Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2002-01-15
2004-05-25
Boykin, Terressa (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C428S064200, C502S150000, C528S198000
Reexamination Certificate
active
06740730
ABSTRACT:
The present invention relates to a novel polycarbonate and its use as a material for the production of moulded bodies and semi-finished products, especially for transparent applications, such as data stores or audio compact disks, sheets, multi-wall sheets, films, lamp housings, panes, especially panes for motor vehicles, headlamp lenses, but also for electrical applications or house building.
The preparation of aromatic polycarbonates by the melt transesterification process is known from the literature and is described, for example, in the Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer, Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and, starting from DE 1 031 512, in some patents.
In EP-B-360 578 there are described polycarbonates containing, end groups other than phenol. The polycarbonates obtained according to EP 360 578 have a markedly increased content of erroneous structures as compared with the polycarbonates synthesised in solution. As the result, such materials have disadvantages as regards melt stability, thermostability and constancy of colour.
The object was, therefore, to develop polycarbonates and a process for their objective preparation, having greater stability.
The object has been achieved by the synthesis of polycarboriates having a markedly reduced concentration of erroneous structures.
The present invention provides solvent-free, low-branching, thermoplastic, aromatic polycarbonates prepared by the transesterification process and having weight-average molecular weights M
w
of from 2000 to 150,000, preferably from 4500 to 55,000, based on diphenols, chain terminators of formula (I)
wherein R, R′ and R″ may each independently of the others represent H, optionally branched C
1
-C
34
-alkyl/cycloalkyl, C
7
-C
34
-alkaryl or C
6
-C
34
-aryl, and, optionally, branching agents, characterised in that structural elements of formula (II)
HO—Z(COOH)—OH (II)
have a value after total saponification and HPLC determination of less than 300 ppm, preferably from 0.03 ppm to 250 ppm, Z being as defined for formula (VI) and the acid group being in the or the position relative to a hydroxy group.
As compared with polycarbonates mis-structured in the usual manner, the polycarbonates according to the invention exhibit a substantially increased hydrolytic stability and an improved critical thickness, with otherwise comparable mechanical and thermal properties.
The polycarbonates according to the invention are prepared in the melt from dihydroxy compounds, dicarbonates, chain terminators and, optionally, branching agents.
Chain terminators within the context of the invention are those of formula (I)
wherein R, R′ and R″ may each independently of the others represent H, optionally branched C
1
-C
34
-alkylcycloalkyl, C
7
-C
34
-alkaryl or C
6
-C
34
-aryl, for example
o-n-butylphenol, m-n-butylphenol, p-n-butylphenol,
o-isobutylphenol, m-isobutylphenol, p-isobutylphenol,
o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol,
o-n-pentylphenol, m-n-pentylphenol, p-n-pentylphenol,
o-n-hexylphenol, m-n-hexylphenol, p-n-hexylphenol,
o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol,
o-phenylphenol, m-phenylphenol, p-phenylphenol,
o-isooctylphenol, m-isooctylphenol, p-isooctylphenol,
o-n-nonylphenol, m-n-nonylphenol, p-n-nonylphenol,
o-cumylphenol, m-cumylphenol, p-cumylphenol,
o-naphthylphenol, m-naphthylphenol, p-naphthylphenol,
2,5-di-tert-butylphenol, 2,4-di-tert-butylphenol, 3,5-di-tert-butylphenol,
2,5-dicumylphenol, 3,5-dicumylphenol,
4-phernoxyphenol, 2-phenoxyphenol, 3-phenoxyphenol,
3-pentadecylphenol, 2-pentadecylphenol, 4-pentadecylphenol,
2-phenylphenol, 3-phenylphenol, 4-phenylphenol,
tritylphenol, 3-triphenylmethylphenol, 2-triphenylmethylphenol,
also benzotriazole derivatives of the general formula (III)
wherein R
a
to R
f
are as defined above for R, R′and R″, and chroman compounds such as
preferably high-boiling phenols such as tritylphenol, cumylphenol, pentadecylphenol or chromans,
or also in the form of compounds that are capable of transesterification under the synthesis conditions, such as, for example, carbonates, oxalates; o-carboxylic acid esters or the like, with preference being given to the free phenols or the carbonic acid diesters of formula (IV)
and formula (V)
wherein R, R′ and R″ correspond to those of formula (I). Phenols or transesterification-active substances can be added to the synthesis individually or in the form of a mixture. Preferred mixtures are those with diphenyl carbonate. It is possible to add the phenol or the phenol-carrying compound at any time during the reaction, preferably at the beginning of the reaction, and the addition can be divided into several portions. The total amount of carbonic acid ester is from 100 to 130 mol %, preferably from 103 to 120 mol %, based on the dihydroxy compound.
For the preparation of polycarbonates by the process according to the invention it is possible to use a chain terminator or a mixture of several chain terminators, so that there may be present as an end group in the polycarbonate according to the invention phenol but also phenol together with other chain terminators. From 0.4 to 17 mol %, particularly preferably from 1.3 to 8.6 mol % (based on the dihydroxy compound), of chain terminator are preferably added. The addition may take place either before the reaction or wholly or partially during the reaction.
Dihydroxy compounds within the context of the invention are those of formula (VI)
HO—Z—OH (VI)
in which Z is an aromatic radical having from 6 to 30 carbon atoms which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or hetero atoms as bridge members.
Examples of dihydroxy compounds of formula (VI) are
hydroquinone,
resorcinol,
dihydroxydiphenyls,
bis-(hydroxyphenyl)-alkanes,
bis-(hydroxyphenyl)-cycloalkanes,
bis-(hydroxyphenyl) sulfides,
bis-(hydroxyphenyl) ethers,
bis-(hydroxyphenyl) ketones,
bis-(hydroxyphenyl)-sulfones,
bis-(hydroxyphenyl) sulfoxides, &agr;&agr;′-bis-(hydroxyphenyl)-diisopropylbenzenes and their nuclear-alkylated and nuclear-hydrogenated compounds.
These and other suitable diphenols are described, for example, in U.S. Pat. Nos. 3,028,365, 3,148,172, 3,275,601, 2,991,273, 3,271,367, 3,062,781, 2,970,131 and 2,999,846, in German Offenlegungsschrift 1,570,703, 2,063,050, 2,063,052, 2,211 0956, in French Patent Specification 1 561 518 and in the monograph “H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964”.
Examples of preferred diphenols are:
4,4′-dihydroxydiphenyl,
2,2-bis-(4-hydroxyphenyl)propane,
2,4-bis-(4-hydroxyphenyl)-2-methylbutane,
1,1-bis4-hydroxyphenyl)cyclohexane,
1,1-bis-(4-hydroxyphenyl)4-methyicyclohexane,
&agr;,&agr;′-bis-(4-hydroxyphenyl)-p-diisopropylbenzene,
&agr;,&agr;-bis-(4-hydroxyphenyl)-m-diisopropylbenzene,
bis-(4-hydroxyphenyl)sulfone,
bis-(4-hydroxyphenyl)methane,
1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
2,2-bis-(2,6dimethyl-4-hydroxyphenyl)propane,
2,2-bis-(4-hydroxyphenyl)hexafluoropropane,
1,1-(4-hydroxyphenyl)- 1-phenylethane,
bis-(4-hydroxyphenyl)diphenylmethane,
dihydroxydiphenyl ether,
4,4′-thiobisphenol,
1,1-bis-(4-hydroxyphenyl)-1-(1-naphthyl)ethane,
1,1-bis-(4-hydroxyphenyl)-1-(2-naphthyl)ethane,
2,3-dihydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethyl-1H-inden-5-ol,
2,3-dihydroxy-1-(4-hydroxyphenyl)-1,3,3-trimethyl-1-H-inden-5-ol, 2,2′3,3′-tetrahydro-3,3,3′3′-tetramethyl-1,1′spirobi[1H-indene]-5,5′s-diol.
Special-preference is given to resorcinol,
1,1-bis-(4-hydroxyphenyl)-1-(1-naphthyl)ethane,
1,1-bis-(4-hydroxyphenyl)-1-(2-naphthyl)ethane,
2,2-bis-(4-hydroxyphenyl)propane, &agr;,&agr;′-bis-(4-hydroxyphenyl)-p-diisopropylbenzene,
&agr;,&agr;′-bis-(4-hydroxyphenyl)-m-diisopropylbenzene,
1,1-bis-(4-hydroxyphenyl)cyclohexane,
1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
bi
Bunzel Lothar
Hucks Uwe
Kratschmer Silke
Bayer Aktiengesellschaft
Boykin Terressa
Franks James R.
Gil Joseph C.
Preis Aron
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