Polycarbonate-ABS moulding compounds

Details Polycarbonate-ABS moulding compounds Polycarbonate-ABS moulding compounds

2000-07-07

2001-12-04

Hoke, Veronica P. (Department: 1714)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Processes of preparing a desired or intentional composition...

C524S119000, C524S141000, C524S145000

Reexamination Certificate

active

06326423

ABSTRACT:

The present invention relates to polycarbonate-ABS moulding compositions containing phosphorus compounds which have excellent mechanical properties, in particular excellent notched impact strength, stress cracking behavior and heat resistance.
Metal salts of organic monophosphates or diphosphoric acids are well known. They have been used hitherto as heat and UV stabilisers in halogen-containing moulding compositions such as PVC (JP 010 792 44, JP 540 915 53, JP 580 277 34) or in polyamides (JP 450 168 26B4).
Polycarbonate-ABS blends are a well known class of substances for applications in the automotive sector and in the electrical engineering/electronics sector. The favourable combination of properties of good heat resistance and good mechanical values, for example, in terms of the notched impact strength or stress cracking behavior, has always proved to be advantageous. If, nevertheless, the notched impact strength or the stress cracking resistance should be insufficient for certain parts, the conventional procedure is to increase the rubber content. This measure is, however, always associated with a marked reduction in the heat resistance.
It has now been found that this problem may be solved using the phosphorus compounds according to the invention.
The present invention provides thermoplastic moulding compositions containing
A 5 to 95, preferably 10 to 90, particularly preferably 20 to 85 parts by wt., particularly 50 to 85 parts by wt. of polycarbonate and/or polyester carbonate,
B 0 to 50, preferably 1 to 30, particularly preferably 2 to 25 parts by wt. of a vinyl (co)polymer of one or at least two ethylenically unsaturated monomers,
C 0.5 to 60, preferably 1 to 40, particularly preferably 2 to 30 parts by wt. of graft polymer with a glass transition temperature of <10° C., obtainable by graft polymerisation of at least 2 of the monomers selected from chloroprene, butadiene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (meth)acrylate with 1 to 18 carbon atoms in the alcohol component, and
D 0.5 to 20 parts by wt., preferably 1 to 18 parts by wt., particularly preferably 2 to 15 parts by wt. of phosphorus compound corresponding to formula (Ia) and/or (Ib)
or to the formula (II)
wherein
R
1
and R
2
independently of one another, mean optionally halogenated C
1
-C
24
-alkyl, C
5
-C
6
-cycloalkyl, C
6
-C
20
-aryl or C
7
-C
12
-aralkyl in each case optionally substituted by halogen and/or C
1
-C
10
alkyl, or
R
1
and R
2
in the case of formula (II) may also form an alkylene radical, preferably with up to 6, particularly 2 or 3 carbon atoms, or an arylene radical, preferably phenylene,
Me stands for a metal selected from the 1st to 3rd main group or from the subsidiary group VIII, IB and 2B of the periodic system,
and n is determined by the valency of the metal ion.
Component A
Aromatic polycarbonates and/or aromatic polyester carbonates according to component A suitable according to the invention are known in the literature or may be prepared according to processes known in the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the preparation of aromatic polyester carbonates, see e.g. DE-OS 3 077 934).
Aromatic polycarbonates are prepared e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, according to the phase boundary process, optionally with the use of chain terminators, for example, monophenols and optionally with the use of trifunctional or more than trifunctional branching agents, for example, triphenols or tetraphenols.
Diphenols for the preparation of aromatic polycarbonates and/or aromatic polyester carbonates are preferably those corresponding to formula (II)
wherein
A means a simple compound, C
1
-C
5
-alkylene, C
2
-C
5
-alkylidene, C
5
-C
6
-cycloalkylidene, —O—, —SO—, —CO—, —S—, —SO
2
—, C
6
-C
12
-arylene, on which further aromatic rings optionally containing heteroatoms may be condensed,
or a radical corresponding to formula (III) or (IV)
B in each case means C
1
-C
12
-alkyl, preferably methyl, halogen, preferably chlorine and/or bromine,
x in each case, independently of one another, is 0, 1 or 2,
p is 1 or 0,and
R
3
and R
4
which may be chosen individually for each X
1
, independently of one another, mean hydrogen or C
1
-C
6
-alkyl, preferably hydrogen, methyl or ethyl,
X
1
is carbon and
m is an integer from 4 to 7, preferably 4 or 5, provided that on at least one atom X
1
, R
3
and R
4
are simultaneously alkyl.
Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl) -C
1
-C
5
-alkanes, bis-(hydroxyphenyl)-C
5
-C
6
-cycloalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl)sulfoxides, bis-(hydroxyphenyl)ketones, bis-(hydroxyphenyl)sulfones and &agr;, &agr;-bis-(hydroxyphenyl)diisopropylbenzenes and the derivatives thereof brominated and/or chlorinated on the nucleus.
Particularly preferred diphenols are 4,4′-dihydroxydiphenyl, bisphenol A, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1 -bis-(4-hydroxyphenyl)cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxydiphenylsulfide, 4,4′-dihyroxydiphenylsulfone and the di- and tetrabrominated or chlorinated derivatives thereof such as, for example, 2,2-bis-(3-chloro-4-hydroxyphenyl)propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane.
2,2-bis-(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.
The diphenols may be used on their own or as any mixtures.
The diphenols are known in the literature or are obtainable according to processes known in the literature.
Chain terminators suitable for the preparation of thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert.-butylphenol or 2,4,6-tribromophenol, and also long-chain alkyl phenols such as 4-(1,3-tetramethylbutyl)phenol according to DE-OS 22 842 005 or monoalkylphenol or dialkyl phenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert.-butylphenol, p-iso-octylphenol, p-tert.-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminators to be used is generally between 0.5 mole-% and 10 mole-%, based on the mole sum of the diphenols used in each case.
The thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M
w
, measured, e.g. by ultracentrifuging or scattered light measurement) from 10,000 to 200,000, preferably 20,000 to 80,000.
The thermoplastic, aromatic polycarbonates may be branched in a known way and preferably by the incorporation of 0.05 to 2.0 mole-%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example, those with three and more phenolic groups.
Both homopolycarbonates and copolycarbonates are suitable. For the preparation of copolycarbonates according to the invention according to component A, 1 to 25 wt. %, preferably 2.5 to 25 wt. % (based on the total amount of diphenols to be used) of polydiorganosiloxanes with hydroxyl aryloxy end groups may also be used. These are well known (see, for example, U.S. Pat. No. 3,419,634) and may be prepared according to processes known in the literature. The preparation of copolycarbonates containing polydiorganosiloxanes is described, e.g., in DE-OS 3 334 782.
Preferred polycarbonates, apart from bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15 mole-%, based on the mole sums of diphenols, of other diphenols mentioned in preference or particular preference, particularly 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane.
Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorid

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