DE2241161A1 - VINYL CHLORIDE GRAFT POLYMERISATES AND METHOD FOR THEIR PRODUCTION - Google Patents

Description

The invention relates to homogeneous graft polymers based on vinyl chloride and on copolymers and / or terpolymers of ethylene and propylene »optionally in a mixture with a polymer of an alpha-olefin, and a process for their manufacture. ■. '

The graft polymers are particularly useful for applications which require excellent impact properties and excellent processing and application properties. .

309812 / Π01

The problem of the incompatibility of polyvinyl chloride and elastomers in general, and in particular of copolymers and terpolymers based on ethylene and propylene are known per se.

Various possibilities have been proposed to improve the compatibility of these plastics with one another, and in particular the grafting of vinyl chloride containing the dissolved elastomer by a method in aqueous suspension. This procedure requires the elastomer to be dissolved and suspended in the vinyl chloride this solution.

However, this is only in the case of solutions with lower Concentration of elastomers of low molecular weight easily possible.

On the other hand, it is known that the degree of increase in impact resistance of synthetic resins such as polyvinyl chloride a function of the molecular weight with the help of elastomers of the elastomer and / or the concentration of the elastomer in the composition. So far, using polyvinyl chloride -compatible synthetic resins based on elastomers with high molecular weight or in high concentration not getting produced.

The object of the invention is to avoid these disadvantages. It has now been found that the production of homogeneous Graft polymers of vinyl chloride, which have increased Contain low or high molecular weight elastomers, d. H. of graft polymers, which 26 to 90 wt.% and in particular 40 to 60% by weight of one or more elastomers

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Containing elastomer is possible.

The invention "also relates to a method of manufacture this graft polymer, which is characterized by the fact that one carries out the polymerization of vinyl chloride in the absorbed phase, on the grains or beads of the parent polymer and that the amount of vinyl chloride to be introduced into the autoclave regulates in such a way that the

original granulate form or pearl form of the ötammpolymer or framework polymers, is maintained in the reaction mass.

The polymerization of vinyl chloride according to the invention Procedure can only take place in the absorbed phase.

Polymerization of vinyl chloride in the absorbed phase is understood to mean that the polymerization is carried out under similar conditions will that all of the vinyl chloride introduced into the autoclave through the grains or beads of the parent polymer is absorbed and that there is no free in the reaction mass Vinyl chloride, for example in the form of droplets. ·

Because of the absence of liquid vinyl chloride in the autoclave one avoids the formation of vinyl chloride homopolymers outside the grains of the parent polymer.

In order to maintain these conditions, the pressure prevailing in the autoclave is set to a value above 6 kg / cm and below the saturation vapor pressure of vinyl chloride at the

Maintained polymerization temperature.

The Polymerieationstemperatur is between 40 ° and 100 ⁰ C.

The ratio of vinyl chloride to parent polymer that is to is present at any point in time in the polymerization medium,

12 / 1101.-,

is critical. It should be so that one "at the chosen The polymerization temperature maintains the initial bead or granular form of the parent polymer at all times, d. H. that excessive swelling of the parent polymer due to excessive absorption of vinyl chloride is avoided, causing sticking or re-agglomeration of the Grains or pearls of the parent polymer could occur.

This ratio is determined by the in the reaction vessel
The amount of vinyl chloride introduced for the polymerization is regulated. The initial amount can be determined by a preliminary test, which is carried out under the polymerization conditions but without using the catalyst.

The ratio of vinyl chloride to polymer is between 0.1 and 2.8 and preferably between 0.6 and 1.5

It was found that the parent polymer grains depending on the requirement the polymerization were able to rapidly produce new amounts of vinyl chloride to absorb. In this way you can with continuous or discontinuous introduction of additional amounts of vinyl chloride and optionally catalyst inside the grains of the parent polymer or of the parent polymers significantly larger amounts of vinyl chloride polymerize when they match the initial ratio of vinyl chloride to parent polymer. Still supposed to at every point in time in the autoclave the granular shape of the parent polymer be maintained.

In this mode of operation, all of the vinyl chloride introduced into the autoclave is absorbed by the parent polymer and polymerizes in direct contact with this, whereby a Increase in the graft yield, which by the following Relationship is given: '■

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ρ; grafted vinyl chloride. 100 grams of polymerized vinyl chloride

results. In this way, the degree of grafting of the Stem polymer increased. The grafting yield and the degree of grafting still increase when the ratio of vinyl chloride to parent polymer is lower.

All copolymers of ethylene-propylene can be used as the base polymer and terpolymers of ethylene-propylene-not conjugated diene can be used.

The copolymers and terpolymers which have a propylene content between 10% and 90 mol% and preferably 20 to 60 mol% are particularly suitable for carrying out the invention. .

Those in the terpolymers with ethylene or propylene Linked, non-conjugated dienes are preferably selected from;

- the aliphatic, non-conjugated dienes such as pentadiene- (1,4) J ₁ hexadiene-0,5) and hexadiene- (1,4)

- the monocyclic, non-conjugated dienes of the type 4-vinylcyclohexene, 1,3-divinylcyclohexane, cycloheptadiene- (1,4),

Cyclooctadiene (1.5)

- the alicyclic, non-conjugated, serving an endocyclic Have bridges such as dicyclopentadiene, norbornadiene, methylennorbornene and ethylidene norbornene. '

Terpolymers suitable as elastomers are particularly advantageous the terpolymers based on ethylene, propylene and dicyclopentadiene and / or ethylidene norbornene, hexadiene (1,4) and Methylennorbornene.

309812/1101.

Certain elastomers, and particularly the low molecular weight elastomers, which are produced by the absorption of a small amounts of vinyl chloride can become sticky and agglomerate, as such in the process according to the invention Not used.

a mixture This elastomer is therefore used as the base polymer Polyethylene and / or polypropylene.

Bas polyethylene and / or polypropylene, the amount of which depends on the physical properties of the elastomer used as well as the final, desired ratio of parent polymer depend on vinyl chloride, are used to allow easy granulation of the mixture and excessive Avoid swelling or agglomeration due to absorption of vinyl chloride.

Generally the amount is polyethylene and / or polypropylene the higher the lower the viscosity of the elastomer.

The amount of polyethylene and / or polypropylene that is included in the Elastomers can be incorporated, from 1 to 30 wt.% and preferably from 10 to 50 percent by weight of the blend of polyolefin and elastomer. On the other hand, the use of high molecular weight elastomer enables production of graft polymers, which are very elastomeric have a greatly increased degree of grafting. The parent polymers can and in particular be used in the form of beads those which have an average particle size distribution between 1 and 5 mm or in the form of an aqueous latex des Elastomers, produced by customary procedures, are present.

As catalysts for the polymerization according to the invention Processes can use all catalysts or catalyst systems,

309812/1101

which free hadicals produce those in the vinyl chloride are soluble, are used »·

The amount of catalyst used is preferably between 0.01 and 5% by weight based on the monomer used "or the monomers used, it can be in the form of a solid or in solution in vinyl chloride or in one of the parent polymers • swelling solvents are introduced. ·

The usual additives for a polymerization in aqueous dispersion can be entered.

As a dispersion aid, which has a good wetting agent effect compared to the parent polymer, one can use the macromolecular Colloids AHXd ionic or nonionic surfactants Use substances.

The dose of dispersion aid is · in contrast to the classical polymerization procedures are not critical.

It has been found that reduced doses of .Dispersionshilfsmittel can use, which are below those required in classical polymerization procedures are. . - ■ ■. ·:.

You can also use synthetic resins. Better stabilization obtained by adding the usual stabilizers for polyvinyl chloride to the reaction medium before the polymerization or in the course of the polymerization. . ..; ^: ; _ ·,

The process according to the invention is also suitable for the polymerization of vinyl chloride and other copolymerizable monomers, such as vinylidene chloride, methylene _; , Propylene ,, etc.

Improve built into other synthetic resins and especially in polyvinyl chloride and post-chlorinated polyvinyl chloride the grafted products obtained according to the invention die Impact strength considerable. The impact strength of the grafted products is the same with the same amount of base polymer much higher than that of the ungrafted, appropriate mixtures.

Masses that are to 100 TIe. Vinyl chloride polymer, 1 to 25 pieces. "and preferably 5 to 20 parts. of the products according to the invention contain.

The properties described above with respect to the homogeneous graft polymers according to the invention result in materials for numerous applications and in particular for the production of corrugated or flat plates, foils, containers, etc.

The inventive method which allows the production of homogeneous graft polymer and the grafting yield improved, it has also yet another economic advantage for the lack of fouling in the ■ reaction vessel for the polymerization, whereby this is mainly due to the absence of a liquid phase of vinyl chloride .

The invention is explained in more detail below with the aid of examples.

Examples 1 until 14

The properties of the elastomers used as the base polymer

are listed in Table I below.

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Table ί

Designation- Elastome- Type of Ter- Unsaturation Propylene- Reduced tion of the renart monomer of joint viscosity Polymers ♦ mole.% In m xylene

g / kg at 120 ^° C;

Κοηζ. «= 2κ / 1

A. ÄPR - - 32 0.980 B. IPR - - 47 . 0.380 C. APR -. 36 0.240 D. ■ APR Dicyclopene
tadien +
Ethylidene
norborria 0.65 36 0.328 E. ÄPI Dicyclopene
tadien 0.7 36 0.206 F. APOI Dicyclopene
tadien +
Ithyliden- '
norbornen 0.41 34 0.148 G APT 38 0.216

* ÄPR «copolymers from ethylene propylene

ÄPT - Terpolymer made from ethylene-propylene-non-conjugated diene

The polymerization technique used was as follows;

In an autoclave of 3 1, which is continuously running at 500 rpm

using a stirrer with two blades inclined at 45 °

was stirred, water and suspension aid were introduced

and the beads of the parent polymer in the

Table II entered the ratios. ·

After the introduction of the catalyst, vinyl chloride was in a entered such an amount that at the polymerization temperature

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from 62 ⁰ C the polymer remained in its original granulate form.

The amounts of vinyl chloride incorporated were determined by a preliminary test determined, which was carried out under the same polymerization conditions, but in the absence of the catalyst.

In examples 1, 2, 3 »5, 8, 10, 11, 12, 1? and was 14 all vinyl chloride introduced at startup. In Examples 4, 6, 7 and 9 a certain amount of vinyl chloride was used entered at the beginning, and when the pressure dropped this became

to its initial value by successive additions of Vinyl chloride recycled.

After filtration, washing and drying, the obtained, grafted product obtained.

There was no incrustation on the walls of the Reaction vessel observed.

The degree of grafting (T) of the obtained polymers became as follows Equation calculates:

100

where A is the total weight of the parent polymer in the sample and B is the weight of ungrafted parent polymer.

Examples 6, 7 and 9 were obtained by adding a new amount of vinyl chloride to that in Examples 3, 5 and 8 obtained graft polymer was polymerized to the content of vinyl chloride in the graft polymer and

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thus also the degree of grafting of the elastomer.

The products obtained have the same properties as when in a stage with successive additions of Vinyl chloride would have been worked. ■

Example 14- shows that if the previously ' conditions described, and especially when a partial dissolution of the elastomer and the disappearance of the grain shape occurs, solidification occurs during polymerization.

Examples 10 to 13 suggest that the addition of polyethylene and / or polypropylene to form low molecular weight elastomers enables the simple production of graft polymers according to the method according to the invention, the good physical · have lical properties.

In addition to the use of elastomers with any desired molecular weight, the process according to the invention enables increased degrees of grafting even to 100% to be achieved, ie the entire elastomer has been grafted, see Examples 8 and 9 ». · ...- ■■■

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(O 00

K)

Beisolel

used weight of vinyl cii.lo ri d:

- initially

- in the course of the polymerization

Polymer Λ

Polymer B

in example 3

arhaltenes

Graft poly

neres

in example 5

received

Grafted poly

mere s

Polymer E

in example 8

received

Graft poly

neros

Folyinorea C

Polynares D

Polymeric F

Polymeric G

V / ater

Polyvinylalk. Lauroyl peroxide polymerization temperature

300+

5x60

300

1350 1.2 7.2

Ί0

11

12th

125

205

205

246

164

205

205

500

246

1435 0.73 1.72

750

0.25

0.25

⁰ C

Table II (continued)

Conditions * ^,
'u', property ^ *. ~ 2 3 4th 5 6th 7th 8th 9 10 11 12th 13th 14th Reaction
duration h *>' 6th 6.5 ■ 6.5 7th 9.5 7.5 7.5 7.25 6th 6.5 5.5 ■ -6 4th more effective 8 4
Initial pressure ^J
more effective ο -, *
Final pressure kg / cm - ¹ * ⁰ 9.1
1.6 9.4
2 9.2
2.6 ' ⁹
1.6 9.1
3.3 9.2
2.5 9.4
2 9.5
3 9.5
4th 9.4
3 9
4th 9.2
3 6th
3: Polymerization _Qo
yield,% ί ^yu 95 91 95 88 91 88 72 87 ·, 5 85 90 85 ^ 90 • cn
14th
ai Degree of grafting of!
Parent polymers! 50
% ■ i. 55 56 70 45 ' 75 65 100 100 45. . 50 70 80 Weight ^v I
relationship !
Polyvinyl chloride "* - _r
S "tärampbJ.y. ^ ^E ^ s, ^4ü / p ^l 49/51 54/46 80/20 49/51 78/22 79/21 44/56 70/30 46/54 58/42 47/53 56/44

Example 1 ^

The same procedure was used as in the examples described above, except that an aqueous latex containing 40% polymer B was used instead of the elastomer grains or beads.

The amounts of vinyl chloride and initiator added are as in Example 5 of Table II.

After a reaction time of 6 hours, a polymerization yield above 90% and a degree of grafting of 57% were obtained.

The weight ratio of polyvinyl chloride to parent polymer is 51 / 4-9.

Examples 16 to 37

In a polyvinyl chloride, which was obtained by suspension polymerization and had a K value of 64 measured in a solution of cyclohexanone, and in a chlorinated polyvinyl chloride which contained 66% chlorine, the polymers obtained in the aforementioned examples were incorporated in such a way that the content of the product in the elastomers or in the mixture of the elastomers and the polyethylene and / or the polypropylene was 5ι 7 »5 and 10% by weight.

For comparison, mixtures of polyvinyl chloride were also produced, which contained 5th, 7.5 and 10% of the ungrafted parent polymers, Examples H18 through R23.

The processing of the mixtures based on polyvinyl chloride was niin by kneading in a mixing roll at 180 for 5 ⁰ C in the presence of the usual components performed. The skin obtained was converted ^{into plates by pressing at 190 °} C. for 5.

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The mixtures based on chlorinated "polyvinyl chloride wurdeöwährend worked through 5 min at 200 ⁰ Q in the presence of the usual ingredients. The sheet obtained was transferred by pressing at 190 ⁰ C for 5 min in flattening *

Subsequently, the. IZQD ~ impact strength at ambient temperature (20 ⁰ C) determined according to the standard AB ¹ M D 256/56 *

The results of these experiments are shown in Table IXI below .listed; it follows that the invention Graft polymers increase the impact strength of compounds based on polyvinyl chloride and chlorinated polyvinyl chloride, and that this has an improved impact strength in comparison point to the ungrafted mixtures.

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Table III

example

Composition of the mixture

Content of grafted or ungrafted Staitnpolymerem,%

IZOD impact strength (20 ⁰ C) according to standard ASTI4 D256 / 56 kg.cm/cm

R16 Polyvinyl chloride A. - 3.5 R17 chlorinated polyvinyl
chloride B. 7.5 3.4 R18 Polyvinyl chloride
+ Polymer C. 7.5 R19 C. 5 8th R20 E. 10 8th R21 7.5 7th R22 1 7.3 5 R23 Polyvinyl chloride
+ Polyethylene 4th 7.5 10.5 24 4th 5 11.5 25th 7th 7.5 9 26th Polyvinyl chloride 7th 5 15th 27 7th
9 7.5 7.4- 28 9 10
5 12.5 29
30th Graft polymer
from the examples 10 10 80
9 31 10 5 16 32 12th 7.5 9 33 12th 5 14th 34 13th 7.5 10 35 7 _t 3 14.5 36 13.5

chlorinated polyvinyl chloride + graft polymer from Example 7

7.5

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Claims (1)

Patent claims Homogeneous graft polymers of vinyl chloride, g e k e η η - ·· ζ ei c h η e t by a content of 26 to 90 wt.% and -in particular from 40 to 60 wt.% Of one of one or several copolymers and / or terpolymers of ethylene and propylene formed base polymers, optionally mixed with polyethylene and / or polypropylene * Process for the preparation of homogeneous graft polymers of vinyl chloride according to Claim 1, characterized in that the polymerization of vinyl chloride is carried out in the absorbed phase on the grains or beads of the parent polymer and that the amount of to be introduced into the autoclave vinyl chloride so that the initial granular form of the parent polymer is maintained in the reaction mass. 3. The method according to claim 2, characterized in that that the parent polymer is used in the form of a latex. 4. The method according to claim 2, characterized t that the vinyl chloride is continuous or in 'successive fractions in the course of the polymerization introduces. 5. The method according to claim 2, characterized et that the polymerization is carried out in the presence of a stabilizer for polyvinyl chloride, which previously or is introduced in the course of the polymerization. 3 0 9 8 12/1101 6. Use of the homogeneous graft polymers according to claim 1 In an amount of 1 to 25% by weight and in particular 3 to 20% by weight in plastic mixtures, which are polyvinyl chloride and / or post-chlorinated polyvinyl chloride. 3 0 9 812/1101