DE3917041A1 - Poly:di:organo:siloxane]-polycarbonate blocks condensation prods. - Google Patents

Abstract

Polydiorganosiloxane-polycarbonate block copolymers (I) based on dihydroxydiphenyl-cycloalkanes of formula (II) are claimed, (I) have Mw 10,000-300,000, and contain 21-99.5 wt.% aromatic carbonate and 79-0.5 wt.% polydiorganosiloxane. R1, R2 = H, Ha1 (pref. C1 or Br), 1-8C alkyl, 5-6C cycloalkyl, 6-10C aryl or 7-12C aralkyl (pref. phenyl-(1-4C-alkyl, esp. benzyl); m = 4-7, pref. 4 or 5; R3, R4 = H or 1-12C alkyl (individually varibale for each X); X = carbon; R3 and R4 both = alkyl on at least one X atom. Pref. polysiloxane block is the residue of an alpha, omega-bis-hydroxyaryloxy -polysiloxane with degree of polymerisation (DP) 5-200, pref. with formula (III) (with Ar = bisphenol residue of formula (II) or (IV) (see below); R, R1 = opt. branched alkyl or halo- alkyl, alkenyl, aryl or halo-aryl, pref. Me; no. of diorganosiloxy units n = o + p + q = 5-200, pref. 20-160).

Description

Subject of the German patent application P 38 42 931.4 (Le A 26 318) are new polydiorganosiloxane-polycarbonate Block condensates based on special dihydroxydiphenylcyclohexanes, their production and their use for the production of moldings of all kinds. The content at Polydiorganosiloxanstruktureinheiten preferably the Formula (IIa)

is 25 to 0.5 wt .-%, the content of complementary, aromatic carbonate structural units

wherein -O-D-O- is the divalent diphenolate of one Si-free diphenols, namely a radical (Ia)

and optionally a radical (IIIa)

-O-AR⁰-O- (IIIa).

The meaning of the general symbols respectively Variables in the formulas (Ia), (IIa) and (IIIa) corresponds those of formulas (I), (II) and (III) of Main application P 38 42 931.4.

Further details are in the following Text of the parent application P 38 42 931.4 (Le A 26 318) through page 18 of the present invention Additional application:  

Subject of the present invention according to P 38 42 931.4 are thermoplastic polydiorganosiloxane Polycarbonate block copolymers based on Dihydroxydiphenylcycloalkanes of the formula (I)

wherein
R¹ and R² independently of one another are hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl and C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl, in particular benzyl,
m is an integer from 4 to 7, preferably 4 or 5,
R³ and R⁴ are individually selectable for each X, independently of one another hydrogen or C₁-C₁₂-alkyl
and
X means carbon,
with the proviso that on at least one atom X R³ and R⁴ are simultaneously alkyl.

X, R³ and R⁴ are preferably simultaneously alkyl on 1-2 atoms, in particular only on one atom. Preferred alkyl radical is methyl; the X atoms in the α- position to the diphenyl-substituted C atom (C-1) are preferably not substituted by alkyl, while the alkyl disubstitution in the β position to C-1 is preferred.

Particularly preferred dihydroxydiphenylcycloalkanes of the formula (I) are those having 5 and 6 ring C atoms in the cycloaliphatic radical (m = 4 or 5 in formula I), for example diphenols of the formulas

The polydiorganosiloxane-polycarbonate invention Block copolymers are characterized by high heat resistance, Strength, good UV stability and low temperature toughness out.

Polydiorganosiloxane polycarbonate block copolymers basically known (see US-PS 31 89 662, 34 19 634, DE-OS 33 34 782, 35 06 472, EP-A 122 535, 135 794).

The thermoplastic polydiorganosiloxane polycarbonate block copolymers of the present invention have a weight average molecular weight M w of from 10,000 to 300,000, preferably from about 15,000 to 80,000 (as determined in a known manner by ultracentrifugation or scattered light measurement) of aromatic carbonate structural units of from 75 to 99.5 wt .-% and a content of Polydiorganosiloxanstruktureinheiten from 25 to 0.5 wt .-%; they can be made out

• a) α, ω- bis-hydroxyaryloxy-polydiorganosiloxanes having a degree of polymerization n of from 5 to 200, preferably those of the formula (II),
• b) diphenols of the formula (I) and, where appropriate, the Formula (III), wherein the content of diphenols of Formula (I) of 1 to 100 mol%, preferably 10 to 80 mol%, based on the molar sum of (I) and (III), and if necessary  
• c) chain terminators and optionally
• d) branching,

by two-phase interfacial polycondensation with Phosgene.

Suitable α, ω -bis-hydroxy-aryloxy-polydiorganosiloxanes (a) are, for. B. from US-PS 34 19 634 known.

Preferred α, ω- bis-hydroxyaryloxy-polydiorganosiloxanes are those of the formula (II):

wherein
Ar is the radical of a diphenol of the formula (I) or of the formula (III) without the two hydroxyl groups and
R and R 'are linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl,
and
the number of diorganosiloxy units and thus the degree of polymerization n = o + p + q = 5 to 200, preferably 20 to 160, is.

In formula (II), the radicals R and the radicals R 'are independent from each other. They are preferably C₁-C₂₀-alkyl, C₂- C₆-alkenyl, C₆-C₁₄-aryl. Halogenated means partial or completely chlorinated, brominated or fluorinated. R and R 'are more preferably methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, Trifluoropropyl, perfluorobutyl and perfluorooctyl.

Diphenols (b) are diphenols of the formulas (I) and (III):

HO-Ar⁰-OH (III)

wherein Ar⁰ are identical or different arylene radicals having preferably 6 to 30 carbon atoms. Examples of diphenols of the formula (III) are:
hydroquinone
resorcinol
dihydroxybiphenyls
Bis- (hydroxyphenyl) -alkanes
Bis- (hydroxyphenyl) -cycloalkanes
Bis (hydroxyphenyl) sulfides
Bis (hydroxyphenyl) ether
Bis- (hydroxyphenyl) -sulfoxides
Bis (hydroxyphenyl) sulfones and
α, ω- bis (hydroxyphenyl) diisopropylbenzenes
and their nuclear alkylated and nuclear halogenated derivatives. These and other suitable aromatic dihydroxy compounds are, for. For example, in US-PS 30 28 365 and 29 99 846 and in DE-OS 15 70 703, 20 36 052, 20 63 050, 22 11 957, French Patent 15 61 518 and in the monograph "H. Schnell , Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 ".

Preferred diphenols of the formula (III) are:
z

wherein
X is a single bond, -CH₂-, -C (CH₃) ₂-, O, S, SO₂,

mean and
Y¹ to Y⁴ are identical or different and are hydrogen, C₁-C₄-alkyl, preferably methyl, or halogen, preferably chlorine or bromine.

Examples for this are:
2,2-bis (4-hydroxyphenyl) propane
1,1-bis (4-hydroxyphenyl) -cyclohexane
2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane
2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane
Bis- (3,5-dimethyl-4-hydroxyphenyl) -methane and
Bis (4-hydroxyphenyl) sulfide.

One or more diphenols of the formula (I) and optionally one or more diphenols of the Formula (III) can be used.

Diphenols of the formula (I) can be known per se Manner by condensation of phenols of the formula (V)

and ketones of the formula (VI)

in the formulas (V) and (VI) X, R¹, R², R³, R⁴ and m have the meaning given for the formula (I). They are described in German Patent Application P 38 32 396.0.

Chain terminators (c) are aromatic compounds with a functional group such as aromatic acid halides or phenols, especially the common ones Phenols such as p-tert-butylphenol, p-chlorophenol, 2,4,6- Tribromophenol and phenols can be used in conventional amounts, depending on the desired molecular weight of Determine block copolymers. Particularly preferred are as Chain terminators Phenols of the formula (IV)

In general, 0.5 mol% to 10.0 mol%, based used on diphenols used.

As branching d) are those with three or more than three functional groups, especially those with three or more than three phenolic hydroxyl groups, the commonly known amounts of branching agents, between 0.05 and 2 mol%, based on incorporated Diphenols are to be kept.

Some of the usable compounds with three or more as three phenolic hydroxyl groups are, for example 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, 2,6-  bis- (2'-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4- Hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane and 1,4- Bis- (4,4'-dihydroxytriphenyl-methyl) -benzene. Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, Trimesic acid, cyanuric chloride and 3,3- Bis- (4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 3,3- Bis (4-hydroxy-3-methyl-phenyl) -2-oxo-2,3-dihydroindole.

Suitable organic solvents for the two-phase interfacial polycondensation are for the production of aromatic polycarbonates known; examples are Methylene chloride and chlorobenzene.

The amounts of organic solvent (= organic Phase) are preferably chosen so that the two-phase interfacial polycondensation in 5 to 20% Solution in organic solvent, preferably 10 to 15% solution expires.

Suitable basic compounds for the formation of aqueous alkaline phase are z. LiOH, NaOH, KOH, Ca (OH) ₂ and Ba (OH) ₂.

In the two-phase interfacial polycondensation, the Volumes of aqueous-alkaline phase and total organic Phase preferably the same.

The pH of the aqueous phase is during the reaction between pH 9 to 14, preferably between pH 12 to 13.  

Suitable catalysts for the polycondensation after The two-phase interface method is that for the Polycarbonate synthesis known tertiary aliphatic Amine catalysts such as trimethylamine, triethylamine, n- Tripropylamine, n-tributylamine or N-ethylpiperidine; optionally, the known quaternary can Ammonium salts such as tetrabutylammonium bromide be used.

The amount of catalyst for the two-phase interfacial process varies depending on the diphenol used 0.2 to 5 mol%, when using tetramethyl-substituted Diphenols between 5 to 10 mol%, in each case based on the total amount of diphenols (b).

The amounts of diphenol (b) and α, ω- bis-hydroxyaryloxypolydiorganosiloxane (a) depend on the desired content of poly (diorganosiloxane) units in the block copolymer. The reaction of the reactants is usually quantitative.

The α, ω- bis-hydroxyaryloxypolydiorganosiloxanes and the chain terminator may be added in the two phase interfacial condensation together with the diphenols (b) prior to phosgene introduction or separately during or after the phosgene introduction, but in any case prior to the addition of the polycondensation catalyst.

As a "carbonate donor" for two phase interfacial polycondensation serve in a known manner carbonic acid halides,  especially carbonic acid chlorides, such as phosgene, COBr₂, or the bischloroformate of Diphenols in an appropriate amount, each per Mol halogenated carbonic acid group less than ½ mol Diphenol is used.

The aromatic thermoplastic block copolymers can from the reaction mixtures just like aromatic Polycarbonates are separated. This will be first the organic, containing the copolycarbonate dissolved Phase separated, washed and then the copolycarbonate isolated by evaporation of the solution, wherein preferably as the final stage of the work-up process Evaporating extruder is used.

The thermoplastic block copolymers of the invention can contain anti-aging agents that increase the stability significantly increase the process products. For modification the products of the invention may, for. B. Carbon black, kieselguhr, kaolin, clays, CaF₂, CaCO₃, aluminas, Glass fibers and inorganic pigments both as Fillers as well as a nucleating agent added become. Likewise, they can the usual for polycarbonate Mold release agents, such. As glycerol stearate his.

The polydiorganosiloxane-polycarbonate invention Block copolymers are thermoplastic molding compositions which are applicable wherever their essential characteristics, such as high heat resistance, strength, Toughness and UV stability are required.  

They can be used to produce moldings of any kind be used according to known methods. In particular For example, moldings can be produced by extrusion or injection molding become.

Examples of producible molded bodies are body parts and housing parts, for. B. for electrical equipment and Appliances such as household appliances, building boards and foils.

The notched impact strength was based on DIN 53 452 / ISO 180-1A on flat bars (80 mm × 10 mm × 4 mm) determined; the heat resistance by method Vicat (B) according to DIN 53 460 / ISO 360.  

Examples Example 1: Preparation of bisphenol (I, 1)

In a 1 liter round bottom flask equipped with stirrer, dropping funnel, thermometer, reflux condenser and gas inlet tube are presented 7.5 mol (705 g) of phenol and 0.15 mol (30.3 g) of dodecylthio and at 28 to 30 ° C with dry HCl Gas saturated. To this solution, a solution of 1.5 mol (210 g) of dihydroisophorone (3,3,5-trimethyl-cyclohexan-1-one) and 1.5 mol (151 g) of phenol are added dropwise within 3 hours, further HCl Gas is passed through the reaction solution. When the addition is complete, HCl gas is passed in for a further 5 h. It is allowed to react for 8 hours at room temperature. Subsequently, the excess phenol is removed by steam distillation. The remaining residue is extracted twice with petroleum ether (60-90) and once with hot methylene chloride and filtered off.
Yield: 370 g
Melting point: 205-207 ° C

example 2

14.73 g (0.048 mol) of bisphenol (I, 1), 97.11 g (0.425 mol) of bisphenol A, 33.7 g (0.84 mol) of NaOH and 1916.25 g of water in an inert gas atmosphere under Stirring solved. Then add a solution of 6.82 g of polydimethylsiloxane block (Pn = 73) with bisphenol A end groups (= 5 wt .-% SiMe₂O) and 1.152 g (12.25 mmol) of phenol in 1250 g of methylene chloride. In the well-stirred solution at pH 12 to 13 and 21 to 25 ° C 79.5 g (0.80 mol) of phosgene were introduced. Thereafter, 0.68 ml of ethylpiperidine are added and the mixture is stirred for another 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent.

example 3

29.45 g (0.095 mol) of bisphenol (I, 1) 75.3 g (0.33 mol) Bisphenol A, 33.7 g (0.84 mol) of NaOH and 1916.25 g of water are dissolved in an inert gas atmosphere with stirring. Then a solution of 6.8 g of polydimethylsiloxane is added. Blocks (Pn = 73) with bisphenol A end groups (= 5% by weight) SiMe₂O) and 1.035 g (11.0 mmol) of phenol in 1250 g of methylene chloride. In the well-stirred solution were at pH 12 to 13 and 21 to 25 ° C 79.5 g (0.80 mol) phosgene introduced. Thereafter, 0.68 ml Ethyl piperidine was added and stirred for 45 min. The Bisphenolatfreie aqueous phase is separated, the organic phase, after acidification with phosphoric acid, with Washed water until neutral and freed from the solvent.

Example 4 (Comparative)

43.13 g (0.19 mol) of bisphenol A, 13.5 g (0.34 mol) of NaOH and 766.5 g of water are in an inert gas atmosphere dissolved with stirring. Then you add a solution of 2.73 g of the polydimethylsiloxane block (Pn = 73) with Bisphenol A end groups (= 5 wt .-% SiMe₂O) and 0.34 g  (3.6 mmol) of phenol in 500 g of methylene chloride. In the Well stirred solution were at pH 12 to 13 and 21 to 25 ° C 31.7 g (0.32 mol) of phosgene initiated. After that 0.27 ml of ethylpiperidine are added and 45 min touched. The bisphenolate-free aqueous phase is separated, the organic phase, after acidification with Phosphoric acid, washed neutral with water and from Solvent freed.

Example 5 (comparison)

6.2 g (0.02 mol) of bisphenol (I, 1) 18.24 g (0.08 mol) Bisphenol A, 24.0 g (0.6 mol) of NaOH and 270 g of water are dissolved in an inert gas atmosphere with stirring and 0.3384 g (36 mmol) of phenol in 250 g of methylene chloride added. The well-stirred solution was at pH 12 to 13 and 21 to 25 ° C introduced 19.8 g (0.20 mol) of phosgene. Thereafter, 0.1 ml of ethylpiperidine are added and still the organic phase after acidification with phosphoric acid, washed neutral with water and from the solvent freed.  

Tabular property comparison

In extension of the invention of the parent application P 38 42 931.4 has now been found that the increase the content of polydiorganosiloxane structural units (IIa) to 25 to 79 wt .-% in the block copolymer, and consequently, the reduction of the aromatic carbonate structural units

to 75 to 21 wt .-%, preferably to a content of 30 wt .-% to 70 wt .-% of (IIa) and on a content from 70% to 30% by weight of aromatic carbonate structural units

to polydiorganosiloxane polycarbonate block copolymers which leads to high toughness and strength good flexibility compared to polydiorganosiloxane Distinguish polycarbonate block copolymers based on bisphenol A.  

The present invention thus provides polydiorganosiloxane Polycarbonate block condensates according to Main application P 38 42 931.4 (Le A 26 318), which thereby are characterized in that they have a content of aromatic carbonate

wherein -ODO- is the divalent diphenolate radical of a Si-free diphenol, from 75% to 21%, preferably from 70% to 30%, by weight, and containing polydiorganosiloxane structural units, but with degrees of polymerization "n" from 3 to 200, preferably from 5 to 125 and in particular from 20 to 80, from 25 wt .-% to 79 wt .-%, preferably from 30 wt .-% to 70 wt .-% have, and that they have weight average molecular weights w of from 10,000 to 300,000, preferably from 15,000 to 80,000. w determined in a known manner by ultracentrifugation or scattered light measurement.

Here, the content of -O-D-O- from 1 to 100 mol%, preferably 10 to 100 mol%, and especially 30 to 100 mol% of Diphenolatresten (Ia) and in complementary molar amounts of 99 to 0 mol%, preferably from 90 to 0 mole% and especially 70 to 0 mol% of diphenolate (IIIa) together.  

Again, this corresponds to the meaning of the general Symbols or variables in the formulas (Ia) and (IIIa) those of the formulas (I) and (III) of the above main application P 38 42 931.4.

Preferred polydiorganosiloxane structural units are again those of the formula (IIa)

where again R and R 'are linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, the sum of the diorganosiloxy units n = o + p + q but 3 to 200, preferably 5 to 125 and especially 20 to 80, and where o, p and q can be any integer positive numbers from zero to 200 inclusive, the sum of which is naturally based on the number "n".

According to the parent application P 38 42 931.4 are in Formula (IIa) the radicals R and the radicals R 'independently from each other. They are preferably C₁-C₂₀-alkyl, C₂-C₆-alkenyl, C₆-C₁₄ aryl. Halogenated means partially or completely chlorinated, brominated or fluorinated.  

R and R 'are more preferably methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chloromethyl, Trifluoropropyl, perfluorobutyl and perfluorooctyl.

The preparation of the polydiorganosiloxane according to the invention Polycarbonate block condensates are analogous to Process of the parent application.

The subject of the present invention is thus also a Process for the preparation of the polydiorganosiloxane according to the invention Polycarbonate block condensates

• a) α, ω- bis-hydroxyaryloxy-polydiorganosiloxanes having a degree of polymerization "n" of from 3 to 200,
• b) Si-free diphenols HO-D-OH, which consists of diphenols the formula (I) and optionally the formula (III), the content of diphenols of the formula (I) from 1 to 100 mol%, based in each case to the molar sum of 100 mol% of (I) and (III), and if necessary
• c) chain terminators and optionally
• d) branching,

by two-phase interfacial polycondensation with phosgene, according to parent application P 38 42 931.4 (Le A 26 318), characterized in that the amount of a) and  b) in a known manner each dimensioned so that from the amount of polydiorganosiloxane structural units from 25% by weight to 79% by weight, preferably from 30% by weight to 70 wt .-%, resulting and the amount of aromatic carbonate

wherein -O-D-O- is the divalent diphenolate of one Si-free diphenol is, from 75 wt .-% to 21 wt .-%, preferably from 70% to 30% by weight.

Preferred degrees of polymerization "n" are again 5 to 125 and in particular 20 to 80; preferred diphenol molar ratios (I) to (III) are also in turn of 10 mol% to 90 mol% to 100 mol% to 0 mol%, and especially from 30 mol% to 70 mol% to 100 mol% 0 mol%, in each case again based on the molar sum Diphenols of (I) and (III).

Further details of the manufacturing process for the polydiorganosiloxane-polycarbonate according to the invention Block condensates are the main application set forth above P 38 42 931.4 (Le A 26 318).

This applies to the diphenols of the formulas (I), (III), for the chain terminators and for the branching and the reaction conditions.  

It is particularly noteworthy that the implementation the reactant is usually quantitative.

The block copolymers according to the invention can be prepared from Reaction mixtures just like aromatic polycarbonates be separated. First, the organic, the copolycarbonate dissolved phase separated, washed and then the copolycarbonate by evaporation the solution isolated, being used as the final stage of the work-up process preferably an evaporation extruder is used.

The block cocondensates of the invention may contain anti-aging agents contain the stability of the process products increase significantly. For modification the products of the invention may, for. Carbon black, kieselguhr, Kaolin, clays, CaF₂, CaCO₃, aluminas, glass fibers and inorganic pigments both as fillers and also be added as a nucleating agent. As well can they the mold release agents customary for polycarbonate, such as Pentaerythritol stearate, glycerin stearate contain.

The polydiorganosiloxane-polycarbonate invention Block cocondensates are molding compounds that are applicable everywhere are where their essential properties such as high toughness, Strength and flexibility are required. Due to their good permeation properties are suitable These polysiorganosiloxane polycarbonate block copolymers also as membranes.  

They can be used to produce moldings of any kind be used according to known methods. In particular For example, moldings can be produced by extrusion or injection molding become.

Examples of producible shaped bodies are covers, Plugs, hoses and damping elements.

The storage modulus values of Examples 8 and 9 were Shear modulus curves using a Rheometrics Dynamic Analyzer were taken. The device works with a forced torsional vibration with a frequency of 1 Hz.

The Shore hardnesses A and D were according to DIN 53 505/150 868 certainly.  

example 6

62.99 g (0.203 mol) of bisphenol (I, 1), 24 g (0.105 mol) of bisphenol A, 54 g (1.35 mol) of NaOH and 3070 g of water are dissolved in an inert gas atmosphere with stirring. Then add a solution of 109.6 g of polydimethylsiloxane block (Pn = 32) with bisphenol A end groups (= 45 wt .-% SiMe₂O) and 1500 ml of methylene chloride. 126.8 g (1.28 mol) of phosgene are introduced into the well-stirred solution at pH 12 to 13 and 21 to 25 ° C. Then 1.12 ml of ethylpiperidine are added and the mixture is stirred for another 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent.
Shore Hardness A: 86
Shore hardness D: 42

example 7

32.98 g (0.106 mol) of bisphenol (I, 1), 15.6 g (0.39 mol) NaOH and 519.1 g of water are in an inert gas atmosphere dissolved with stirring. Then you add a solution of 17.45 g of the polydimethylsiloxane block (Pn = 78) with Bisphenol (I, 1) end groups (= 40 wt .-% SiMe₂O) and Add 0.271 g (2.88 mmol) of phenol in 375 ml of methylene chloride. In the well-stirred solution were at pH 12 to 13 and 21 to 25 ° C 25.33 g (0.256 mol) of phosgene initiated.  

Then 0.22 ml of ethylpiperidine are added and the mixture is stirred for another 45 minutes. The bisphenolate-free aqueous phase is separated off, the organic phase, after acidification with phosphoric acid, washed neutral with water and freed from the solvent.
Tg (DSC): 226.2 ° C

example 8

12.46 g (0.04 mol) of bisphenol (I, 1), 13.5 g (0.34 mol) NaOH and 766.5 g of water are in an inert gas atmosphere dissolved with stirring. Then you add a solution of 41.12 g of the polydimethylsiloxane block (Pn = 10) Bisphenol A end groups (= 45 wt .-% SiMe₂O) and 0.207 g (2.2 mmol) of phenol in 375 ml of methylene chloride. In the Well stirred solution were at pH 12 to 13 and 21 to 25 ° C 31.7 g (0.32 mol) of phosgene initiated. After that will be 0.27 ml of ethylpiperidine was added and 45 min touched. The bisphenolate-free aqueous phase is separated, the organic phase, after acidification with phosphoric acid, washed neutral with water and from the solvent freed.

Temperature (° C) Memory module G '(MPa) 0 130 40 88 100 32

Shore hardness D: 45  

Example 9 (Comparative)

11.04 g (0.0484 mol) of bisphenol A, 13.5 g (0.34 mol) of NaOH and 766.5 g of water are in an inert gas atmosphere dissolved with stirring. Then you add a solution of 36.86 g of the polydimethylsiloxane block / Pn = 10) with Bisphenol A end groups (= 45 wt .-% SiMe₂O) and 0.377 g (4.02 mmol) of phenol in 375 ml of methylene chloride. In the Well stirred solution were at pH 12 to 13 and 21 to 25 ° C introduced 31.8 g (0.32 mol) of phosgene. After that will be 0.28 ml of ethylpiperidine was added and 45 min touched. The bisphenolate-free aqueous phase is separated, the organic phase, after acidification with phosphoric acid, washed neutral with water and from the solvent freed.

Temperature (° C) Memory module G '(MPa) 0 3.8 40 1.3 100 -

Shore Hardness A: 50

Claims (7)

1. polydiorganosiloxane-polycarbonate block copolymers according to the main application P 38 42 931.4 (Le A 26 318), characterized in that they contain a content of aromatic carbonate structural units wherein -ODO- is the divalent diphenolate radical of a Si-free diphenol, from 75% to 21% by weight and containing polydiorganosiloxane structural units having degrees of polymerization "n" of from 3 to 200 and from 25% to 79% by weight % and that they have weight average molecular weights w of 10,000 to 300,000. 2. Polydiorganosiloxane-polycarbonate block copolymers according to claim 1, characterized in that it a content of aromatic carbonate structural units from 70% to 30% by weight and a content at Polydiorganosiloxanstruktureinheiten of 30 wt .-% to 70 wt .-% have. 3. Block copolymers according to claim 1, characterized in that the content of -ODO- from 1 to 100 mol% of Diphenolatresten (Ia) wherein
R¹ and R² are independently hydrogen, halogen, preferably chlorine or bromine, C₁-C₈-alkyl, C₅-C₆-cycloalkyl, C₆-C₁₀-aryl and C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl, an integer from 4 to 7, R³ and R⁴ are individually selectable for each X, independently of one another hydrogen or C₁-C₁₂ alkyl and
X represents carbon, with the proviso that at least one atom X R³ and R⁴ are simultaneously alkyl, and from 99 to 0 mol% of Diphenolatresten (IIIa) -O-Ar⁰-O- (IIIa), wherein
Ar⁰ same or different arylene radicals are. 4. block copolymers according to claim 3, characterized that the content of -O-D-O- from 10 to 100 mol% of (Ia) and from 90 to 0 mol% of (IIIa) consists. 5. block copolymers according to claim 1, characterized in that the Polydiorganosiloxanstruktureinheiten correspond to the formula (IIa), wherein R and R 'represent linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, the sum of the diorganosiloxy units n = o + p + p is 3 to 200, and wherein o, p and q are any integer positive integers, including zero to 200 inclusive, each sum of which is oriented to "n". 6. A process for preparing the polydiorganosiloxane polycarbonate block copolymers

• a) α, ω- bis-hydroxyaryloxy-polydiorganosiloxanes having a degree of polymerization "n" of from 3 to 200,
• b) Si-free diphenols HO-D-OH, and optionally
• c) chain terminators and optionally
• d) branching,

by two-phase interfacial polycondensation with phosgene according to the main application P 38 42 931.4, characterized in that the amount of a) and b) in a known manner in each case such that from the amount of Polydiorganosiloxanstruktureinheiten from 25 wt .-% to 79 wt .-% and the amount of aromatic carbonate structural units wherein -ODO- is the divalent diphenolate residue of a Si-free diphenol, resulting from 75% to 21% by weight.