DE2353428A1 - Thermoplastic polycarbonate/graft copolymer compsn - contg thermoplastic polycarbonate, styrene/acrylonitrile graft copolymer, and styrene/acrylonitrile copolymer - 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

From DAS 1 IJo "I ² H" are mixtures of 90-3o percent by weight of a polycarbonate made from di- (monohydroxyphenyl) -substituted aliphatic hydrocarbons and Io -7o percent by weight of a graft polymer made from polybutadiene and a mixture of acrylonitrile and an aromatic vinyl ! hydrocarbon has been produced is known. When processed by injection molding, these molding compounds result in moldings with insufficient strength of the confluent seams. For example, a lattice-like molded body produced by injection molding can break as soon as it is removed from the mold. ·

Subject of the main patent. ...... (Patent Application P 22 59 565.9) are therefore, the polycarbonates and graft copolymers containing molding compositions of harzblldenden monomers on a rubber, and this deficiency have not. "■ - ■ '.'" - ". "- .."'-"-.-..-'■:"""."

1,) 70-5o parts by weight of a thermoplastic polycarbonate and

2.) 3o - 7o parts by weight of a mixture 2.1) 25 to 100 percent by weight of a graft copolymer

from a on a 2ο 1.1) rubber, polymerized 2.1.2.) Mixture of monomers

Le A 14 751-1

509819/1060

2.1.2.1) 95 - 5ο percent by weight styrene, methyl methacrylate or mixtures thereof

2.1.2.2) 50 - 5 percent by weight of acrylonitrile, methyl methacrylate or mixtures thereof and

2.2) O - 75 percent by weight of a copolymer of 2.2.1) 95 - 50 percent by weight styrene, <X-methylstyrene,

Methyl methacrylate or mixtures thereof 2.2.2.) 5o - 5 percent by weight acrylonitrile, methacrylonitrile,

Methyl methacrylate or mixtures thereof where

a) the weight ratio of (2.1.1) rubber: (2.1.2) monomer mixture is 85:15 to 40:60

b) the graft copolymer (2.1) in the molding composition composed of particles with an average diameter of 0.2 to 5 / U, preferably 0.2 to 1.0 / U

c) the molding compound 10-35 wt .-%, preferably 15-30 wt .-% of the Contains rubber (2.1.1).

These molding compounds have high strength in the flow seam. It is generally well above Io cmkp / cm ² . It is possible to use these products to produce complex moldings that have many confluence lines, such as, for. B. grid to produce. The mechanical properties of such molded bodies are comparable to those of corresponding bodies made of pure polycarbonate.

In principle, all thermoplastic polycarbonates can be used. Polycarbonates are known. You will go through Implementation of di- or polyhydroxy compounds with phosgene or diesters of carbonic acid. Particularly suitable Dihydroxy compounds include dihydroxydiary alkanes those which carry alkyl groups or chlorine or bromine atoms in the o-position to the hydroxyl group. Preferred dihydroxy

Le A 14-751-1 - 2 -

509819/1060

Diarylalkanes are: 4,4'-dihydroxydiphenylpropane-2,2 (bisphenol A), tetramethylbisphenol A, tetrachlorobisphenOi A, tetrabromobisphenol-A and bis- (4-hydroxyphenyl) -p-diisopropylbenzene. ; Except for polycarbonates made using dihydroxydiarylalkenes alone; branched polycarbonates can also be used. For their preparation, part of the dihydroxy compound, e.g. B. 0.2-2 percent, replaced by a polyhydroxy compound. Suitable polyhydroxy compounds are, for. S. l, ^(f 4, 4,?. '-Dihydroxytriphenylmethyl) 4-bis- benzene / Phloroglücin, ■ 4, 6-dimethyl-2,4,6-fcrl- (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2; 4:, 6-tri- (4-hydroxyphenyl) -heptane, 1,5,5-tri- (4'-hydroxyphenyl) -benzpl, 1,1,1-TrI- (4- hyaroxyphenyl) ethane and 2 _ί 2-bis ^ ~ 4,4-f4,4'-dihydroxy-cyclohexyl ^ -propane.

Polycarbonates of the type indicated above are ζ. Tie: US patents 3,028,365, 2,999,835, 3,148,172, 3,271,368, 2 97o 137, 2 991 273, 3 271 367, 3 23o 078, 3 ol4 89I and 2 999 846. Preferably the polycarbonates Molecular weights between Io 000 and 60,000, in particular 2o 000 and 4o 000. \ .- ■; ■. .. "'■" -;

The second / component, the molding compounds, is a rubber-based graft copolymer. In these products, a monomer mixture of 95 - 50 percent by weight of styrene, methyl methacrylate or mixtures thereof and 5 - 50 percent by weight of acrylonitrile, methyl methacrylate or mixtures thereof is graft polymerized onto a rubber. Suitable rubbers are in particular. Polybutadiene, butadiene / styrene copolymers with up to 30 wt -.% Of copolymerized styrene, copolymers of butadiene and acrylonitrile with up to 20 wt, -% of acrylonitrile, or Copölyjnerisate of butadiene with up to 20 wt -.% Of a lower alkyl ester of Acrylic or methacrylic acid (e.g., methyl acrylate, ethyl acrylate, methyl methacrylate and; ethyl methacrylate), in principle all elastic components are suitable, provided they show rubber-elastic behavior.

LeA 14 751-1

5098 19/1060

The weight ratio of rubber to graft polymerized Monomers must be 85:15 to 40:60. The graft polymers must be in the molding composition in the form of particles with a mean Diameters of 0.2 to 5 / U, preferably 0.2 to 1 / U are present.

Such graft copolymers are known. You v / ground e.g. B. produced by polymerizing the monomers over radical catalysts in the presence of a rubber latex. The Gro'P? the rubber particles in this latex is preferably in the range of 0.2 to 1 / U because polymerize through the graft of the monomers, the particles are not significantly enlarged.

In addition to the graft copolymer, the molding composition can also contain a copolymer of the graft monomers or similar monomers. Ss are copolymers of 95-5o percent by weight of styrene, cc -methylstyrene, methyl methacrylate or mixtures thereof with 5-5o percent by weight of acrylonitrile, methacrylonitrile, methyl methacrylate or mixtures thereof. Such copolymers are often formed as by-products during graft polymerization, especially when large amounts of monomers are grafted onto small amounts of rubber. It is possible to mix in separately prepared copolymers of this type in addition to or instead of the copolymers formed in this way.

This invention relates to molding compounds made from:

1.) 7o - 5o parts by weight of a thermoplastic polycarbonate

and.

2.) J) O - 70 parts by weight of a mixture of 2.1) 25 - loo percent by weight of a graft copolymer from one to one

2.1.1) rubber polymerized

2.1.2) mixture of monomers

2.1.2.1) 95 - 50 percent by weight styrene, methyl methacrylate or mixtures thereof

Le A 14 751-1 - 4 -

50-9 819/1060

2.1.2.2) 5o - 5 percent by weight of acrylonitrile, methyl methacrylate or mixtures thereof and

2.2) Ö - 75 percent by weight of a copolymer of 2.2.1) 95 - 5o percent by weight styrene, methylstyrene,

Methyl methacrylate or mixtures thereof 2.2.2.) 5o - 5 percent by weight of acrylonitrile / methacrylonitrile,

Methyl methacrylate or mixtures thereof where. V

a) the weight ratio of (2.1.1) rubber: (2.1.2) monomer mixture is 85: 15 to 4o: βο

b) the graft copolymer (2.1) in the molding composition composed of particles with an average diameter of 0.2 to 5A preferred 0.2 to 1.0 / U

c) the molding compound Io - 35 wt .- ^, preferably 15 - J5o wt - # contains the rubber _(2.1.1).:

according to the main patent. ... ... (patent application P 22:59 565.9), which are characterized in that the thermoplastic aromatic polycarbonate a mixture of

(1.1) of 50 - 85 wt -.% Of a polycarbonate on Bas is a halogen-free aromatic di- or polyhydroxy compound and (1.2) from 15 - 50 wt -.% Of a halogen-containing polycarbonate of the

formula

* ~ - - shark,

η Hal

where η = 15 to 200

X = alkyls or alkylidene with 1 - 5 carbon atoms, cycloalkylene or cycloalkyls with 5-15 carbon atoms, single bond,

- 0 - or

Hai = chlorine or bromine:

is. The proportions of (1.2) are to be selected so that 10 50 wt -% of contained halogen-containing high molecular HomopοIycarbonate in the final blend..

Le A 14751-1 ~ ⁵ ~

509819/1060

The polycarbonates according to (1.1) are known. They are manufactured as stated in the main patent.

The polycarbonates according to (1.2) are also known. As the Formula shows, they are made by reacting at least 2 aromatic, radicals containing at least 2-valent phenols, the Carry a total of 4 halogen atoms (chlorine or bromine), obtained with phosgene or diesters of carbonic acid. Preferred their molecular weight is 16,000 to 35,000.

Compared to the polymer mixtures of the main patent, the only halogen-free or only halogen-containing polycarbonates or polycarbonates with halogen-containing and halogen-free structural elements, the mixtures of the present Invention a significant improvement in the heat resistance according to Vicat and a higher modulus of elasticity on.

The two or three components of the molding compositions of the present Invention can be produced separately and then on known Mixing devices are mixed. Suitable for this are, for. B. Mixing mills, twin screw extruders or Indoor mixer. It is also possible to first use the mixture of the graft copolymer and the copolymer d. H. the under to produce a combined mixture by working up the two components together and then using this mixture to unite the polycarbonate. When mixing, the molding compounds can also fillers, glass fibers, pigments or other additives such as stabilizers, flame retardants, superplasticizers, Lubricants, mold release agents, antistatic agents are added,

. The molding compositions of the present invention can be used for production can be used by moldings of any kind. In particular, moldings can be produced by injection molding. Examples of molded bodies that can be produced are: Housing parts of all types (e.g. for household appliances such as juice presses, coffee

Le A 14 751-1

5 0 9 8 19/1060

machines, mixers) or cover plates for the construction sector, you are used in particular in the field of electrical engineering because they have very good electrical properties. Another form of processing is the production of Molded bodies by deep drawing from previously produced plates or foils. / -. ■ -. - ..-. "": ".- V

Le A 14 751-1 '. ~; \ \ _ γ _

5098 19/1060

example

1.) Polycarbonates

The viscosities C ^ _re i) are in methylene chloride at 25 ° C

and a concentration of 5 g / l. A) Polycarbonate based on bisphenol A.

= approx. 31,000

B) Copolycarbonate based on 80 mol% bisphenol A and 20 mol% tetrabromobisphenol A ° lrel ^{= 1 '25}

= approx. 30,500

C) Low molecular weight polycarbonate based

of tetrabromobisphenol A rel

= approx. 4,500

D) High molecular weight polycarbonate based on

Tetrabromobisphenol A T -, = 1.08

= approx. 16,000

E) High molecular weight polycarbonate based on

Tetrabromobisphenol A- ^ _r , = 1.08

= approx. 35,000

F) Copolycarbonate based on 84 mol% bisphenol A and 16 mol% tetrachlorobisphenol A ^ _{r 1} = 1.27

= approx. 31,000

G) High molecular weight polycarbonate based on

Tetrachlorobisphenol A m = 1.12

= 23,000

Le A 14 751-1 - 8 -

5 09819/1060

• a ·

2.) Graft copolymer / copolymer mixtures Mixture H

60 parts by weight of a graft polymer prepared by Grafting of 35 parts by weight of styrene and 15 parts by weight of acrylonitrile to 50 parts by weight of a coarse polybutadiene (according to the information in the German Auslegeschriften 1,247,665 and 1,269,360 on an emulsion polymerization), the mean particle diameter of the polybutadiene graft base in latex form is between 0.3 and 0.4 / 11, and

40 parts by weight of a styrene-acrylonitrile copolymer with a styrene-acrylonitrile ratio of 70:30 and an intrinsic viscosity of £% J '= 79.1 (measurement in dimethylformamide at 20 ° C.), mixed by co-precipitation of the corresponding Latices;

Mixture J)

70 parts by weight of a graft polymer prepared by Grafting of 16.25 parts by weight of styrene and 8.75 parts by weight Acrylonitrile to 75 parts by weight of a coarse polybutadiene, (according to the information in the German Auslegeschriften 1,247,665 and 1,269,360 via an emulsion polymerization) wherein the mean particle diameter is between 0.3 and 0.4 / U, and

30 parts by weight of a copolymer of styrene-acrylonitrile in a ratio of 80:20 and an intrinsic viscosity "of £ \ __ 7 = 10 6 mixed by co-precipitation of the corresponding latices.

The following table contains molding compositions according to the invention produced by mixing in an internal mixer and their physical properties Properties.

Le A 14 751-1

50 9 8 19/1060

Tabel

-i> example. 1 23456789 10

S '■

Polycarbonate A) 40 '- 32 32 40 - 40 40 50 60

^H polycarbonate B) 40 - - - -

Polycarbonate C) - - 8 - - -20

Polycarbonate D) - __ 8 - - - - 20 10

Polycarbonate E) - - - - 20- __

cn polycarbonate F) - - - - 50

co polycarbonate G) - - - - - - - 20

^ Mixture H) 60 60 60 60, - -

co mixture J) - - - - 40 50 40 40 30 30

^ I, notched impact strength 24 24 17 23 24 '22 20 24 23 22

ο cmkp / cm ^

2 ° Vicat B ^x ^ ^oC 115 114. 112 126 128 115 113 123 127

¹ Ε module ³ ^ kp / cm ^{2 2O 000} 19 * 700 18,000 24,900 26 _o 300 19,700 .. 19,200 25,800 26,000 26,000

'' measured according to DIN 53 460
^xx 'measured according to DIN 53 455

co cn co

K) CX)

Claims (2)

2253428 Claim; 'Molding compounds from: ■ "... ■ 1.) 7 ° -3 ° parts by weight of a thermoplastic polycarbonate and. '-' ^ 2.) 3o - 7o parts by weight of a mixture 2.1) 25 to 100 percent by weight of a graft copolymer " from one to one 2.1.1) rubber polymerized 2.1.2) mixture of monomers 2.1.2.1) 95-5o percent by weight styrene, methyl methacrylate; or mixtures thereof 2.1.2.2) 5 <J -5 percent by weight acrylonitrile, methyl methacrylate or mixtures thereof and 2.2) '■■ 0-75 percent by weight of a copolymer of 2.2.1) 95 - 5o percent by weight styrene, methylstyrene, Methyl methacrylate or mixtures thereof 2.2.2.) 5o - 5 percent by weight acrylonitrile, methacrylonitrile, Methyl methacrylate or mixtures thereof where. : a) the weight ratio of (2.1.1) rubber: (2.1.2) monomer mixture 85: IS t> ls ^ "O: -βο is b) the graft copolymer (2.1) in the molding composition composed of particles with an average diameter of 0.2 to 5 / U is preferred 0.2 to 1.0 / U c) the molding compound Io - 35 wt .- #, preferably 15 - 35o wt .- ^ des Rubber (2.1.1) contains, _ according to main patent .... ... (patent application P 22 59,565.9), characterized in that the thermoplastic aromatic polycarbonate is a mixture of (1.1) 50-85 wt .- ^ of a polycarbonate based on a halogen-free aromatic di- or polyhydroxy compound and (1.2) 15-501 wt -.% Of a halogen-containing Polyearbonats the Le A 14 751-T 509 8 19/106 formula Hal Hal, Hal Hal where η «= 15 to 200 X = alkylene or alkylidene with 1-5 carbon atoms, cycloalkylene or, cycloalkylidene with 5-15 carbon atoms, single-ended, - 0 - or Hai ta chlorine or bromine 1st, and the proportions of the halogen-containing high molecular weight homopolycarbonates are to be chosen so that in the final Mixture 1.0 - 30 wt. Tf are included. Le A 14 751-1 - 12 - 509819/1060