Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2000-12-21
2004-06-08
Szekely, Peter (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S122000, C524S138000
Reexamination Certificate
active
06747078
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to thermoplastic polycarbonate moulding compositions which contain phosphazenes and special graft polymers produced by means of redox initiator systems and are distinguished by substantially improved mechanical properties.
BACKGROUND OF THE INVENTION
DE-A 196 16 968 describes polymerisable phosphazene derivatives, a process for the production thereof and the use thereof as curable binders for lacquers, coatings, fillers, surfacing compositions, adhesives, mouldings or films.
WO 97/40 092 describes flameproofed moulding compositions prepared from thermoplastic polymers and unsubstituted phosphazenes of the type PN
n-x
H
l-y
.
EP-A 728 811 describes a thermoplastic blend consisting of aromatic polycarbonate, graft copolymer, copolymer and phosphazenes which exhibits good flameproofing properties, impact strength and heat resistance.
Neither WO 97/40 092 nor EP-A 728 811 describe a combination of phosphazenes and the special graft polymers.
EP-A-315 868 (=U.S. Pat. No. 4,937,285) describes moulding compositions made from thermoplastic polycarbonates which contain redox graft polymers. No mention is made of adding phosphazenes.
SUMMARY OF THE INVENTION
The object of the present invention is to provide flame-resistant polycarbonate/ABS moulding compositions having very good mechanical properties such as notched impact strength, stress cracking resistance, flame resistance and weld line strength. This range of properties is required in particular for applications in data processing, such as for example thin-walled casings for monitors, printers etc.
It has now been found that PC/ABS moulding compositions which contain phosphazenes and a graft polymer produced by means of a redox initiator system exhibit the desired properties.
The present invention accordingly provides thermoplastic moulding compositions containing
A) 40 to 99, preferably 60 to 98.5 parts by weight of aromatic polycarbonate and/or polyester carbonate
B) 0.5 to 60, preferably 1 to 40, in particular 2 to 25 parts by weight of graft polymer, characterised in that the graft polymers B comprise
B.1) 5 to 95, preferably 30 to 80 wt. % of one or more vinyl monomers and
B.2) 95 to 5, preferably 20 to 70 wt. % of one or more particulate diene rubbers having a glass transition temperature of <10° C., preferably of <0° C., particularly preferably of <−20° C., which are produced by emulsion polymerisation, wherein the graft polymerisation is performed using an initiator system comprising an organic hydroperoxide and ascorbic acid,
C) 0 to 45, preferably 0 to 30, particularly preferably 2 to 25 parts by weight of at least one thermoplastic polymer selected from the group comprising thermoplastic vinyl (co)polymers and polyalkylene terephthalates,
D) 0.1 to 50, preferably 2 to 35, in particular 5 to 25 parts by weight of at least one component selected from the group comprising phosphazenes of the formulae
in which
R is in each case identical or different and denotes amino, C
1
to C
8
alkyl, in each case optionally halogenated, preferably halogenated with fluorine, or C
1
to C
8
alkoxy, C
5
to C
6
cycloalkyl, C
6
to C
20
aryl, preferably phenyl or naphthyl, C
6
to C
20
aryloxy, preferably phenoxy, naphthyloxy, or C
7
to C
12
aralkyl, preferably phenyl-C
1
-C
4
-alkyl, in each case optionally substituted by alkyl, preferably C
1
-C
4
alkyl, and/or halogen, preferably chlorine and/or bromine
k denotes 0 or a number from 1 to 15, preferably a number from 1 to 10,
E) 0 to 5, preferably 0.1 to 1, particularly preferably 0.1 to 0.5 parts by weight of fluorinated polyolefin.
DETAILED DESCRIPTION OF THE INVENTION
Component A
Component A aromatic polycarbonates and/or aromatic polyester carbonates which are suitable according to the invention are known from the literature or may be produced using processes known from the literature (c.f. in relation to the production of aromatic polycarbonates, for example Schnell,
Chemistry & 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; in relation to the production of polyester carbonates for example DE-OS 3 077 934).
Aromatic polycarbonates are produced for example by reacting diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or greater than trifunctional branching agents, for example triphenols or tetraphenols.
Diphenols for the production of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of the formula (II)
wherein
A means a single bond, C
1
-C
3
alkylene, C
2
-C
5
alkylidene, C
5
-C
6
cycloalkylidene, —O—, —SO—, —CO—, —S—, —SO
2
—, C
6
-C
12
arylene, onto which further aromatic rings optionally containing heteroatoms may be fused,
or a residue of the 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 mutually independently mean 0, 1 or 2,
p means 1 or 0 and
R
5
and R
6
individually selectably, mutually independently for each X
1
, mean hydrogen or C
1
-C
6
alkyl, preferably hydrogen, methyl or ethyl,
X
1
means carbon and
m means an integer from 4 to 7, preferably 4 or 5, providing that R
5
and R
6
are simultaneously alkyl on at least one atom X
1
.
Preferred diphenols are hydroquinones, resorcinol, dihydroxydiphenols, bis-(hydroxy-phenyl)-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 together with the ring-brominated and/or ring-chlorinated derivatives thereof.
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′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfone together with 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-bis3,5-dibromo-4-hydroxyphenyl)propane.
2,2-Bis-(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.
The diphenols may be used individually or as any desired mixtures.
The diphenols are known from the literature or are obtainable using processes known from the literature.
Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert.-butylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenols having a total of 8 to 20 C atoms in the alkyl substituents, such as 3,5-di-tert.-butylphenol, p-iso-octylphenol, p-tert.-octylphenol, p-dodecylphenol and 2-(3,5dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)phenol. The quantity of chain terminators to be used is generally between 0.5 mol. % and 10 mol. %, relative to sum of moles of the diphenols used in each case.
The thermoplastic, aromatic polycarbonates have weight average molecular weights (M
w
, measured for example by ultracentrifugation or light scattering) of 10000 to 200000, preferably of 20000 to 80000.
The thermoplastic, aromatic polycarbonates may be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol. %, relative to the sum of diphenols used, of trifunctional or greater than trifunctional compounds, for example those having three and more than three phenolic groups.
Both homopolycarbonates and copolycarbonates are suitable. Component A copolycarbonates according to the invention may be produced by also using 1 to 25 wt. %, p
Eckel Thomas
Wittmann Dieter
Zobel Michael
Bayer Aktiengesellschaft
Franks James R.
Gil Joseph C.
Preis Aron
Szekely Peter
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