Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2002-01-15
2003-12-16
Buttner, David J. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S474000, C525S479000, C528S025000, C528S026000, C528S028000, C528S029000, C528S203000
Reexamination Certificate
active
06664342
ABSTRACT:
The invention relates to aromatic polycarbonates, containing aspartate-functional silicones, that are distinguished by very good low-temperature impact strength and very good ESC behaviour.
Aromatic polycarbonates are highly impact-resistant plastics which are distinguished by very good impact resistance at room temperature. One disadvantage is their susceptibility to solvents (stress cracking, ESC behaviour) and their declining notch impact strength at temperatures below 0° C.
It has now been found that aromatic polycarbonates containing aspartate-functional silicones, which can be produced by incorporation of the aspartate-functional silicones during the synthesis of polycarbonate from bisphenols and derivatives of carbonic acid or by reaction of unmodified aromatic polycarbonate with aspartate-functional silicones, are distinguished by very good low-temperature impact strength and very good ESC behaviour.
The invention therefore provides aromatic polycarbonates with 1 to 30 wt.%, preferably 5 to 15 wt. %, aspartate-functional silicones, obtainable by reaction of bisphenols and aspartate-functional silicones with derivatives of carbonic acid or by reaction of polycarbonates with aspartate-functional silicones.
Use is preferably made of aspartate-functional silicones that are obtainable by addition of fumarate and/or maleates of the formula (I)
ROOC—CH═CH—COOR (I)
where R stands for a C
1
-C
4
alkyl or alkenyl residue onto amino-functional silicones.
These compounds are new and are likewise a subject of the invention.
Preferred compounds of the formula (I) are methyl maleate, methyl fumarate, ethyl maleate, ethyl fumarate, n-propyl maleate, n-propyl fumarate, isopropyl maleate, isopropyl fumarate, n-butyl maleate, n-butyl fumarate, i-butyl maleate, i-butyl fumarate, sec-butyl maleate, sec-butyl fumarate, tert-butyl maleate, tert-butyl fumarate, allyl maleate or allyl fumarate.
The amine-functional silicones are available by reaction of open-chain siloxanes and/or cyclic oligosiloxanes, in which 45 to 100% of the substituents on the siloxane groups are methyl groups and the remainder are preferably phenyl groups, with aminosilanes, preferably with aminosilanes of the formula (II)
H
2
N—X—Si(OR)
n
(CH
3
)
3−n
(II)
where
R conforms to the meaning stated above,
X is a divalent organic residue with 2 to 22 carbon atoms, preferably —CH
2
—CH
2
—CH
2
— and
n is 1 or 2 or 3, preferably 2 or 3, with 2 being quite particularly preferred.
Conversion is preferably effected at temperatures from 120 to 250° C. in the presence of acidic catalysts such as, for example, p-toluenesulfonic acid, basic catalysts such as, for example, alkali alcoholates, or metal catalysts such as, for example, dibutyltin oxide, SnCl
2
, Sn(II) carboxylates or salts of transition metals.
The amino-functional silicones that are used in accordance with the invention may also be produced by hydrosilylation, analogous to polymerisation, of SiH-functional silicones with unsaturated amines, preferably allylamine.
The amine equivalent weight of the aspartate-functional silicones according to the invention and of the amino-functional silicones used as educts amounts to 1,000 to 50,000 g/g. equiv., preferably 4,000 to 20,000 g/g. equiv. The molecular weight of the aspartate-functional silicones amounts to 2,000 to 5,000,000 g/mol, preferably 20,000 to 2,000,000 g/mol.
Production of the aspartate-functional silicones is effected by amino-functional silicones being converted with compounds of the formula (I).
The molar ratio of amino groups to compounds of the formula (I) amounts to 1:1 to 1:20, preferably 1:2 to 1:10; the reaction is carried out for 1 to 10 hours at 80 to 220° C., preferably in the absence of solvents or catalysts, the excess of compounds of the formula (I) subsequently being distilled off at a pressure from 1 to 100 mbar and at temperatures from 150 to 250° C. In a preferred embodiment the amino-functionalisation of the open-chain siloxanes and/or cyclic oligosiloxanes with aminosilanes and the subsequent conversion with compounds of the formula (I) are carried out in succession in a one-pot reaction.
In the case where use is made of aminopropyl methyldiethoxysilane by way of aminosilane for the amino-functionalisation and diethyl maleate by way of compound of the formula (I), an aspartate-functional silicone is obtained that contains the following structural unit:
The aspartate-functional silicones according to the invention can be employed as soft blocks or as impact-strength modifiers for plastics.
Suitable aromatic polycarbonates by way of reaction partners in accordance with the invention for the aspartate-functional silicones are those based on diphenols of the formula (III)
in which
A is a single bond, C
1
-C
5
alkylene, C
2
-C
5
alkylidene, C
5
-C
6
cycloalkylidene, —S— or SO
2
,
B is chlorine, bromine
x is 0, 1 or 2 and
p is 1 or 0
or alkyl-substituted dihydroxyphenyl cycloalkanes of the formula (IV)
in which
R
1
and R
2
signify, independently of one another, hydrogen, halogen, preferably chlorine or bromine, C
1
-C
8
alkyl, C
5
-C
6
cycloalkyl, C
6
-C
10
aryl, preferably phenyl, and C
7
-C
12
aralkyl, preferably phenyl-C
1
-C
4
-alkyl, in particular benzyl,
m signifies an integer from 4 to 7, preferably 4 or 5,
R
3
and R
4
, capable of being chosen individually for each Z, signify, independently of one another, hydrogen or C
1
-C
6
allyl
and
Z signifies carbon, with the proviso that on at least one atom Z R
3
and R
4
simultaneously signify alkyl.
The following may be mentioned by way of examples: hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfoxides, bis(hydroxyphenyl)sulfones and &bgr;,&bgr;-bis(hydroxyphenyl)diisopropylbenzenes as well as the ring-alkylated and ring-halogenated compounds thereof.
Suitable diphenols are described, for example, in U.S. Pat. Nos. 3,028,365, 2,999,835, 3,062,781, 3,148,172 and 4,982,014, in German Offenlegungsschriften 1 570 703 and 2 063 050 and also in the monograph “H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964”.
Preferred diphenols are
4,4′-dihydroxydiphenyl,
2,2-bis(4-hydroxyphenyl)propane,
2,4-bis(4-hydroxyphenyl)-2-methylbutane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
&agr;,&agr;-bis(4-hydroxyphenyl)-p-diisopropylbenzene,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-chlorohydroxyphenyl)methane,
bis(3,5-dimethyl-4-hydroxyphenyl)methane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
bis(3,5-dimethyl-hydroxyphenyl)sulfone,
2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane
&agr;,&agr;′-bis(3,5-dimnethyl-4-hydroxyphenyl)-p-diisopropylbenzene,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimlethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3-methylcyclohex and,
1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-4-methylcyclohexane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl) propane and
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
Particularly preferred diphenols are, for example:
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-4-methylcyclohexane.
In particular, 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)3,3,5-trimethylcyclohexane are preferred.
Use may also be made of arbitrary mixtures of the aforementioned diphenols.
For the purpose of improving the rheological behaviour, small quantities, preferably quantities between 0.05 and 2.0 mol. % (relative to moles of diphenols employed), of trifunctional or more than trifunctional compounds, in particular those with three or more than three phenolic hydroxyl groups, may also be used
Horn Klaus
Köhler Burkhard
Bayer Aktiengesellschaft
Buttner David J.
Gil Joseph C.
Preis Aron
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