DE19962016A1 - Oligomeric bischlorocarbonic acid esters from selected cycloaliphatic bisphenols and other bisphenols - Google Patents

Abstract

The invention relates to oligomeric bischlorocarbonic acid esters which, in a two-phase reaction, can be obtained from selected cycloaliphatic bisphenols and other bisphenols by introducing phosgene.

Description

The invention relates to oligomeric bischlorocarbonic acid esters in a two-phase reaction from selected cycloaliphatic bisphenols and other bisphenols are accessible by introducing phosgene.

Bischlorkohlensäureester are suitable as starting materials for the production of polycarbonate cyclen (as a precursor for high molecular weight polycarbonates according to DE 196 36 539) and of linear polycarbonates, e.g. B. from solution polymerization.

The bisphenol 1,1-bishydroxyphenyl-3,3,5-trimethylcyclohexane (TMC bisphenol) produces polycarbonates with a high glass transition temperature. Often because of the better ver Workability Desired polycarbonates with a lower glass transition temperature.

For example, B. copolymers with other bisphenols.

In principle, it is possible to use an oligomeric bischlorocarbonate precursor TMC bisphenol (precursor 1; V1) with another oligomeric bischlor coal Mix acid ester precursor (precursor 2; V2) before the reaction. However arises then no statistical sequence of the monomeric bisphenols in the subsequent reaction (V1) and (V2) but blocks of pre-stage 1 and pre-stage 2. Therefore it is desirable to produce oligomeric bischlorocarbonate precursors which themselves are statistically constructed from TMC bisphenol and other bisphenols.

The invention therefore relates to mixtures of bischlorocarbonic acid esters of the formulas (I), (II) and (III)

wherein
R ¹ and R ² independently of one another are 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 are} independently hydrogen or C ₁ -C ₆ alkyl and
X is carbon,
with the proviso that on at least one atom X per repeating unit in (I) or (III), R ³ and R ⁴ simultaneously mean alkyl,
Z is an aromatic radical having 6 to 30 carbon atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic radicals or cycloaliphatic radicals which are different from the cycloaliphatic radicals in (I), or heteroatoms as bridge members ,
p, q, r and s stand for 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 preferred

with Me = methyl radical

The bischlorocarbonic acid ester mixtures are preferably prepared by introducing phosgene into a mixture of bisphenols of the formulas (IV) and (V) in a molar ratio of 1:10 to 10: 1.

HO-Z-OH (V)

In a two-phase system made up of water and an organic solvent, preferably methylene chloride, at -5 ° C to 40 ° C, the pH of the aqueous Phase by adding or submitting an alkali or alkaline earth hydroxide between 1 and 13, preferably between 2 and 9.

X, R ¹ , R ² , R ³ , R ⁴ and m have the meaning given in formula (I).

Alkyl at 1-2 atoms X, in particular only at one atom X per molecule (IV), R ³ and R ⁴ are preferred at the same time.

The preferred alkyl radical is methyl; the X atoms in the α position to the diphenyl Substituted carbon atom (C-1) are preferably not dialkyl-substituted; Alkyl disubstitution in the β-position to C-1 preferred.

Dihydroxydiphenylcycloalkanes with 5 and 6 ring carbon atoms in the cycloaliphatic radical (m = 4 or 5 in formula (IV)) are preferred, for example the diphenols of the formulas (IVa) to (IVc))

the 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (formula (IVa) with R ¹ and R ² being H) being particularly preferred. The polycarbonates can be prepared from diphenols of the formula (I) in accordance with German patent application P 38 32 396.6.

For the repeating units, in addition to the diphenols of the formula (IV), other diphenols, for example with the formula (V)

HO-Z-OH (V)

used.

Suitable diphenols of the formula (V) are those in which Z is an aromatic radical with 6 to 30 carbon atoms, which can contain one or more aromatic nuclei, can be substituted and aliphatic radicals or other cycloaliphatic radicals as which may contain the formula (I) or heteroatoms as bridge members.

Examples of the diphenols of the 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, α, α'-bis (hydroxyphenyl) diisopropylbenzenes and their core alkylated and core halogenated compounds.

Preferred are α, α'-bis (hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (hydroxy phenyl) -p-diisopropylbenzene and 2,2-bis (4-hydroxyphenyl) propane in particular preferably α, α'-bis (hydroxyphenyl) -m-diisopropylbenzene and 2,2-bis - (- hydroxy phenyl) propane.

These and other suitable diphenols are e.g. B. in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ", described.

Of course, mixtures of bisphenols (V) and other bisphenols can be used.

Other preferred bisphenols for this purpose are, for example:
4,4'-dihydroxydiphenyl, 2,4-bis (4-hydroxyphenyl) -2-methane butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, α, α'-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-hydroxyphenyl) 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.

The bisphenols of the formula (IV) are preferably 1,1-bishydroxyphenyl-3,3,5- trimethyl-cyclohexane or 1,1-bishydroxyphenyl-3-methyl-cyclohexane, particularly preferably 1,1-bishydroxyphenyl-3,3,5-trimethyl-cyclohexane.

2,2-Bishydroxyphenylpropane were preferably used as bisphenols of the formula (V) (BPA), 1,1-bishydroxyphenylethane or 2,2-bishydroxyphenylbutane, especially preferably 2,2-bishydroxyphenylpropane used.  

Another object of the invention is the use of the invention Bischlorkohlensäureestergemische for the production of cyclic Cooligocarbonate.

The cyclic cooligocarbonates are synthesized by the synchronous addition of Solution of the bischlorocarbonic acid ester mixture in methylene chloride and 3-15 mol% an organic amine, preferably triethylamine, to a two-phase Mixture of methylene chloride and water, the pH of the aqueous phase by adding or submitting an alkali or alkaline earth hydroxide between 7 and 13, is preferably kept between 9 and 11 and the temperature is 0 ° C to 40 ° C, is preferably 30 ° C to 40 ° C. Possibly, up to 10 mol% of other bisphenols used.

Another object of the invention is the use of the invention Bischlorocarbonate mixtures for the production of linear statistical copoly carbonate.

The high molecular weight polycarbonates from the bischlor coal according to the invention acid esters, if appropriate in combination with other bishlorocarbonic acid esters, can be produced according to the known polycarbonate production processes, preferably according to the phase interface method (cf. H. Schnell "Chemistry and Physics of Polycarbonates ", Polymer Reviews, Vol. IX, page 33 ff., Interscience Publ. 1964).

The synthesis of the linear, statistical copolycarbonates takes place e.g. B. by a Two phase reaction of a solution of the bischlorocarbonate mixtures in Methylene chloride with inorganic bases dissolved in water, preferably alkali hydroxides, at a pH of 7-13 and a temperature of 0 ° C-40 ° C in Presence of 0.01-2 mol% of an organic amine, preferably triethylamine or N-ethylpiperidine, where 0-80 mol% bisphenols of the formula (IV) and (V) and 0-7 mol% monophenols can be added.  

Monofunctional compounds in conventional concentrations serve as chain terminators for the known regulation of the molecular weight of the polycarbonates. Suitable compounds are e.g. B. phenol, tert-butylphenols or other alkyl substituted phenols. Small amounts of phenols of the formula (V1) are particularly suitable for regulating the molecular weight

wherein
R represents a branched C ₈ and / or C ₉ alkyl radical.

The proportion of CH ₃ protons in the alkyl radical R is preferably between 47 and 89% and the proportion of CH and CH ₂ protons between 53 and 11%; R is also preferably in the o- and / or p-position to the OH group, and particularly preferably the upper limit of the ortho portion 20%. The chain terminators are generally used in amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on the diphenols used.

The copolycarbonates obtained have neither block-like nor alternating Structures. They are structured statistically.

The invention is illustrated by the following examples.  

Examples example 1 Production of a bischlorocarbonate mixture according to the invention

In a mixture of 155 g (0.5 mol) TMC-bisphenol, 114 g (0.5 mol) BPA and 1.2 l of methyl chloride are introduced at 0 ° C 300 g phosgene in 150 minutes. At the same time, 25 percent. NaOH metered in so that the pH of the mixture is between 2 and 5. You need about 1 liter of NaOH. After the phosgene the pH value is set to 8 to 9 and nitrogen is introduced as long as until the solution is phosgene free. After phase separation, the organic phase washed with 1N HCl and then with water, dried over sodium sulfate and evaporated. The yield was 285 g, the content of hydrolyzable chlorine 14.5%. A mixture of the non-oligomerized bicarbonate would theoretically contain 18.0% hydrolyzable chlorine. Therefore there is a share of Oligochlorocarbonic acid esters with p, q, r and s <1 before.

Example 2 Preparation of a cyclic oligocarbonate (Usage example)

200 ml of methylene chloride, 7 ml of water and 2 ml of 9.75 are placed in a 1 liter flask molar NaOH in water and 2.4 ml of triethylamine and at 40 ° C under vigorous stirring synchronously 200 ml of a solution of 78.8 g of bischlor coal acid ester mixture from Example 1 in methylene chloride, 59 ml of a 0.75 molar NaOH in water and 25 ml of a 10% solution of triethylamine in Methylene chloride metered in within 28 minutes, the metering of Bischlorkohlensäureesterlösung takes place below the liquid level. After Phase separation is washed with 1N HCl and three times with water and the  evaporated organic phase. 60.2 g of a material are obtained, which is determined by HPLC approx. 80% consists of cycles.

Example 3 Production of a linear polycarbonate (Usage example)

39.4 g of the bischlorocarbonic acid ester according to Example 1, 62 g of 45% NaOH, 0.53 g of p-tert-butylphenol and 400 g of methylene chloride, gives 0.1 g of N-ethyl Add piperidine and stir for 1 h. Acidify with HCl, separate the orga African phase, and evaporated in a vacuum drying cabinet. 30 g are obtained a polycarbonate with a relative solution viscosity of 1.29 (0.5% in Methylene chloride at 25 ° C) with a glass transition temperature of 199 ° C.

Claims (4)

1. Mixtures of bicarbonate of formulas (I), (II) and (III)
in which
R ¹ and R ² independently of one another are 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 are} independently hydrogen or C ₁ -C ₆ alkyl and
X is carbon,
with the proviso that on at least one atom X per repeating unit in (I) or (III) R ³ and R ⁴ simultaneously mean alkyl,
Z is an aromatic radical with 6 to 30 C atoms, which contains one or more aromatic nuclei, can be substituted and can contain aliphatic radicals or cycloaliphatic radicals which are different from the cycloaliphatic radicals in formula (I), or can contain heteroatoms as bridging elements,
p, q, r and s stand for 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. 2. Mixtures according to claim 1, wherein
Z the leftovers
corresponds to
where Me means methyl radical. 3. Use of the bischlorocarbonic acid ester mixtures according to claim 1 or 2 for the production of cyclic cooligocarbonates. 4. Use of the bischlorocarbonic acid ester mixtures according to claim 1 or 2 for the production of linear statistical copolycarbonates.