CS225121B2 - The shaping matter - Google Patents

Abstract

Thermoplastic moulding compsn. consists of (I) 70-30 pts. wt. thermoplastic polycarbonate, and (II) 30-70 pts. wt of a mixt of (a) 35-100 wt.% graft polymer obtd. by polymerising a mixt of 95-50 wt.% styrene and/or methyl methacrylate, and 50-5 wt.% acrylonitrile and/or methyl methacrylate onto a rubber, and (b) 75-0 wt.% copolymer of 95-50 wt.% styrene, alpha-methylstyrene and/or methylmethacrylate, and 5-50 wt.% acrylonitrile, methacrylonitrile and/or methyl methacrylate. The wt. ratio of rubber to monomer mixt. in (IIa) is 85:15 to 40:60, the graft copolymer in the compsn consists of particles having a dia. of 0.2-5.0 esp 0.2-1.0 mu, and the compsn. contains 10-35 esp. 10-30 wt.% rubber. Compsn. gives injection mouldings with a strong weld line, thus avoiding breakage during removal from the mould. Good mechanical and electrical properties.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to polycarbonate-based door materials.

In German Patent No. 1,170. 141 are described tverovací hmoOy which sestávvjí 90 EŽ 30% hmoonootních polycarbonate derived from the di / manohhdřoxyfenyVsubbsituovaoých alifailctych hydrocarbons' and from 10 to '70% UmoonostnícU graft polymer prepared from a mixture polybutedienu ^JLK> yloo01rilu and vinylarometického hydrocarbon. However, the injection molding of these masses yields shaped articles and low clamping strength (seam strength due to the joining of two parts of the material coming into the mold from different misses). For example, with corrugated grid-shaped objects, the molding may break even when it is removed from the mold.

It is an object of the invention to provide molding compositions which do not have this disadvantage.

The subject of the invention is a molding Um ot ota, characterized in that it consists of

70 to 30 parts by weight of a thermo-plastic thermoplastic polycarbonate composed of a mixture of 50 to 50 parts. 85% of mono-mono polycarbonate made of polyphenol. and 15 to 50% of the mono-monosubstituted polycarbonate of the general formula

where o is the number 15 to 200,

X represents an alkylene or alkyldeen group; 1 to 5 atoms. C 5 -C 15 cycloelkylene or cycloalkylene, or C 1 -C 15 -deen, a single bond, -O- or a group of formula

where

Hal represents a chlorine atom or '. bromine and

2. 30 to 70 parts by weight of the polybutyrene which is grafted to the monomer mixture of 95 to 50% styrene mono-monohydrate and 50 to 5% mono-mono-styrene.

In the molding composition according to the invention, up to 75% of the mono-monosilic graft polybadiene may be replaced by a copolymer of 95 to 50% of the mono-mono-styrene, elf-methylstyrene or their mixtures, and 50 to 5% of the mono-monosilic polymers.

Preferably, the weight ratio of polybutyria to monomer in the oily and oily grafts ranges from 85:15 to 40:60.

The total content of polybutyria in the molding compositions according to the invention is from 10 to 35%, preferably from 15 to 30% of Umoonoot, and the polytatadiene is preferably present in the compositions in the form of particles having a mean diameter in the range of 0.2 to 10 µm.

High-precision welds are obtained from the poring compositions according to the invention

As a result, the weld strength is considerably higher than 10 kJ / m, so that complicated moldings can be easily manufactured from numerous welds. Mechaiú - the properties of these moldings are similar to vlastnossi moldings of pure polycarbomate.

As the non-halogen-containing polycarbonates, any of the thermoplastic polycarbonates may be included in the present invention. Preferred polycarbonates are already known. In general, they are prepared by reacting dihydroxy or polyhydroxy compounds with phosgene or diesters of carbonic acid. Particularly suitable dihydroxy compounds are 4,4 ' -dihalkyldiaryl-aryl, including those having an alkyl group in the o-position to the hydroxyl group. Preferred are dihydroxydiorylcarbans of the following compounds: 4,4'-dihydropyloxydiphenylllpane-2,2 (bisphenol A), tetrepetylbisphenol A and iit-b4-hydroxyphenylphenylbp-ditlpolpyibenzene. Branched polycarbonates are also suitable. In their preparation, a portion of the dihydroxy compound is replaced with a polyhydric compound. Examples of suitable polyhydroxy compounds include: 1,4-Ms / 4 ', 4,2'-piperidinylbenzene, florudium, 4,6-diyl-2,4,4'-trihydroxy (heptene). 2,4,6-Diphenyl-2,4,6-tri- (4-indolylphenyl) helene, 1,3,5-tri (4-indoxylphenylbenzene), 1,1,11,15-tributylphosphine / ethane and 2,2-bis- [4,4-44,4'-ditydooydieeyl] ethyl-cycloalkylene.

... The dihydroxy compounds to be used for the preparation of the halogenated polycarbonates include: 4.4% of dihrtiardarecanediated chlorine or bromine atoms in the o-position to the hydroxyl group. Preference is given to using trichlorotrifent A and tetra-bisphenol A.

The polycarbonates used in the molding compositions according to the invention are known substances which have been described, for example, in United States Patent Nos. 3,028,365, 2,999-835, 3-,148,172, 3,271,368, 2,970,137, 2,991,273, Nos. 3,271,367, 3,208,078, 3,041-891 and 2,999,846. Polycarbonates having a potency of between 10,000 and 60,000, and especially polycarbonates having a molar cell diameter of from 20,000 to 40,000, are preferred. Halogen containing polycarbonates derived from polycarbonates phenols containing at least 2 benzene nuclei, and not 4 chlorine or bromine atoms, have a molecular weight of 16,000 to 35,000.

The second component of the door mixes is grafted llybutadirn. In the manufacture of this product, the polybutadiene rubber is grafted on! a blend comprising 95 to 50% by weight of styrene and 50 to 5% by weight graft copolymers of this type are known. They are obtained, for example, by polympnation of the monommers in the presence of a rubbery latex from ptlybutedirn using radical initiators. The particle size of the polybutadiene in the latex is preferably in the range of 0.2 to 1 µm, since the graft polymerization of the monomers does not increase the size of the particles. *

As already mentioned, a portion of not more than 75% of the acute graft polybutediene graft can be replaced by copolymer of monommers used to graft polybutadiene or similar monomers. Polymers of this type often originate as secondary products in the graft polymer, particularly when polybutadiene is grafted on the milled polymer. ! large - many monomers. Instead of the copolymers thus formed, similar copolypers produced separately can be added partially or completely to the molding compositions according to the invention.

The components of the molding compositions according to the invention can be prepared separately and then mixed in the blended mixers. For example, calendars, twin screw extruders or kneaders can be used as mixers. It is also possible to proceed by first producing a graft of llybutyrene and a polymer and then mixing the mixture with the mixture of carbon-carbonates. When mixing the ingredients, fillers, glass fibers, pigments or other additives such as stabilizers, flame retardants, flow controllers, lubricants, seperators and antistatic agents can be added.

The molding compositions according to the invention are suitable for the production of any shaped articles, for example for the production of injection molded articles. Examples of moldings which can be made of the inventive molding compositions are all kinds of housings (for example, housings of apparatus used in doaacnoott, such as fruit presses and mixers) or cover panels in the building industry. The compositions of the present invention are also well suited for use in electrical engineering because of their very good electrical properties. Other moon processing is the production of shaped articles by deep-drawing pre-fabricated plates or sheets.

EXAMPLE 1 (Comparative Example) The weight parts of an ABS resin non-graft polymer base consisted of

(a) 30 parts by weight of graft polymer (I), prepared by grafting 35 parts by weight of styrene, and - 15 parts by weight of acrylonitrile, not less than 50 parts by weight. parts of coarse-grained polybutedleum (produced by the emulsion polymerization described in DAS 1,247,665 and DAS 1,269,360), wherein the polybutadiene base particles are latex-free graft particles and have a mean diameter of from 0.3 to 0.4 µm and

b) 70 scales. parts of styrene-α-acrylonitrile styrene: atarУon0iril copolymers

70:30 and limit visibility Mslem. ^[ η ^{] 79.1} (measured in methylmethylamide at 20 ° C.), at 40 ° C, was thoroughly mixed in a kneading machine with 40 weights. parts of an aromatic polycarbonate no base 4, ⁴ -dihydrn:) Xp-2,2'-difolyoΓpnoJ »ou (bisphenol A) having a relative viscosity of Solution _Ί Γβ ι 1.28 (measured at a concentration of 5 g / 1 V- meeylenchloridu at 25 ° C) and the resulting product is granulated.

Example 2.

weight parts of ABS resin based on grafted polymer assembly! of

(a) 65 parts by weight of the grafted polymer (I) - according to Example 1; and

b) 35 scales. parts of the copolymer ttyreolkr ^y lnoitrii 70:30 viskózoío limiting number №9,1, at ²³⁰ DEG ^C. to a homogenous mixture ^^ ⁴⁰ VTO. ^d aromaHcké clay ^y ^ ^p ol ^y kar ^b ^^ sulfonate based on bisphenol A, having a relative Solution vitkonitaηrel 1280 is described in the Example 1.

Example 3 by weight parts of an ABS resin based on graft polymer consists of

(a) 65 parts by weight of the graft polymer (I) according to Example 1; and

b) 35 scales. parts of copolymers of class 70:30 with a linear viscosity number [b] of 3 79.1 are mixed homogeneously at 250 ° C and 50% by weight. parts of the aromatic polycarbonate do not run Msfeool A, the relative viscosity of which is 1.280, as described in Example 1.

Too much weight. parts of the ABS resin consisting of a graft polymer consisting of

a) 80 scales. parts of the graft polymer (I) of Example 1; and

b) 20 scales. parts of styrene-alkryonOitri 81:19 copolymers with a limit viscosity of about ^W = 80 ^, 9, г

is mixed at 250 ° С in a kneading machine of 30 scales. parts of an aromatic polycarbonate not based on bisphenol A whose relative solution viscosity η = 1.29 and the resulting product are granulated as in Example 1.

Example 5 weight parts of a graft polymer ABS resin consisting of

a) 80 scales. parts of the graft polymer (I) of Example 1; and

b) 20 scales. parts of a 80:20 styrene acrylonitrile copolymer whose viscosity limit [η] is 81.3 is extruded in a 60-weight, two-walled extruder. parts of an aromatic polycarbonate not based on bisphenol A having a relative solution viscosity of χ = 1.260 and the resulting product is granulated.

Example 6 weight parts of a graft polymer based ABS resin consisting of

a) 65 scales. parts of the grafted polymer prepared by grafting 16.25 wt. parts of styrene and 8.75 weight. 75 parts by weight of acrylonitrile. parts of coarse-grained polybutediene (produced by the emulsion polymerization described in DAS 1,247,665 and DAS 1,269,360), wherein the base polybutediene particles used for latex grafting have an average diameter of from 0.3 to 0.541 t; and

b) 35 scales. parts of a 80:20 styrene acrylonitrile copolymer with a viscosity limit number of 106, is extruded at 230 ° C in a two-walled extruder of 40 weight. parts of an aromatic polycarbonate not based on bisphenol A having a relative solution viscosity of P = 1.26; the resulting product is granulated.

Example 7 weight parts of a non-graft polymer ABS resin consisting of

a) 50 scales. parts of the graft polymer (I) according to Example 1 e

b) 50 scales. 60 parts by weight of styrene acrylonitrile copolymer 60: 135 with a viscosity limit W of 79.7 is mixed with 250 parts by weight of aromatic polycarbonate on a basis of 93 mol. % of bisphenol A and 7 mol. % of tetrebromobisphenol A, the relative solution viscosity of which is Pp _rel = 1.31, and the resulting product is granulated as in Example 1.

EXAMPLE 1 8 parts by weight of an ABS resin based on a graft polymer consisting of

a) 90 scales. parts of the graft polymer prepared by grafting 25 weights. parts of styrene and 5 weights. 70 parts by weight of acrylonitrile. parts of coarse-grained polybutadiene (produced by the emulsion polymerization described in DAS 1 247 665 e DAS 1 269 360), wherein the polybutadiene base particles used without latex grafting have an average diameter of 0.3 to 0.4 (U e

b) 10 scales. parts in styrene-ecrylonitrile copolymer 90:10 in a viscosity limit lea [n] = 79.9, · are mixed in a kneading machine at 280 ° C with 70 weights. parts of an aromatic polykerbonátu based on bisphenol A having a relative viscosity in solution _RQ ^ n = 1260 and the resultant product is as following grenuluje příkledu first

Example 9 weight parts of ABS resins on the backbone of a grafted polymer consisting of

a) 95 scales. parts of graft polymer prepared by grafting 45 weights. parts of styrene and 15 weights. parts of acrylonitrile not 40 weight. parts of coarse-grained polybutadiene (produced by the emulsion polymerization described in DAS 1 247 ¢ 65 and DAS 1 269 360), wherein the base polybutadiene particles used for latex grafting have an average diameter of 0.3 to 0.4 <

b) 5 scales. parts of styrene-acrylonitrile copolymers of 70:30 with a viscosity limit M = 80.7 are extruded in a double-rack xtrud.ru at 220 ° C. 30 scales. parts of an aromatic polycarbonate based on bisphenol A having a relative solution viscosity of η _ρβ1 = _1.280 and the resulting product is granulated.

Example 10 weight parts of a graft polymer based ABS resin consisting of

a) 50 scales. parts of graft polymer prepared by grafting 24 weights. parts of styrene and 16 weights. 60 parts by weight of acrylonitrile. parts of coarse-grained polybutadiene (produced by the emulsion polymerization described in DAS 1 247 665 and DAS 1 269 360), wherein the base polybutadiene particles used for latex grafting have an average diameter of 0.3 to 0.4a

b) 50 scales. parts by weight of 85:15 styrene-acrylonitrile copolymers having a viscosity limit number of I = 81.0 are homogenized by 8 40% by weight. parts of an aromatic polycarbonate based on 85 mol. % of bisphenol A and 15 mol. % tetrachlorobisphenol A having a relative solution viscosity of η = 1.32 and the resulting product ee granulated as in Example 1 ·

Example 11 (comparative example) of weight parts of an ABS resin based on a graft polymer consisting of

a) 70 scales. parts of the grafted polymer (II) prepared by grafting 35 weights. parts of styrene and 15 weights. 50 parts by weight of acrylonitrile. parts of finely divided polybutadiene with an average particle diameter of 0.05 to 0.15 µm; and

b) 30 scales. · Mixes at 50 ° C with 245 parts by weight of polystyrene-ecrylonitrile copolymers 70:30 with a viscosity limit [n] = 80.9. parts of an aromatic polycarbonate based on bisphenol A having a relative solution viscosity of η _Λ 1.30 and the resulting product is extruded as in Example 1.

Values of weld resistance, thermal shape stability according to Vlčat (Vicat temperature in ° C) and elastic modulus!

Polymer blend of example Total coarse particle content Polybutadlene fine particles Oe ^ os! in weld to ^J / m ² VL scan temperature (° C) Spring modul 61 ti (MPa) 1 9.0 3 138 2 400 2 19.5 12 130 2 000 3 16.3 11 135 2 100 4 28.0 19 Dec 120 1 600 5 16.0 10 133 2 050 6 29.3 22nd 118 1 560 7 15.0 11 135 2 200 8 18.9 «- 12 132 2 000 9 26.6 ¹⁶ . 133 2 280 10 18.0 13 ' 133 2 200 11 • 17 ^, 5 3 135 2 000

Example 12

1. PolylrarbonOty

The viscosity (η _Γβ γ) »e is determined in mseylene chloride at 25 ° C at a concentration of 5 g / l; M = weight center! m ^ o-ek ^ lovt weight

A · bisphenol-A-polycarbonate

B. copolycarbonate of 80% by weight bisphenol A and 20 mol. % of tetrrabromobispheool A

C. Oxygen tetrafluoromethylphenol-A-polycarbonate

D. outgrowth tetra bromo-biophenol-A-polycarbonate

E. Highly olefinic tetra-bromobenzophenol-A-polycarbonate

F. copolycarbonate from 84 mod * bisphenool A and 16 mol. * tetrachlorobisfeooli A

G. High-alpha-tetrachloride-A-polycarbonate

2. Mass of germany grafted copolymer · r / copol2m · r mixture h

4 _r ei = 30

Ы * = about 31,000 ⁿ re1 ^{= 1} > ²⁵

M = ®si 30 5000 w => ⁰³

M = ee 4 500 η _Γβ1 = i, ° ⁸

M = about 16,000

W ' ^{* 1} ' ° 8

Mw = asL 35,000

Jrel = ^{1 '27}

M = about 31,000 rel ~ ^1.12 &lt; tb &gt; parts of styrene and 15 weights. parts · ta · yllntrlll to 50 weights. parts of the coarse-grained polybutadlene (produced by the polymerization described in DAS 1,247,665 and DAS 1,269,360), wherein the basic polybutadiene particles used for grafting in the latex form have an average diameter of from 0.3 to 0.4 L and by weight. 70 parts by weight of the styrene-acrylonitrile copolyotre * with a styrene-etoylonitrile ratio of 70:30 with an intrinsic viscosity [7] of 79.1 (determined in dimethylformamide at 20 ° C). The mixture is obtained by co-precipitation of latexes.

Mixture J scales. parts of the graft copolymer obtained by grafting 16.25 wt. parts of styrene and 8.75 weight. parts by weight to 75 parts by weight. parts of coarse-grained polybutadiene (produced by the emulsion polymerization described in DAS 1,247,665 and DAS 1,269,360), wherein the polybubadiene base particles used for latex grafting have an average diameter of 0.3 to 0.4% and weights. parts of poplar 80:20 having an intrinsic viscosity [η] = 106. The mixture is obtained by co-precipitation of latexes.

The following table shows the composition and physical properties of the compositions of the invention obtained by blending and ingredients in a kneading machine.

Table

Example 1 2 3 4 5 6 7 8 9 10 polycarbonate - A. 40 - 32 32 40 - 40 40 50 60 Polycarbonate B. - 40 - - - - ’- - - - polycarbonate C. - - 8 - - - 20 May - - - polycarbonate D.  - ’- - 8 - - - ' - 20 May 10 polykarborót E. - - - - 20 May - - - - - polykarboiét - F. - - ’- - 50 - - '- - polycarbonate G. - - - - . · ’- - - 20 May _of - - mixture H. 60 60 60 6 °: ’- - - - - - mixture J. - - _w - - 40 50 40 40 30 30 notched ^ 3 ^ (^ en ^ E ^ and ^ <^ (3t ⁽ Μ / ο ² ) Vicat temperature B ^x ^ (° C) 24 24 17 23 · 24 22 -. 20 May 24 23 22nd 115 114 112 126 128 115 113 123 127 126 module оти ^ сти (Me) ** 2 000 1 970 1 800 2 490 2 630 1 970 1 920 2 580 2 600 2 600

^{x 'p} determined ccording DIK ⁵³⁴⁶⁰ xx determined by DIK 53455

Claims (4)

CLAIMS 1. A molding composition comprising: 70 to 30 parts by weight of thermo-pyrophic thermoppaetic polycarbonate - consisting of 50-85% of the hmoonootic carbonate made of polyphenol - halogen-free 15 to 50% of the hmoonooted carbon-containing polycarbonate of formula n where n denotes the number 15 to 200, X represents a C 1 -C 5 alkylene or alkylidene group, a C 5 -C 15 cycloalkylene or cycloalkylidane group, a single bond, -O-, or a group of the formula wherein Hel represents a chlorine or bromine atom o 30 to 70 parts by weight of polybutadiene to which a monomer mixture consisting of 95 to 50% by weight of styrene and 50 to 5% by weight of acrylonitrile is grafted. 2. The molding composition according to claim 1, wherein not more than 75% by weight of graft polybutadiene is replaced by a copolymer of 95 to 50% by weight of styrene, [alpha] -methylstyrene or a mixture thereof and 50 to 5% by weight of acrylonitrile, methacrylonitrile or a mixture thereof. - 3. The molding composition according to claim 1, wherein the weight ratio of polybutadiene to the monomer mixture grafted thereon is 65:15 to 40:60. 4. Molding composition according to claim 1, characterized in that it contains from 10 to 35% by weight, preferably from 15 to 30% by weight, of polybutadiene in the form of particles having an average diameter in the range from 0.2 to 1.0 .mu.m.