DD156980A5 - ATOMIC AND AMIDIMIDE UNITS CONTAINING COPOLYMERS - Google Patents

Abstract

Amidinoid units (AI units) and etherimide units (EI units) containing copolymers which are useful for coating purposes and for the production of pressed parts.

Description

Berlin, 9/9/1981 AP C 08 L / 226 934/2 (58 659/11)

Etherimide and amidimide units containing copolymers

Field of application of the invention

The invention relates to copolymers containing amidimide units (AI units) and etherimide units (units of units) which are useful for coating purposes and for producing pressed parts.

C / harakterj-st_ik_ of the known technical solutions

Polyamideimides are known to have good chemical resistance and moderate heat resistance. While such polyamide-imides can be dissolved in suitable solvents for coating purposes, such polyamide-imides are quite difficult to compress and require excessively high temperatures and pressures of polyetheramides in the press cycle it is known that _s they have good high-temperature properties and practicable pressing cycles are more accessible; However, it would be advantageous to improve the chemical resistance of these polyetherimides and to reduce their costs for the application areas of compression and coating «

The aim of the invention is the provision of new polymers with favorable chemical and physical properties, which are suitable for coating purposes and for the production of pressed parts.

09/07/1981

AP C OS L / 226 934/2 (58 659/11)

j? ung.

The invention has the object containing copolymers with the desired properties is based to provide _s Ätherimid- and amide-imide units ©

According to the invention, a copolymer is provided that o.: ...., ....

(a) 5 to 95 mole percent chemically bound AI units of the general formula

H 0

and

(b) 95 to 5 mole percent chemically bound EI units of the general formula.

0 - R -

wherein R is selected from the class consisting of

(a) the following divalent organic radicals

and

and

br

(b) bivalent organic radicals of the general formula

 "/ O -"

in which .X is the radical -CH ₂ ~, the index y is an integer with a value of 1 to 5 inclusive, and

R is a bivalent organic radical selected from the class consisting of

(a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and halogenated derivatives thereof,

(b) alkylene radicals and cycloalkylene radicals having 2 to 20 carbon atoms,

(c) C, _ ns ~ alkylene endblocked polydiorganosiloxanes, and

(d) divalent radicals of the following general formula

in which Q is a bivalent radical selected from the class consisting of

__S and -

and the index χ means an integer from 1 to 5 inclusive.

0 0 1! - II C- Il 0

The bound, randomly arranged units or block copolymers can, as such, have the general formula III

~ 5-

V * ¹ -

5-R-O

(III)

in which R and R are as defined above, the indices m and η are integers which, independently of one another, are at least equal to 1, e.g. 5 to 5000 or above, and the index ρ is an integer greater than 1, e.g. with a value of 5 to 10,000, or above, and advantageously with a value of 10 to 1000.

Prior to imidization, the copolymers are in the amide form, as exemplified by the following general formula

It

'C-OH

HO

O + -0-5-0 ·

, C-OH

CNR ¹

and specifically by the following general formula

-OH

ö "

, -β- 9 * 7 * 1981

AP C 08 L / 226 934/2 (58 659/11)

_s is given in the formulas the radical R ₉ R _s and the indices m, η and ρ have the meaning given above *

According to the invention has been evaluated in tests found j that copolymers comprising units of the general formulas chemically bound I and II over a wide range of ¹ molar concentration can produce _9, wherein the properties of the copolymers compared with the properties of homopolymers of these units modified are * in some cases, the improvement of the properties was unexpected _s when taking into account the proportion of either the AI unit or the EI-unit, which in the copolymer was present *, through the preparation of the copolymers described above, the usefulness of the latter can be considerably In addition, by combining these two units in the copolymer, products can be obtained which require a lower cost than is usually associated with the preparation of polyetheramides alone

without a significant loss (if any) in the physical properties.

A preferred class of copolymers encompassed by the general formula III are such copolymers,

1-

consisting essentially of about 2 to 5000 or more units, and preferably from 5 to 100 units of EI units of general formula IV

O = O

in which R has the meaning given above

2 and R is the formula below

CH.

having.

Included in the etherimide units of general formula IV as part of the copolymer molecule are the following chemically bonded units V, VI and VII

O-R

(VI) and

(VII)

1 2

and mixtures thereof, in which R and R have the same meaning as above.

The copolymers of the general formula III can be obtained by reacting an aromatic bis (anhydride) of the general formula VIII

O-R.

a trimellitic acid chloride (TMAC) of the formula IX

(IX)

and an organic diamine of general formula X.

NH,

(X)

- js -

wherein the radicals R and R have the same meaning as above.

A total of from 0.95 to 1.05 moles of the anhydrides of the formulas VIII and IX can be used per mole of the organic diamine of the general formula X. It is preferred to use substantially equal molar amounts of (a) the anhydrides of formulas VIII and IX, and (b) the organic diamine. The copolymers used in the present invention may be those in which from 10 to 5,000, or more units of one of the formulas I and II are present, and the index ρ in the formula III is 5 or higher, e.g. the value 10 to 1000, has.

The acyl halide derivative of formula IX derived from trimellitic anhydride (1,3,4-benzenetricarboxylic anhydride) may have at least one acyl halide and that in the 4-position, and includes derivatives such as the 4-acid chloride, 1,4- and 2, ^ - diacid chloride. The bromide and other reactive halide derivatives are also suitable.

In the preparation of the copolymers, chain terminators such as aniline or monoorganoic acid derivatives or monoanhydrides can be used.

In general, the copolymers of the present invention can be obtained by reacting the selected organic diamine and the particular dianhydride and monoanhydride of Formulas VIII and IX, respectively, in the presence of a dipolar aprotic organic solvent under ambient conditions to produce a copolymeric amic acid. Upon further heating, the amic acid converts into the

-40-

- -er -

Imide form, wherein the copolymer contains the units of general formulas I and II in a random distribution. Depending on the solid content of the polyamic acid solution, the reaction may be completed in 0.5 to 2 hours or more. After completion of the reaction, the solution may be poured onto a substrate so that evaporation of the organic solvent occurs. By heating to temperatures in the range of 150 ° to 200 ° C or higher, the copolymeric polyamic acid is converted to the polyimide form, so that the copolymer at this point has good heat resistance, chemical resistance such as solvent resistance, and pressability. Such formulations are particularly useful as a paint coating for wires and impart solvent resistance and heat resistance properties to various substrates.

The aromatic bis (ether hydride) of formula VII can be prepared by hydrolysis, followed by dehydration, of the reaction product of the nitro-substituted phenyldinitrile and subsequent reaction with a dialkali metal salt of a dihydric aryl compound in the presence of a dipolar aprotic solvent, the alkali metal salt having the general formula

Alk-O-R ¹ -O-Alk

has, in which R has the same meaning as above and is preferably the same radical as R and Alk represents an alkali metal ion. To convert the resulting tetranitriles into the corresponding tetraacids and dianhydrides, various well-known methods can be used.

Among the alkali metal salts of the dihydric phenols described above are sodium and potassium salts of the following dihydric phenols:

2,2-bis (hydroxyphenyl) -propane, 2,4'-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) -methane, 2,2-bis (4-hydroxyphenyl) -propane (hereinafter referred to as "bisphenol-A" or as " BPA "), 1,1-bis (4-hydroxyphenyl) -ethane, 1/1-bis (4-hydroxyphenyl) -propane, 3,3-bis (4-hydroxyphenyl) -pentane, 4,4 · -dihydroxybiphenyl , 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl, 2,4-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, etc.

Of the organic diamines of general formula X, for example, the following compounds are included:

m-phenylenediamine,

p-phenylenediamine,

4,4'-diaminodiphenyl propane, 4,4'-diaminodiphenylmethane, benzidine,

4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-Diaminodipheny1 ether, 1 i 5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4 -diaminotoluene,

2,6-diaminotoluene,

£, ' El AJ H JG -JL- Λ * ^ *

AP C 08 L / 226 934/2 (58 659/11)

2,4 ~ bis (ß «-amino - tert -butyl _c) toluene, bis (p-ß-diethyl-o-arninopentyl) -benzene 1 ₉ 3 ~ 4 ~ diamino-isopropylbenzene _s • 1,2-bis (3-aniinopropoxy) ~ _s m ~ äth.an xylylenediamine _t

Bis (4tarainocyclohexyl) methane ₉ 3 "Metiiylheptameth.ylendiamirij 4f 4 ~ BimethylheptaDieth.ylendiarain, 2,1I-dodecanediamine, 2,2-Diniet hy! Propylenediamine, octamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-Dimethylhexamethylendiaiiiin, 3-Methylheptainethylendianiin,

5-methylnonamethylenedianiine, 1,4- = cyclohexanediamine, 1,12-octadecanediamine, bis (3-aminopropyl) sulfide,. F-methylene-bis (3 ~ aniin.opropyl) -aniin _s hexamethylenediamine, Nonamethylendiarain, 2,6-Diatnino toluene, bis (3-aininoprbpyl) ~ tetramethyldisiloxane, etc.

The copolymeric formulation may be reinforced with various particulate fillers such as glass fibers, silica, fillers, carbon whiskers, up to an amount of 50% by weight of the copolymer, or above,

AusführungsbeJ.sp_i_el.

The following examples serve for further explanation

nin.ht bfi.qfihränken * All

-AZ-

Parts are parts by weight, unless expressly stated otherwise.

example 1

A copolymer containing AI units and EI units was prepared by reacting 2 g of 4,4'-methylenedianiline, 1.56 g of 4,4'-BPA-dianhydride and 1.47 g of 4-chloroformyl phthalic anhydride in 15 ml N-methylpyrrolidone produced. The mixture was stirred at room temperature until it became clear, whereby the temperature of the mixture rose to 40 ° C. After cooling, the copolymer preparation became a film at a temperature of about 150 to 28 ° C. This polymer had a molar ratio of 30 mole percent EI units and 70 mole percent AI units and softened at about 300 C.

B e i / s ρ i e 1 2

This example illustrates the preparation of a homopolyetherimide which will be further compared to a copolymeric preparation containing the same diaminoorganic compound. The process and apparatus for making such homopolyetherimides are described in U.S. Patent 3,884,767. 5.2 g (0.01 mol) of 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] -propane dianhydride (hereinafter referred to as "BPA dianhydride") and 1.08 g (0.01 mol ) m-Phenylenediamine were dissolved in 30 ml of N-methylpyrrolidone. After stirring the mixture, the temperature rose to 42 ° C due to the exothermic reaction, whereby a clear, homopolymeric amic acid solution was obtained. From this solution a film was molded at 280 ° to 300 ⁰ C, to give a imidized, polymeric film.

Beep! 3

This example illustrates the preparation of a homopolymeric amide. Specifically, 2.1 g (0.01 mol) of trimellitic acid chloride (TMAC; Formula IX) and 1.08 g (0.01 mol) of m-phenylenediamine were dissolved in -30 ml of N-methylpyrrolidone. The mixture was stirred, the solution heated to about 4 ° C by the exothermic reaction to yield a clear, polymeric amic acid amide. A portion of this solution was poured onto a flat surface at 280 ° to 300 ° C to yield an imidized homopolymeric Al film.

B e 1 s ρ i e 1 4

A copolymer was prepared by mixing 1.89 g (0.009 mol) of TMAC, 0.52 g (0.001 mol) of BPA dianhydride and 1.08 g (0.01 mol) of m-phenylenediamine dissolved in 30 ml of N-methylpyrrolidone. manufactured. After stirring at room temperature the mixture rose due to the exothermic reaction to about 47 C to at which point get a clear polymeric Amidsäureamid solution wurde.- From this solution a film at a temperature of 280 ° to 300 ⁰ C was poured and provided an imidized copolymer film.

B e i s ρ i e 1 5

Using the conditions and use of the reactants of Example 4, TMAC, bisphenol-A-dianhydride and m-phenylenediamine were reacted in the same manner to prepare copolymeric formulations which, after casting, imidized to films at elevated temperatures of 280 ° to 300 ° C , copolymer films with good abrasion resistance. Table I below shows the proportions of the various ingredients and the temperature to which the solutions of the three reactants after stirring increased due to the exothermic reaction. In any case

table

Example no. TMAC mol BPA-dianhydride mol m-phenylenediamine mol Exothermic temperature ( ⁰ C) 4 5A 5B 5C 5D 5E 5F * I Weight (g) 0.009 0.008 0.006 0.004 0.002 0.001 0.005 Weight (g) 0.001 0.002 0.004 0.006 0.008. 0.009 0.005 Weight (g) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 47 48 46 44 43 44 '41 1.89 1.6 8 1.26 0.84 0.42 0.21 1.05 0.52 1.04 2.08 3.12 4.16 4.68 2.6 1.08 1.08 1.08 1.08 1.08 1.08 1.08

Used 15 ml of N-methylpyrrolidone

30 ml of N-methylpyrrolidone were used to prepare the starting solution of the three reactants.

The glass transition temperatures T. (which measures the degree of softening of the polymers) of all the copolymers of Examples 4 and 5A to 5F were determined and are set forth in Table II below.

T a b e 1 1 e

II

Example no. ^Tg <° C). 5A - 5B 223 5C 221 5D 204 5E 5F 212 209 2 193 3 241 4 222

The copolymers obtained in Examples 4 and 5A to 5F can be represented by the following general formula XI

in which the units are in random order, the indices m and η are integers. are greater than 1 and substantially correspond to the molar concentrations of the reactants originally used, and the index ρ is an integer greater than 1.

Example 6

Using the same conditions as in Example 4, ^ 2.1 g (0.01 mol) of TMAC and 2.48 g (0.01 mol) of 4,4'-diphenyldiaminosulfone of the following formula XII

(XII)

dissolved with stirring in 15 ml of N-methylpyrrolidone; the temperature of the mixture increased to 37 ° C due to the exothermic reaction. The clear, polymeric amic acid-amide solution that was obtained was poured out at 280-300 ° C to yield an imidized homopolymeric film.

Example 7

Using the conditions given in Example 4, 5.2 g (0.01 mol) of BPA dianhydride and 2.48 g (0.01 mol) of the derivative of Formula XII used in Example 1 were dissolved in 15 ml of N-methylpyrrolidone was dissolved, whereby after stirring, in which due to the exothermic nature of the reaction, a temperature increase to 38 C was recorded, obtained a clear, homopolymeric amic acid solution. A film cast from this solution at 280 ° to 300 ° C provided an imidized homopolymeric film.

-is-

- J \ sf ~

B e i s ρ i e 1

In this example, copolymers of TMAC, BPA dianhydride, and the sulfone of Formula XII are prepared by dissolving the reactants in 15. ml N-methyl pyrrolidone and stirring the mixture to form a clear, polymeric amic acid amide. In each case, films were cast at 280 ° to 300 ° C to obtain the imidized copolymer films having good abrasion resistance. Table III below shows the weight and molar concentrations of the ingredients, the exothermic temperatures and the glass or glass transition temperatures (T) for each of the formulations described in Examples 6-8.

The imidized copolymers in Example 8 can be represented by the following formula XIII

O-

in which the indices m, η and ρ have the same meaning as above.

The following examples illustrate the preparation of homopolymers from either a dianhydride with 4,4'-oxydianiline of Formula XIV

(XIV)

T a b e 1 Γ e 'III

Example no. TMAC mol BPA-dianhydride mol sulfone * mol Exothermic temperature ( ⁰ C) ^T g (° C) 6 7 8A 8B SC Weight (g) 0.005 0.002 0.008 Weight (g) 0.005 0.008 0.002 Weight (g) 0.01 0.01 0.01 37 37 41 39 • 37 220 220 181 208 1.05 0.42 1.68 2.6 4.16 1.04 2.48 2.48 2.48

4,4'-diaminodiphenylsulfone

y j

from TMAC and the same oxydianiline, as well as copolymers made from the mixture of oxydianiline, BPA dianhydride and TMAC.

B ice ρ ie 1 9

5.2 g (0.01 mol) of BPA-dianhydride and 2 g (0.01 mol) of 4,4'-oxydianiline were dissolved in 15 ml of N-methylpyrrolidone and used to prepare a clear, polymeric amic acid solution with exothermic increase of Temperature stirred at 51 ° C. From this solution was cast at 280 ° to 300 ⁰ C, a film that provided an imidized, homopolymeric film.

B ice ρ ie 1 10

2.1 g (0.01 mol) of TMAC and 2.0 g (0.01 mol) of 4,4x-oxydianiline were dissolved in 15 ml of N-methylpyrrolidone and the mixture was vigorously stirred, whereupon an exothermic rise in temperature to 53 ° C took place. The clear, homopolymeric amic acid amide solution which was obtained was cast at 280 ° to 300 ° C to form an imidized, homopolymeric film.

B ice ρ ie 1 11

In this example, TMAC, BPA dianhydride and 4,4'-oxydianiline were copolymerized in a similar manner to Example 4 by dissolving the reactants in 15 ml of N-methylpyrrolidone and then the polymeric amic acid-amide solution at 280 ° to 300 ° C cast to a film for the formation of an imidized, copolymeric film. Table IV below shows the weight and molar concentrations of the reactants and the exothermic temperature of each mixture as a result of stirring the reactants.

T a b e 1 1 e IV

Example No. ' , TMAC mol BPA Diahhydrid mol 4,4'-oxydianiline mol J Exothermic temperature ( ⁰ C) HA HB Weight (g) 0.005 0.008 Weight (g) 0.005 0.002 Weight (g) 0.01 0.01 41 50 1.05 1.68 2.6 1.04 1.98 2.0

The Exnfriertemperaturen T of the homopolymers and copolymers prepared in Examples 9, 10, HA and HB were determined and are shown in Table V below.

T a b e 1 1 e

Example no. ^T g:: = ..: ( ⁰ C) 9 10 HA HB   , 213 230 205 206

The in the examples HA and. HB obtained copolymers can be used as such in the in the following formula XV

-Κ

In the formula, the indices m and η have values which correspond to the molar concentrations of the reactants used. and the index ρ is an integer greater than 1.

-as

The following examples illustrate the preparation and properties of homopolymers and copolymers prepared using 4,4'-methylenedianiline of the formula XVI

(XVI)

prepared as an organic diamine.

B 'e i s ρ i e 1 12

2.1 g (0.01 mol) of TMAC and 1.98 g (0.01 mol) of 4,4'-methylenedianiline were dissolved in 15 ml of N-methylpyrrolidone and stirred until the mixture as a result of the exothermic reaction, a temperature of 54 ° C reached. The resulting clear, homopolymeric acid amide solution was cast at 280 to 300 C to form an imidized, homopolymeric film.

B e i s ρ i e 1 13

5.2 g (0.01 mol) of BPA-dianhydride and 1.98 g (0.01 mol) of 4,4'-methylenedianiline were dissolved with stirring in 15 ml of N-methylpyrrolidone, wherein due to the exothermic reaction, an increase in temperature of the mixture to 49 C was effected. The resulting clear, homopolymeric amic acid solution was cast as a film at 280 ° to 300 ⁰ C to form a homopolymer, imidized film.

B e i s ρ i e 1 14

In this example, using the same conditions as in Example 4, TMAC, BRP-dianhydri.d and 4,4'-methylenedianiline are mixed together and dissolved in 15 ml of N-methylpyrrolidone to prepare a copolymeric amic acid-amide solution prepared according to the Pour at 280 ° to 300 ° C

provided an imidized, copolymeric film. Table VI below shows the weight and molar concentrations of the reactants, as well as the exothermic temperatures.

Table VI

Example no. .TMAC mol BPA-dianhydride mol methylenedianiline mol Exothermic temperature ( ⁰ C) 14A 14B Weight (g) 0.005 0.008 Weight (g) 0.005 0.002 Weight (g) 0.01 0.01 41 49 1.05 1.68 2,6 ^ 1,04 1.98 1.98

From each of the polymers of Examples 12, 13, 14A and 14B, the glass transition temperature T was determined, which is given in Table VII below. These copolymers can be represented by the general formula XVII

ti

in which the indices m, η and ρ have the same meaning as above.

T a b e 1 1 e VII

Example No. / .... T ..: =: .. ( ⁰ C) 12 13 14A 14B 215 187 220 229

It is obvious to a person skilled in the art that, in addition to the diamino compounds used to make the above copolymers, other diamino compounds can be used, numerous examples of which have been given above. In the same way, other dianhydrides than the bisphenol A dianhydride used in the examples of the present invention may be used to prepare other copolymer types.

Finally, the molar proportions of reactants can be widely varied to form units of varying molar range, as described above, without departing from the scope of the present invention ,

Other polymers and resins may be added to the claimed copolymers in amounts ranging from 1 to 50 percent by weight, or more, based on the total weight of the copolymer. Among such polymers which may be added are, for example, polyolefins, polystyrene, polyphenylene oxides, as shown in US Pat. No. 3,306,875, epoxy resins, polycarbonate resins, as shown in US Pat. No. 3,028,365, silicone Resins, polyarylene polyethers, as shown in US Pat. No. 3,329,909, and many others known to those skilled in the art.

The compositions of the present invention find use in a wide variety of physical forms, including their use as films, molding compounds, etc. When used as films or processed into compacts, these copolymers, including the laminated products made therefrom, have not only good physical properties Room temperature properties but maintain their strength and excellent workload response at elevated temperatures for long periods of time,

Films made from the copolymers of the present invention can be used in applications where films have previously been used. They are used effectively for packaging and wrapping in an extensive manner. The preparations of the present invention

can be used for motor vehicles and aircraft for decorative and protective purposes, and as high-temperature electrical insulation for engine muffler liners, in transformers and as dielectric capacitors.

Optionally, solutions of the curable formulations described herein may be coated on electrical conductors such as copper, aluminum, etc., and then the coated conductor heated to elevated temperatures to remove the solvent and cause hardening (imidization) of the resinous composition thereon. If desired, an additional overlying layer may be applied to such insulated conductors, including the use of polymeric coatings such as polyamides, polyesters, silicones, polyvinylformal resins, epoxy resins, polyimides, polytetrafluoroethylene, etc. '

Areas of application for which these resins are recommended include their use as binders for asbestos fibers, carbon fibers and other fibrous materials in the manufacture of brake linings. In addition, abrasive wheels and other abrasive articles of such resins may be prepared by incorporating abrasive grains such as Alundum, silicon carbide, silicon nitride, carborundum, diamond dust, cubic boron nitride, etc., and molding or compressing the mixture under heat and pressure to achieve the desired configuration and shape Grinding and emery purposes.

Claims (3)

-39- -Ä8- 09/07/1981 AP C 08 L / 226 934/2 (58 659/11) Brfi ndiingsansprutch Copolymers characterized by the. general formula A .0 "in (Γ c t! or B Il C-OH -MR Il HO ti - R - OAQ , G-OH "CNR ¹ -, wherein R is selected from the class consisting of (a) the following divalent / organic residues CH. and br and (b) bivalent organic radicals of the general formula -3Ί - "se in which X is the radical -CH ₂ -, the subscript y is an integer having a value of 1 to 5 inclusive, and R is a bivalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having 2 to 20 carbon atoms, (c) C, ₂ _o \ -alkylene endblocked polydiorganosiloxanes, and (d) divalent radicals of the following general formula in which Q is a bivalent radical selected from the class consisting of and "-C _x H _2x " and the index χ means an integer from 1 to 5 inclusive, the indexes m and η are integers having, independently of each other, at least the value 1, and the index ρ is an integer greater than 1. ta? 09/07/1981 AP C OS L / 226 934/2 (58 659/11) 2 _β CopolyniereSy characterized in that it (a) 5 to 95 mole percent chemically bound units of the general formula and (b) 95 to 5 mole percent of chemically bound units of the general formula 0 - R - 0 .. contains, in which R is selected from the class consisting of (a) the following divalent organic radicals 3 OH V_ / V = - ™ / CH, CH, and br br (b) bivalent organic radicals of the general formula in which X is the radical -CH ₂ -, the index y is an integer with a value of 1 to 5 inclusive, and R is a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals having 6 to 20 carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals having 2 to 20 carbon atoms, (c) Polydiorganosiloxanes with C, ₂ _o>"alkylene end groups, and (d) divalent radicals of the following general formula J 4 9.7 * 1981 AP G 08 L / 226 934/2 (58 659/11) in which 'Q is a bivalent radical selected from the class consisting of OO -8-, -S-, -S- and -C It and the index χ means an integer from 1 to 5 inclusive. 3 · Copolyrneresj characterized by having the general formula in which the indices ta and n _{s are} independent, integers of at least 1 are _s and the index ρ is an integer greater than 1 » e Copolymeresy characterized by ^ that it is the general formula -3S- AP C 08 L / 226 934/2 (58 659/11) in which the indices in and n _{s are} independent, integers of at least 1, and the index ρ is an integer greater than 1 « 5 ", Gopolymeres, characterized in that it is the general formula has, in v / elcher, the indices m and n, independent, whole Numbers are at least 1, and the index ρ is a whole number greater than 1 ^ (ι Copolymeres _s characterized in that it is the general formula 9 * 7 * 1981 AP C 08 L / 226 934/2 (58 659/11) has j In which the indices Di and n _{s are} independent ^ integers of at least 1, and the index ρ is an integer greater than 1 © 7 ". CopolvmereSj characterized in that it is the general formula has j in which the indices m and n _{s are} independent, integers of at least 1, and the index ρ is an integer greater than 1 · "