Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phenol – phenol ether – or inorganic phenolate
Reexamination Certificate
2002-03-20
2003-07-08
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phenol, phenol ether, or inorganic phenolate
C528S198000
Reexamination Certificate
active
06590058
ABSTRACT:
This invention relates to oligomeric bischloroformic acid esters which are obtainable, in a two-phase reaction, from selected cycloaliphatic bisphenols and other bisphenols by introducing phosgene.
Bischloroformic acid esters are suitable as educts for the production of cyclic polycarbonate compounds (as a precursor for high-molecular polycarbonates in accordance with DE 19 636 539) and of linear polycarbonates, for example, from solution polymerisation.
The bisphenol 1,1-bis(hydroxyphenyl)-3,3,5-trimethylcyclohexane (TMC bisphenol) produces polycarbonates having a high glass temperature. Polycarbonates having a lower glass temperature are often required, because of their better workability.
Suitable compounds are, for example, copolymers with other bisphenols.
It is in principle possible to mix an oligomeric bischloroformic acid ester precursor of TMC bisphenol (precursor 1; V1) with another oligomeric bischloroformic acid ester precursor (precursor 2; V2) prior to the reaction. But a statistical sequence of the monomeric bisphenols (V1) and (V2) is not then obtained during the subsequent reaction, and blocks of precursor 1 and precursor 2 are formed instead. For this reason it is desirable to prepare oligomeric bischloroformic acid ester precursors which are themselves built up statistically from TMC bisphenol and other bisphenols.
The invention accordingly provides mixtures of bischloroformic acid esters corresponding to formulae (I), (II) and (III)
wherein
R
1
and R
2
independently of one another denote 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 is an integer from 4 to 7, preferably 4 or 5,
R
3
and R
4
independently of one another denote hydrogen or C
1
-C
6
-alkyl and
X denotes carbon,
with the proviso that, on at least one X atom per repeat unit in (I) or (III), R
3
and R
4
simultaneously denote alkly,
Z is an aromatic group having 6 to 30 C atoms and can contain one or more aromatic nuclei, can be substituted and can contain aliphatic groups or cycloaliphatic groups which differ from the cycloaliphatic groups in (I), or hetero atoms as bridge-type cross-links,
p, q, r and s represent a natural number from 1 to 15 and the molar ratio of the cycloaliphatic bisphenol units to the aliphatic bisphenol units is 1:10 to 10:1.
Z is preferably
wherein Me=methyl group.
The mixtures of bischloroformic acid esters are preferably prepared by introducing phosgene into a mixture of bisphenols corresponding to formulae (IV) and (V) in the molar ratio of 1:10 to 10:1
in a two-phase system consisting of water and an organic solvent, preferably methylene chloride, at −5° C. to 40° C., the pH value of the aqueous phase being maintained at between 1 and 13, preferably between 2 and 9,by the addition or previous provision of an alkali metal hydroxide or alkaline-earth hydroxide.
Here X, R
1
, R
2
, R
3
, R
4
and m have the meanings given for formula (I).
Preferably on 1 to 2 X atoms and in particular on only one X atom per molecule (IV), R
3
and R
4
simultaneously denote alkyl.
The preferred alkyl group is methyl. The X atoms in the a-position to the diphenyl-substituted C atom (C-1) are preferably not dialkyl-substituted, but alkyl disubstitution is preferred in the &bgr;-position to C-1.
Dihydroxydiphenylcycloalkanes having 5 and 6 C atoms in the ring in the cycloaliphatic group (m=4 or 5 in formula (IV)) are preferred, for example, the diphenols corresponding to formulae (IVa) to (IVc)
wherein 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (formula (IVa) with R
1
and R
2
denoting H) is particularly preferred. The polycarbonates can be produced from diphenols corresponding to formula (I), in accordance with the German Patent Application P 3 832 396.6.
For the repeat units, other diphenols, for example, corresponding to formula (V)
HO—Z—OH (V)
are used in addition to the diphenols corresponding to formula (IV). Suitable diphenols corresponding to formula (V) are those wherein Z is an aromatic group having 6 to 30 C atoms and can contain one or more aromatic nuclei, can be substituted and can contain aliphatic groups or cycloaliphatic groups other than those corresponding to formula (I) or hetero atoms as bridge-type cross-links.
Examples of diphenols corresponding to formula (V) 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 as well as ring-alkylated and ring-halogenated compounds thereof.
Preferred diphenols are &agr;,&agr;′-bis(hydroxyphenyl)-m-diisopropylbenzene, &agr;,&agr;′-bis(hydroxyphenyl)-p-diisopropylbenzene and 2,2-bis(4-hydroxyphenyl)propane; &agr;,&agr;′-bis(hydroxyphenyl)-m-diisopropylbenzene and 2,2-bis(4-hydroxyphenyl)propane are particularly preferred.
These and other suitable diphenols are described, for example, in the monograph: H.Schllell. “Chemistry and Physics of Polycarbonates”, Interscience Publishers, New York. 1964.
Mixtures of bisphenols (V) and of other bisphenols may, of course, also be used as cobisphenols.
For this, examples of other preferred bisphenols are: 4,4′-dihydroxydiphenyl, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, &agr;,&agr;′-bis(hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxy-phenyl)propane, bis(3,5-dimethyl-4,4-hydroxyphenyl) sulfone, 2,4-bis(3,4-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
Compounds used as bisphenols corresponding to formula (IV) are preferably 1,1-bis(hydroxyphenyl)-3,3,5-trimethylcyclohexane or 1,1 -bis(hydroxyphenyl)-3-methylcyclohexane, particularly preferably 1,1-bis(hydroxyphenyl)-3,3,5-trimethyl-cyclohexane.
Compounds used as bisphenols corresponding to formula (V) are preferably 2,2-bis(hydroxyphenyl)propane (BPA), 1,1-bis(hydroxyphenyl)ethane or 2,2-bis(hydroxyphenyl)butane, particularly preferably 2,2-bis(hydroxyphenyl)propane.
The invention also provides the use of the mixtures of bischloroformic acid esters according to the invention for the production of cyclic cooligocarbonates.
The synthesis of the cyclic cooligocarbonates is carried out by synchronous addition of the solution of the mixtures of bischloroformic acid esters in methylene chloride and of 3 to 15 mol. % of an organic amine, preferably triethylamine, to a two-phase mixture of methylene chloride and water, during which the pH value of the aqueous phase is maintained at between 7 and 13, preferably between 9 and 11,by the addition or previous provision of an alkali metal hydroxide or alkaline-earth hydroxide, and the temperature is 0° C. to 40° C., preferably 30° C. to 40° C. If necessary, in addition up to 10 mol. % of other bisphenols are added.
The invention also provides the use of the mixtures of bischloroformic acid esters according to the invention for the production of linear statistical copolycarbonates.
The high-molecular polycarbonates obtained from the bischloroformic acid esters according to the invention, optionally in combination with other bischloroformic acid esters, can be produced by the known processes for polycarbonate production, preferably by the phase interface process (cf. H. Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Vol. IX, page 33 ff., Interscience Publishers, 1964.)
The synthesis of the linear statistical copolycarbonates is carried out, for example, by a two-phase reaction of a solution of the mixtures of bischloroformic acid esters in methylene chloride with inorganic bases, pre
Chen Yun
Ebert Wolfgang
Köhler Burkhard
Bayer Aktiengesellschaft
Boykin Terressa M.
Gil Joseph C.
Preis Aron
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