JPS584055B2 - Polyether imide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyetherimide that can be produced by reacting an aromatic bis(ether dicarboxylic) acid and an organic diamine in an organic solvent at heated temperatures.

In the prior art prior to the present invention, polyimides produced by the reaction of organic diacid anhydrides and organic diamines are generally thermosetting, and polyimides are produced by producing polyamic acid as an intermediate. It was getting worse.

Edwards U.S. Patent No. 31796
As shown in No. 14, polyamic acid is prepared by combining an organic diacid anhydride and an organic diamine with a dipolar intermediate solvent.
It is preferably obtained by reacting at a temperature of .degree. C. or lower.

One reason for such tight control of temperature is that if the water formed by the reaction occurs too quickly, it will depolymerize the polymer.5 Also, if the temperature is above the optimum range, imidization will occur and the polymer will depolymerize. decreases the solubility of the solution and reduces the shelf life of the solution.

The present invention combines an aromatic bis(ether dicarboxylic) acid or "tetracarboxylic acid" represented by the following formula: with an organic diamine represented by the following formula: H2NR1Nf2 (■) at a temperature of at least 130°C.
It is based on the discovery that thermoplastic polyetherimides can be produced by reaction in the presence of organic solvents at temperatures of .

R in the above formula is (a) a divalent organic group represented by the following formula: and (b) a divalent organic group represented by the following formula: B-S
a divalent group selected from the group consisting of 1, m is O or 1, y
is an integer from 1 to 5), and R1 is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and halogenated derivatives thereof A (b) alkylene group, C(2.) polydiorganosiloxane with alkylene end groups or from 2 to carbon atoms
20 cycloalkylene groups, and (c) a divalent group included in the following formula: A component selected from the group consisting of It is a divalent organic group selected from the group consisting of

The method for producing the polyetherimide of the present invention is as follows:
) The aromatic bis(ether dicarboxylic) acid of the above formula (1) and the organic diamine of the above formula (I) are heated at at least 130°C in the presence of a non-polar organic solvent or a phenol solvent.
(2) separating the polyetherimide from the mixture produced by step (1) above.

As the aromatic bis(ether dicarboxylic) acid represented by the above formula (I), there are compounds having the following formula.

selected.

Examples of the tetracarboxylic acid included in formula (1) include 2,2-bis(4-2,3-dicarboxyphenoxy)
phenyl]propane, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether, 1,3-bis(2,3-dicarboxyphenoxy)benzene, 4,4'-bis( Examples include 2,3-dicarboxyphenoxy)diphenyl sulfide and 1,4-bis(2,3-dicarboxyphenoxy)benzene.

Examples of the tetracarboxylic acids contained in formulas (1) and (V) include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 4,4'-bis(3, 4-dicarboxyphenoxy) diphenyl ether, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide, 1,3-bis(3,4-dicarboxyphenoxy) ) benzene, 1,4-bis(3,4-dicarboxyphenoxy)benzene, 4-(2,3-dicarboxyphenoxy)-4'-(3
,4-dicarboxyphenoxy)diphenyl-2,2-
There are 7 Lopans, etc.

Aromatic bis(ether dicarboxylic) acids of formula (I) are disclosed in U.S. Patent Application No. 28 filed by Darrel Heath and Joseph Wirlh and assigned to the assignee of the present application.
No. 1,749 (filed August 18, 1972) shows some of them.

These tetra acids are nitro-substituted phenyldinitriles and 2
It is obtained by hydrolyzing the reaction product of a phenolic compound with a metal salt in the presence of a dipolar neutral solvent.

For example, an alkali metal salt of a dihydric phenol of the following general formula: AIK-0-R''-0- is prepared in dimethylformamide with a penzenoid type compound of the following formula in which the NO2 group can take any position on the benzene ring: It can be reacted with AIK (wherein R2 is a divalent aromatic group and ARK is an alkali metal ion).

Various well-known methods can be used to convert the produced tetranitrile to the corresponding tetra-acid.

Another method for making aromatic bis(etherdicarboxylic) acids of formula (I) is disclosed in patent application No. RI-5720, filed December 28, 1972 by Durrell Heath and Thor Takekoshi and assigned to the assignee of the present application. application)
shown inside.

That is, N-monosubstituted ditrophthalimide is reacted with alkaline diphenoxide to produce aromatic bis(ether phthalimide) as an intermediate.

A tetra acid is produced by hydrolyzing this aromatic bis(ether fucurimide) to form a tetra acid salt and then acidifying it.

The following two alkali metal salts of the above dihydric phenol are used.
Contains sodium and potassium salts of functional phenols.

2,2-bis(2-oxyphenyl)propane A2,4
'-dioxydiphenylmethane, bis(2-oxyphenyl)methane, hereinafter referred to as 'bisphenol A1 or 'BP
2,2-bis(4-oxyphenyl)propane, 1,1-bis(4-oxyphenyl)ethane, described as "A"
1,1-qs(4-oxyphenyl)propane, 2.2
-qs(4-oxyphenyl)pentane, 3,3-71
(4-,d-xyphenyl)pentane, 4,4'-dioxyphenyl, 4,4'-dioxy-3,3'-dimethylbifuronyl A2,4'-dioxybenzophenone A4
,4'-dioxydiphenyl sulfoxide A4,4'-
Dioxydiphenyl sulfide A3,4'-dioxydiphenylmethane A4,4'-dioxybenzophenone A4,4'-dioxydiphenyl ether, hydroquinone, resorcin, etc.

Examples of the organic diamine of the above formula (I) include the following.

m-phenylenediamine, p-phenylenediamine A4
, 4'-diaminodiphenylpropane A4,4'-diaminodiphenylmethane, benzidine A4,4'-diaminodiphenyl sulfide A4,4'-diaminodiphenyl sulfone, 4,4'-V aminodiphenyl ether ,
1,5-diaminonaphthalene A3,3'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,4-bis(β-amino-t-butyl)gluene, bis(p-β-
A￣m-t-phyllophenyl) ether, bis(p-β
1,2-bis(3-aminopropoxy)ethane, m-xylylenediamine, p-
Xylylene diamine A2,4-diaminotoluene, 2,
6-diaminotoluene, bis(4-aminocyclohexyl)methane, 3-methylheptamethylenediamine, 4,
4-dimethylhebutamethylenediamine, 2,11-dodecanediamine, 2,2-dimethylpropylenediamine,
Octamethylene diamine, 3-methoxyhexamethylene diamine, 2,5-dimethylhexamethylene diamine,
2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, ■,4-cyclohexanediamine, 1,12-octadecanediamine, bis(3-aminopropyl) sulfide, N- Methyl-bis(3-aminopropyl)amine, hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, decamethylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(4-aminobutyl)tetramethyldisiloxane, etc. .

An aromatic bis(ether dicarboxylic) acid of formula (I) and an aromatic bis(etherdicarboxylic) acid of formula (
Among the non-polar organic solvents that can be used alone or in mixtures to carry out the reaction with the organic diamine of I) are, for example, benzene, toluene, xylene, ethylbenzene, At lobilbenzene, chlorobenzene, At lobilbenzene, Trichlorobenzene, biphenyl, terphenyl, acetophenone, penzophenone, nitrobenzene, anisole, phenetol, V phenyl ether, diphenyl sulfide, chlorinated biphenyl, chlorinated diphenyl ether, dichloroethane, tetrac ethane, trichloroethylene, tetrac Examples include oral ethylene, methylcyclohexane, octane, isooctane, and decane.

Among the phenolic solvents that can be used in the practice of this invention are phenol, o-, p- and m-chlorophenols; O-, p- and m-7 resols, mixtures thereof known as cresylic acid; Examples include mixtures of phenol and cresylic acid, ethylphenol, isopropylphenol, lerl-j thylphenol, xylenol, phenylphenol, and the like.

Aromatic bis(etherdicarboxylic) acid of formula (1) and formula (
The polyetherimide, which is the reaction product of I) with the organic diamine, is soluble in certain organic solvents and can be cast into a thermoplastic film from a solution in the organic solvent.

These polyetherimides can be molded at temperatures up to 400°C.

A preferred class of injection moldable materials are polyetherimides which are the reaction products of organic diamines of formula (I) and aromatic bis(ether dicarboxylic) acids of formulas (I) to (V).

These injection moldable materials can be heated between 200°C and 400°C.
It is soluble in organic solvents such as methylene chloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, metacresol, and the like.

The moldable reaction products are, for example, conventional silica fillers such as perlite, fume silica, etc., carbon whiskers, glass fibers, etc., combined with polyetherimide 10.
Reinforcement can be achieved by adding 10 to 60 parts of filler to 0 parts.

In carrying out the process of the present invention, the reaction is carried out between an aromatic bis(ether dicarboxylic) acid and an organic diamine in an inert organic solvent, which inert solvent may be the non-polar solvent or phenol described below. means solvent.

The order of addition of either reactant is not critical.

Preferably, the reaction between the tetraacid and the organic diamine is carried out in an inert atmosphere such as nitrogen.

Experience has shown that sufficient organic solvent can be used to provide a solids content in the range of 1 to 90%.

The reaction temperature is 130-300°C, preferably 150-250°C.
It can be carried out at a temperature of

In order to bring the aromatic bis(ether carboxylic) acid and the organic diamine into good contact with each other, the reaction mixture can be mixed by stirring or the like.

It has been found that optimal polymer molecular weights are obtained using equimolar amounts of reactants, but for effective results 0.5 to 2 moles, preferably 0.9 to 1.1 moles of aromatic Group bis(ether dicarboxylic) acids can be used per mole of organic diamino.

The polyetherimide contains about 5 to 500, preferably 1
0 to 50 repeating units of aromatic bis(ether dicarboxylic) acid-organic diamine reaction product are included.

Includes amino or phthalate end groups.

The reaction time of the tetraacid of formula (1) with the organic diamine of formula (II) is between 0.5 and 20 hours depending on factors such as the temperature used, the degree of agitation, the nature of the reactants, the solvent used, etc. It can be changed with

Throughout polymer formation, water produced by the reaction is continually removed.

The progress of the reaction can be easily determined by the amount of actual water produced as a percentage of the theoretical value.

In certain cases, a mixed solvent system consisting of a low-boiling azeotropic solvent and a high-boiling solvent can be used.

When the reaction is complete, the polyetherimide can be recovered, such as by cooling the polymer solution and pouring it into a precipitant such as methanol, followed by washing and P-filtration.

The following examples are provided to enable those skilled in the art to carry out the invention, but are intended to be illustrative and not limiting.

All parts are parts by weight.

Example 1 Hydrolysis of 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane as a tetraacid with base from the corresponding bisimide and its treatment with a strong mineral acid. It was produced by acidification of the salt.

The above bisimide was prepared with the corresponding N-phenyl-4-nitrophthalimide and the sodium diphenoxide salt of bisphenol A by the following method.

29.8g (0.131 mol) bisphenol A15
10.44.9 sodium hydroxide, 250 cc dimethyl sulfoxide, and 66 in the form of a 0% aqueous solution
A mixture consisting of cc of toluene was stirred at reflux for 7 hours under a nitrogen atmosphere.

Final drying was accomplished by refluxing toluene through a recirculation trap filled with calcium hydride.

Tor. The ene was distilled off and the reaction mixture was cooled to 60°C.

Then 70.0 g (0.26 mol) of N-phenyl-4
-Nitrophthalimide and 250 cc of dimethyl sulfoxide were added and the resulting solution was stirred at 60°C for 45 minutes.

Add 25 CC of glacial acetic acid and bring the reaction mixture to 1400 °C.
diluted with g of water.

A fine solid was separated which was isolated by P filtration, washed with water and dried.

After recrystallization from acetonitrile and benzene, 4
4.4.9 white needles were obtained.

m. p. 214℃. Analysis 'C43H30N2o6, calculated values: C, 77.0, H, 4.51, N, 4.18
, Actual yield: C, 76.7, H, 4.5, N, 4.1A Judging from the manufacturing method and the results of elemental analysis, the product is 2,2-
Bis(4-(N-phenylphthalimido-4-oxy)
phenyl]propane.

Consisting of 60.2 g of 2,2-bis(4-(N-phenylphthalimido-4-oxy)phenyl)propane, 57.37 g of sodium hydroxide lagoon solution as a 50% aqueous solution, and 350 CC of water. Blend the mixture for 25 minutes at 160~
Heated at 175° C. under 150 psi pressure.

The mixture was then steam distilled for 45 minutes.

The aqueous residue was acidified with hydrochloric acid.

The product separated from the aqueous solution was washed with water and recrystallized from 50% acetic acid.

32.9 l of product were obtained.

mp 208-216°C, analysis: calculated as C31H24o10; C, 66.9, H, 4.3.

Actual yield: C, 66.5, H, 4.4. Considering the production method and elemental analysis results, 2,2-bis(4-(.3,4-V carboxyphenoxy)phenyl)propane was obtained. Ta.

Approximately equimolar amounts of the above tetraacid and 4,4'-diaminodiphenyl ether were heated under reflux (140 DEG C.) for 4 hours in a nitrogen atmosphere in the presence of benzene and toluene.

The mixed solvent system described above was used in an amount sufficient to provide a polymerization mixture with a benzene to toluene ratio of about 3=1 by volume and a polymerization mixture containing about 90% by weight solvent.

After removing the toluene by distillation, the mixture was further diluted with 2 L.
The mixture was heated at 182° C. for an hour.

The mixture was then cooled to room temperature and the polymer was precipitated in methanol.

A polymer with an intrinsic viscosity of 0.40 in dimethylformamide was obtained in 94% yield.

Based on the method of manufacture, this polymer was a polyetherimide containing the following repeating units.

Example 2 2,2-bis(4-(N-phenylphthalimido-3-oxy)phenyl]propane was hydrolyzed at 170°C (115 psi) in the presence of an aqueous alkaline solution by the method of Example 1 to produce the corresponding tetra-acid. was produced in 97% yield.

Analysis: C31H240A. As, calculated value; C, 66.
9, H, 4.3o Actual yield value; C, 66.5, H, 4.5.

Considering the production method, the product is 2,2-bis(4-(2,3
-dicarboxyphenoxy)phenyl]t/tan.

3.000 parts of the above tetraacid, 1.068 parts of 4,4'
A mixture of monodiaminodiphenylmethane, 40 parts of m-cresol and 5 parts of toluene was heated to reflux for 2 hours.

The water produced during the reaction was continuously removed by azeotropic distillation.

The resulting viscous reaction product mixture was poured into methanol.

The product precipitated.

The product has an intrinsic viscosity of 0 in dimethylformamide.
．． 71, and the glass transition temperature was 232°C.

In view of the manufacturing method, the product was a polyetherimide with a molecular structure represented by the recovery unit below.

Example 3 4,4'(N-phenylphthalimito-4-oxy)diphenyl sulfide was hydrolyzed to produce the corresponding tetraacid in 94% yield by the method described above.

The melting point was 111-120°C (decomposition).

A mixture of 5.565 parts of 4,4-bi+(3,4-dicarboxyphenoxy)diphenyl sulfide A and 1.162 parts of hexamethylene diamine, 40 parts of trichlorobenzene and 5 parts of toluene was The mixture was heated under reflux for 3 hours, and the water produced during this time was removed as an azeotrope.

The product precipitated on cooling.

The reaction mixture was diluted with 200 parts of methanol and the product was isolated by filtration.

The product yield was 96%.

Based on the method of manufacture, the product was a polyetherimide consisting primarily of the following repeating units:

Example 4 1,4-bis(N-phenylphthalimito-4-oxpoly)benzene was hydrolyzed to produce tetraacid in 97% yield by the method of Example 1.

The product is dehydrated by heating at 200-210°C26
Melted at 2-265°C.

Considering the manufacturing method, this product is 1,4-bis(3,4
-dicarboxyphenoxy)benzene.

4.343 parts of the above tetraacid, 2.700 parts of bis(4
-aminophthyl)teramethyldisiloxane, 50 parts of phenol and 10 parts of toluene.
The mixture was heated to reflux for a period of time, and the water produced during this period was continuously removed by azeotropic distillation.

A fibrous yellow product was isolated by precipitation in methanol.

Analysis: Calculated value as C34H38N2St207; C
,63.5,H,6.0,N,4.4,81+8.70
Actual yield value: C, 63.1, H, 6.3, N, 4.8, Si
, 9.4.

The glass transition temperature of the product was 52°C.

In view of the above analysis results and manufacturing method, this product was a polyetherimide mainly consisting of the following repeating units.

Example 5 4,4'-bis(N-F-Gj-FCl-3-oxy)diphenyl ether was hydrolyzed using an aqueous sodium hydroxide solution under pressure using a temperature of 180°C.

Upon acidification of the reaction mixture, a white product precipitated.

This was filtered, washed and dried.

This material melted at 252-255°C.

Considering the manufacturing method, this product is 4,4'-bis(2,
It was 3-dicarpoxyphenoxy) diphenyl ether.

A mixture consisting of 5.304 parts of the above tetraacid, 1.081 parts of m-phenylenediamine, 40 parts of phenol and 10 parts of toluene was stirred and heated to reflux for 1.5 hours, and the water produced during this time. was removed by azeotropic distillation.

The resulting viscous solution was poured into methanol and the white fibrous product was collected by filtration.

The yield was 97%.

The intrinsic viscosity of the product in m-cresol is 0.34
It was dll9.

The glass transition temperature of the product was 234°C.

Based on the method of manufacture, the product was a polyetherimide consisting primarily of the following repeating units:

Example 6 2.782 parts of 2,2-bis(4-(2,3-dicarboxyphenoxy)phenyl)propane, 2.782 parts of 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl) phenoxy)phenyl]propane, 1.982 parts of 4,4'-diaminodiphenylmethane, 60 parts of phenol and 10
of toluene was heated to reflux for 2 hours.

Water produced throughout the reaction was continuously removed by azeotropic distillation.

The reaction product mixture was poured into methanol and the white fibrous polymer was collected by filtration.

The yield of polymer was 6.4 parts (94%).

The glass transition temperature of this material was 227°C.

In view of the manufacturing method, this polymer consisted primarily of the following repeating units.

The foregoing examples represent only some of the numerous polyetherimides that can be made by practicing the present invention.

The present invention broadly relates to a method for producing polyetherimide, which includes the use of the tetraacid represented by the above formula (1) and the organic diamine represented by the above formula (I).

Preferred embodiments of the present invention will be described below.

1. In the method for producing polyether i￣g, A (■) in the presence of an organic solvent, a tetraacid of the following formula: and an organic diamine of the following formula: H2NR'NH2 are reacted while removing water produced by the reaction,
and (2) separating the polyetherimide from the material produced by (1) above, and in the above formula, R is (a) the following divalent organic group: and (b) the following general A divalent organic group of the formula: a component selected from the group consisting of divalent groups having the formula: -S, m is O or 1, and y is an integer from 1 to 5. ), and R1
(a) aromatic hydrocarbon groups having 6 to 20 carbon atoms and their halogenated derivatives; (b) alkylene groups;
2,8) polydiorgasosiloxanes with alkylene end groups, cycloalkylenes of 2 to 20 carbon atoms, and (c) divalent groups of the formula: -S-, -Cx
H2c1, X is an integer of 1 to 5, and m is as defined above.

2. The method of item 1 above, wherein the reaction is carried out in the presence of a non-polar organic solvent.

3. The method of item 1 above, wherein the reaction is carried out in the presence of a phenol solvent.

4. The method of item 1 above using a mixture of a phenol solvent and a low boiling azeotropic solvent.

5. The method of item 1 above using a mixture of a non-polar solvent and a low boiling azeotropic solvent.

6. The method of item 1 above, wherein the tetraacid is 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)-Dman.

7. The method of item 1 above, wherein the tetraacid is 2,2-bis[2,3-dicarboxyphenoxy]phenyl]propane.

8. The method of item 1 above, wherein the tetraic acid is 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfite.

9. The method according to item 1 above, wherein the tetraic acid is 1,4-bis(3,4-dicarboxyphenoxy)benzene.

10. A method according to the above item 1, in which the tetraacid is 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether.

11. The method of item 1 above, wherein the organic diamine is bis(4-aminobutyl)tetramethyldisilosane.

12. The method of item 1 above, wherein the organic diamine is 4,4'-diaminodiphenyl ether.

13. The method of item 1 above, wherein the organic diamine is 4,4'-diaminodiphenylmethane.

14. The method of item 1 above, wherein the organic diamine is hexamethylene diamine.

15. Organic diamine. The method of item 1 above, wherein m-phenylenediamine is used.

Claims (1)

[Claims] 1(A) A reaction occurs between a tetraacid of formula and an organic diamine of formula H2NR1NH2 at ambient temperature in the presence of an organic solvent to form a polyamic acid, and then (B ) A method for producing polyetherimide by a stepwise method comprising the step of heating the polyamic acid produced in the step of the above person) to a temperature of at least 200°C to produce polyetherimide [However, in the above formula, R is (a) The following divalent organic group: and (b) The divalent organic group of the following general formula: and -S-
a component selected from the group consisting of divalent groups having the formula, m is 0 or 1, and y is an integer from 1 to 5; and R
1 is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and its halogenated derivative A(b) an alkylene group, C(2
~8) Polydiorganosiloxane having an alkylene end group, cycloalkylene having 2 to 20 carbon atoms, and (c) a divalent group included in the following formula: -CxH2x1, where X is 1 5, and m is a divalent organic group selected from the group consisting of at least 13 in the presence of a solvent or a phenolic solvent
A process for the preparation of polyethers as described above, characterized in that it is carried out at a temperature of 0° C., thereby avoiding the need to form the polyamic acid at ambient temperature in the presence of an organic solvent.