DE2063052A1 - Saponification-resistant polycarbonates - Google Patents

Description

Saponification-resistant polycarbonates

Addition to patent C ² .vJiH _t * patent application ^ Λ ^ ΛΗί'Λ. (Le A 13 359).

Subject of the main patent

(Le A 13 359)) is a process for the production of Polycarbonaten with freezing temperatures of at least 180 ⁰ G, which contain only those of the formula 1 of bifunctional structural units and have an average degree of polymerization P * of at least 30, where P * are identical or non-identical structural units of the formula 1,

wherein R X

, O ₂ H ₅ or CH (CH ₃ J ₂ and a single bond, an alkylene or alkylidene group with 1-5 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5--15 carbon atoms, an ether bond or a keto bond mean that in the implementation of the alkali metal salts of bisphenols of the formula g

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in which R and X have the abovementioned meaning> en | in aqueous solution or suspension, optionally with the addition of aqueous alkali, in the presence of an inert one Solvent with phosgene and / or bischlorocarbonic acid esters of the aforementioned bisphenols or in the implementation of the bischlorocarbonic acid esters of the aforementioned bisphenols in a mixture of an inert solvent and aqueous alkali and which is characterized in that, optionally in the presence of chain limiters, the Reaction to high molecular weight polycarbonates by adding Io - 2oo mol percent, based on bisphenol used, initiates at tertiary amines and observes a reaction time between 5 and 0.1 hours.

As an extension of the process it has now been found that one also bisphenols of formula 2

where R = R ² =

CH ,,

i ₃ , C ₂ H ₅ or CH (CH ₃ ) ₂ , CH _{1, C 2} H ₅ or CH (CH ₅ ) ₂ and

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R ^ = CH ,, G ₉ Hn or CH (CH,) ,, are, the substituent R is omitted if the linkage of the aromatic B with the aromatics A and G on the aromatics A and G ortho to the hydroxyl groups in A and G is present, and the substituent R is omitted if the linkage of the aromatic B with the aromatics A and C on the aromatics A and G is para to the hydroxyl groups in A and G, alone or together with the bisphenols of the formula 2 can be used for the synthesis of high molecular weight polycarbonates according to the process specification given in the main patent. '

The present invention therefore relates to a method

according to patent (patent application ?, Vl ^ JAi'ß

(LeA 13 359)) for the production of high molecular weight polycarbonates which either only contain bifunctional structural units of the formula ±,

wherein R ¹ = CH ₅ , C ₂ H ₅ or CH (CH ₃ ) ₂ ,

R ² = CH ₃ , C ₃ H ₅ or GH (CH ₃ ) ₂ and

R ³ = CH ₃ , C ₂ H ₅ or -CH (CH ₃ J ₂ ,

the substituent R is omitted if the linkage of the aromatic B with the aromatics A and C on the aromatics A and G is ortho to the carbonate groups in A and G, and the substituent R ⁵ is omitted if the linkage of the aromatic B with the aromatics A and C to the

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Aromatics A and C para to the carbonate groups in A and C is present, or apart from the bifunctional structural units of formula 4. nor those of formula i in each contain any percentage and have an average degree of polymerization T? of at least 30 on identical or non-identical structural units of the formula 4_ and optionally of the formula i, have the in the implementation of

a) Alkali salts of the bisphenols of the formula 2

and optionally g with phosgene and / or b) bischlorocarbonic acid esters of the bisphenols

Formulas 2 and optionally 2 and / or c) oligomeric carbonates of the bisphenols of the formulas

2 and optionally 2, which may contain chlorine

have acid ester end groups,

in a mixture of an aqueous phase and an inert organic solvent, preferably aqueous alkali as Acid acceptor is added, and is characterized in that the reaction to high molecular weight Polycarbonates, optionally in the presence of chain limiters, by adding 10-200 mole percent on the bisphenols used in each case, initiates at tertiary amines and a reaction time between 5 and 0.1 hours.

Suitable bisphenols of the formula 2 are, for example

'<■, -X ¹ -Bis- (4-hydroxy-3,5-dimethylphenyl) -p-diisopropylbenzene / χ, X ¹ -Bis- (4-hydroxy-5,5-diethylphenyl) -p-diisopropylbenzene. ^ , .X ^l -Bis- (4-hydroxy-3,5-diisopropylphenyl) -p-diisopropylbenzene Ct ', iX ^t -Bis- (4-hydroxy-3-methyl-5-isopropyl-phenyl) -p-diisopropyl-

benzene

(, '- Bis- (2-hydroxy-3,5-dimethy! Phenyl) -p-diisopropylbenz oil

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; χ,: λ '-Bis- (4-hydroxy-3 , 5 ~ dimethylphenyl) -m-diisopropylbenzene ^Λ χ, A ¹ -Bis- (4-hydroxy-3,5-diethylphenyl) -m-diisopropylbenzene .χ, - ¹ -Bis- (4-hydroxy-3,5-diisopropylphenyl) -m-diisopropylbenzene X, X'-Bis- (4-hydroxy-3-methyl-5-isopropyl-phenyl) -m-diisopropylbenzene X, .i * -Bis- (2-hydroxy-5,5-dimethylphenyl) -m-diisopropylbenzene

These new ί, x'-bis (hydroxy-dialkyl-phenyl) -diisopropylbenzenes were prepared according to the instructions given in Examples 1-4.

Bisphenols of formula 2 are, for example, those already written in the main patent (patent application .... (Le. A 13 359) Links:

Bis (3,5-dimethyl-4-hydroxyphenyl) methane Bis (3,5-diisopropyl-4-hydroxyphenyl) methane 2,2-bis (j5-methyl-5-isopropyl-4-hydroxyphenyl) propane 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane 2,2-bis- (3,5-diethyl-4-hydroxyphenyl) -propane 2,2-bis (; 3,5-dimethyl-4-hydroxyphenyl) pentane

l, l-bis- (3 _J 5-dimethyl-4-hydroxyphenyl) -cyclohexane bis- (3,5-dimethyl-4-hydroxyphenyl) -ether bis- (3,5-dimethyl-4-hydroxyphenyl) bis- ( 3,5-dimethyl-4-hydroxyphenyl) carbonyl

According to patent application ... (LeA 13 359) phenol or substituted phenols such as p-tert-butylphenol or 2,6-dimethylphenol can be used with good success. As already mentioned in the application ... (LeA 13 359), this has to be taken into account the amine concentrations used of more than 1.0 mol percent, based on the bisphenol present, completely unpredictable and surprising, since phenols in general react to a considerable extent with the as catalysts amines used for the polycondensation, so that a

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reproducible control of the molecular weight of the high molecular weight Polycarbonates cannot generally be achieved with phenols (see Deutsche Auslegeschrift 1 190 185, Page 1).

In addition, it can be shown that, for example, in the synthesis of polycarbonate from ^, Dc ¹ -Bis - (^ - hydroxyphenyl) -pdiisopropylbenzene amounts of 2-5 mol percent, z. B. triethylamine, based on the iy, X'-bis (4-hydroxyphenyl) -p-diisopropylbenzene used, greatly reduce the yields of high molecular weight polycarbonate.

From this, as well as from what is set out in the main application (see e.g. the German cited in the main application Offenlegungsschrift 1 57o 7o3, pages] 5 and 4) shows that that for the production of high molecular weight polycarbonates from bisphenols, which are ortho to the phenolic Hydroxyl groups are peralkylated, special process conditions are required in order to achieve good yields High molecular weight products with an average degree of polymerization of over 30, preferably more than 55 »come to the from the previous practice of polycarbonate production not only differ greatly, but also not suggested by them have been. The process according to the invention thus even allows the bisphenols of the formula 3 to be converted into polycarbonates condense, which have molecular weights in excess of 200,000. The bisphenols of the formula 3 can of course be used in principle also polycondense according to conventional methods (cf. German Offenlegungsschrift 1 495 642), however, this requires reaction times which are many times higher than those of the process according to the invention and therefore not for the economical production of polycarbonates from the bisphenols of formula 3 are just suitable.

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The bischlorocarbonic acid esters of the abovementioned bisphenols of the formulas 3 and 2 can be prepared by processes known per se, e.g. can be prepared according to the procedure of Example 9.

The bispine oils of the formulas 3 and 2 can also be used to obtain olifromene carbonates with predominantly chlorocarbonic acid ester end groups. If these are produced by the two-phase interface process, they can also be polycondensed in situ, without isolating them, by adding the catalytically effective amount of tertiary amine according to the invention to give the desired high molecular weight polycarbonates.

The process for the production of the homo- and copolycarbonates according to the invention can thus be both one-step and be carried out in several stages.

Tertiary amines suitable for the process are e.g. B. trimethylamine, Triethylamine, dimethylbenzylamine and triethylenediamine.

'' Suitable solvents for the polycarbonates and thus usable for the process are e.g. chlorinated hydrocarbons, such as Methylene chloride, chloroform and 1,2-dichloroethane or else chlorinated aromatics such as chlorobenzene dichlorobenzene and chlorotoluene.

The high molecular weight polycarbonates produced by the process according to the invention, like those of patent application Le A 13 359, are excellent thermoplastics and can be easily processed into molded articles, foils and films. They can also be used well in mixtures with fillers, for example minerals, carbon black, glass fibers and with pigments, dyes, UV absorbers and other additives. The polycarbonates according to the invention often have glass transition temperatures of at least 14O ⁰ C, sorgar of more than 180 ⁰ C. They are also extremely resistant to hydrolysis, saponification and

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aminolysis stable. They can therefore be used with great advantage in particular where there is a need for high thermal stability and a high resistance to hydrolysis, saponification and aminolysis is important. For example, you can for the production of pipelines for hot alkaline or acidic solutions, high-quality seals, crockery, of devices that can be sterilized with superheated steam and of films for the packaging of foodstuffs. Due to the Good solubility in solvents such as toluene and xylene, they can also be used as paints, for example for coating Serving plastics.

By incorporating additional bisphenols or aliphatic dihydroxy compounds into the polycarbonates according to the invention their properties can be modified.

The process described for the bisphenols of the formula 3 can also be used to prepare bisphenols of the formula 5 (cf. Examples 5-8), where R ^ represent substituents, for example alkyl, phenyl and halogen substituents

These bisphenols are also extremely suitable as comonomers in the sense described above for modifying the new high molecular weight homo- and copolycarbonates which can be produced by the process according to the invention «,

The bisphenols of the formula 5 type can of course be used too high molecular weight even after conventional methods

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Cular polycarbonates (see. Examples 13 and 14) with, compared to polycarbonates from ortho to the phenolic OH groups unsubstituted bisphenols, increased resistance to saponification Polycondensation and better solubility in a variety of organic solvents.

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Examples 1-8

The following examples deal with the preparation of those substituted in the o-position to the hydroxyl groups QL, oC -Bis- (hydroxyphenyl) -diisopropylbenzenes »

Method A:

1 mol of iX, {X ^f -dihydroxy-diisopropylbenzene is dissolved in 5-6 mol of the 2-substituted or the 2,4- or 2,6-di-substituted phenol. This solution is added dropwise to 5-6 moles of the same phenol, which are saturated with hydrochloric acid gas, over the course of 1-2 hours while stirring and passing in hydrochloric acid at 40-60.degree. After a further 1-2 hours, hydrochloric acid, water and excess phenol are distilled off as much as possible in vacuo and the residue is recrystallized 1-2 times from a suitable solvent, depending on the contamination.

Method B:

First, proceed as under A, including the removal of excess phenol by distillation. then however, the residue is fractionated in a high vacuum and the fraction boiling above 200-220 ° is crystallized from a suitable solvent.

The bisphenols obtained according to method A or B are colorless, crystalline substances, the structure of which has been secured analytically •is. The table below includes following the above methods Manufactured bisphenols, for their characterization melting point and hydroxyl number or weight percent phenolic Hydroxyl are indicated.

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Table 1: q, g'-bis (hydroxyphenyl) diisopropylbenzenes, substituted in o-stoilung to the OH groups, prepared as described above

E.g.

description

M.p. analysis

method

CO
CO
K>
CO ι

^J , üt .'-bis (4-hydroxy-3,5-dimethyl-157-9 ° phenyl) -p-diisopropylbenzene

'Xt ot ¹ -Bi s - (4-hydroxy-3,5-diethyl phenyl) -p-diisopropylbenzene

1O3-5 ^c

- 105-7

pyl-phenyl) -p-diisopropylbenzene

ι 4 <x, a'-bis (2-hydroxy-3,5-dimethyl- 179-180 ° phenyl) -p-diisopropylbenzene

, 7, _i 5 ( ^l -Bis- (4-hydroxy-3-isopropyl-134-6 ° phenyl) -p-diisopropylbenzene

. ^,. ^ '- bis (4-hydroxy-3-tert-butyl-166-7 ° phenyl) -p-diisopropylbenzene phen.OH

found: 8.4-8.7 wt

calculated: 8.5 wt .-? o

found: 243-246

calculated: 245

found: 214-221

calculated: 219

phen.OH

found: 8.6-9.0
calculated: 8.5 wt.

found: 268
calculated: 262

found: 237-241

calculated: 245

O CD CO O

a ', o (' - bis (4-hydroxy-3-isobutyiphenyl) -p-diisopropylbenzene

8 cCtjC ¹ -Bis- (4-hydroxy-3-phenyl-phenyl) -p-diisopropylbenzene

la £ ',. £' -Bis- (3,5-dimethy 1-4-

hydroxyphenyl) -m-diisopropylbenzene

104-5 OHZ 242-247 found: : 245 ■ calculated 135-7 ° OHZ 231-4 found: : 225 calculated 8.3-8.7 wt
: 8.5 wt .- * 132-134 phen.OH
found:
calculated

phen.OH = phenolic hydroxyl OHZ = hydroxyl number

cn co ο cn

Example 9 / S

Preparation of the bishopric carbonic acid ester of Qc, ¹ X ¹ -Bis- (4-hydroxy-3,5-dimethy! Phenyl) -p-diisopropy! Benzene

Loo.5 gi ^, y .'-Bis- (4-hydroxy-3,5-dimethylphenyl) -p-disopropylbenzene (0.25 mol) was slurried in 450 ml of toluene. At -5 to ⁰ ° C., 74.2 g of phosgene (0.75 mol) were introduced into this slurry. Then, 61.8 g of N, N-dimethylaniline (0.51 mole) dissolved in 5o ml of toluene, at 0 - 25 ⁰ C are added dropwise with stirring. After adding 100 ml of toluene, the batch was heated to 80 ° C. in the course of 2 hours while stirring. Excess phosgene and 100 ml of toluene were then drawn off. After standing for 15 hours, 800 ml of methylene chloride were added to the batch. The clear liquid solution was washed free of electrolytes 3 times with 500 ml of 5% hydrochloric acid and then with water. The toluene and methylene chloride were then stripped off. After drying, 125 g white crystals were obtained with a melting point of 156-158 ⁰ C. (955 * of theory) The analysis showed 13.4 % chlorine (theory: 13.4-5 % chlorine).

Example Io

Polycarbonate from the bishopric carbonic acid ester of OQX'-bis- (4-hydroxy-3,5-dimethy! Phenyl) -p-diisopropy! Benzene

20.9 g of sodium hydroxide (0.52 mol) were dissolved in 300 ml of water. To this, 1. ol g of triethylamine (0.01 mol) were added. A solution of 52.7 g of bishopric carbonate of V, X ^l -bis- (4-hydroxy-3,5-dimethylphenyl) -p-diisopropylbenzene (0.1 mol) in 300 ml of methylene chloride was then added all at once with thorough stirring vigorously stirred for another 2 1/2 hours. The reaction mixture was kept at 20-25 ° C. and under nitrogen throughout the experiment. The aqueous phase was bisphenol-free. The organic phase was diluted with 600 ml of methylene chloride and free of electrolytes three times with 300 ml of 5 percent hydrochloric acid and then with water

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washed. The solution was then concentrated to 300 ml and the polymer was precipitated therefrom by dropping it into 4 l of methanol and then dried. Ausbeutes 41 g (= 96 $ of theory) of white fluffy polycarbonates / "= I ₉ 647 (in methylene chloride at 25 ° G _$ c = 5 g / l), Grenzsvlskositäts" (light scattering) number EH] = 108j molecular weight M ^ = 171 A colorless, clear, viscous EIIm was obtained from a methylene chloride solution.

Properties of the polycarbonate measured on S ¹ IIm: tear strength £> _R = 650 kp / cm ²

_{Elongation at break} 6 Ώ =

Ε-module from tensile test = 26,000 kp / cm freezing temperature (differential thermal analysis) = 2ol ° C

Example 11

Polycarbonates made from ο ^, Οί * -Bis- (4-hydrpxy-3j5-d _i imethylphenyl) -p - diisopropylbenzene and phosgene

50.4 g of sodium hydroxide were dissolved in 600 ml of water. 600 ml of methylene chloride were added to this. With vigorous stirring, 80.4 g 0 _(J, 0 ( '- bis (4-hydro3cy-3 _i) 5 »diraetiiylphenyl) -p" diisopropy benzene (0.2 mol) * The forming sodium salt of Bisphenol was sparingly soluble in water and a suspension formed. Phosgene was introduced with vigorous stirring until the aqueous phase was bis-phenol-free. The pH of the aqueous phase was kept at 13 by adding sodium hydroxide. 02 g of triethylamine (0.02 mol) and 64 ml of aqueous sodium hydroxide (containing 32 g of sodium hydroxide) were added and the mixture was stirred vigorously for a further 3 hours took place analogously to Example 10 »Yield: 82 g (= 95 f of theory) of white, flaky polycarbonate ^ _{χ @ 1} = 1.617, Grensviskos-

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number £> ζ] = 103, molecular weight M ^ (light scattering) = 166,000. A clear, colorless, tough film was obtained from a methylene chloride solution of the polymer.

Example 12

Copolycarbonate from the bischlorocarbonic acid ester of -X, X ^! Bis (4-hydroxy _"J 3 5-dimethylphenyl) -p-diisopropylbenzene and of bisphenol A

12.8 g of sodium hydroxide (0.32 mol) and 4.56 g of bisphenol A (0.02 mol) were dissolved in 300 ml of water. Then 100 ml of methylene chloride and 0.8l g of triethylamine (0.008 mol) were added. With vigorous stirring, 31.7 g of bishopric carbonic acid ester of ct, oCi.Bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene (0.06 mol), dissolved in 200 ml of methylene chloride, were then added on a. Stirring was continued for 3 hours. The reaction temperature was kept at 20-25 ° C., nitrogen was used. The aqueous phase was bisphenol-free. Working up of the mixture was carried out analogously to Example 1. Yield: 30 g (= 97 of theory) of white fluffy Copolycarbonatν = l, 53o (loo ml methylene chloride solution at 25 ⁰ C). Film made from methylene chloride solution: clear, colorless, tough, freezing temperature (differential thermal analysis) = 188 ° C.

Example 13

Made of polycarbonate %, X '-Bis- (4-hydroxy-3-isopropy! Phenyl) -p-diisopropy! Benzene

In 260 ml of water, 2o.4 g (0.51 mol) of sodium hydroxide were added solved. For this purpose, 21.5 g (0.05 mol); X, fX * -Bis- (4-hydroxy-3-isopropylphenyl) -p-diisopropylbenzene were added with thorough stirring and added 26o ml of methylene chloride. 9.9 g (0.1 mol) of phosgene were then added to the reaction mixture with thorough stirring initiated. After the phosgene had been passed in, 0.101 g (0.001 mol!) Of triethylamine, dissolved in 2 ml of water, were added and more

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Vigorously stirred for 90 minutes. The entire reaction was stirred under nitrogen at 20 - 25 ⁰ C performed. After the stirring, the phases were separated. The aqueous phase was bisphenol-free. The organic phase was washed 3 times with 400 ml of dilute hydrochloric acid solution and then with water until the washing water was free of electrolytes. It was then added dropwise to 8 l of methanol. The precipitated polymer was dried. There were 22 g (= 96 fo of theory) of white, flaky polycarbonate ^ _rel = 1,969 (0.5 g / 100 ml of methylene chloride at 25 ⁰ C and a glass transition temperature of 102 C (differential thermal analysis) obtained from its solution in methylene chloride colorless, clear PiIm could be drawn.

Example 14

Polycarbonate from o (, X'-bis ~ (4-hydroxy-3-phenyl-phenyl) -p-diisopropylbenzene

20.4 g (0.51 mol) of sodium hydroxide were dissolved in 26o ml of water. 24.9 (0.05 mol) 3 (, X ^f -Bis- (4-hydroxy-3-phenylphenyl) -p-diisopropylbenzene and 260 ml methylene chloride were then added to the reaction mixture with thorough stirring 9 g (0.1 mol) of phosgene were passed in. After the phosgene had been passed in, 0.101 g (0.001 mol) of triethylamine, dissolved in 2 ml of water, were added and the mixture was vigorously stirred for a further 150 minutes Following the subsequent stirring, the phases were separated. The aqueous phase was bisphenol-free. The organic phase was washed five times with 400 ml of dilute hydrochloric acid and then with water until the washing water was free of electrolytes. It was then added dropwise to 8 l of methanol precipitated polymer was dried. There were white, flaky polycarbonate with η _rel = 1,918 (0.5 g / 100 ml of methylene chloride at 25 ⁰ C) and a Sinfriertemperatur of 147 ⁰ C (differential thermal analysis) was obtained 25 g (95% of theory =) ,

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from its solution in methylene chloride a colorless clear one Film could be drawn.

Table 2t Examples of the resistance of the polycarbonates produced by the process according to the invention to aqueous sodium hydroxide at 100.degree.

Decrease in weight of pieces of film 4x5 cm, approx. 7o thick, Weight 150-2oo mg. The film pieces were washed with water and dried before each weighing.

Handling time Weight loss in mg the end
E.g. Io the end
Ex. 11 1000 Polycarbonate
from bisphenol A. 0 0 completely dissolved

Table ^; Examples of the resistance of the polycarbonates produced by the process according to the invention to 10% aqueous hydrochloric acid at 100.degree.

Pieces of film 7o - loo / um thick s = very brittle, very easily fragile u s = unchanged, clear and tough

Handling time properties of the movies the end
E.g. Io the end
Ex. 11 Polycarbonate
from bisphenol A. U U 1000 S.

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Table 4; Examples of the resistance of the polycarbonates produced by the process according to the invention to concentrated aqueous ammonia solution at 25.degree

Pieces of film 7o - loo / Um thick u = unchanged, clear and tough

Treatment time Properties of the films the end
E.g. Io the end
Ex. 11 250 Polycarbonate
from bisphenol A. U U completely-dissolved

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Example 15

Polycarbonate made from> t _t ^ '- bis (4 ~ hydroxy-3,5-dimethylphenyl) -mdiisopropylbenzene and phosgene

24.8 g (0.62 mol) of NaOH were dissolved in 210 ml of HpO. _{210 ml of GHpOl 2} and 20.1 g (0.05 mol) of ^{ate ^ 1} -bis (4-hydroxy ~ 3,5-dimethy 1-phenylHindus opropylbenzene were added to this solution with vigorous stirring 14.8 g (0.15 mol) of phosgene were passed in and then 8 g of NaOH, dissolved in 10 ml of H ₂ O, and 0.7 ml (0.005 mol) of triethylamine were added g (0.05 mol) of COCl _{2 were introduced} with stirring and the mixture was stirred for a further 2 hours. The entire experiment was carried out under N ₂ and the temperature was kept at 20-25 ° C. The preparation of the batch was carried out analogously to Example 10, the aqueous one Phase was bisphenol-free.

Yield: 21 g of white, flaky polycarbonate ( $ 98> d. Th.) TX _rel = 1.468, intrinsic viscosity £ pz ~] = 81, molecular weight H (light scattering) = 110 100, freezing temperature (differential ^{thermal analysis) = 142 0} C. From a CHpCl ^ j of the polymer a clear, viscous PiIm was obtained.

Example 16 Copolycarbonate from the bischlorocarbonic acid esters of

(3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene and 2,2-bis-

(3,5-dimethyl-4-hydroxyphenyl) propane

22.4 g (0.56 mol) of NaOH and 1.4 ml (0.01 mol) of triethylamine were dissolved in 400 ml of H _{2 O.} A solution of 400 ml of CH ₂ Cl ₂ , 36.9 g (0.07 mol) of bischlorocarbonic acid ester of * i, <X'-bis- (3,5-dimethyl-4-hydroxyphenyl) -p- was then added with thorough stirring. diisopropylbenzene and 12.3 g (0.03 mol) of bischlorocarbonic acid ester of 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane all at once ^

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added and stirred vigorously for a further 3 hours. During the entire experiment, the reaction solution was heated to 2 o - 25 ⁰ C ■ and under N _? held .. The aqueous phase was bisphenol-free. Working up was carried out as in Example 10. Yield: 38 g (= 96 fo of theory) of white, flaky copolycarbonate, f -, = 1.462. A colorless, clear, viscous PiIm could be obtained from a CH ₂ C1 _{2 solution of the polymer.}

Example 17

Polycarbonate from the bischlorocarbonic acid ester of oj, ⁰ ^ -Bis- (4-hydroxy-3,5-dimethylphenyl) -p-diisopropylbenzene with 2 _{tons of} 6-dimethylphenol as a chain terminator

20.9 g (0.52 mol) of NaOH, 1.01 g (0.1 mol) of triethylamine and 0.183 g (0.0015 mol) of 2,6-dimethylphenol were dissolved in 300 ml of H _{2 O.} A solution of 52.7 g (0.1 mol) of bishopric carbonic acid ester of: \, oO-bis (4-hydroxy-3,5-dimethylphenyl) -p-diisopropylbenzene in 300 ml of CH ₂ Cl _{2 was then added with thorough stirring} added all at once and stirred vigorously for a further 2 1/2 hours. During the entire experiment, the reaction mixture was kept at 20-25 ^° C. and under N ₂ . The aqueous phase was bisphenol-free. The batch was worked up analogously to Example 10. Yield 41 g (= 95 # of theory), white, flaky polycarbonate, />; __-, = 1.306. A colorless, clear, tough film was obtained from a CH _{o Cl-p solution.}

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209829 / IQtiü

Claims (1)

Claims; 1. Procedure according to the main patent (patent application f Ρ $ ίλ * {('λ. (Le A 13 359)) for the production of high molecular weight polycarbonates which either contain only those of formula 4 on M-functional structural units, J "] R ² S ⁰¹ S K V where R ¹ = GH ² ₅ , O ₃ H ₅ or GH (CH ₃ ) ₂ R ² β GH ₃ , ³ G ₂ H ₅ or and ₅ R ³ = GH ₃ , G ₂ H ₅ or GH (GH ₃ ) ₂ are, the substituent R- is omitted if the linkage of the aromatic B with the aromatic A and G on the aromatics A and C is ortho to the carbonate groups in A and G, and the substituent R ⁵ is omitted if the linkage of the aromatic B with the aromatics A and G on the aromatics A and C is para to the carbonate groups in A and G, or apart from the bifunctional structural units of the formula 4 also those of the formula 1, Le A 13 425 - 21 - 209829/1044 where R = CH ₅ , CgHc, or CH (0H ₅ ) ₂ X = a single bond, an alkylene or alkylidene group with 1-5 C atoms, a Cycloalkylene or cycloalkylidene radical with 5-15 carbon atoms, an ether bond or a keto bond, included in any percentage and an average degree of polymerisation ¥ clay at least 30, based on identical or non-identical structural units of the formula £ "^ d, optionally of the formula i, have the in the implementation of a) Alkali salts of the bisphenols of the formula 2 and optionally 2 with phosgene and / or b) bisphenol bisphenols Formulas 3 and optionally £ and / or c) oligomeric carbonates of the bisphenols of the formulas I and optionally 2, the optionally chlorine have carbonated ester end grappen, in a mixture of an aqueous phase and an inert organic phase Solvent, preferably aqueous alkali as acid acceptor is added, ordered and characterized in that the reaction to high molecular weight polycarbonates, optionally in the presence of chain limiters, by adding 10 - 200 mol percent, based on the particular used Bisphenols, initiates at tertiary amines and maintains a reaction time between 5 and 0.1 hours. 2 »Method according to claim 1, characterized in that the product of the amount of amine (molar projsent) and the reaction time (Hours) the value of 15 mole percent. Exceeds hours. Le A 13 425 - 22 - 209829/1044 : ■■ '■■■' S I! JW 3. A process for preparation of polycarbonates with Sinfriertemperaturen of more than 180 G ⁰ according to Claim. 1 4. Use of the prepared by the method of claim 1 high molecular weight polycarbonates for the production of moldings, films, foils and coatings of high hydrolysis saponification and resistance to aminolysis, optionally fillers, fat substances, glass fibers, pigments, dyes and / or contain stabilizers. Le A 13 425 . - 23 - ORIGINAL INSPECTED 209829/1044