DE1694602A1 - Self-extinguishing thermoplastic compound - Google Patents

Description

The subject of the invention are new self-extinguishing polymer masses, which look by a high strength as well as a are characterized by great rigidity and high inflexion temperature under load.

It has already been proposed to create self-extinguishing thermoplastic sole-resistance compounds in the porosity of mixtures of different resins, especially using the following main components:

A polyvinylchloride resin with less than chlorine content 58 pounds and a much higher inflation temperature Load than the non-plasticized polyvinyl chloride of same molecular size,

an oil polymer of a conjugated diene with an un-. saturated nitrile, i.e. a refined polymer that

- ■ 1 - ■ 109831/1644

: '' 3 documents (Art. 7, Paragraph I, Paragraph 2, No. I, Clause 3 of the amendment, v.

Μ / 8462

by polymerizing a monomer mixture.es of styrene and Acrylonitrile is obtained in the presence of a preformed elastomer of the polybutadiene type or a butadiene acrylonitrile ! copolymer or a butadiene acrylate copolymer,

a styrene-acrylonitrile copolymer as a rigid and hard one thermoplastic resin.

For some time now ABS resins have been known which are resistant to higher temperatures than the normal types and which are therefore e ± as thermoresistant. I ^{1 In} addition to butadiene and acrylonitrile, α-methylstyrene, which completely or partially replaces styrene, is used for the production of the thermally resistant ABS resins.

The presence of the OH groups in the main chain of the resin copolymer causes an increase in its vitreous transition temperature and therefore a high inflexion temperature when the mixture in question is contaminated. On the other hand, the thermoresistant ABS resins are with the same content of the elastomeric component is generally less resistant than the normal.

P It has now surprisingly been found that the mixture is a thermoresistant ABS resin with a polychlorovinyl resin (which for the sake of simplicity in the text also as PolyvinyüciL-Chlorid - PVDO - is called) self-extinguishing thermoplastic Results in masses which, compared to analogous mixtures with normal ABS resins, apart from a higher heat

^! have a significantly higher impact resistance.

^s The chemical or physical reasons for this unexpected result are yet not fully understood, there are jedooh reason to believe that they are doing in a different compatibility of the individual components with one another in the mixture.

- 2 109831/1644

16946Ü2

M / 8462 i

The self-extinguishing masses according to the invention, which are characterized by high strength and high heat resistance, contain three main components in the mixture, which, for the sake of simplicity, are designated in the text with the letters A, B, - 0 will.

Component A of the invention consists of a Polychlorvinylharz having a chlorine content from 58 to 73 $> and a Inflextionstemperatur under load, which is considerably higher than that of the non-plasticized polyvinyl chloride of the same molecular size.

There are preferably polychlorovinyl resins with a chlorine content from 60 to 68 # used as resins with a higher Chlorine content cause considerable work difficulties.

There are no precise limits on the molecular weight of the chlorinated vinyl resin · Within a very wide range (e.g. for values from 0.4 to 1.5) the intrinsic viscosity (the is an indirect measure of molecular weight) all chlorinated vinyl resins are suitable for the purposes of the invention.

Palis vinyl resins with a very high chlorine content are used it may be appropriate to reduce the intrinsic viscosity, to get better working conditions «

These products can be manufactured in different ways which are not the subject of the invention.

As an example, the following procedures are: the photocrhemisehe chlorination of granular polyvinyl chloride in aqueous suspension at a temperature lower than 6O ⁰ C, the chlorination of granular polyvinyl chloride in aqueous suspension at a temperature of 60 bit 100 ⁰ C in the absence

1ÖS831 / 1644

M / 8462 If.

Essence of oxygen and under superatmospheric pressure, the chlorination of granular polyvinyl chloride in aqueous suspension "at a temperature lower than 7O ⁰ C, in the presence of a suitable Eadikalkatalysators, such as a peroxide compound or Azobiisobutyraitril.

Instead of a granular PVC ¹ S, it is also possible to use an emulsion of this polymer, which precipitates in the form of a very fine powder in the course of the chlorination. In some cases it is appropriate to add a swelling agent of the polymer, such as chloroform or another chlorinated hydrocarbon, to the suspension.

Instead of the polyvinyl chloride it is also possible to use any of its copolymer lsates with a vinyl chloride content of at least 75% by weight can be used.

Component A can also be a mixture of PVDC and PVC, in some cases the mixture mentioned is advantageous because it is easier to process compared to pure PVDC same total chlorine content.

Component B of the mixtures is a rubber-like polymer, this is usually used for the production of the usual ABS materials is used, it can be a copolymer of a conjugated diene of the following formula:

R ₉ -C = CC = CR- (I)

^ά ι ι t ι 5
HRR ₁ H

in which R = H, CH ₃ , Cl, R _x and R ₂ = H, CH ₃ , R ₃ = H, CH ₃ , COOH is with an unsaturated Mtrile of the following formula:

R.
CH ₂ = C - CN (II)

- 4 -10983171644

1494602

Μ / 8462 ζ

where R = H, OH ₅ , CpH, -, the amount of the unsaturated diene generally varying from 55 "to 85 parts by weight and that of the unsaturated nitrile thus varying from 15 Ms 45 parts by weight.

It is advantageous that the copolymer is a suitable one Networking through any of the known ways of working, 25.B. by introducing a small amount of divinylbenzene into the polymerization mixture is obtained.

The rubber-like copolymer can also contain small amounts of other vinyl monomers, such as acrylic and methacrylic esters etc., included.

The rubber-like polymer can also be a refined poly be merisate, which is obtained by polymerizing a mixture of unsaturated monomers from one or more aromatic vinyl monomers of the following formula III:

σ = CH ₂ (in)

wherein R = H, CH * and R ₁ , R ₂ = H, CH *, 'Cl, and from,; one or more unsaturated nitriles of the formula II in the presence of a preformed elastomer which is obtained from a conjugated diene of the formula I and optionally a small amount (from 0 to 20 56) of the monomers contained in the formulas II and III j. I.

The weight ratio between the monomer mixture and des preformed rubbery copolymer (calculated trooken) is between 90/10 and 20/80, preferably between

109331

1094602

M / 8462 6

90/10 and 40/60, the weight ratio between aromatic Vinyl hydrocarbon and unsaturated nitrile is between 80/20 and 55/45.

Finally, component B can be made from a refined polymer a monomer mixture of an aromatic vinyl monomer of the formula III and an unsaturated nitrile of the formula II on a preformed copolymer of a conjugated Diene of the formula (I) (90-30 parts by weight) and an alkyl acrylate (10-70 parts by weight) of the following formula

CH ₂ = CH = COOE (IV)

wherein R is an alkyl radical with a straight and branched one Chain with 1 "to 12 carbon atoms," consist of ·

The weight ratio between the monomer mixture and the preformed rubber-like polymer (calculated dry) is between 90/10 and 20/80, preferably between 90/10 and 40/60, the weight ratio between aromatic vinyl hydrocarbon and unsaturated nitrile is between 80/20 and 55/45.

A refined tetrapolymer of this type and its manufacturing process are described in the applicant's Italian application 49 585 of July 31, 1964.

Numerous processes for the production of these rubber-like polymers have been described, for example in emulsion or solution or other methods.

The products obtained show some difference in properties. In the range of the dimensions described above are, however, all suitable to the substances according to the invention

- β 109831 / 16U

M / 8462

just as they are suitable for the production of conventional ABS materials.

However, it can be observed that the diene-acrylic ester rubber refined polymers "better usable materials with a "better surface appearance."

In addition to the individual rubber-like polymers, of course mixtures of these are used in any ratio to prepare the compositions according to the invention.

Component C of the mixtures is a rigid and hard thermoplastic resin obtained by copolymerization from 50 to 80 parts by weight of α-methylstyrene and 20 to 50 Parts by weight of one or more unsaturated nitriles according to formula II, i.e. by copolymerization of 50 to 80 Parts by weight of a mixture of α-methylstyrene and an aromatic vinyl monomer according to the formula III and 20 to 50! Parts by weight of one or more unsaturated nitriles according to i of the formula II.!

Rigid copolymers of this type can be produced by emulsion, Block, solution and suspension polymerization can be produced. The properties of these products range from that mentioned The masses are essentially the same and the use of them is obtained by the different procedures Products is alternative.

In order to obtain masses that are easy to process, it is advisable to that the molecular weights of the copolymers are such that the product in the molten state a has low viscosity. Therefore, polymers with an intrinsic viscosity between 0.35 and 0.7 are particularly suitable for the purpose of the invention,

100831/16 * 4

Μ / 8462 Ο

The components B and G can also contain small amounts (Ms to 10 io of the total) of monomers which differ from those described above, without therefore significantly changing them or their mixtures, which are prepared according to the invention. Therefore, the use of components B and C with these changes and the mixtures obtained remain within the scope of the invention.

In addition to the main components mentioned, thermal stabilizers and antioxidants are generally added to the mixture added, numerous other additives can be used as absorbents for ultraviolet rays, pigments, dyes, Fillers, lubricants, etc. can be added.

Examples of these secondary components are: dibutyltin maleate, Lead salt of organic acids, 2,2-methylene-bis- (4-methyl-6-tert-butylphenol), ! hiobis- (disec.-amylphenol), trialkyl-arylphosphites, Stearic acid, carbon black, cadmium yellow, silicon dioxide, glass fibers, linear polyesters, epoxy oils.

The amounts by weight in which the three components A, B and 0 are present in the mixture are, as described above, adjusted so that all the desired properties, i.e. the Self-extinguishing, high deformation temperature and strength along with a high rigidity.

In order to make the mixtures self-extinguishing (based on ASTM D 635) it is necessary that they contain at least 30 parts by weight of component A per 100 parts by weight of the sum of the components. Component A is therefore used in amounts between 30 and 95 # by weight of the mixture.

Component B is used in amounts between 5 and 70 wt .- # of the mixture and components 0 in amounts between

109831/1644

M / 8462 g

.0 and 60 wt .-% of the mixture used.

The masses in which the component G is not specifically added will form a special pail, which is one of the objects of the invention. This is the lall in which the component B by refined polymerization of a mixture of monomers with α-methylstyrene in the presence of any of the preformed ones Elastomers, which were previously described in the description of component B, is obtained, then forms namely, a corresponding amount of a compound corresponding to component G itself. The manufacture of the Mixing can be carried out by any method known to those skilled in the art. So you can use the polymer powder dry mix and then mix them in open cylinder mixers or in closed mixers of the type Melt the Banbury and Buss KoKneader mixers.

The latices and the suspension of the polymers can also mixed, immediately dried or coagulated, then the product obtained is dried and then melted be placed in open or closed mixers.

Finally, it is possible to use solutions of the polymers and to separate them in a known way.

It is necessary to try to get a complete mixture of the substances, since the physical and mechanical Properties are influenced by an imprecise mixing process.

The following examples illustrate the invention. Also the production of intermediate products which are required for the products according to the invention only has the character of examples. Therefore, they do not indicate the only way to carry them out.

- 9 1Ö9831 / 16U

M / 8462

Throughout the examples and in the text "the specified relate Quantities based on weight, unless expressly stated otherwise.

The polyvinyl dichloride prepared according to Example 1 and 2 is 173 (tin mercaptide) and 1.5 9δ Thermolite 13 (dibutyltin maleate), or with other thermal stabilizers analog stabilized with 1.5 $> STANCLERE.

The rubber-like polymers produced according to Examples 4, 5 and 6 are 1.5% (calculated on the dry product) Santowhite L (thio-bis-disec.-amylphenol) stabilized, other analogous antioxidants can be used with the same results.

The physical-mechanical properties determined on Preßformblättern at 20 ° to 210 ⁰ C by heating the sheet for 10 minutes and let rest at a pressure of 200 atm. determined during 5 minutes.

The labeling of the products was carried out according to the following information:

- intrinsic viscosity, defined by the following relationship: -

η spec, - [- η.] = lim - - where

C C ■) O

7 [ ο = viscosity of the solvent
ηχ = viscosity of the solution
c = concentration of the polymer, expressed in g / 100 ml

- 10 -

109831 / 16U

1594602

M / 8462

The solvents used for the chlorinated vinyl resin and the polyvinyl chloride were: tetrahydrofuran ("at 22 ° C.), for the styrene-acrylonitrile copolymer and for the α-methylstyrene-acrylonitrile copolymer: dimethylformamide (" at 22 ^° C.).

-Izod-T _e st according to ASTM D 255-56 -Rockwell hardness according to ASTM D 785-51 -flame resistance: according to ASTM D 635-56

-Vicatgrad: according to ASTM D 1525-58 T using a load from 5 kg.

example 1

This example describes the production of polyvinyl chloride using an alkali catalyst. In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, There is a suction pump for the suction of gases and a discharge valve for the reaction and excess gases, a suspension is introduced with the following composition:

-Polyvinyl chloride (produced in 195 parts by weight of suspension) -H ₂ O ^ 575 "

-HCl (100 #) '125 ^tt

-CHCl ₃ 105 »

-Azobisisobutyrnitril 2 ⁿ

and the chlorination of the resin is carried out under the following conditions:

- 11 -

109831/1644

Μ / 8462 ή%

Temperature 45 ⁰ C
Pressure 1 atm.

Cl ₂ supplied
per 1 kg of suspension 35 g / h

At the end of the reaction, the chlorinated polymer is through Filtration separated from the suspension, then with a solution of sodium carbonate and then with water and methanol washed and finally dried.

Table I shows the properties of the PVC used, the Duration of chlorination and the properties of the PVDC obtained.

Example 2

This example shows the production of polyvinyl dichloride described using rays. In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, suction pump, A suspension is provided for the suction of gases and a discharge valve for the reaction and excess gases imported with the following composition (per kg):

Polyvinyl chloride (prepared in suspension and with [Tl] = 1.09) 195 g

H ₂ O 575 g

CHCl ₃ 105 g

HCl 125 g

The suspension is then chlorinated by introducing gaseous Cl ₂ at a rate of 35 g per 1 kg of suspension / h for a period of 4 hours, during which the reaction mass is kept at 45 ^° C. with stirring.

- 12 -

1Ö9831 / 1SU

! Datelle I j ^

PVDG [ti jj des used duration of the chlorine properties of the obtained PYO dl / «rung, min. Product

σΐ CnI

* dl / g

180 62.8 1.06

180 62.8 1.06

240 63.7 1.00

240 64.1 1.15

270 64.7 1.2

300 65.2 1.06

300 65.2 0.56

I. I. 1.09 O H
Ul II 1.09 co
OO I. III 1.09 31 / rv 1.09 en 7th 1.09 YI 1.09 VII 0.6

Oi OK)

M / 8462 W.

When introducing the chlorine, the reaction vessel is exposed to the rays of a mercury arc lamp of the Philips HPK type of 125 W. The suspension obtained at the end of the reaction is filtered and the solid product is mixed with a 5% solution washed by sodium carbonate and then with water and methanol and then dried.

The product obtained has the following properties: Cl content $> 64.6
[i \] dl / g 1.05

Example 5

This example shows the production of the styrene-acrylonitrile copolymer described.

In an oxygen-free pressure reaction vessel with a stirrer and thermometer, a reaction mixture is introduced with the following composition:

Parts by weight

Styrene 72.5

Acrylonitrile 27.5

Sodium alkyl sulfonate 2.0

tertiary octyl mercaptan 0.40

Ammonium persulfate 0.1

Sodium metabisulphate ° t ° 2

Water 300

It is polymerized between 20 ° and 75 ⁰ C, where the temperature may increase at the expense of the heat of reaction. The U _m-setting time is 1 hour. The remaining monomers are removed. Then the latex is diluted with a

- 14 -

109831/1644

1.W4602

Μ / 8462

CaClp solution "coagulated at boiling temperature, then is centrifuged, washed with hot water and dried. The product obtained shows the following properties:

Acrylonitrile% about 25

intrinsic viscosity dl / g 0.5

Example 4

This example shows the production of the butadiene-acrylonitrile copolymer ". The following reaction mixture is placed in a pressure vessel equipped with a stirrer and thermometer introduced:

Weight Butadiene .-Parts Acrylonitrile 79 Divinylbenzene 21st Potassium salts of modified resin acids 1 Sodium salts of condensed naphtha
linsulfonic acids 3 MiDM (mixture, from Phillips tertiary mercap-
tan) 0.5 Sodium pyrophosphate - 0.4 Ammonium persulfate 0.25 Sodium metabisulfite 0.3 water 0.1 150

The mixture is ^{heated at 45 °} C. and the reaction is carried out, Ms a conversion of about 95 $> is obtained. The remaining butadiene is degassed from the latex obtained, then the latex is coagulated with dilute calcium chloride solution and the grains are filtered and dried in a hot air oven. The product obtained has the following properties:

- 15 -

109831/1644

1594602

M / 8462 4fe

Acrylonitrile content 22 #

Mooney Viscosity ML (1 + 4) x 80

Jelly insoluble in methyl ethyl ketone 70 $>

Example 5

This example shows the production of the refined polymer of styrene-acrylonitrile on polybutadiene ".

In one provided with a stirrer, thermometer and reflux condenser A reaction mixture of the following composition is introduced into the reaction vessel:

Parts by weight

Acrylonitrile 11

Polybutadiene latex produced in emulsion (dry 60 #) 100

Styrene 29

Sodium alkyl sulfate 1.4

Ammonia (30 #) 0.22

Ammonium persulfate 0.3

Sodium metabisulfite 0.025

Water 110

The mixture is ^{heated to 50 0} O, the catalysts are introduced and the temperature is allowed to rise while utilizing the heat of reaction.

The reaction is completed in about 5 hours.

The latex obtained in this way is stabilized with 1,56 phenol antioxidants (calculated on the dry polymer) and is; with a dilute calcium chloride solution, coagulated. The obtained grains are filtered and dried in an air oven,

- 16 - I.

109831 / 164V

M / 8462
Example 6

This example shows the production of the refined polymer of styrene-acrylonitrile on the previously formed butadiene-ethyl aerylate copolymer deserved.

The following reaction mixture is introduced into a pressure vessel equipped with a stirrer and thermometer:

Weight-horny

Butadiene 50.0

Ethyl acrylate 50.0

deionized water 70.0

Sodium alkyl sulfonate 2.5

Sodium salt of condensed naphthalenesulfonic acids 1.0

GiDM 0.25

Sodium pyrophosphate 0.5

Ammonia ( $ 30>) 0.2

Ammonium persulfate 0.35

Sodium metabisulphite 0.1

The mixture is ^{heated to 50 °} C. before the reaction with the catalyst. The reaction has practically ended after 45 hours. After the remaining monomers have been removed, the rubber latex produced in this way is subjected to a finishing polymerization in a reaction vessel equipped with a stirrer, thermometer and reflux condenser. For this purpose, the following mixture is introduced into the reaction vessel:

- 17 -

109831/1644

Parts by weight 2 60 150 1 3 ο, 05 29 11 ο, ο,

M / 8462 W.

Polymer latex (dry basis) deionized water (including the water contained in the latex) Sodium alkyl sulfonate ammonia (30 #) Styrene

Acrylonitrile

Ammonium persulfate sodium metabisulfite

The reaction mass is ^{heated to 50 °} C. before the reaction with the catalyst. The reaction has ended after 4 to 5 hours.

The latex obtained in this way, stabilized with 1 fi Santhowhite 1, calculated on the dry tetrapolymer, is then distilled in a stream of steam and coagulated by adding a dilute calcium chloride solution.

The solid product obtained is dried in a hot air oven.

Example 7

In an oxygen-free pressure vessel with a stirrer and thermometer is provided, a reaction mixture of the following composition is introduced:

α-methylstyrene acrylonitrile
Sodium alkyl sulfonate

Sodium salt of a naphthalenesulfonic acid condenses with formaldehyde

n-Octylmeroaptan ammonium persulfate sodium metabisulfite

Water ^ ww _Ί ο

- Io -

109Ö3 1 / -1.6U

Parts by weight , 5 72 , 5 27 3 , 5 O , 3 O , 3 O , 04 O 300

M / 8462 13

It is polymerized between 4-0 ° and 75 ⁰ C, where the temperature is allowed to rise by utilizing the heat of reaction, but then maintains one hour at 75 ° C. The total reaction time is 4 hours, the residual monomers are removed and the latex is coagulated with a 0.5 # calcium chloride solution at a temperature of 110 ° to 130 ⁰ G under pressure.

The cloudy mass obtained is centrifuged and the polymer is washed with M.ßem water and dried.

Example 8

In an open cylinder mixer, the mixtures are prepared with the indicated in Table II compositions (other than the stabilizers and other auxiliary substances), wherein the components are homogenized for 20 to 30 minutes at about 180 ° to 200 ⁰ C. The polyvinyl dichlorides used in the preparation of the mixtures were obtained according to the procedure described in Example I / III.

The refined polymer of styrene-acrylonitrile on polybutadiene, the styrene-acrylonitrile copolymer and α-methylstyrene Acrylonitrile copolymers were prepared according to the procedures of Examples 5, 3 and 7 in each case.

i The physico-mechanical properties of the mixtures are;

shown in Table II. ;

Experiment a) relates to the properties of polyvinyl chloride as such, experiments b), d) and f) on the properties of the compounds with styrene-acrylonitrile copolymer and serve as a comparison, experiments c), e), g) relate to the properties of the compounds containing a-methylstyrene acrylonitrile copolymers contain and explain the invention.

- 19 109831/1644

Table II

Dimensions

O CiO QO CO

to

Styrene-acrylonitrile copolymer, parts by weight

a-methylstyrene-aorylnitrile copolymer, Parts by weight

Refined polymer of styrene-acrylonitrile on polybutadiene, parts by weight

Polyvinyl chloride, parts by weight

O 7.5 O 10 O 15th 0 O O 7.5 O 10 O 15th O 7.5 7.5 • 10 10 15th 15th 100 85 85 80 80 70 70

properties

Izod test

Bockwell hardness Tieat degree (5 kg) self-extinguishing

, cm / cm at 23 ⁰ C

R scale o "

3.8 45 50 77 65 80 80

124 120 121 118 119 .116 116

113 110 113 111 115.5 109.5 114.5

s ss ssss

β - Self-dissolving

M / 8462

It will be found that the mixtures with α-methylstyrene acrylonitrile copolymer (Trials e, c, g), although they have essentially the same physico-mechanical properties compared to the mixtures with styrene-aeryl nitrile copolymer (Experiments Td, d, f) show show better thermal properties.

Example 9

In an open cylinder mixer with the mixtures indicated in Table III compositions were prepared (except for stabilizers and other auxiliary substances) by the components are homogenized for 20 to 30 minutes at 180 ° to 200 ⁰ C.

The polyvinyl dichloride used in making the blends was obtained according to the procedure described in Example I / V.

The refined polymer of styrene-acrylonitrile on polybutadiene and the styrene-acrylonitrile and α-methylstyrene-acrylonitrile copolymers were prepared following the procedure of Examples 5, 3 and 7, respectively.

The physico-mechanical properties of the blends are described in Table III.

Experiments b) and d) relate to the properties of the mixtures with the styrene-acrylonitrile copolymer and are used for comparison purposes; experiments a) and c) relate to the properties of the mixtures with the α-methylstyrene-acrylonitrile copolymer and explain the invention.

These tests show that the latter mixtures have significantly improved properties compared to the first and also

- 21 109831 / 164.4

M / 8462 J.

in relation to a heat-resistant ABS resin obtained on the basis of the same components B and C (test e_ as a comparison).

- 22 -

1 0 9 8 3 1/1 6

ro

Tabel

III

composition

α-methylstyrene acrylonitrile copolymer Parts by weight

Styrenyl nitrile copolymer Weight 3ELIe

Refined polymer from Styrolacryl-Stril on polybutadiene, parts by weight polyvinyl dichloride, parts by weight

properties

Izod-Iest

23 ⁰ C

O ⁰ O

20 ⁰ O

Eo ctarell hardness e Yioat grade (5 kg) Self-redemption

kg.cm/cm

R scale

45 0 25th 0 0 45 0 25th 25th 25th 25th 25th 30th 30th 50 • 50

75

25th

30th 18th 43 27 18th 11 10 24 21st 11 9.3 7.7 12th 12th 6th 108 107 107 105 106 115 103 116.5 105 112 S. S. S. S. separates

1694.802

M / 8462 ™ * t

Example 10

In an open cylinder mixer with the mixtures indicated in Table IV compositions are prepared (except for stabilizers and other auxiliary substances) by the components are homogenized for 20 to 30 minutes at 180 ° to 200 ⁰ O.

The polyvinyl chloride used in experiments a) and c) was prepared according to the procedure described in Example 2. The polyvinyl dichloride used in experiments b) and d) was prepared according to the procedure described in Example I / V obtain.

The refined polymer of styrene-acrylonitrile on polybutadiene and the α-methylstyrene-acrylonitrile copolymer were according to the procedure described in Examples 5 and 7 manufactured.

The physico-mechanical properties of the mixtures are described in Table IV.

These experiments show the use of a polyvinyl chloride, obtained by chlorinating PVC with ultraviolet rays instead of catalysing it with azobisisobutyrnitrile.

- 24 109831 / 16U

labile

composition

α-methylstyrene acrylonitrile copolymer GTil

refined polymer of styrene acrylonitrile on polybutadiene, parts by weight

Polyvinyl chloride (Example 2), parts by weight Polyvinyl dichloride (example I / V), parts by weight

45 25th 25th 25th 25th 25th 50

properties

Izod test

Rockwell hardness Vicat grade (5 kg) Sella branch extinction

23 ⁰ OO ⁰ C -20 ⁰ C 50

kg.cm/cm 31 30th 26th 43 - 11 15th 24 - 9 15th 12th E scale 113 108 112 107 ⁰ C 121 115 119 117 S. S. S. S.

CD Oi -P-Ct O

1694SQ2

M / 8462 <5 ^

Example 11

In an open cylinder mixer with the mixtures indicated in Table V compositions are prepared (except for stabilizers and other auxiliary substances) by the components are homogenized for 20 to 30 minutes at 180 ° to 200 ⁰ G. The polyvinyl dichloride used in the preparation of the mixtures was prepared according to the procedure described in Example 1 / IV.

The a-methylstyrene-acrylonitrile copolymer and the refined Tetrapolymer of styrene-acrylonitrile on butadiene-ethyl acrylate copolymer were prepared according to the procedure described in Examples 2 and / or.

The physico-mechanical properties of the mixtures are described in Table V.

The table shows the properties for comparison (tests a, b) the ABS impact-resistant substance, the refined polymer based on butadiene ethyl acrylate copolymer was produced, and compared to polyvinyl dichloride as such.

It will also be found that those with the refined tetrapolymer mixtures produced have a much glossier surface than that with the refined polymer of Mixtures made from styrene acrylonitrile on polybutadiene.

- 26 -

109831/1644

Table V .g

¹ 'o>

Composition ίΐ - -

cc-methylstyrene acrylonitrile copolymer

Parts by weight 75 - 45 ο

Refined polymer of styrene acrylonitrile on butadiene ethyl acrylate copolymer

Parts by weight * 25 - ^ p * ■?

Polyvinyldicloride, parts by weight - 100 30 50

properties

* - Izod test

Rockwell hardness, Vicat grade (5 kg)

23 ⁰ C kg.cm/cm 20th 4th 33 51 O ⁰ C - - 16 20th -20 ⁰ O E scale - - 8 Ms 9 11 ⁰ C 108 124 111 112 109 "to
110
burns 117
S. 115
S. 116
S.

¹ M / 8462 «If

Example 12

In an open cylinder mixer with the mixtures indicated in Table VI compositions are prepared (except for stabilizers and other auxiliary substances) by the components are homogenized for 20 to 30 minutes at 180 ° to 200 ⁰ C. The polyvinyl chloride used in the preparation of the mixtures was prepared according to the procedure described in Example I / I.

Bas a-methylstyrene-acrylonitrile copolymer was according to the in Example 7 prepared procedure described. The refined polymer of styrene-acrylonitrile on butadiene-acrylonitrile copolymer was prepared according to Example 5, using a latex of a copolymer brisate from 90 parts of butadiene and 10 parts Acrylonitrile is used instead of a latex based on a butadiene homopolymer. The latex was in emulsion manufactured and contains 58 to 60 # dry matter.

The physico-mechanical properties of the blends are described in Table VI.

The table shows the properties for comparison (search a, b) the ABS impact-resistant substance, which is made with the refined polymer and the resinous copolymer mentioned above and compared to the polyvinyl dichloride itself. Experiments c), d) relate on the substances according to the invention and show that even when using this type of ABS impact-resistant substance Products with good physico-mechanical properties that are self-extinguishing can be obtained.

- 28 -

109831 / 16U

T a b e 1 1 β YI

composition

α-methylstyrene acrylonitrile copolymer, parts by weight

Teredeltea polymer τοη styrene acrylonitrile on Butadienaorylnitriloopolj-

75

45

merisat, parts by weight Parts kg.om/oa 25th - 25th 25th ClO CD O
CD Polyvinyl chloride, wt. - 100 30th 50 -IC-
it*· properties 23 ⁰ C R scale IS » CT> I O ⁰ C ⁰ C 17th 6th 58 85 -E-- Izod test -20 ⁰ C - - 24 69 - - 15th 31 Eookwell hardness 109 125 110 110 Vicat degree 110 104 113 109 Self-extinction burns 8th S. S.

M / 8462 ok

Example 13

In an open cylinder mixer, the mixtures with the compositions indicated in Table VII (from the stabilizers and other elements) are prepared by ^{homogenizing the components at 180 ° to 20O 0} C for 20 to 30 minutes.

The polyvinyl dichloride used in the preparation of the mixtures was obtained according to the procedure described in Example 1 / YII. Bas refined polymer of styrene and acrylonitrile on polybutadiene and the a-methylstyrenaorylnitrile copolymer were prepared according to the in the examples 5 or 7 described mode of operation received.

Table YII shows that mixtures a and b, which contain a low molecular weight polyvinyl chloride, are self-extinguishing and have better properties compared to mixture c (comparative mixture), which contains no PYSC demonstrate.

- 30 -

109831/1644

Table VII composition

a-Methyletyrolaorylnitril-oopolymerisat, Parts by weight Refined polymer of styrene and aoryinitrile on polybutadiene »weight parts

Polyvinyl chloride, parts by weight properties

Iaod test Rockwell hardness Yioat grade (5 kg) self-extinguishing

23 ° C

kg.om/cm R scale 45

25th 30th

25 50

25 75

20th 28 18th 109 108 106 113 115 112 S. S. burns

Claims (1)

1. Self-extinguishing theraoplastic hatred of high Strength and resistance to high temperatures, characterized by (a) 30 to 95 parts by weight of a component A of a PoIyohlorvinylhara having a chlorine content from 58 to 73 £ _»t is preferably 60 to 68% and a Inflexionstemperatur] tei load considerably higher than that of the non-plastiaierten polyvinyl chloride with has the same molecular size, optionally mixed with polyvinyl chloride, (b) 5 to 70 parts by weight of a component B made of a rubber-like polymer, which can be: I. a copolymer of 55 to 85 parts by weight of one or more conjugated dienes of the formula (I) and 15 to 45 parts by weight of one or more unsaturated nitriles of the formula (II), which can optionally be linked and contain small amounts of other yinyl monomers, II. A refined polymer, produced by polymerizing 90 to 20 parts by weight of a honeycomb mixture 80 to 55 parts by weight of one or more aromatic yinyl monomers of the formula (III) and 20 to 45 parts by weight of one or more several unsaturated Hitrue of the formula (II) in the presence from 10 to 80 parts by weight of a preformed elastomer obtained by homopolymerization of a conjugated diene of the formula (I), i.e. by copolymerization of the same diene with small amounts (0 to 20 Jt) of the monomers shown in the formulas (II) and (III) are obtained, III. a refined polymer, produced by polymerizing 90 to 20 weight layers of a monomer mixture - 32 - 109831/1644 M / 8462 ^ 80 to 55 parts by weight of one or more aromatic vinyl monomers of the formula (III) and 20 to 45 parts by weight of one • the multiple unsaturated nitriles of the formula (II) in the presence of 10 to 80 parts by weight of a preformed rubber-like copolymer with 90 to 30 parts by weight of a conjugated diene of the formula (I) and 10 to 70 parts by weight of an 11 -kylaorylats of formula (IV), (o) 10 to 60 parts by weight of a component C from a rigid and hard polymer, produced by copolymerization γόη 50 to 80 parts by weight of α-methylstyrene and 20 to 50 parts by weight of one or more unsaturated nitriles according to the formula (II), ie duroh copolymerization of 50 to 80 parts by weight of a mixture of α-ethylstyrene and one aromatic vinyl monomer according to formula (III) and 20 to 50 Parts by weight of one or more unsaturated nitriles according to the formula (II). 2. mass near claim 1, characterized by (a) 30 to 95 parts by weight of polyvinyl resin as component Jl, (b) 5 to 70 parts by weight of component B, which can be: I. a refined polymer, produced duroh polymerization of 90 to 20 parts by weight of a monomer mixture from 80 to 55 parts by weight of α-methylstyrene or from its mixtures with other aromatic yinyl monomers of the formula (III) and 20 to 50 parts by weight Parts of one or more unsaturated nitriles of the formula (II) in the presence of 10 to 80 parts by weight of a preformed elastomer, the duroh homopolymerization of a conjugated diene of the formula (I), ie duroh copolymerization eyelet the same conjugated bee with small amounts (0 to 20 %) of the monomers shown in the formulas (II) and (III) are obtained, - 33 - 109831 / 16AA M / 8462 * II. A refined polymer produced by polymerizing 90 to 20 parts by weight of a monomer mixture from 80 to 55 parts by weight of α-methyl styrene or from mixtures thereof with other aromatic yinyl monoaers of the formula (III) and 20 to 45 parts by weight of one or more unsaturated nitriles of the formula (II) in the presence of 10 to 80 Parts by weight of a preformed rubber-like elastomer that 90 to 30 parts by weight of a conjugated diene of the formula (I) and 10 to 70 parts by weight of an alkyl aylate of the formula (IV) contains, (c) 10 to 60 parts by weight of component C formed as a by-product in the formation of polymer B. 3. Composition according to claims 1 and 2, characterized in that components B and C by amounts of less than 10 wt .- ^ of monomers, which are different from the by the Formula (I), (II), (III) and (IT) represented monomers are modified. 4. Hasse according to claim 1, characterized in that they are thermal stabilizers, antioxidants, lubricants, pigments, dyes, plasticizers, absorbents used for ultraviolet rays and others when working with plastics · auxiliaries included. - 34 - 1 09831/1