DE1694816A1 - Non-clumping, free-flowing, grainy graft polymer - Google Patents

Description

Description of the patent application

Produits Chimiques, PECHINEY-SAINT-GOBAIIT 16, avenue Matignon, Paris (8) France

concerning

Powerful, free-flowing, granular Graft polymer

The present invention relates to non-clumping graft polymers and copolymers as well as a process for their manufacture.

It is known to use a diene monomer optionally together with one or more vinyl monomers grafting in emulsion onto a polymer or copolymer of a vinyl halide. The received However, graft polymers have a low bulk density, which is generally below 0.17 g / cm lies. In addition, they tend to clump together and the granules therefore clump when the Graft polymer from the polymerization medium as well as during storage and handling together easily.

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In order to avoid this tendency to form lumps, it has already been proposed during the polymerization To use a larger amount of emulsifier or to add an inert one to the dry graft polymer add mineral powder such as silica or talc. True, through this treatment reduces the tendency to form lumps; however, the improvement is not satisfactory and also the purity, the clarity and the mechanical properties of the graft polymer impaired.

It has also already been proposed to add a non-clumping polymer to the graft polymer, the powders of the two polymers with one another

which is mixed or the latces of the two polymers are mixed and the latex mixture is coagulated or sprayed. For this, however, considerable amounts of non-clumping polymer are required, namely at least 50 ° / a up to more than 100 $ based on the amount of graft polymer. The disadvantages of this process are that the heat resistance, the clarity and the reinforcing capacity of the polymers are significantly impaired, the production process is made more difficult and the cost price is increased as a result.

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that it is still known / the coagulated

The latex or the latex mixture must be subjected to a heat treatment in order to remove the particles of the polymer to be able to separate. This increases the overall duration of the manufacturing process and thus the output is reduced.

The method according to the invention avoids the disadvantages mentioned and allows without heat treatment the production of graft polymers that do not clump, i.e. are free-flowing and which have a higher bulk density than the graft polymers obtained by the known processes, without their other properties are noticeably impaired.

The term “polymer” in the present description refers to at least one homopolymer and / or denotes at least one copolymer.

According to the invention a latex is coagulated graft polymer of a clumping and mixed with stirring, preferably at a temperature between 0 and 40 ⁰ C with the latex of a non-clumping polymer and then the product obtained is separated off, washed and dried.

Mixing is done by adding either the latex of the non-clumping polymer to the coagulated

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Latex of the graft polymer or, conversely, the coagulated latex of the graft polymer to the Latex of the non-clumping polymer is added.

The amount of latex of the non-clumping polymer that the coagulated latex of the graft polymer must be added, should be such that 1 to 50 wt .- $, preferably 2 to 10 wt .- ^ non-clumping polymer, calculated as a solid and based on the graft polymer.

Under nichtklumpendem polymer all mean polymers whose glass transition temperature ET (RP Boyer, RS Spencer - Advances in Colloids Science 2 - Interscienee) above ⁰ ° C, preferably above 30 ⁰ C and the modulus of elasticity more at train (ASTM D 638-61T) than 1000 kg / cm, preferably more than 10,000 kg / cm.

The non-clumping polymers must of course with the graft polymers and also with the later use of these graft polymers The required properties are compatible, especially the polymers and copolymers of vinyl compounds, e.g. the polymers and copolymers of vinyl halides, in particular of vinyl chloride and vinyl chloride-vinyl acetate and Vi-

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1A-34 187

- ⁵ - 1 (594816

from
nylidenchloridj alkyl methacrylates whose alkyl

from group contains 1 to 4 carbon atoms; acrylic

of nitriles and methacrylonitriles, if appropriate halogenated styrene and / or methyl styrene, in particular styrene-methyl methacrylate, styrene-acrylonitrile, Styrene-acrylonitrile-methylstyrene; Graft polymers and copolymers, such as styrene and

Acrylonitrile, polybutadiene or the copolymer

Butadiene-styrene, styrene and methyl methacrylate on polybutadiene or the butadiene-styrene copolymer, Vinyl chlorides on the ethylene-vinyl acetate copolymer the polymers and copolymers of olefins and vinyl monomers, as well as all mutually compatible Mixtures of the polymers or copolymers mentioned.

The latex of the non-clumping polymer consists of a dispersion of particles of this non-clumping polymer Polymerisates in an aqueous or aqueous-alcoholic medium, and is preferred by polymerization in emulsion or in fine suspension (suspension fine) of the monomer (s) in received in a known manner "

The known working methods of bulk polymerization, solution polymerization or suspension polymerization can also be used to produce the non-clumping polymer; in general

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I believe that additional measures are required for the formation of the latex. So, for example, must non-clumping polymer dissolved in a solvent, the resulting solution in an emulsifying one Solution dispersed and the solvent evaporated.

The concentration of the particles of the non-clumping polymer in the latex has practically no influence on the properties of the graft polymer to be treated. But it was found to be excellent Results with latexes of non-clumping polymer with a particle size of 0.01 to 10, preferably 0.3 to 0.8vU can be obtained.

The type of emulsifier in the non-clumping polymer is not critical. However, anionic ones are preferred Emulsifiers, e.g. fatty acid salts, alkyl sulfonate or alkyl aryl sulfonate derivatives and alkyl sulfates.

The graft polymers to be treated according to the invention are prepared by emulsion polymerization in accordance with Belgian patent specifications 593 821, 609 158 and 634 or by polymerization in fine suspension. They consist of a main chain, the halogen
contains atoms, / the side chains of a diolefin with conjugated double bonds, optionally in conjunction with at least one copolymerizable vinyl mono-

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mers were grafted on. Such graft polymers are described in Belgian patent 593 821 described.

That, as indicated above, by emulsion polymerization or by fine suspension polymerization The latex obtained from the graft polymer is coagulated in any known manner, e.g. by adding a solution of an acid or a salt such as alum, calcium chloride, sodium chloride, magnesium chloride and / or Magnesium sulfate. The addition is generally carried out at room temperature, with the coagulant in excess is used, which can be up to 3 times the theoretical amount, calculated on the amount used Emulsifier.

The resulting coagulum of the latex of the graft polymer is then mixed with the latex of the non-clumping polymer while stirring. Once all of the latex of the has been added to non-clumping polymer, the stirring is interrupted; set the polymer particles himself off. The granular product is separated off from the liquid phase in a known manner, washed and dried. It consists of 67 to 99%, preferably 91 to 98% by weight of graft polymer and 33 to 1%, preferably to 9 to 2 wt .- ^ of non-clumping polymer.

The microscopic and electron microscopic examination showed that the individual grain consists of a core

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Contains graft polymer with a thin Layer of the non-clumping polymer is coated. Presumably this prevents the granules from clumping together.

Wei's polymers obtained according to the invention have a visual weight of about 0.3 to about 0.65 g / cm

do not bake and cook together.

Films can be made of the inventive anti-caking, free-flowing granular graft polymer well foils, _r pipes, hollow bodies, moldings produced. It is preferably used as a reinforcing agent to improve the toughness of brittle thermoplastic compositions, since it does not impair their clarity, softening temperature and ease of processing. The brittle thermoplastic compositions and the non-clumping graft polymers can easily be mixed in the form of dry powders without the fear of caking.

The invention is described in more detail with reference to the following examples.

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example 1

In a 16 liter stainless steel autoclave equipped with a stirrer, 9 liters of deionized water, 64 g of stearic acid and 65 g of sodium hydroxide are placed, heated to 6ü ° C with stirring and treated with 2,500 g of vinyl chloride, 2 g of potassium persulfate and 1 g Sodium metabisulphite added. The polymerization was continued at constant temperature until the relative pressure reached a value of 5 bar. Then, the unreacted vinyl chloride was degassed and returned to the temperature to 2O ⁰ G.

A solution of 25 g of sodium pyrophosphate and 3 ['. Sodium hydroxide in 100 cm of iron (III) nitrate in 100 cm of water was added. The 'pH VJert was prepared by adding NaOH to 9.4 - 9.5 set and a mixture of 2000 g of freshly distilled butadiene, 500 g of acrylonitrile and 0.9 g of cumene hydroperoxide was added, the temperature was raised to 4ü ° C and held at its value until the relative pressure was 1.5 bar. The non-polymerized butadiene was degassed and the latex obtained was stirred with a solution of 20 p; Dibutyl-p-cresol was added to 100 g of dichloroethane.

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The composition of the graft polymer corresponded practically the proportions of the monomers used.

A portion of the latex obtained was coagulated by adding a CaCl ^ solution in three times the theoretical amount, based on the amount of the emulsifier, at room temperature and with stirring. It was stirred for 10 minutes and then, based on the graft polymer, 10 Gevf .- # PVC with freezing point ET 75 ° G and modulus of elasticity under tension from 29,000 to 35,000 kg / em ^ added. The PVu was in For *. of a latex with 32 % solids, mean particle size 0.3 / U, was added. This latex was vrorden ij-85 5 ^ 7 prepared by Polynerisation in fine suspension at hi> C in the presence of Natriumεtearat by UachseriLassen of the particles after inoculation according to the French patent. 1 As the stirring was interrupted, the solid particles settled; They were spun off, washed and dried without difficulty in spinning off and without heat treatment. Microscopic examination revealed that the individual particles consisted of a core of graft polymer and a thin PVC shell.

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The bulk density and the lump formation index of the polymer obtained were determined.

The bulk density was measured in accordance with the French standard NF T 51 003.

For determining the index of the formation of lumps iii g of polymer were dissolved in a rigid tube from the inner diameter kt mm and the height 30 mm and filled with a piston on the diameter * J> 3 mm and the high compressed 30 mm.

Experiment A: 0.05 kg / 20 ° C

Experiment B: 1 kg / 20 ° C

Experiment C: 1 kg / 55 ° C

After 15 hours, the flask was removed and the press cake formed was checked and rated according to the following scale:

0 compact block,

1 heavily clumped, «falls hard,

2 strongly clumped, falls into compact blocks,

k strongly clumped, difficult to grind powder,

6 clumped, can easily be ground to powder with a finger,

8 »falls into a powder with light finger pressure,

10 the press cake cannot be held between the fingers, but disintegrates immediately.

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The bulk density of the polymer was 0.32 g / cm ^ j according to tests A and B, the lump formation index was 10.

For comparison, the following were made with aliquots of the latex of the graft polymer obtained Tests carried out according to the state of the art.

a) First comparison attempt

The latex of the graft polymer was coagulated as before. The resulting slurry was spun in a sieve centrifuge. It was difficult to spin it off and remove it from the centrifuge because a compact block had formed on the screen of the centrifuge. However, it was possible to obtain a coarse powder with a suitable extraction device which, after drying, had a bulk density of 0.1 g / cm2 and an index of lump formation k (experiment A) or 1 (experiment B).

k) Second comparison attempt

The procedure was as in a), but the coagulate was heat-treated ^{at 85 ° C. for 15 minutes.} The polymer settled out. After being thrown off, it could only be removed with difficulty, because the firm hates one

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compact, rubber-like block formed, which difficult to apply. The powder that could be obtained had a coarse grain that was already out balled up under pinger pressure. After drying, the bulk density was 0.14 g / cm ^ and the lump formation index was 6 (experiment A) or 2 (experiment B).

°) third comparative experiment

The latex of the graft polymer was, based on the graft polymer, with 10 Gexi. ~ ^S / j PVG according to Example 1 was added, The mixture of the two latices viurde by adding with stirring a Gagl ₀ -Losung in three times the theoretical Iienro, based on the amount of the emulsifier, coagulated at 20 ⁰ C, lisch 1; 5 a Hühren viurde the mixture in a centrifuge spun off. Ea formed on the screen of the centrifuge, a compact block.

The product obtained had the following characteristics: Microscopic examination: Composition of individual graft polymeric grains and PVC grains. Bulk density u, 20 / cm- '; Inde :: o formation of lumps: G (experiment A), 2 (experiment β) .

The comparative experiments according to the state of the art produced Schlec? Ito or mediocre results, v-lilirencL the Qi-ΐ ind.imgrji-emaij; ·; it shared te j 'f ropf nol?' mer i nat bernorlcenswer t

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-H-

well not clumped and was free flowing.

Example 2

The coagulated latex according to Example 1, based on the graft polymer, was admixed with 10% by weight of polymethyl methacrylate in the form of a latex with 20% solids and an average particle size of 0.15 / U. The freezing point of the polymethacrylate was 105 ° C, the modulus of elasticity under tension was 3u OGO to 35 COC kg / cm. The Lat '. · ■>:' was obtained by emulsion polymerization at 0O ⁰ C in G-egeuvrart of Ka! lumper sulfate as a catalyst and of 2 wt .- / - UatriumlaurylsulfsU as emulsifier, based on the monomer; been.

The bulk weight and the index of g

of the filtered, washed and dried PoljTaeris "ats were determined according to Example 1: Bulk bulk, 4 g / cm · ^; index of lump formation 10 (test A)
¹ OVAu ο (experiment 3).

Example 3

Example 2 v.tirde x / repeated by replacing the
x ^J olymethylmethscryl? tlatex an? olystyrolletex with
25 Gevi .- ", i 'solid imc. The mean particle size
ü, ü5 / U ver ;; ends vjurclo. This latex went through

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Emulsion polymerization at 70 ⁰ G in the presence of potassium persulfate and 2 wt .- $ sodium stearate, based on the monomer. The freezing point of the polystyrene was 81 ° G, the modulus of elasticity under tension was 30,000 to 35,000 kg / cm ² .

The polymer obtained had a layer weight of 0.32 to 0.35 g / cm ^J ; the lump formation index was 10 (experiment A) and 8 (experiment B).

Examples ^L v till 8

According to Example 1, the latex of a graft polymer was used produced, but the 2,000 g of butadiene and 500 g of acrylonitrile by 1,700 g of butadiene, 800 g Acrylonitrile and 50 g divinylbenzene replaced. The concentration of the graft polymer in the obtained Latex was 3 ^, 5 #.

The latex was made into several 1 OGO cm ^ portions divided that at Bäumtenraeratur by addition a CaClp solution in three times the theoretical amount, based on the emulsifier used, coagulates. These latices were treated with latices of various polymers obtained Products spun off, washed and dried.

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The bulk density and the lump formation index were determined according to Example 1.

In Examples ^, 6 and 7 the latices the non-clumping polymers as in Examples 1, 2 and 3 prepared.

In Examples 5 and 8, the latices of the non-clumping copolymers were by emulsion polymerization at U-5 G in the presence of 1 Gevi. -fa sodium lauryl sulfonate, based on the monomers, or by emulsion polymerization at 70 G in the presence of 2 wt -.% Hatriumdresinat, based on the monomers.

The modulus of elasticity in train of the various polymers was in BeisOiel ^ 29000-35000 kg / cm ^2, in Example 5, 25,000 to 30,000 kg / cm ² in Example 6 30000-35000 kg / cm ^2, in Example 7 30,000 to 35,000 kg / cm ² and in Example 3 35,000 to 4,000 kg / cm ² .

The reaction conditions and the corresponding results are summarized in the following table.

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Table I.

Added latex

at
game Polymer Polymer medium partial
Concentration size
fa _{/ U} 0.3 lienge
cm3 k PVC
ET 75 C 33 0, ü6 100 5 Gopolymerisat
Vinyl chi or id-
Vinyl acetate
90 / 1O _n
ET 65 G 30th 0.05 100 6th Polymethyl
methacrylate
ET 105 C 20th 0, o5 (80
(160 7th Polystyrene
ET 81 ⁰ G 35 0.06 100 β Terpolymer 35
Styrene / acrylonitrile /
<· * »-Methyl stvrol
Ρ.ύ / 10 / lo
around λ -ι c. "η 100

Comparative experiment 1 a

Table I (continuation)

Own: the received Products at
game stocks A. Index of
B. Klunroenbildung
CG
(50 h) iv Bulk
v / ot 10 10 8th 5 0.35 ■ 10 8th ό 6th 0.35 10
ok 10
10 6 6
8 6 7th 0.3 -
0.3 - 10 10 8th o, 3 - 10
0 10
BATH ORIGINAL
υ 8 0.3 -
Comparative
y he * ouoh
1 a 0.16 - - ο, Ί-5 0.35
0.35 0.35 0.35
■ 0.19

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Example 9

According to Example 1, a PVC latex was produced. The unreacted vinyl chloride was degassed, the autoclave contents to 20 ⁰ C cooled, treated with 0.3 g of ethylenediaminetetraacetic acid Hatriumsalz and then a mixture of 1 000 grams of distilled butadiene and 1000 g of methyl methacrylate was added. The reaction mixture was heated to 60 ° C. and kept at this temperature until the relative pressure was 2 bar. Thereupon, the unpolymerized butadiene was degassed, cooled the reaction medium to 20 ⁰ C and treated with a solution of 10 g üibutyl-p-cresol in 50 cnr dichloroethane.

A portion of the latex obtained was coagulated by adding, at room temperature and with stirring, three times the theoretical amount, based on the emulsifier used, to an HgCl ₀ solution. The polymethyl methacrylate latex according to Example 2 was then added.

The product obtained was spun off, washed and dried. Its bulk density was 0.3ö the lump formation index was 10 (test A), or /. lü (experiment B), or 3 (experiment C).

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A comparative test according to the prior art was carried out on the other part of the latex obtained. The latex was coagulated like ζμνοΓ and heat-treated at 8 ° G for 15 min. The polymer sat down away; it was spun, washed and dried. The bulk density was 0.18 g / cnP; the index of clumping bet mg 6 (experiment A) and υ (experiment B).

Example 10

A PVC latex according to Example 1 was produced. The unreacted vinyl chloride was degassed, cooled to 20 ⁰ of the iieaktorinhalt G and treated with 0.3 g of Natriumsais iithylendiamintetraessigsäure and then a mixture of 2000 g of freshly distilled butadiene, styrene New York Convention fjL'O g 500 g of acrylonitrile was added. The mixture was heated to 70 ° C. and held at this temperature until the pressure reached 1.5 bar. The unpolymerized butadiene was degassed and. the emulsion is mixed with a solution of 10 g of trinonyi phenyl phosphite in 50 cm ^ dichloroethane while stirring.

A portion of the obtained latex was coagulated by adding an alum solution at room temperature in a three-fold theoretical amount with stirring. Thereupon Iu Ge \; .- / j, based on the graft polymer, polyiriethyl methacrylate were added in Example y in the form of the latex with 2 u ; j solids and average particle size

^109848/1382

0.05 / U added.

The polymer obtained was spun off, washed and dried. Its bulk weight was included 0.38 g / cm, * the lump formation index was 10 (experiment A) or 10 (experiment B).

For comparison, the other part was made of latex coagulated as before, but then heated to 80 ° C. for 15 min. The product was spun off, washed and dried. Its bulk density was 0.17 g / cnr; the lump formation index was 0 in experiment A and 2 in experiment B.

Example 11

In a 16 liter stainless steel autoclave equipped with a stirrer, 9 liters of deionized water, 50 g of lauryl alcohol sulfate, 2 g of potassium persulfate, 1 g of potassium mettaabisulfite, up to pH 9, i * - 9.5 and 2,500 g of vinyl chloride were placed. The reaction mixture was ^{heated to 55 °} C. and kept at this temperature up to a pressure of k bar. Then, the unreacted vinyl chloride was degassed and cooled the reactor contents to 20 ⁰ G.

A solution of 25 g of sodium pyrophosphate was obtained and 3 g NaOH in 100 CiP water, a solution of 25 g

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Glucose and 0.225 g iron (III) nitrate in 100 em ^ water, 1,500 g freshly distilled butadiene, 500 g ethyl acrylate, 500 g styrene and 50 g divinylbenzene washed with $ * ÖB were added. The Reakbi onsgemiscii was heated to 40 ⁰ C and held for 10 h "at this temperature. The degree of conversion 95 Thereafter amounted to 97 $» The reactor contents vrurde 20 ⁰ G cooled and cm, a solution of 15 g of dibutyl-p-cresol in 100 ^ Part of this latex was coagulated with three times the theoretical amount of GaGIg solution, based on the emulsifier used, and 10% by weight, based on the graft polymer, of PVC in the form of its latex with 3% pesticides and the middle Particle size 0.1 / u mixed. The freezing point of the PVG was about 75 ° C, the modulus of elasticity and tension was 29,000 to 35,000 kg / cm ^2. The latex was emulsion polymerization at 50 G in the presence of 0.5 wt. -> j potassium laurate, based on the ionomer, has been produced,

The product obtained was spun off, washed and dried. Its bulk weight was 0.36 c / cm- ^; the lump formation index was in Experiment Λ and in experiment B 10 each.

By comparison, the other part of the latex was coagulated as before and then heated ^{to CO 0 C for 15 min.}

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The centrifuged, washed and dried product had a bulk density of 0.16 g / cnr and an index lump formation 8 in test A, or 2 in test B.

Example 12

A graft polymer was prepared as in Example, but the quantitative ratio of the monomers was chosen so that the graft polymer was 5 parts by weight of vinyl chloride units, h parts by weight of butadiene units, 1 part by weight of acrylonitrile units, 0.25 part by weight of styrene units and 0.25 parts by weight of divinylbenzoleinlÄten contained.

The graft polymer according to Example 11 treated with the PVC latex according to Example 1 and the product obtained had a bulk density of

ü fkZ g / cm j the index of the lump formation in test B was 10.

For comparison, part of the polymer latex was treated according to comparison experiment 1c. The product obtained had a rubble weight of L-, 25 pi / cm ^J \ its lump formation index was 2 in test B.

if
Also are the graft polymer latex before

Coagulate 50 ) Ό PVC latex was added, resulted in the

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Trial B for the clumping index only that Value 6 and the bulk density was about 25 g / cm.

Examples 13 to 16

According to Examples ^ to 8 was a graft polymer produced and the latex obtained divided into several parts, which are at room temperature by adding a CaClg solution in threefold theoretical amount, based on the emulsifier used, were coagulated.

Each portion of the coagulated latex was given an aqueous PVC emulsion, each with a different viscosity index added. The viscosity index was determined in accordance with the French standard MF T 51 013.

These different PVC grades had the same freezing point of 75 ° C and a similar modulus of elasticity under tension between 29,000 and 35,000 kg / cm ² .

The different latexes of the anti-caking polymers were prepared as follows: Example 13: polymerization at 58 ⁰ C in the presence of 2 parts by weight j5 Hatriumstearat, based on the monomer J Example 1 * 1: emulsion polymerization at 40 ° C in the presence of 1 wt. - # liatrium dodecylbenzenesulfonate,

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based on the monomer; Example 16: polymerization in a fine suspension at 39 ⁰ C in Gegenviart of sodium laurate and soluble in organic media catalyst. The polymer latex in Example 15 was produced according to Example 1.

The test conditions and the corresponding results are summarized in the following table and the results of comparative tests compared, in which the same PVC latices the latex of the graft polymer before coagulation were added.

Table II

For PVC medium PVC viscosity PVC used game particle size index based on

/ ^u graft polymer by weight - ^c fi

110 5

175 5

160 2

15 0.8 130 5

12th 0.03 13th 0.05 IV 0.3

Comparison search 0.03 HO 10

50

0.05 175 10

0.3 lüO 10

20th

0.3 100 10

20th

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10 2
6th 1 Table II (continued) - 0.38 10
10 6th
8th at
game Products received
Bulky weight index of lump formation
ß / cm3 Experiment A Experiment B Experiment G - 0.30
- 0.30
■ 0.38 10
10
10 8th
10
10 8th 12th 0.28
0.35 - 10
10 10
10 8th 13th o, 27
0.33 - 6th
8th 0
6th 0
0 14th 0.28 -
0.28 -
0.35 - 6th 0 0 15th 0.30
0.48 8th
8th 0
2 0
0 Comparison
try 0.19
0.33 8th
8th ü
0 ü
0 0.20 0.19
0.23 0.19
0.23

Claims

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Claims (1)

DB. ING. F. WUESTHOFF β MUNICH 8O DIPL. ING. G. PULS SCHWBIGSRSTRASSE \ »B.E. v. PECHMANN TKlFO * »IMI1 PATENT LAWYERS TEIiIGUMlUDUB> l FlOTlCMATm IA- 3'I- 137 Pat enta η sayings 1. light-clumping, free-flowing, granular j / graft polymer, thereby g e k e η η ζ ei c h η e t that the 6? up to 99, single grain from a core of / preferably 91 Mn 98 wt clumping graft polymer and a shell of 33 to 1, preferably 9 to 2% by weight per year of non-clumping free-flowing a Polymer and the bulk weight 0.3 to 0.5 g / om- amounts to. 2. A process for the preparation of the graft polymer according to claim 1 by treating a clumping graft polymer with a non-clumping polymer , characterized in that the latex of the graft polymer is coagulated and then with the latex of the non-clumping polymer with stirring and preferential prices at a temperature of 0 to kO G mixed, whereupon the product obtained is separated off, washed off and dried. 3. The method according to claim 2, characterized in that, based on the graft polymer, 1 to 50, preferably 2 to 10 Gev, ^T .-;> non-clumping polymer, calculated as a solid, is used. BATH ORIGINAL 109846/1382 IA-34-187 k. Process according to Claim 2 or 3, characterized in that a non-clumping polymer with a glass transition point above O ⁰ G, preferably above 3O ⁰ G and a modulus of elasticity below ο
Tensile strength above 1,000 kg / cm, preferably above 10 kg / cm used. 5. The method according to claim 2 to k, characterized in that a latex of the non-clumping polymer with a particle size between 0.01 and 10 / U, preferably between 0.3 and 0.8 / U, is used. ό. Process according to Claims 2 to 5, characterized in that the non-clumping Polymer The polymers and copolymers of vinyl compounds and / or the polymers and copolymers of olefins and vinyl monomers are used. 7. The method according to claim 2 to 6, characterized in that there is a graft polymer used, whose main chain contains halogen atoms and whose side chains by grafting a diolefin with conjugated double bonds, optionally in conjunction with a vinyl monomer. 8. Use of the graft polymers according to claim for improving the notched impact strength of brittle ones thermoplastic hating. 109846/1382