DE3100874A1 - "COPOLYMERS CONTAINING AETHERIMIDE AND AMIDE UNITS" - Google Patents

Description

Dr. rer. nat. Horst pupil

PATENT ADVOCATE

_ 9 _ 0000 Frankfurt / Main 1.1 January 3, 1981

Kaiserstrasse 41 Dr. Sch / Um / Hk

Telephone (0611) 235555 Telex: 04-16759 mapat d Poitschedc account: 282420-602 Franlcfurt-M.

Bank account: 225/0389 Deutsche Bank AG, Frankfurt / M.

8588-RD-12312

GENERAL ELECTRIC COMPANY

1, River Road Schenectady, N.Y., U.S.A.

Copolymers containing etherimide and amide units

The invention relates to copolymers which have amide recurring units (A) and etherimide recurring units (EI), which are useful for coating purposes and for the production of pressed parts. In particular concerns the invention is a copolymer that

(a) 5 to 95 mol percent of chemically bonded units of the general formula I.

H

- N-C

O H

: —Ν — R

(D

and

(b) 95 to 5 mol percent of chemically bonded units of the general formula II

(II)

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Il

contains, where the -C units of the general formula I are in the meta-position or in the para-position to one another, and

R is selected from the class consisting of

(a) the following divalent organic radicals

Br

and

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310087A

(b) divalent organic radicals of the general formula

in which X denotes the radical -C H ~ -, the index y is an integer with a value from 1 to 5 inclusive, Lind

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

(a) aromatic hydrocarbon radicals with 6 to 20 Carbon atoms and halogenated derivatives thereof,

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

(c) Polydiorganosiloxanes with C / ₂ _q \ -alkylene end groups, and

(d) divalent radicals of the general formula below

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

Il

—C—, —S—, —S— and

Il

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

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

ti

be considered in which R and R are those given above The indices m and η are whole numbers which, independently of one another, have at least the value 1, e.g. 5 to 5000 or above, and the index ρ is an integer with a value greater than 1, e.g. with a value from 5 to 10,000 or above, and advantageously with a value from 10 to 1,000.

Before imidization, the copolymers are in the amide form before, as exemplified by the general formula below

HO-

- ♦ i-C

and specifically by the general formula

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Ri-

is indicated, where in the formulas the radicals R, R and the Indices m, η and ρ have the meaning given above.

From polyamides of the general formula

C-N-R

in which the radical R and the index ρ have the meanings given above, it is known to be a good one have chemical resistance and heat resistance. Although such aromatic polyamides in suitable solvents Can be solved for coating purposes, such polyamides are often difficult to compress and require excessively high temperatures and pressures in the press cycle. Polyetherimides are known to be good Have high temperature properties and are more accessible to practically feasible pressing cycles; however it would be of Advantage of improving the chemical resistance of these polyetherimides and their costs for the areas of application of pressing and coating.

It has now been found in the course of studies which led to the present invention that copolymers which

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contain chemically bound units of the general formulas I and II over a wide range of molar concentrations, can produce, with the properties of copolymers compared to the properties of homopolymers these units can be modified. In some cases the improvement in properties was unexpected when looking at the Share of either the Α-unit or the EI-unit taken into account, which was present in the copolymer. By making the copolymers described above, the usefulness of the copolymers can be expanded considerably. Also, by combining these two units in the copolymer products are obtained which require a lower cost than is usually the case with the Manufacture of polyetherimides alone is associated with no significant loss (if any occurs) is recorded in the physical properties.

A preferred class of copolymers differentiated from the general Formula III are encompassed are those copolymers consisting essentially of about 2 to 5000 or more units, and preferably from 5 to 100 units of EI units of the general formula IV

exist, in which R has the meaning given above

ο
and R is the formula below

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having.

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

NO

O = C

- (VI) and

0 R

(VII)

1 2

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

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

O = C fV ^ I ^ V * »C = O

(VIII)

an isophthaloyl or terephthaloyl chloride (hereinafter referred to generally as "phthaloyl chloride") of the general Formula IX

(IX)

in which the —C-Cl groups are in the meta or in the para position are to each other, and an organic diamine of the general formula X

H ₂ N-R ¹ -NH ₂ (X)

in which the radicals R and R have the same meaning as above own, implements.

A total of from 0.95 to 1.05 moles of the two compounds can be used per mole of the organic diamine of the general formula X of the general formulas VIII and IX are used. It is preferred to use substantially equal molar amounts of

(a) the compounds of the general formulas VIII and IX, and

(b) to use the organic diamine. The in the present

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Copolynveres used in the invention can be those in which there are from 10 to 5000 or more units of either of the formulas I and II, and the subscript ρ in the formula III has the value 5 or higher, e.g. the value 10 to 1000.

The acyl halide derivatives of the general formula IX, which are derived from terephthalic or isophthalic acids, can can also be converted into the bromide and other reactive halide derivatives besides the chloride derivatives.

Chain terminators such as aniline or monoorganic acid derivatives or monoanhydrides can be used in the preparation of the copolymers be used.

In general, the copolymers of the present invention can be obtained by using the selected organic Diamine and the special dianhydride and phthaloyl chloride of the general formulas VIII and IX in the presence of a dipolar, aprotic, organic solvent under ambient conditions to produce a copolymeric amic acid implements. Upon further heating, the amic acid converts to the imide form, the copolymer being the units of contains general formulas I and II in a random distribution. Depending on the solids content of the polyamic acid solution the reaction can be completed in 0.5 to 2 hours or more. After the reaction has ended, the Solution are poured onto a substrate so that evaporation of the organic solvent occurs. By heating up At temperatures in the range from 150 ° to 200 ° C. or higher, the copolymeric polyamic acid is converted into the polyimide form around, so that the copolymer at this point has good heat resistance, chemical resistance, such as solvent resistance-

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speed, and compressibility. Such preparations are particularly useful as a lacquer coating for wires and impart the properties of solvent resistance and heat resistance to various substrates.

The aromatic bis (ether anhydride) of the general formula VIII can be obtained by hydrolysis, followed by dehydration, of the reaction product of the nitro-substituted phenyl dinitrile and subsequent reaction with a dialkali metal salt of a divalent 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

sits and is preferably the same as R and Alk means an alkali metal ion. To convert the tetranitriles obtained into the corresponding tetraacids and dianhydrides various well known methods can be used.

Of the alkali metal salts of the dihydric phenols described above, sodium and potassium salts of the following, dihydric phenols, includes:

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 referred to as "BPA"), 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 3,3-bis (4-hydroxyphenyl) pentane, 4,4 "-dihydroxybiphenyl,

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4,4'-dihydroxy-3,3 ', 5,5 * -tetramethylbiphenyl, 2,4-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4 * -dihydroxydiphenyl-sulfide, etc.

The organic diamines of the general formula X include, for example, the following compounds:

m-phenylenediamine,

p-phenylenediamine,

4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine,

4,4 * -diaminodiphenyl-sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether (4,4'-oxydianiline), 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4-bis (B-amino-tert-butyl) -toluene, Bis (p - $ - methyl-o-aminopentyl) -benzene, 1,3-diamino-4-isopropylbenzene, 1,2-bis (3-aminopropoxy) ethane, m-xylenediamine,

p-xylylenediamine,

Bis (4-aminocyclohexy1) methane, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine,

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2,2-dimethyl propylenediamine, Octamethylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylendlamine, 1,4-cyclohexanedi amine, 1,12-octadecanediamine, bis (3-aminopropyl) sulfide, N-methyl-bis (3-aminopropyl) -amine, hexamethylenediamine, Nonamethylenediamine, 2,6-diaminotoluene, Bis (3-aminopropyl) -tetramethyldisiloxane, etc.

The copolymeric formulation can be of various particulate form Fillers such as glass fibers, silica fillers, carbon whiskers, up to an amount of 50 percent by weight of the copolymer or above.

The following examples serve to explain the invention further, but are not intended to restrict it. All parts are parts by weight unless expressly stated otherwise.

example 1

This example illustrates the preparation of a homopolyamide from isophthaloyl chloride and 4,4'-oxydianiline. This homopolymer will then later be compared with a copolymeric preparation containing the same diaminoorgano compound contains. Specifically, 2.03 g (0.01 mol) of isophthaloyl chloride and 2.0 g (0.01 mol) of 4,4'-oxydianiline were contained in 15 ml

1 30048/0662

N-methylpyrrolidone dissolved. As a result of the stirring, warmed up the mixture by the exothermic reaction to a temperature of 64 ° C with the formation of a homopolymeric amide solution. A film was cast from this solution at 280 ° to 300 ° C., a homogeneous polyamide film being obtained.

B e 1 game 2

By reacting 2.0 g (0.01 mole) 4,4'-oxidiane! 1in, 4.16 g (0.008 moles) 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (bisphenol-A) and 0.41 g (0.002 moles) isophthaloyl chloride (IC) in 15 ml of N-methylpyrrolidone, a copolymer with Α units and EI units was produced. The mixture was stirred at room temperature until it became clear, the mixture exotherming to 52 ° C. To Cooling, the copolymeric preparation was poured onto glass to form a film at a temperature of about 280 ° to 300 ° C, to imidize the amic acid groups. This polymer that has a molar ratio of 80 mole percent EI units and 20 mole percent Α units had the following formula XI

in which the units are in a random order, the indices m and n, independently, integers with a Are greater than 1, and the subscript ρ is an integer with a value greater than 1.

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Example 3

Isophthaloyl chloride, bisphenol A dianhydride and 4,4'-oxydianiline were each in varying proportions using 15 ml of N-methylpyrrolidone as a solvent implemented using the conditions given in Example 2. Table I below shows the proportions and the molar concentrations of the ingredients, the exothermic temperature rise of each reaction, and the measured Glass transition temperature T, which determines the degree of softening of the polymer

Ren measures the homopolymer of Example 1 and the copolymers of Examples 2 and 3. The copolymers described in Example 3 can be represented by the same general formula, as described in Example 2, in which the indices m and η have the same meaning as above and are substantially the same as the molar concentrations of the reactants used.

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Tabel

example
No. IC Mole BPA dianhydride Mole 4,4 * -oxydianiline Mole Exotherm
temperature
( ⁰ C) T
G
(° C) 1 weight
(G) - weight
(G) - weight
(G) - - 200 2 - - - - - - - 221 3A - 0.005 - 0.005 - 0.01 55 213 3B 1.02 0.008 2.6 0.002 2.0 0.01 59 234 1.62 1.04 2.0

O CD OO

Example 4

Using the same reaction conditions as in Example 1, 2.03 g (0.01 mol) of isophthaloyl chloride and 1.98 g (0.01 mole) 4,4'-methylenedianiline of formula XII

(XII)

carefully mixed with each other in 15 ml of N-methylpyrrolidone, the mixture heated exothermically to 55 ° C. with the formation of a clear, polymeric amide resin solution. It was a film was cast at 280 ° to 300 ° C. to form a homogeneous film.

example

Using the conditions given in Examples 2 and 4, isophthaloyl chloride, BPA dianhydride and 4,4'-methylenedianiline in 15 ml of N-methylpyrrolidone to form reacted a clear, polymeric amic acid-amide solution, which yielded an imidized, polymeric film when one it was poured from the solution as a film at 280-300 ° C. Table II below shows the weights and molar concentrations the ingredients used to make the copolymer, the exothermic temperature of each reaction, and the glass or glass transition temperature T for the homopolymer and the copolymers made with the methylenedianiline.

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Tabel

II

cn ro to

example
No. IC weight
(G) Mole BPA dianhydride Mole 4,4 "-methylene dianiline Mole Exotherm
temperature
( ⁰ C) ( ⁰ C) 4th
5A
5B
5C 0.41
1.02
1.62 0.002
0.005
0.008 weight
(G) 0.008
0.005
0.002 weight
(G) 0.01
0.01
0.01 52
48
47 234
211
229
239 4.16
2.6
1.04 1.98
1.98
1.98

CD CD OO

Those made using 4,4'-methylenedianiline Copolymers as such of the formula XIII

-m: o

C (CH,

· - * n

in which the indices m and η have the same meaning as above and the molar concentration reflect the reactant, and the index ρ is an integer with a value greater than 1.

Example 6

Using the conditions described in Example 1, there was obtained 2.03 grams (0.01 moles) of isophthaloyl chloride and 2.48 grams (0.01 mol) 4,4'-diaminodiphenyl sulfone of the formula XIV

(XIV)

dissolved in 15 ml of N-methylpyrrolidone and mixed carefully to the point where the mixture reached a temperature of 59 ° C due to the exothermic reaction. From this polymer solution was poured Amidharζ a film at 280 ° to 300 ⁰ C to obtain a homogeneous, flexible film.

example

Using the conditions given in Examples 2 and 4, isophthaloyl chloride, BPA dianhydride and

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4.4 x reacted diaminodiphenyl sulfone in 15 ml of N-methylpyrrolidone to form a clear polymeric amic acid solution which yielded a imidized, polymeric film, if it is cast as a film from the solution at 280 ° to 300 ⁰ C. Table III below shows the weights and molar concentrations of the ingredients used to make the copolymers, the exothermic temperature of each reaction, and the glass or glass transition temperature T for the homopolymer and copolymers made with the diaminodiphenyl sulfone.

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Table III

example
No. IC weight
(G) Mole BPA dianhydride Mole SuIfön * Mole Exotherm
temperature
( ⁰ C) - o ^g
( ⁰ C) 6th - - weight
(G) - weight
(G) - - 186 7A 0.41 0.002 - 0.008 - 0.01 4i 156 7B 1.02 O, OO5 4.16 0.005 2.48 0.01 48 168 2.6 2.48

4,4'-diaminodiphenyl sulfone

The copolymers of Example 7 can be exemplified by the following formula XV

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

B e i S ρ 1 e 1

Using the conditions described in Example 1, 2.03 g (0.01 mol) of isophthaloyl chloride and 1.08 g (0.01 mol) of m-phenylenediamine dissolved in 15 ml of N-methylpyrrolidone were stirred vigorously to a point where at which the mixture reached a temperature of 63 ° C as a result of the exothermic reaction. The resulting clear, homopolymeric amide solution was poured out at 280 ° to 300 ⁰ C on an area to form a homogeneous film.

B e 1 game 9

Using the conditions described in Examples 2, 4 and 7, isophthaloyl chloride, BPA dianhydride and m-phenylenediamine were reacted in 15 ml of N-methylpyrrolidone to form a copolymeric amic acid-amide solution which provided an imidized, polymeric film with good abrasion resistance when it was cast onto a heated surface at a temperature of 280 ° to 300 ⁰ C. Table IV below shows the amounts of reactants used to prepare the copolymers

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Table IV

example
No. IC weight
(G) MoI BPA dianhydride MoI m-phenylenediamine MoI Exotherm
temperature
( ⁰ C) 245 8th - - weight
(G) - weight
(G) - - 191 9A 0.41 0.002 - 0.008 - 0.0] 54 242 9B 1.02 0.005 4.16 0.005 1.08 0.01 48 244 9C 1.62 ο, οοδ 2.6 0.002 1.08 0.01 46 1.04 1.08

O CD OO

for each of these copolymers ^ reached exothermic temperature, as well as the glass or glass transition temperature T for the homopolymer in example 8 and the copolymers in the examples 9A, 9B and 9C.

The copolymers of example? can be exemplified by the formula XVI

IL

are shown, in which the indices m and η are integers and essentially the molar concentrations reflect the respondent, and the index ρ a is an integer with a value greater than 1.

example

If in the preceding examples in the preparation of the copolymers using those used for this purpose Various diamino compounds replaced isophthaloyl chloride by terephthaloyl chloride, become copolymers obtained, which are encompassed by the formula II, and those in the application areas of coating, insulation and pressing are useful.

It is obvious to a person skilled in the art that in addition to the diamino compounds used to prepare the above copolymers, other diamino compounds can be used, of which numerous

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abundant examples have been given above. In the same way other than that in the examples of the present Invention applied bisphenol A dianhydride other dianhydrides for the production of other types of copolymers can be used, many examples of which were also given above. Finally, the molar proportions the reactant to a large extent to form units of varying molar range as above has been described, can be varied without departing from the scope of the present invention.

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

The formulations of the present invention find utility in a wide variety of physical forms, including their use as films, molding compounds, etc. When used as films or processed into molded parts these copolymers, including the laminated products made therefrom, not only have good physical properties Properties at room temperature, but they retain their strength and excellent response Workload at elevated temperatures for long periods of time.

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Films made from the copolymers of the present invention can be used in applications where films were previously used. you will be extensively used for packaging and wrapping in an effective manner. The preparations of the present invention can be used for automobiles and aircraft to be decorative and protective purposes, and as electrical high-temperature insulation for motor slot linings, in transformers and can be used as dielectric capacitors.

Optionally, solutions of the curable solutions described here Preparations applied as a layer to electrical conductors such as copper, aluminum, etc. and the coated conductor then to remove the solvent and to harden (imidization) the resinous preparation on it being heated to elevated temperatures. If desired, an additional, overlying conductor can be added to such insulated conductors Layer are applied, the use of polymeric coatings, such as polyamides, polyesters, SiIiconen, Polyvinyl formal resins, epoxy resins, polyimides, polytetrafluoroethylene, etc., is included.

Applications for which these resins are recommended include their use as binders for potassium titanate fibers, Glass fibers, carbon fibers and other fibrous materials for making composites. aside from that grinding wheels and other abrasive articles can be made from such resins by incorporating abrasive grains such as Alundum, silicon carbide, silicon nitride, carborundum, diamond dust, cubic boron nitride, etc., and molding or pressing the mixture under heat and pressure to achieve the desired configuration and shape for grinding and emery purposes, getting produced.

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Claims (6)

Dr. rer. nat. Horst Schüler PATENTANWALT 6000 Frankfurt / Main 1, Ί January 3, 1981 Kaiserstraße 41 Dr.Sch / Om / Hk Telephone (0611) 235555 Telex: 04-16759 mapat d Postal check account: 282420-602 Frankfurt-M Bank account: 225/0389 Deutsche Bank AG, Frankfurt / M. 8588-RD-12312 GENERAL ELECTRIC COMPANY 1, River Road Schenectady, N.Y., U.S.A. claims 1. Copolymers, characterized in that they are from the class of compounds of the general my formulas, consisting of A O II N-C and B Ί ι -C-N-R H -R-O Jf -R-O-f-0 C- OH l · ' 130048/0562 Il are selected in which the —C groups of the unit with the index m are either in the meta position or in the para position to one another, and in which
R is selected from the class consisting of (a) the following divalent organic radicals CH. CH CH. CH Br and Br 130048/0562 (b) divalent organic radicals of the general formula in which X _{denotes the radical -CH 2} -, the index y is an integer with a value from 1 to 5 inclusive, and R is a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals with 6 to 20 Carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals with 2 to carbon atoms, (c) Polydiorganosiloxanes with C, -_ ο \ -alkylene end groups, and (d) divalent radicals of the general formula below in which Q is a residue selected from the class consisting of 0 0 Il Il -, —S—, —S— and —CH and the subscript χ denotes an integer with a value from 1 to 5 inclusive, the subscripts m and η are integers which, independently of one another, have at least the value 1, and the index ρ is an integer with a value greater than 1. 130048/0562 2. Copolymer, characterized in that that it (a) 5 to 95 mol percent of chemically bonded units of the general formula O H and (b) 95 to 5 mol percent of chemically bonded units of the general formula contains, the -C groups in the units of (a) are in the meta-position or in the para-position to each other, and in what R is selected from the class consisting of (a) the following divalent organic radicals 130048/0562 and Br Br (b) divalent organic radicals of the general formula in which X denotes the remainder ~ CH -, the index y is an integer from 1 to 5 inclusive, and 130048/0562 R is a divalent organic radical selected from the class consisting of (a) aromatic hydrocarbon radicals with 6 to 20 Carbon atoms and halogenated derivatives thereof, (b) alkylene radicals and cycloalkylene radicals with 2 to 20 carbon atoms, (c) Polydiorganosiloxanes with C, 2_o \ -alkylene end groups, and (d) divalent radicals of the general formula below in which Q is a divalent radical selected from the class consisting of Il Il S-. and and the index means an integer with a value from 1 to 5 inclusive. 3. Copolymer, characterized in that that it's the general formula iip) ? * - © - Hi 0 - H K -Ao —— ο Γ " -C (Oi ₁ in which the indices m and n, independently, whole 130048/0562 _. "7 - Are numbers of at least 1, and the subscript ρ is an integer with a value greater than 1. 4. Copolymer, characterized in that that it's the general formula -11 in which the subscripts m and n are, independently, integers of at least 1, and the subscript ρ is an integer with a value greater than 1. 5. Copolymer, characterized in that that it's the general formula in which the subscripts m and n are, independently, integers of at least 1, and the subscript ρ is an integer with a value greater than 1. 6. Copolymer, characterized in that it has the general formula 130048/0562 O VhVo in which the indices m and n, independently, whole Are numbers of at least 1, and the subscript ρ is an integer with a value greater than 1. 1300A8 / 0562