Mixtures of cyclic oligocarbonates, their production and use

Details Mixtures of cyclic oligocarbonates, their production and use Mixtures of cyclic oligocarbonates, their production and use

2000-05-17

2001-10-02

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

Reexamination Certificate

active

06297346

ABSTRACT:

According to EP 0 359 953 (Le A 26 344), diphenols of formula (I)
are known, in which
R
1
and R
2
, independently of each other, represent hydrogen, a halogen, preferably chlorine or bromine, a C
1
-C
8
alkyl, a C
5
-C
6
cycloalkyl, a C
6
-C
10
aryl, preferably phenyl, and a C
7
-C
12
aralkyl, preferably a phenyl-C
1
-C
4
alkyl, particularly benzyl,
m is an integer from 4 to 7, preferably 4 to 5,
R
3
and R
4
present, individually for each X, and independently of each other, hydrogen or a C
1
-C
6
alkyl, and
X represents carbon,
with the provisio that R
3
and R
4
simultaneously represent alkyl on at least one X atom.
R
3
and R
4
preferably simultaneously represent alkyl on 1 to 2 X atoms, particularly on one X atom only.
The preferred alkyl radical is methyl, the X atoms in the &agr;-position to the di-phenyl-substituted C atom (C-1) are preferably not dialkyl-substituted, however, alkyl substitution in the &bgr;-position to C-1 is preferred. Most preferably, an X atom is dialkyl-substituted in the &bgr;-position and an X atom is monoalkyl-substituted in the &bgr;′-position.
These known diphenols also comprise dihydroxydiphenylcycloalkanes containing 5 and 6 ring C atoms in their cycloaliphatic radical (m=4 to 5 in formula (I)), such as diphenols of formulae
for example, where 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (formula II) is particularly preferred industrially.
EP 0 359 953 also mentions mono- and bis-chloroformates of diphenols of formula (I) (page 10, lines 12-14 of this European Patent, see U.S. Pat. No. 4,982,014, column 9, lines 6 to 9, also).
Details of the preparation of these bischloroformates are not mentioned, and neither are mixtures with pre-phosgenates containing chloroformates.
It has now been shown that by employing a special preparation of the bis-chloroformates of diphenols of formula (I) they are obtained admixture with pre-phosgenates which contain chloroformates. This preparation can be effected analogously to that described in Macromolecules 1991, 24, pages 3035-3044.
The present invention thus relates to mixtures of bischloroformates of diphenols of formula (I) with pre-phosgenates, which contain bischloroformates, of diphenols of formula (I), namely to mixtures of bischloroformates of formula (V)
where R
1
to R
4
, “m” and “X” have the meaning given for formula (I), and “p” is a number from 1 to 4 on average.
The present invention also relates to a process for producing mixtures of bischloroformates of formula (V), which is characterised in that phosgene is passed into a two-phase mixture of an organic solvent, preferably methylene chloride, with diphenols of formula (I), and water, at temperatures from −5° C. to +40° C., and a solution or suspension of an alkali metal or alkaline earth metal hydroxide is simultaneously added so that the pH is between 1 and 8, preferably between 2 and 5.
The mixtures of bischloroformates of formula (V) according to the invention are particularly suitable for the production of mixtures of cyclic aromatic oligocarbonates.
Thus the present invention also relates to the use of the mixtures of formula (V) for the production of mixtures of cyclic aromatic oligocarbonates.
The reaction of the mixtures of formula (V) to form mixtures of cyclic oligocarbonates is effected by adding a solution of (V) in an organic solvent, preferably methylene chloride, and an organic amine, preferably triethylamine, synchronously and drop-wise to a two-phase mixture of an organic solvent, preferably methylene chloride, and water, at temperatures of 0° C. to 40° C., preferably 30° C. to 40° C. A solution or suspension of an alkali metal or alkaline earth metal hydroxide is simultaneously added so that the pH is between 7 and 13, preferably between 9 and 11.
The preparation can be conducted analogously to that described in the Indian Journal of Technology 31 (1993), pages 234-246.
The mixtures of cyclic oligocarbonates exhibit various degrees of polycondensation “q”, which on average are between 2 and 20.
Thus the present invention also relates to a process for producing mixture of cyclic oligocarbonates of formula (VI)
wherein R
1
to R
4
“m” and “X” have the meaning give for formula (I), and “q” is a number from 2 to 20 on average, which is characterised in that a solution of (V) in an organic solvent, preferably methylene chloride, and an organic amine, preferably triethylamine, are added synchronously and drop-wise to a two-phase mixture of an organic solvent, preferably methylene chloride, and water, at temperatures of 0° C. to 40° C., preferably 30° C. to 40° C. A solution or suspension of an alkali metal or alkali metal or alkaline earth metal hydroxide is simultaneously added so that the pH is between 7 and 13, preferably between 9 and 11.
The present invention further pates to the mixture of cyclic oligocarbonates of formula (IV) which are obtainable by the process according to the invention.
Determination of the terminal groups serves as proof that cyclic structures are present; this is effected by determining the phenolic OH terminal groups photometrically after coloration with TiCl
4
, and by determining the nitrogen-containing terminal groups by combustion/chemiluminescence.
The oligocarbonate mixtures obtainable according to the invention have maximum terminal group contents of 0.3 mole, preferably a maximum of 0.1 mole, per mole of oligocarbonate mixture.
Cyclic oligocarbonates and the production thereof are known. (See DE-AS 1 229, 101, U.S. Pat. No. 3,386,154, U.S. Pat. No. 4,727,134, J. Am. Chem. Soc. 1990, 112, pages 2399-2402, Macromolecules 1991, 24, pages, 3055-3044 and Indian Journal of Technology, Vol 31, 1993, pages 234-246, for example). These literature references do not include diphenols (I), however.
Secondly, according to EP-0 359 953 or U.S. Pat. No. 4,982,014, subsidiary amounts of cyclic oligocarbonates can be formed in conjunction during the production of polycarbonates from diphenols (I). The polycarbonate mixtures obtained according to this European Patent or U.S. Patent have terminal group contents of at least 1.5 mole per mole of polycarbonate mixture, however.
Cyclic oligocarbonates are known according to U.S. Pat. No. 4,616,077. However, these also contain other structural units (see U.S. Pat. No. 4,616,077, column 2, line 52 et seq.—column 3, line 10, in particular).
The mixtures of cyclic oligocarbonates of formula (VI) which are obtainable according to this invention can be converted by ring-opening polymerisation in a known manner (see for example the method according to Indian Journal of Technology 31 (1993) pages 234-246) into the high molecular weight polycarbonates of EP 0 359 953 or U.S. Pat. No. 4,982,014.
Thus the present invention also relates to the use of mixtures of cyclic oligocarbonates of formula (VI) for the production of high molecular weight polycarbonates with an M
w
of at less 10,000, preferably between 10,000 and 500,000 (M
w
=weight average molecular weight determined by gel permeation chromatography).
The present invention further relates to a process for producing high molecular weight, thermoplastic aromatic polycarbonates with an M
w
of at least 10,000, preferably between 10,000 and 500,000, which contain, as bifunctional structural units, only those of formula (VII)
wherein R
1
to R
4
“m” and “X” have the meaning given for formula (I), which is characterised in that cyclic oligocarbonate mixtures of formula (VI) are heated for 15 seconds to 60 minutes, preferably for 3 minutes to 30 minutes, at 200° C. to 400° C., preferably 220° C. to 350° C., in the presence of 0.001% by weight to 0.1% by weight, preferably 0.005% by weight to 0.05% by weight, with respect to the oligocarbonate mixture of formula (VI), of a catalyst.
Suitable catalysts for a ring-opening anionic polymerisation of this type are described in U.S. Pat. No. 4,650,852 and U.S. Pat. No. 4,605,731, for example. Examples of preferred catalysts include tetrabutylammonium tetraphenylborate, tetramethylammonium tetraphenylborate, lithium tetraphenyl

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