JPS6232143A - Thermoplastic molding material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Thermoplastic aromatic polyponates 98 having a weight average molecular weight Mw (Mw measured by light scattering) between 00
1 to 1% by weight, preferably 78 to 20% by weight, especially 6
4 to 30% by weight (B) Thermoplastic polyalkylene terephthalates 1 to 98% by weight, preferably 20 to 78% by weight, especially 30% by weight
from 0 to 64% by weight, and if appropriate (C) from 0 to 30% by weight, preferably from 1 to 20, in particular from 3 to 12%, by weight of an elastomeric polymer with a glass transition temperature below -20°C. The material is characterized in that it contains (D) polycarbonate-polyphenylene oxide block cocondensate from 1 to 30% by weight, preferably from 1 to 20% by weight, especially from 3 to 15% by weight, in each case. Component (A) + (B)
The present invention relates to a thermoplastic molding material in which the sum of the weight percentages of + (C) + (D)' is 100 weight percent.

Components (A) to (D) Component (A) Aromatic polycarbonates (A) in the context of the present invention
) are understood to be the known homopolycarbonates, copolycarbonates and mixtures of these polycarbonates, for example based on at least one of the following diphenols: hydroquinone, resorcinol, dihydroxydiphenyls, bis- (hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-
Cycloalkanes, bis-(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-
(Hydroxyphenyl)-sulfoxides, bis-(hydroxyphenyl)-sulfones and α,α′-bis-(hydroxyphenyl)-diisopropylbenzenes, and nuclear alkylated and nuclear/\logenated derivatives of these. . These suitable diphenols and others are described, for example, in U.S. Pat. No. 3,028.

No. 365, No. 3,275,601, No. 3,148.1
No. 72, No. 3,082,781, No. 2゜991.27
No. 3 and No. 2,999,846.

Preferred diphenols include, for example, 4,4'-dihydroxydiphenyl, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, α,α'-bis-(4-
hydroxyphenyl)-p-diisopropylbenzene,
2.2-bis-(3-methyl-4-hydroxyphenyl)-propane and 2,2-bis-(3-chloro-4-
hydroxyphenyl)-propane.

Particularly preferred diphenols are, for example, 2°2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-
Furopane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and 1,1-bis-(
4-hydroxyphenyl)-cyclohexane.

Aromatic polycarbonates (A) include a small amount of trifunctional or more than trifunctional compounds, such as those having 3 or more than 3 phenolic hydroxyl groups;
Preferably (based on the diphenols used) 0
．． Branching can be achieved by mixing 0.05 to 2.0 mol%.

Aromatic polycarbonates (A) generally have a viscosity of to, ooo to 200.0, determined by measuring the relative viscosity at a concentration of 0.5 g in 100 mu of solution in methylene chloride at 25°C or by light scattering.
000, preferably from 20,000 to 80,000.

For example, a small amount of low molecular weight polycarbonates with an average degree of polycondensation of 2 to 20 and a Mw of 10,000 to 200.00 are used.
0 high molecular weight polycarbonates.

Chain terminators such as, for example, phenols, halogenophenols or alkylphenols, carboxylic acid chlorides and phenylchlorocarbonate esters can be added in calculated amounts using known methods to determine the molecular weight Mw of the polycarbonates (A). used. Preferred chain terminators are described in DE 2,842,005.

The polycarbonates (A) used according to the invention are prepared in known manner by phase boundary methods or by processes in homogeneous solution (pyridine method) or, if appropriate, by melt transesterification methods.

Polyalkylene terephthalates (B) in the context of the present invention include aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic These are reaction products of diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates (B) can be prepared by known methods from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms (Plastic Handbook). Kunst st off-Hand
buch) Volume ■ p695 onwards, Carl Hanser Verlag
(see Munich 1973).

Preferred polyalkylene terephthalates (B) contain at least 80 mol%, preferably at least 90 mol% of terephthalic acid groups, based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol%, based on the diol component. It shall contain ethylene glycol and/or butane-1,4-diol groups.

Preferred polyalkylene terephthalates (B) include groups of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, in addition to terephthalic acid esters. It can contain up to 20 mol%, for example, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4.4'
- such as diphenyldicarboxylic acid, succinic acid, adipic or sebacic acid, azelaic acid or cyclohexanediacetic acid groups.

Preferred polyalkylene terephthalates (B) include, in addition to ethylene glycol or butane-1,4-diol groups, other aliphatic diols having from 3 to 12 carbon atoms or from 6 to 21 carbon atoms. It can contain up to 20 mol% of alicyclic diols, such as propane-1,3-diol, 2-ethylenepropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane. -1,6-diol, cyclohexane-1,4-dimetatool, 4-methylpentane-2,4-diol, 2-methylpentane-
2,4-diol, 2,2,4-)limethylpentane-1,3- and -1,5-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3 -diol, hexane-2,5-diol,
1.4-di(β-hydroxyethoxy)-benzene,
2,2-bis-(4-hydroxycyclobexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3-β-hydroxyethoxyphenyl) -propane and 2,2-bis-(4-hydroxypropylphenyl)-propane (see DE 2.407.674, DE 2.407.776 and DE 2,715,932). ).

Polyalkylene terephthalates (B) can be used for example in German Patent Publication No. 1,900,270 and in U.S. Pat.
．． Branching can be achieved by mixing relatively small amounts of trihydric or tetrahydric alcohols or tribasic or tetrabasic carboxylic acids, such as those described in No. 692.744. Examples of preferred nucleating agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

It is expedient to use not more than 1 mol % of branching agent, based on the acid component.

Particularly preferred polyalkylene terephthalates (B) are those prepared exclusively from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and/or butane-1,4-diol; It is a mixture of alkylene terephthalates.

Preferred polyalkylene terephthalates (B) are also copolyesters prepared from at least two of the abovementioned acid components and/or at least two of the abovementioned alcohol components; particularly preferred copolyesters are: They are poly-(ethylene glycol/butane-1,4-diol) terephthalates.

The polyalkylene terephthalates preferably used as component (B) are generally in each case phenol 10
- from 0.4 to 1.5 dl/g, preferably from 0.5 to 1.3 dl/g, especially from 0.6 to 1.2 dl/g, measured at 25° C. in dichlorobenzene (1:11 i parts). It has an intrinsic viscosity of

Polymers with a glass transition temperature lower than 20℃
C) is the following heptamines: chloroprene, butadiene, isoprene, isobutyne, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and acrylic (methacrylic acid) esters having 1 to 18 carbon atoms in the alcohol component. copolymers, in particular graft copolymers, having elastomeric properties obtained substantially from at least two of the
En der Organischen Che
mie”), (Houben-W
eyl), Volume 14/1, Georg Thieme Verlag, Stuttgart 1961 p.
393-406 and Sea, Bee, Bucknall (C0B
"Reinforced Plastics"("T
Applied Science Publishers (Appl, 5cienc)
e Publishers), London
n) Polymers as described in 1977. Preferred polymers (C) have a gel content of more than 20% by weight, preferably more than 40% by weight.

Preferred polymers (C) include vinyl acetate groups 45
% by weight and load 2.1 according to DIN53 735
Measured at 190°C under 6kp, from non-flowable to i
, ooo, preferably ethylene/vinyl acetate copolymers having a melt index of 0.1 to 20.

Similarly preferred polymers (C) are ethylene/propylene copolymers and ethylene/propylene copolymers in which the weight ratio of ethylene to propylene groups is in the range 40:60 to 90:10, preferably 40:60 to 65:35. /genter polymers (EPM and E
PDM rubber).

Mooney viscosity (running time in minutes) of uncrosslinked EPM and EPDM rubbers
e 1 +4 ) is between 25 and 100, preferably between 35 and 90. Uncrosslinked EPM and EPDM
The gel content of the rubber is less than 1% by weight.

Ethylene/propylene copolymers (EPM) used
) contains virtually no double bonds, while ethylene/propylene/genterpolymers (E
PDM) may contain from 1 to 20 double bonds per 1000 carbon atoms. Examples which may be mentioned as suitable diene monomers in EPDM are conjugated dienes, such as isoprene and butadiene, and non-conjugated dienes with 5 to 25 carbon atoms, such as 1.4-pentadiene, 1.4- hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, Alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-impropenyl-5-norbornene, and tricyclodienes, such as 3-methyltridiclo (5,2,1,0,2,6)-3,8-decadiene. Hexa-1,5-diene of non-conjugated dienes,
Ethylidene-norbornene or dicyclopentadiene may be mentioned as preferred. The diene content in EPDM is preferably 0.5 to 10% by weight. EPM and EPDM rubbers are described, for example, in German Patent Application No. 2.808.709.

Other preferred polymers (C) consist of polymerized vinyl aromatic blocks and polymerized diene blocks. Vinyl aromatic monomer (X) and conjugated diene (
selectively hydrogenated block copolymers of Y), ie of the x-Y type. These block copolymers and their production are known.

“Encyclopedia of Polymer Science and Technology”
pedia of Polymer 5cfen
ce and Technology”)?IIj
Volume 15, Interscience
e), :, -3-ri (N, Y,) (1971) p508
The procedures described below can generally be used to prepare suitable x-Y block copolymers of water lily, alpha-methylstyrene, vinyltoluene or mixtures and conjugated dienes such as butadiene and isoprene. Selective hydrogenation of such products is likewise known, whereby the ethylenic double bonds are essentially completely hydrogenated,
Aromatic double bonds are largely retained. Such selectively hydrogenated block copolymers are described, for example, in German Pat.
．． No. 000.282.

Preferred polymers (C) further include, for example.

Styrene- and/or acrylonitrile- and/or acrylic acid (methacrylic acid) alkyl ester-grafted polybutadienes, butadiene/styrene copolymers and polyacrylic acid (methacrylic acid)
Copolymers of esters such as styrene or alkylstyrene and conjugated dienes (high impact polystyrene)
, namely acrylic acid or methacrylic acid esters of the type described in German Patent Application No. 1,694,173 (=US Pat. No. 3,564,077), vinyl acetate,
Acrylonitrile, copolymers with styrene and/or e.g.
butadiene/acrylonitrile copolymers, polyisobutynes or polyisopropenes, such as those described in U.S. Pat.

Particularly preferred polymers (C) are, for example, German Patent Publication No. 2,035,390 (=U.S. Pat. No. 3,644.
574) or German Patent Publication No. 2,248.24
No. 2 (= British Patent Specification No. 1,409.275)
Particularly preferred polymers (C) are ABS polymers (both of the copolymer and graft polymer type) as described above. Particularly preferred polymers (C) are also 1. 10 to 35, preferably 20 to 35, based on at least one acrylic (methacrylic) ester and/or mixture, in particular 15 to 25% by weight
% of acrylonitrile and 65 to 90, preferably 65 to 80% by weight, based on the mixture, of styrene, II, 60 to 90, preferably 65 to 90, especially 75 to 85, based on the grafted product. Weight%, ■
Graft polymers obtainable by a grafting reaction using a butadiene polymer having at least 70ii% of butadiene groups as a graft base, preferably as a graft base
The gel content of the polymer (C) is 70% or more (measured in toluene), the degree of grafting G is 0.15 to 0.55, and the average particle diameter d5o of the graft polymer (C) is 0.2 to 0.6. , preferably from 0.3 to 0.51 Lm.

Acrylic acid (methacrylic acid) esters are in particular esters of acrylic acid and methacrylic acid with monohydric alcohols having 1 to 8 carbon atoms.

In addition to the butadiene group, the graft base (■) contains up to 30% by weight, based on (2), of other ethylenically unsaturated heptamers, such as styrene, acrylonitrile or acrylics having 1 to 4 carbon atoms in the alcohol component. acids or esters of methacrylic acid (methyl acrylate,
such as ethyl acrylate, methyl methacrylate and ethyl methacrylate). A preferred graft base (1) consists of pure polybutadiene.

In graft polymerization, as is known, the graft polymers are not completely grafted onto the graft base H. In accordance with the present invention, graft polymers are to be considered as products of graft polymerization, ie products which, in addition to the actual graft polymer, also contain homopolymers and copolymers of the graft monomers used.

Also includes acids.

The degree of grafting G means the weight ratio of one grafted graft to the graft base, and has no dimension.

The average particle size dso is the diameter above and below which in each case 50% by weight of the particles fall. This is ultracentrifugation (ult)
By measuring ra-centrfuge) (W, 5chaltan),
Nie/Tsch, Lange (H, Lange), Colloids and Polymers (Kolloid, Z, und Z, Po
lymere) 250 (1972), 782-796)
Alternatively, by electron microscopy and subsequent particle counting (G, Kampf, x-), Schuster (H).

5chuster)-, Applied Polymerization Jitsume (Angew
, Makromoloekulare Chemie
) above A, (1970), 111-129) or can be measured by light scattering measurement.

Particularly preferred polymers (C) are, for example.

a) 25 to 98% by weight based on (C), -20
a graft base of acrylate rubber having a glass transition temperature below °C; b) 2 to 75% by weight based on (C) of at least one polymerizable ethylenically unsaturated monomer, in which These are graft polymers in which the graft monomer is a homopolymer or copolymer produced in the absence of 25°C and has a glass transition temperature higher than 25°C.

The acrylate rubber (a) of polymer a (C) is preferably a polymer of acrylic acid alkyl esters,
If appropriate, it may contain up to 40% by weight of other polymerizable ethylenically unsaturated heptamers. If the acrylate rubber used as graft base (a) as described on page 13 is now a product with an already grafted diene rubber core, the diene rubber core is not included in the calculation of this percentage. Preferred polymerizable acrylic esters include esters of alkyls having 1 to 8 carbon atoms, such as methyl, ethyl, butyl, octyl and 2-ethylhexyl esters, halogenoalkyl esters, preferably halogeno, such as chloroethyl acrylate. −
Included are alkyl esters having 1 to 8 carbon atoms, and aromatic esters such as benzyl acrylate and phenethyl acrylate. These can be used individually or as a mixture. The acrylate rubber (a) can be non-crosslinked or crosslinked, preferably partially crosslinked.

For crosslinking, heptamers with more than one polymerizable double bond can be copolymerized. Examples of preferred crosslinking polymers include 3, such as ethylene glycol dimethyl acrylate and allyl methacrylate.
consisting of an unsaturated monocarboxylic acid having from 8 to 8 carbon atoms and an unsaturated-hydric alcohol having from 3 to 12 carbon atoms or a saturated polyol having from 2 to 4 OH groups and from 2 to 20 carbon atoms. Esters; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate and in cyanurate and tris-acryloyl-5-)lyazines, especially triallyl cyanurate; such as di- and trivinylbenzenes. Polyfunctional vinyl compounds: and also triallyl phosphate and diallyl phthalate.

Preferred crosslinkers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl) socyanurate, trivinyl cyanurate, triacryloyl hexahydro-
5-triazine and triallylbenzenes.

The amount of crosslinking monomers is preferably based on the graft base (
0.02 to 5, especially 0.05 to 2, based on a)
Weight%.

In the case of cyclically bridged polymers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to below 1% by weight of the graft base (a).

Besides the acrylic esters, "other" preferred polymerizable ethylenically unsaturated monomers which can be used, if appropriate, for the preparation of the graft base (a), are, for example, acrylonitrile, styrene, α-methylstyrene. , acrylamides, and vinyl alkyl ethers having 1 to 6 carbon atoms. Preferred acrylate rubbers as graft base (a) are emulsion polymers with a gel content of 60% by weight or more.

The gel content of graft base (a) is determined in dimethylformamide at 25°C (M.

Hoffin (M, Hoffman), x-) Chi, Ri L/
-F- (H, Kromer), R, Kuhn (R,
Kuhn), polymer analyzer and m (polymer
analytik Iund II), Georg Thieme Verlag (Georg Thieme V
erlag), Stuttgart (Stuttgar)
t) 1977).

Acrylate rubbers as graft base (a) can also be crosslinked diene rubbers of one or more conjugated dienes, such as polybutadiene, or copolymers of conjugated dienes with ethylenically unsaturated monomers, such as styrene and/or acrylonitrile. , as a core.

The content of the polydiene core in the graft base (a) is from 0.1 to 8o, preferably 10o based on (a).
It can be set to 50% by weight. The shell and core, independently of each other, can be uncrosslinked, partially crosslinked or hyperlinked.

Particularly preferred graft bases (a) for graft polymers (C) based on polyacrylic esters can be summarized as follows: 1. Acrylic ester polymers and copolymers without diene rubber core and 2. Diene rubber core. Acrylic ester polymers and copolymers containing.

The grafting yield is i.e. monomer (b) to be grafted.
The quotient of the amount of and the amount of grafting monomer (b) used is:
Generally 20 to 80i [1%. Measurements were performed using M, Hoffm & nn,
/ Mama-H, Kromer) and Earl, Tarn (R
, Kuhn) (7) Polymer analysis (Polymeran
alytik) No. 1 O, Georg Thieme Verlag, Stuttgart, 1977.

Preferred grafting monomers (b) are α-methylstyrene, styrene, acrylonitrile, methyl methacrylate or mixtures of these seven monomers. Preferred grafting monomer mixtures have a weight ratio of 90:10 to 50.
: It is a mixture of 50% styrene and 7% crylonitrile.

Such graft polymers (C) based on polyacrylic esters are described, for example, in German Patent Publication No. 2.444.
584 (=U.S. Pat. No. 4,022.748) and German Patent Publication No. 2,726.256 (=U.S. Pat. No. 4,096,202).

Particularly preferred graft polymers of this type contain from 2 to 20, preferably from 2 to 15% by weight, based on (C), of monomers (b), from 80 to 98%, based on (C),
It is obtained by grafting, preferably from 85 to 97% by weight, onto a completely crushed latex of (a) suspended in water, without a suspending agent. The powdered graft polymer obtained is then dried to obtain an average particle size d5o of (C) in the mixture according to the invention of 0.05 to 3 m.
It can be homogenized with other components in the desired proportions under the action of shearing forces, preferably from 0.1 to 2, in particular from 0.2 to 1 gm.

The expression "in the absence of suspending agents" means the absence of substances which, depending on their nature and amount, can suspend the grafting monomer (b) in the aqueous phase. This definition does not exclude the presence of substances which, for example, have acted as suspending agents in the preparation of the graft base (a) to be grafted; in such cases, in other words:
The flocculating or precipitating agent used to break up the latex (a) must be added in an amount that compensates for the suspending action of the substances used in the previous step, while the grafting monomer (b) is in the aqueous phase. It must be ensured that no (stable) emulsions are formed.

The graft polymer (C) produced in this way in the absence of suspending agents can be dispersed to very low particle sizes in other resin components as a component of the molding material according to the invention, which is more Even relatively long processing times at high temperatures may remain relatively unchanged.

The expression "very low particle size" means that the number, shape and size of the grafted polymer particles to be used, after homogenization, are similar to the number, shape and size of the grafted polymer particles introduced into the other molten resin components. This means that Sae and Sho match very well.

Obtained as an aqueous emulsion (latex), the latex particles are 1 to 20% by weight based on (&),
Also acrylate rubbers which preferably contain from 1 to 10% by weight of monomers already grafted in the aqueous emulsion and whose homopolymers or copolymers have a glass transition temperature above 0°C. Can be used as graft base (a).

Preferred grafting monomers of this type are alkyl acrylates, alkyl methacrylates, styrene, acrylonitrile α-methylstyrene and/or
or vinyl acetate.

Such a graft base (a) is produced, for example, by emulsion polymerization or emulsion graft polymerization. However, these also allow the preparation of 7 acrylate rubbers in solution or in bulk, and then grafting the grafting monomers on top, and subsequently converting these rubbers into aqueous emulsions suitable for further grafting processes. It can be manufactured by transferring to

The preferred graft base (L) for the 7 acrylate rubber of this particular embodiment is thus, in addition to the polymers listed on page 9, also a diene rubber core, if appropriate, and an ethylenic rubber core. There are also graft polymers made in water-based emulsions of acrylic ester polymers or copolymers containing saturated polymerizable heptamers.

Component (D) The polycarbonate-polyphenylene oxide block condensate in the context of the present invention comprises from 5% to 95% by weight, based on the total weight of the difunctional structural units of the block condensate, of the following formula (I) (Il In the formula, the groups R are of the same kind or different kinds and represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and x is a group R-C-R, -0-, -S- t represents -5O2-■, and "m" and "n" represent integers from 1 to 200, based on the total weight of the structural unit represented by and the difunctional structural unit of the block condensate. to 5% by weight of the following formula (II) [-0-Z-0-C-] (n), where -0-2-0 is a difert group having 6 to 30 carbon atoms. .

Contains other structural units represented by Polymers.

A preferred difelto group -0-2-0- has the following formula (m
) In the formula, A is a single bond, fullkylene having 1 to 6 carbon atoms, and 2 to 6 carbon atoms.
fulkylidene, cycloalkylidene having 5 to 6 carbon atoms,
-c-, -5o2 or a group represented by the following formula (&), where the groups R' are the same or different, H,
CH3, CIL or Br, and p is zero or 1.

These block condensates and their preparation are described in the German patent application Ring P 34 45 440.3 (LeA 23
440) and P 35° 25337.1 (L
eA 23 104). These compounds can be prepared using the phase boundary method known for the production of aromatic thermoplastic polycarbonates according to the following formula (Ia), where R, X, m and n have the meanings given in the case of formula (I). have

from the nylene oxides to other diphenols HO-Z-OI ((II a) chain terminators, phosgene and, if appropriate, branching agents). Manufactured using

The organic phase of the phase boundary method is, for example, as known in the art, CH2c
x2. It shall consist of chlorobenzene or a mixture of these.

The aqueous alkaline phase generally contains 8 to 14, preferably 9
It shall have a pH value of 13 to 13.

The volume ratio of the organic to inorganic phases is generally between 1:6 and 1:1.

The amount of organic phase is generally determined by the amount of block polya) produced.
The choice is made such that the ether polycarbonate is obtained as a solution with a concentration of 0.5 to 20% by weight.

The molar amount of phosgene is up to 150 mol %, based on the total number of moles of the diphenol component used.

Suitable catalysts for the manufacturing process range from 0.01 to 5 mol % based on the total number of moles of diphenol component used.
of tertiary amines and/or quaternary ammonium salts and/or quaternary phosphonium salts.

Preferred catalysts are triethylamine, tetrabutylammonium bromide and N-ethylpiperidine.

German patent applications P 34 45 440.3 and P
35 25 Aromatic block polyether polycarbonates prepared according to 337.1 are prepared by evaporation of the isolated and purified organic phase from the phase boundary process in a vacuum extruder, if passing through. isolated by conventional methods.

The polyether-polycarbonates or polycarbonate-polyphenylene oxide block condensates of German patent application P 34 45 440.3 or P 35 25 337.1.

Generally, they have a relative solution viscosity of 0.8 to 2, in particular 1.2 to 1.5, measured on a solution of 0.5 g of substance in 100 mJL of CH2C12 solution. These can be processed into high quality molded bodies by injection molding on commercially available machines at temperatures between 250°C and 380"C. It can also be extruded into semi-finished products by extrusion in an extruder at temperatures between 250°C and 380°C.

Further details regarding these block condensates, their preparation and their industrial use can be found in the German patent application P 3
4 45 440.3 and P35 25 337.1
It is described in.

The incorporation of mesoheboriphenylene ether blocks in polycarbonates by the phase boundary method is also described in German Patent Publication No. 3,211,636.

In the context of the present invention, the preferred amount of CI) is from 10 to 95% by weight, and that of (■) is therefore from 90% to 5% by weight.

A polycarbonate-polyphenylene oxide block condensate in the context of the present invention may also contain from 2% to 50% by weight, preferably from 5% to 30% by weight, based on the total weight of the block condensate, of the following formula (IV , 1) and (IV, 2) each (IV, 1 )
IIV, in formula 21.

The radical R" is of the same or different kind and represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and r" is an integer from 4 to 100, preferably from 6 to 30. Polymers comprising 50% to 98% by weight, preferably 70% to 95% by weight of structural units represented by formula (II) based on the total weight of monofunctional structural units and block condensates be.

Such polycarbonate-polyphenylene oxide block condensates are in turn prepared in a known manner by phase boundary methods to form the corresponding polyphenylene oxides (ffa), where R" and "r" represent formulas (IV, 1) and ( Diphenols having the meanings given in each case 1, 2) can be prepared from HO-Z-OH (■a) and phosgene (see, for example, German Patent Application No. 3,211,636).

-Functional polyphenylene oxides (■a) are known from the literature and can be prepared by methods known from the literature (
For example, German Patent Publication No. 3,211.636, German Patent Publication No. 2,126°434 and US Patent No. 3.
306.875), thus, for example, formula (IV
The -functional polyphenylene oxides of a) are prepared by oxidizing the corresponding phenols (ffb) R// with oxygen (e.g. air) in the presence of catalytic compounds of copper salts and tertiary amines. can do.

Polycarbonate-polyphenylene oxide block condensates having structural units of formulas (IV,1) and (IV,2), respectively, are in turn generally treated with 100 m of CH2Cl
Measured on a solution of 0.5 g of substance in 2 solutions, 0.
It has a relative solution viscosity of 8 to 2, especially 1.2 to 1.5.

These block condensates having structural units of formulas (rv, t) and (IV, 2) can be processed by injection molding or extrusion molding using commercially available machines.

The -functional polyphenylene oxide of formula (IT a) to be used has an average number average molecular weight Mn of 500 to 10.
,000, preferably 800 to 3°000,
The difunctional polyphenylene oxide of formula (Ia) to be used has an average number average molecular iMn of 600 to 3,00.
0, preferably 800 to 1.500, and in both cases can be determined by osmotic methods in CH2Cuz as solvent.

Diphenols (IIa) are either known or can be produced by known methods. Preferred diphenols (■a) include bisphenol A = 2.2-bis-(4-hydroxyphenyl)-propane, tetramethylbisphenol A, 1, 1-bis-(4-hydroxyphenyl)-isobutane, 1 .1-bis-(4-hydroxyphenyl)-cyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and its di- and tetrahalogenated derivatives. Preferred chain terminators for the preparation of block condensates having structural units of the formula CI), in which bisphenol A is particularly preferred; it is also possible to use any desired mixtures of the abovementioned diphenols. is 4-hydroxydiphenyl, p-nonylphenol, 4-(1,1,3,3-tetramethylene-ethyl)-
Monofunctional aromatic hydroxy compounds such as phenol, chlorocarbonate esters such as ethyl and phenylchlorocarbonate, and aliphatic and aromatic carboxylic acid chlorides such as stearyl chloride and naphthalene carboxylic acid chloride. Particular preference is given to the chain terminators described in EP-A-36,080, such as p-isooctylphenol and p-innonylphenol.

These substances are 0.1 to 1'O mol%, preferably 0.3 to 70% by mole, based on the diphenols used.
Only mole % amounts are used.

Preferred branching agents for the production of block condensates having structural units of formula (I) are trimesic acid trichloride, cyanuric acid trichloride, in an amount of 0.01 to 1.0 mol%, based on the diphenols used. , 3.3″, 4.
Trifunctional or more than trifunctional carboxylic acid chlorides, such as 4'-benzophenonetetracarboxylic acid tetrachloride, 4'-5.8-naphthalenetetracarboxylic acid tetrachloride or biromellitic acid tetrachloride, or 0.0% based on diphenols.
chloroglucinol in an amount of 01 to 1.0 mol%, 4
,6-dimethyl-2.4゜6-tri(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl=2
．． 4,61-tri(4-hydroxyphenyl)-hebutane, 1.3.5-tri(4-hydroxyphenyl)-benzene, 1,1.1-tri(4-hydroxyphenol)-ethane, tri(4- hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2
,4-bis-(4-hydroxyphenylisopropyl)
-Phenol, tetra-(4-hydroxyphenyl)-
Methane, 2,6-bis-(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4 -[4-hydroxyphenylisopropyl]-phenoxy)-methane and 1.4
-bis-[(4,4"-dihydroxytriphenyl)-
trifunctional or more than trifunctional phenols, such as methyl]-benzene.

The incorporation of branching agents into polycarbonates by phase boundary methods, including into segmented polynityl-polycarbonates, is known (in this connection, see German Patent Publication No. 1,570). , No. 533,
U.S. Reissue Statement (U, S, Reissue 5pe
citation) No. 27,682, German Patent Publication No. 26 36 784 (LeA 17 025
) and German Patent Publication No. 2,726,376)
.

Mixtures of polycarbonates and polyesters are known (for example from German Patent Specification 1°187.793).
(see German Patent Publication No. 1, 694.124 and German Patent Publication No. 2,622.414).

Mixtures of polyesters and grafted polymers are likewise known (e.g. U.S. Pat. No. 3,919).
, 353 and 3, 564.

No. 077, German Patent Publication Section 2. ss 9,33a'' or US Pat. No. 4,096,202 and German Patent Publication No. 2.726.258).

Mixtures of polycarbonates and polymers are likewise known (for example from patent application Publ. No. 18.611/68).
No. 3,663,471, U.S. Patent No. 3,437,
631, US Pat. No. 4,299,928 or German Patent Publication No. 3.114,494).

Mixtures of polycarbonates, polyesters and grafted polymers are likewise known (for example U.S. Pat. No. 3,864,428 and German Patent Publication No. 2,343,609 or U.S. Pat. No. 4,264).
No. 487 and European Patent Publication No. 25,920 or US Pat. (See Specification No. 1.007.724).

Although molding materials composed of polycarbonates, polyesters, and elastomeric polymers have many useful properties, they still need improvement in at least one aspect, and that is their sticking points.
ck point) is too low. The sticking point is understood to be the temperature of the injection molding surface above which the injection molded product sticks to the surface and is difficult to separate from the mold, requiring a higher mold release force. The injection mold is usually
Cooled with water or oil. In complex molds, however, there are often regions (for example small cores) that cannot be cooled sufficiently and whose temperature rises rapidly due to the melt flowing into them. If a sticking point is thus reached, the cycle time must be increased to allow the mold time to cool between injections.

In the present invention, it has been found that the sticking point of molding materials consisting of polycarbonates, polyesters and elastomeric polymers is considerably increased by the addition of polycarbonate-polyphenylene oxide block condensates.

polycarbonate, polyalkylene terephthalate and, if appropriate, one or more Thermoplastic molding materials based on polymers are disclosed in F-Itsu Patent Publication No. 3,118,697 (LeA
21047). However, this German patent publication does not give any further examples or details about the adhesive properties of such molding materials, but only comments that a mold release agent can be added (p. 26). Molding materials based on polycarbonates, polyalkylene terephthalates and, if appropriate, elastomeric polymers, the thermal distortion resistance and deformation properties of which are improved by the addition of aromatic thermoplastics based on polyetherimides, are described in European Patent Specification No. 0. 133°23
No. 6 (LeA 22 330-EP). Similarly, no further details are given in this European Patent Application about the adhesive properties of such molding materials, and only a comment is made that a mold release agent can be added again. (p24).

The molding materials according to the invention can be produced in conventional mixing equipment such as roll mills, kneaders and single-screw and multi-screw extruders. The mixing temperature is between 200°C and 340°C, preferably between 220°C and 340°C.
The temperature shall be between 00°C.

Although in most cases it is advantageous for all resin components to be mixed in a single step, one or sometimes two components may be retained initially and this or these may be mixed at a later point. It may also be a good idea to do so.

In this connection, the molding material according to the invention containing 0% by weight of component (C) has a somewhat modified pattern of properties compared to the molding material according to the invention containing component (C); In particular, it has also been found that although the former have lower toughness, they have higher resistance to thermal strain and higher stability when exposed to heat over long periods of time.

The molding material according to the present invention comprises components (A) + (B) + (
C) + 5 based on the total weight of 100% by weight of (D)
Up to % by weight of ethylene homopolymers or copolymers can be included to increase resistance to gasoline. Ethylene copolymers in this context are:
The groups are polyethylenes which, in addition to ethylene groups, consist of other copolymerizable supermer groups to the extent of up to 30% by weight, based on the ethylene copolymer. Other copolymerizable supermers for the production of these ethycine copolymers are, for example, those listed above for the production of graft bases and grafts for acrylic acid (methacrylic acid) and component (C). These are monomers.

If appropriate, the molding material according to the invention may contain a nucleating agent,
It may contain additives customary for polycarbonates and/or polyesters, such as stabilizers, fillers and reinforcing substances, flame retardants and/or dyes.

The filled or reinforced molding material may contain up to 60% by weight of fillers and/or reinforcing substances, based on the reinforced molding material. The preferred reinforcing material is glass a
It is m. Preferred fillers, which may also have a reinforcing effect, are glass beads, mica, silicates, quartz, titanium dioxide and wollastonite.

Polyester molding materials finished with flame retardants generally contain less than 30% by weight of flame retardant, based on the flame retardant molding material.

The known flame retardants for polycarbonates or polyesters or elastomeric polymers are possible, such as polyhalogenodiphenyls, polyhalogenodiphenyl ethers, polyhalogenophthalic acids and derivatives of these and polyhalogeno-oligo- and -polycarbonates. The corresponding bromine compounds are particularly effective. These things are also generally
It also contains a synergist, such as antimony trioxide.

The molding material according to the invention can be molded at temperatures between 220° C. and 340° C., in particular by both injection molding and extrusion methods.
It is possible to process shaped bodies, in particular any desired type of shaped body, for example sheets or films.

The molded body that can be obtained from the molding material according to the present invention is
For example, used in electrical engineering and the automotive industry.

The parts mentioned in the examples below are parts by weight.

Percentages relate to weight.

Ingredients used: ■, polycarbonate of bisphenol A, phenol and phosgene, 0.5% in methylene chloride at 25°C
Relative viscosity 1.285°■ measured in solution with phenol 10-dichlorobenzene cmi ratio 1:l
) in a Ubbelohde viscometer at 25°C.
1.18 dl/g measured with viscometer)
Polybutylene terephthalate with an intrinsic viscosity of .

(2) Polyethylene terephthalate having an intrinsic viscosity of 0.78 dl/g as measured in H.

■, Melt index 6-8g 710 minutes (DIN
19 under a load of 2.16 kp according to 53 735
measured at 0°C) and density 0.924 g/cm3 (DI
N 53 479), weight ratio 8
Terpolymer of 9/4/7 ethylene, acrylic acid and t-butyl acrylate.

■ Graft polymer, graft base 80% of crosslinked polybutadiene (gel content >70% measured in toluene) and graft 20 of methyl methacrylate
%.

■ Graft polymer, graft base of cross-linked polybutadiene 80% (gel content >70% measured in toluene) and 72 parts of styrene and 2 parts of acrylonitrile
20% graft consisting of 8 parts.

(2) A graft polymer having a core-jacket structure having the following composition expressed by the weight ratio of the heptamers forming the graft polymer: n-butyl arylate/butane-1,3-diol diacrylate/diallyl maleate/methyl methacrylate. )=79°210.410.4/20.0°■9 A graft polymer having a core-jacket structure produced by the following multi-stage method.

1. Production of graft base 1.1 Production of polybutadiene latex An emulsion having the following composition was heated at 65°C in a reaction vessel to about 2.
Polymerization is carried out over a period of 2 hours, with stirring, until complete conversion of the 7-mer.

100 parts of butadiene, 1.8 parts of sodium salt of disproportionated abietic acid, 0.257 parts of sodium hydroxide, 0.3 parts of n-dodecylmercaptan, 1.029 parts of sodium ethylenediaminetetraacetate, 0.0 parts of potassium persulfate.
023 parts and 176 parts of water.

Contains polybutadiene particles with an average diameter (ds.) of 0.1 part m. A latex with a concentration of approximately 36% is obtained.

1.2 Production of acrylate rubber containing a polydiene core.

The following mixture is initially introduced into a reaction vessel at 63°C with stirring: 200 parts of Nilatex 1.1 and 5.0 parts of water.
00 parts, potassium persulfate 14 parts, triallyl cyanuride
) 0.9124 parts and n-butyl acrylate 399 parts
．． Part 09.

The following mixtures are weighed separately into the reaction vessel at 63° C. over a period of 5 hours: Mixture I: 90 parts of sodium C14-18 alkyl sulfonate and 900 parts of water it.

Mixture 2 23.09 parts of nitriaryl cyanuride and n-butyl acrylate) 10,101 Department.

The mixture is then fully polymerized at 65° C. for 2 hours. The polymers produced have a gel content of 85-95% and a gel content of 0.
It has an average particle diameter (ds.) of 51 parts m (polymer content in latex: 38%).

2.1 Production of emulsion graft polymers 2.1
．． 17'FIJ Ray) Emulsion graft polymer of 90% rubber 1.2 and 10% styrene+7crylonitrile.

The following ingredients are first introduced into the reaction vessel: 3.296 parts of Nilatex 1.2, 1.5 parts of potassium persulfate, and 90 parts of water.

The following mixtures are weighed separately into a reaction vessel at 65° C.: Mixture I: 39 parts of acrylonitrile and styrene.
100 parts of Mixture 2 150 parts of diwater and 4 parts of sodium alkyl sulfonate having 14 to 18 carbon atoms.

The mixture is then fully polymerized at 65° C. for 4 hours (polymer content in latex: 37.8%).

2.2 Preparation of graft polymer C from emulsion graft polymer.

The following components are first introduced into the reaction vessel at 70°C:
18,800 parts of water and 240 parts of magnesium sulfate.

With stirring, 11.200 parts of Latex 2.1.1 are now allowed to flow into the reaction vessel over a period of 2 hours.

When the addition is complete, 1 part of potassium persulfate is added to the reaction vessel, and 148 parts of acrylonitrile and 38 L of styrene are then metered in uniformly over 1 hour with stirring. The suspension is subsequently stirred at 90° C. for 1 hour. Polymer C is then isolated.

(2) Preparation of polyfunctional polyphenylene oxide segment a, Mn about 1,500 Mix 16 g of CuC, 30 g of 4-dimethylaminopyridine and 1,400 tnl of chlorobenzene to make about 10
2 hours into the mixture at a layer height of Cm (1501
part time) I blew air into it.

After addition of 1.220 g of 2.6-dimethylphenol and 6.600 ml of chlorobenzene, further air was blown in at a layer height of approximately 45 cm (150 M/h).
The temperature of the reaction mixture initially rose from 21°C to 29°C.

After 16.5 hours, the solids in the solution still contained 1.28% by weight of OH groups. The oxidation was interrupted and the reaction mixture was reduced to C
H30HIOJl and 40% concentration aqueous HCJL2QOm
Mix and stir the mixture thoroughly. The precipitated polyphenylene oxide was filtered off with suction, washed with CH30H and then with water and dried at 60° C. in a vacuum drying cabinet. The yield was 1,014 g, about 82% of theory. Molecular weight determination by osmometry in CH2CfL2 yields a Mn of 1,513.

b, Mn approximately 4,500 The batch described in paragraph a was prepared with 0.39% by weight of O solids in solution.
It was stopped only when it contained 'H. Yield is 1.052
g=about 85% of theory 0Mn was 4,567.

X, Production of difunctional polyphenylene oxide segments Behold the mouse! Leopard Mutual A CuCfLlog, 4-dimethylaminopyridine 50g
and 1,500 ml of chlorobenzene to create a
Air is passed for 2 hours (150 views/hour) at a layer height of 0 cm.

2.6-dimethylphenol 977g and 2.2-
Bis-(3,5-dimethyl-4-hydroxyphenyl)
568g of propane and 7.000m4 of chlorobenzene
Further air was blown into the solution at a bed height of approximately 50 cm (15 (HL/h)). The temperature of the reaction mixture initially rose from 20 °C to 31"
When an H content of 4.2% by weight was reached, the reaction was stopped,
This solution was washed with an aqueous solution of the trisodium salt of ethylenediaminetetraacetic acid in dilute HCfL, an aqueous solution of NaHCO3, and water.

The difunctional polyphenylene oxide remaining upon evaporation of the solution had 796(7)Mn (determined by osmolarity measurement in CH2CQ2 solution).

Analysis by gel chromatography showed only about 1.3% by weight of -functional substituents.

b, Mn=1 250 Cu (1115g, 4-dimethylaminopyridine 35g
and chlorobenzene 1.51, approximately 10 cm
Air was passed through the mixture for 1 hour (100 views/hour) at a bed height of .

2. After addition of 285 g of 2-bis-(3,5-dimethyl-4-hydroxyphenyl)furopane, 977 g of 2,6-dimethylphenol and 7.7 g of chlorobenzene, 1
00 views/hour passed through the air.

The reaction, in which the temperature initially increased from 20° C. to 28° C., was discontinued when a solid OH content of about 2.8% by weight was reached.

The finishing for this batch was as described in section a.

The Mn of the product was approximately 1,260. The product contained approximately 2% by weight of monofunctional components.

Preparation of Xl, polycarbonate-polyphenylene oxide block cocondensate a) From IKa: Bisphenol A I, 598 g (7 mol) and N
800 g (20-terres) of aOH was dissolved in 45 ml of water under N2. -Functional polyphenylene oxide IKa
C containing 525 g (0.35%) [2C! L
2 to 30! After adding 1.3 kg of COCl2 to 1
It was introduced within hours under vigorous stirring, the pH being maintained at 13-14 on the one hand and the temperature at 20-22.degree.

After addition of 40 ml of N-ethylpiperidine, the mixture was subsequently stirred for 1 part at pH 13-14.

The phases were then separated, the organic phase was washed, half of the solvent was distilled off from it, and the block cocondensate was precipitated with an inproper tool and dried in vacuo at 100°C.

Yield: 2,136 g, η = 1.31 tel (determined on a solution of 0 product in 100 Jl of CH2CJ12 solution) b) From Xb: XIa was repeated but 1.60 instead of IXa
0 g (0,355 mol) of IXb was used and the reaction was run under higher dilution (30 fL compared to XIa).
Instead, there are 60 sentences of CH2C exchange 2).

1.6 kg of C0CJI2 was further used (1°3 kg
), the yield was 3.283 g. η was 1.346.

el c) From Xa: Bisphenol A I, 598 g (7 mol) and N
8800 g of aO was dissolved in 4 SfL of water under N2.

50 sentences of 0820 sentence 2 and 54.1 g (4 mol%) in which 1.600 g (2 mol) of Xa was dissolved
After adding t-butylphenol, phosgene 1.3k
g was allowed to pass for 1 hour while stirring vigorously. Further processing was as described in Section XIa. Yield was 3.286 g, η = 1.306.

el d) From Xb: Repeated Xlc, but 2.500 instead of Xa
g xb was used.

Yield is 4,176g, η is 1,336, el there were.

The composition of the compound mixtures and joint sticking points are summarized in Table 1.

The mold release experiment was conducted using an apparatus whose principle is shown in FIG. When the injection mold is opened after the injection operation, the molded body (
cone) remains on top of the core, and from here ejector A
be pushed away. Above the sticking point, the molded body breaks when pushed away from the core K.

For details on the mold release test, please refer to “Plastics” (“Kunst
Stoffe”) 66 (1976) p210.

In Figure 1, the numbers have the following meanings: 1 hydraulic ejector, 2 mechanical pressure recorder, 30 - docel (wire strain gauge), 4 liquid oscillograph, 5 injection mold, 6 thermostat, 7 temperature recorder. Total, 8 injection devices, 9
Yes, it's a pyrometer, a 10 revolution counter.

[Brief explanation of the drawing]

The attached drawing is a schematic drawing of an apparatus for actually measuring the improvement of the mold release properties of thermoplastic molding materials according to the present invention.

Claims (1)

[Scope of Claims] 1. The following component (A) 98 to 1% by weight of thermoplastic aromatic polycarbonates having a weight average molecular weight Mw (Mw is measured by light scattering) between 10,000 and 200,000, (B) 1 to 98% by weight of thermoplastic polyalkylene terephthalates, and if appropriate (C) 0% of an elastomeric polymer having a glass transition temperature below -20°C.
A thermoplastic molding material containing from 30% by weight,
This product is characterized in that it contains (D) 1 to 30% by weight of a polycarbonate-polyphenylene oxide block cocondensate, in each case components (A) + (B
) + (C) + (D) The sum of weight % is 100 weight %. 2. (A) 78 to 20% by weight, (B) 20 to 7% by weight
8% by weight, (C) from 1 to 20% by weight, and (D) from 1 to 20% by weight. 3. (A) 64 to 30% by weight, (B) 30 to 6%
4% by weight, (C) from 3 to 12% by weight, and (D) from 3 to 15% by weight. 4. A molding material according to claim 1 consisting of components (A) + (B) + (D) and if appropriate (C), which also contains ethylene homopolymers or copolymers, cores. nucleating agent, (nucleating ag
ent), stabilizers, fillers, reinforcing substances, flame retardants and/or
Or molding materials that also contain dyes.