⁰ U 140 ⁰ C, 15 minutes | 160 ° C, 15 minutes

Copolymer of the invention

Polyvinyl chloride (1)

Polyvinyl chloride (2)

2280
1400
2300

26th
41
28

45 59 50

From Table II it can be seen that the invention produced copolymer has a lower heat resistance than that of the same Temperature produced polyvinyl chloride and the polyvinyl chloride of the corresponding average Degree of polymerization.

Example 4

In a manner similar to Example 2, 100 parts of vinyl chloride are mixed with 0.1 part of 1,2-ethanediol divinyl ether in the presence of 150 parts of demineralized water, 0.1 part of polyvinyl alcohol and 0.1 part of lauroyl peroxide Copolymerized for 15 hours at 55 ° C. Unreacted monomers are released from the reaction mixture separated off, and the copolymer obtained is dehydrated and dried. It will obtained in 86% yield a white powdery copolymer, which is more than 95% a sieve with a clear mesh size of 0.351 mm passes. The average degree of polymerization of the mixed polymer is 1390.

The physical properties of this copolymer with polyvinyl chloride are as follows compared.

100 parts each of the copolymer and polyvinyl chloride of a similar average poly-

5 ·. nitf'sationsgrad be admixed with 3 parts of an organotin as a stabilizer and 0.5 part of a lubricant, rolled for 5 minutes at 160 ⁰ C and pressed for 10 minutes at 170 ⁰ C. Then the stiffness temperature and the brittleness temperature

of the manufactured panels checked. In Table IV are the results compiled.

Table IV

polymer Average
t'cilymcrisations-
Degree Stiffness »·
temperature
"C BrittleKcilSlcmpe-
rature
⁰ C Copolymer of the invention
Polyvinyl chloride 1390
1350 73
68 -3
-1-8

From Table IV it can be seen that the invention The copolymer produced has a higher stiffness temperature and a lower brittleness temperature than the polyvinyl chloride has the corresponding average degree of polymerization.

Example 5

In a manner similar to that in Example 2, 100 parts of vinyl chloride are copolymerized with 0.3 parts of 1,4-butanediol divinyl ether in the presence of ISO parts of deionized water, 0.1 part of polyvinyl alcohol and 0.1 part of lauroyl peroxide for 17 hours at 55.degree. Unreacted monomers are separated off from the reaction mixture, and the copolymer obtained is dehydrated and dried. It is a white powdery copolymer in 86 ° / _o sodium

IO yield obtained, more than 96% of which passed a sieve with an internal mesh size of 0.351 mm. The average degree of polymerization is 1740.

The physical properties of the copolymer with polyvinyl chloride are as follows compared.

Each 100 parts of the copolymer, and polyvinyl chloride of the like, average degree of polymerization are mixed with 3 parts Organozinnmerkaptid as a stabilizer and 0.5 part of a lubricant, rolled for 5 minutes at 160 ° C and pressed for 10 minutes at 17O ⁰ C. Then the rigidity temperature, the brittleness temperature and the impact resistance according to C har ρ y of the obtained plates are examined. The results are shown in Table V.

Table V

polymer

Average degree of polymerization Stiffness temperature

Brittleness temperature

Impact strength according to Ch ar py

cm kg / cm

Copolymer of the invention
Polyvinyl chloride

1740
1800

75
69

-3

+8

4.6
3.6

From Table V it can be seen that the copolymer produced according to the invention has a higher Stiffness temperature, a lower brittleness temperature and a higher impact resistance than the polyvinyl chloride of the corresponding average degree of polymerization.

Example 6

In a similar manner as in Example 2, 100 parts of vinyl chloride with 0.1 part of 1,12-Octadecandioldivinyläther and 1 part Laurylvinyläther in the presence of 150 parts of deionized water, 0.1 part of polyvinyl alcohol and 0.06 part of lauroyl peroxide for 11 hours at 64 ⁰ C. copolymerized. The unreacted monomers are separated off from the reaction mixture, and the resulting copolymer is dehydrated and dried. A white, pulverulent copolymer is obtained in a yield of 75 ° / t , more than 98% of which passes through a sieve with a mesh size of 0.351 mm. The average degree of polymerization of the mixed polymer is 750.

The physical properties of this copolymer are compared with polyvinyl chloride.

Each 100 parts of the copolymer, and polyvinyl chloride of similar degree of polymerization are mixed with 3 parts of organotin mercaptide as a stabilizer and 0.5 part of a lubricant, rolled for 5 minutes at 16O ⁰ C and pressed for 10 minutes at 170 ° C. The flowability, the stiffness temperature, the tensile strength, the elongation and the impact resistance according to C har ρ y of the panels obtained are then tested. The results are shown in Table VI

The flowability is determined with reference to the outflow (cm ^s / sec), which is obtained when a 5 minute to 18O ⁰ C preheated mm sample from a nozzle having a cross section of 1 and Einei length of 10 mm under a pressure of 200 kg / cm ^{2 is} pressed out .

Table VI

polymer average
licher poly
merization
Degree Flow
capability
cm '/ sec Stiffness
temperature
• c Tensile strength
speed
kg / cm * strain
V. Flip bend
strength
after
Charpy
cm kg / cm * Temperate copolymer of the invention
Polyvinyl chloride 750
800 0.00039
0.00024 67
67 620
600 160
140 4.4
3.2

From Table VI it can be seen that the invention

ternary copolymer produced according to the 65 ^pie "

corresponding polyvinyl chloride with regard to the flow In a similar device as in Example 2

ability, tensile strength, elongation and 100 parts of vinyl chloride, 150 parts of desalinated

Impact resistance is superior. Water, 0.3 part sodium dodecyl sulfate, 0.1 part

209 614/183

IU Octadecandioldivinyläther, 1.0 molar equivalent of Rongalit, based on the charged hydrogen peroxide initially introduced and the mixture is placed for 8 hours at 50 ⁰ C for polymerization. During the polymerization, 0.003 parts of hydrogen peroxide are introduced continuously as a dilute aqueous solution. A good latex is obtained which contains 35 percent by weight copolymer, based on the latex, and which does not contain any living serum. The yield of copolymer is 95 ⁰ I ₀ of theory. The latex obtained is spray dried in a conventional manner. The copolymer has an average degree of polymerization of 1700.

10

The physical properties of the copolymer are compared with those of polyvinyl chloride.

In each case 100 parts of the! Copolymer and polyvinyl chloride of similar average PoIymerisationsgrad are mixed with 3 parts of a lubricant organotin mercaptide as a stabilizer and 0.5 part, rolled for 5 minutes at 160 ^c C and pressed for 10 minutes at 17O ° C. Then the stiffness temperature, the brittleness temperature and ίο the impact strength according to C har ρ y of the panels obtained are examined. The results are shown in Table VII.

Table VII

polymer average
licher poly-
merization
Degree Stiffness
temperature
⁰ C Brittleness
temperature
⁰ C Flip bend
strength
after
C h a r ρ y
cm kg / cm ² Copolymer of the invention 1700
1800 73
69 -1
+8 4.4
3.6 Polyvinyl chloride

From Table VII it can be seen that the copolymer prepared according to the invention improved Possesses properties.

Example 8

In a manner similar to that in Example 2, 100 parts of vinyl chloride are mixed with 0.3 parts of 1,12-octadecanediol divinyl ether and 5 parts of vinyl acetate in the presence of 150 parts of deionized water, 0.1 part of polyvinyl alcohol Copolymerized and 0.4 parts of L ^ uroylperoxyd at 45 ° C for 15 hours.

The unreacted monomers are separated off from the reaction mixture, and the resulting copolymer is dehydrated and dried. There is obtained a white powdery copolymer in 75% yield, the _98/0 a sieve of mesh size 0.351 mm to more than happens °. The average degree of polymerization of the copolymer is 2050.

The physical properties of the copolymer are compared with those of polyvinyl chloride.

Each 100 parts of copolymer, and polyvinyl chloride of the like, average degree of polymerization of an organotin · maieat stabilizer and 0.5 parts mixed with 4 parts of a lubricant "rolled for 5 minutes at 160 ⁰ C and pressed for 10 minutes at 170 ⁰ C. The flowability, the stiffness temperature, the tensile strength, the elongation and the impact resistance according to C har ρ y of the panels obtained are then tested. The results are summarized in Table VIII.

Table VIII

polymer average
licher poly-
merization
Degree Flow
capability
cm '/ sec Stiffness
temperature
⁰ C Tear
strength
kg / cm « strain
% Flip bend
strength
after
C h a r ρ y
cm kg / cm ¹ Ternary copolymer of the invention
Polyvinyl chloride 2050
1800 0.00041
0.00002 68
69 610
610 140
140 3.5
3.6

From Table VIII it can be seen that the ternary copolymer produced according to the invention is a has better flowability at higher temperatures than polyvinyl chloride.

Example 9

(Test ^{report) 6s}

The purpose of the tests below is to determine whether a result is as good as after Process according to the invention can be achieved if, under otherwise identical conditions, di Polymerization of vinyl chloride. instead of in the presence of a glycol to be used according to the invention divinyl ethers in the presence of an appropriate amount of other ethers with two terminal olefinic ethers Carries out double bonds, namely from de USA.-Patent 3,025,280 for this purpose rx knew butanediol diallyl ether or that from de French patent specification 801 462 for this purpose known divinyl ether.

83

In these Verglebhsversuchen a SO-ml glass ampoule under a nitrogen atmosphere with 100 parts of monomeric vinyl chloride, 600 parts water, 0.3 parts of polyvinyl alcohol, 0.2 part of lauroyl peroxide and said comonomers in Table IX i ^H respectively. the quantity specified there. The glass ampoule is then melted shut and shaken in a water bath kept ^{constant at SS ° C.}

After ten hours of polymerization, the ampoule is opened, unreacted monomers are separated off, and the polymer obtained is dehydrated and dried.

The yield of polymer, the average The degree of polymerization and the gel content of the product are determined.

The average degree of polymerisation is determined analogously to Example 1.

The gel content is determined by dissolving 0.4 g of the polymer in 100 ml of nitrobenzene, which does not dissolved parts of the polymer filtered off, the specific viscosity of the dissolved parts measured and from the Specific viscosity value according to JIS (Japanese Industrial Standards) K 6721 calculated the gel content.

The results of these experiments are summarized in Table IX:

Table IX

tries Comonomer crowd
· / · yield Average PcIy Gel content No. Art 0 V. degree of merization Vt 1 0.2 82 1070 0 2 Divinyl ether 0.4 86 1070 0 3 Divinyl ether 0.2 83 1100 0 4th Butanediol diallyl ether 0.4 56 1620 3.6 5 Butanediol diallyl ether 0.2 39 1220 26.0 6th Butanediol divinyl ether 0.4 84 1500 0.5 7th Butanediol divinyl ether 0.2 86 1640 0.8 S. Octadecanediol divinyl ether 0.4 81 1520 0.6 9 Octadecanediol divinyl ether 80 1720 0.9

In Table IX, the Comcnomertnengen used are each given in percent by weight, moved to the vinyl chloride used.

As can be seen from the values in Table IX, the method according to the invention (experiments 6 to 9) is superior to both the method according to French patent specification 801 462 (experiments 2 and 3), with the no significant increase in the average molecular weight compared to homopolymerization of vinyl chloride (experiment 1) can be achieved, as well as the method according to US Pat. No. 3,025,280 (experiments 4 and 5), with which one Increase in the average molecular weight is achieved, but with a considerable reduction in the rate of polymerization (lower Yields) and a considerable gel content of the polymer must be bought.

Claims (1)

Patent claims: 1. Process for the preparation of vinyl chloride copolymers by polymerizing Vinyl chloride with at least one other unsaturated monomer, characterized in that the polymerization in the presence of a glycol divinyl ether of the general formula = CH-O-CH ₂₁₁ -O-CH = CH ₁ ^6o is carried out, in which C ₁₁ H ₁ * means one unbranched or branched saturated hydrocarbon radical, η is an integer with a value of 2 to 20 and the two vinyl ether radicals are on different carbon atoms. 2. The method according to claim 1, characterized in that the glycol divinyl ether is used in an amount of 0.01 to 10 percent by weight, based on the total weight of the monomers used. 3. The method according to claim 1, characterized in that the glycol divinyl ether in one Amount of 0.05 to 1 percent by weight, based on the total weight of the monomers used, is used. 4. The method according to claim 1 to 3, characterized in that the glycol divinyl ether 1,2-ethanediol divinyl ether, 1,4-butaudiol divinyl ether or 1,12-octadecanediol diviny ether is used. 5. The method according to claim 1 to 4, characterized in that the polymerization and suspension polymerization in the presence of polyvinyl alcohol, a cellulose derivative or a sorbitan ester as a suspension stabilizer and lauroyl peroxide, Düsopropylperoxydicarbonat, benzoyl peroxide or azobisisobutyronitrile is performed as a polymerization initiator at a temperature between 30 and 70 ⁰ C. . 6. The method according to claim 1 to 5, characterized in that the olefinically unsaturated Monomer in an amount of less than 50 percent by weight, based on the weight of vinyl chloride and the olefinically unsaturated monomer, is copolymerized with. 7. The method according to claim 6, characterized in that the olefinically unsaturated monomer Vinyl acetate, a vinyl ester of a higher aliphatic carboxylic acid, vinylidene chloride Acrylic acid ester, a methacrylic acid ester or a higher alkyl vinyl ether is used. 183