JPH07119281B2 - Novel method for producing polyesterimide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a novel polyesterimide having excellent solubility and low-temperature moldability.

[Conventional technology]

Polyimide resins have excellent heat resistance, but many of them are insoluble and infusible, and therefore have poor moldability. Therefore, to form a film or the like, a varnish dissolved in an organic solvent in the state of a polyamic acid as a precursor has been used.
However, the polyamic acid varnish has to be stored at low temperature because its molecular weight is lowered by hydrolysis.
Further, since the solvent easily absorbs moisture, there is a problem that the resin is deposited due to the moisture absorption. After forming it into a film,
There is a problem that voids remain in the molded product because condensed water is generated during imidization.

In addition, there is a problem in that it cannot be used for a heat-sensitive substrate because it needs to be heated to a temperature of 300 ° C. or higher during imidization.

In order to solve this problem, a polyimide having a softening point and capable of being molded has been developed.

For example, JP-A-62-10051 discloses that a compound represented by the general formula (A) A polyimide composed of a diamine represented by (wherein X'represents C = O or SO ₂ ) and pyromellitic acid is disclosed, but this polyimide has a softening point and can be molded.

In addition, in order to solve the above problems, polyester imides soluble in organic solvents have been developed. For example, a polyesterimide consisting of alkylenebis trimellitate and diisocyanate shown in JP-B-43-22120 and a polyesterimide consisting of aromatic bis-trimellitate and diamine shown in JP-B-47-30437 are soluble in cresol. is there.

[Problems to be Solved by the Invention]

The polyimide disclosed in JP-A-62-10051 has a softening point and can be molded, but the softening point is too high.
It must be molded at temperatures above 0 ° C. Further, since the polyimide is hardly soluble in an organic solvent, in order to mold it into a film, it is filmized using a varnish prepared by dissolving a polyamic acid which is a precursor thereof in an organic solvent, and is imidized by heating it to a high temperature. However, there is a problem as described above.

The polyester imide disclosed in JP-B-43-22120 has a remarkably poor heat resistance because it has an alkylene chain in the main chain, and the polyester imide disclosed in JP-B-47-30437 has a softening point that is too high. It is necessary to mold at a temperature above.

[Means for solving the problem]

The present invention has the general formula (I) (Wherein Ar represents a divalent aromatic group) and the general formula (II) (However, in the formula, X represents C = O or SO ₂ , and Y
Relates to a method for producing a polyesterimide, which comprises reacting a compound represented by an amino group or an isocyanate group).

The acid dianhydride represented by formula (I) will be described below.

In the general formula (I), examples of Ar include a divalent group represented by the following (a) or (b).

(A) (In the formula, R is a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a halogen such as chlorine, bromine, and fluorine, an alkoxy group such as a methoxy group, an ethoxy group, a trifluoromethyl group, and pentafluoroethyl. Group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, and other fluorine-substituted alkyl groups, and the like, and p is the number of Rs bonded to the benzene ring and is an integer of 0 or 1 to 3. When p is 2 or more, plural Rs may be the same or different.) (B) (However, in the formula, Y is CH _{2 m} , C = O, -S-, S
O ₂ , Here, m is an integer of 1 or more, R ″ and R are each independently a lower alkyl group such as a methyl group, an ethyl group or an isopropyl group, a halogen such as chlorine, bromine or fluorine, a methoxy group or an ethoxy group. Fluorine-substituted alkyl groups such as alkoxy groups, trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, and perfluorooctyl groups are shown, and q and r are the bonds of R ″ and R to the benzene ring, respectively. Is a number and represents an integer of 0 or 1 to 4, n is an integer of 1 or more, and R ″, Y and R
And a plurality of R, Y and R may be the same or different in each case.) Specific examples of the acid dianhydride represented by the general formula (I) include catechol bistrimellitate. Dianhydride, resorcinol bis trimellitate dianhydride, dihydroxybenzene bis trimellitate dianhydride, bisphenol A bis trimellitate dianhydride, tetrachlorobisphenol A
Examples thereof include bis trimellitate dianhydride, tetrabromobisphenol A bis trimellitate dianhydride, biphenyl bis trimellitate dianhydride, and bis trimellitate dianhydride represented by the following general formula (III).

General formula (III) In the present invention, the reaction partner of the acid dianhydride contains the compound represented by the general formula (II) as an essential component.

As the compound represented by the general formula (II), a compound represented by the general formula (I
In I), those in which an amino group and oxygen are bound to the para-position or meta-position with respect to the isopropylidene group are preferable, and in particular, at least one of two amino groups and two oxygens.
It is preferred that the individual is in the meta position relative to the isopropylidene group.

In the general formula (II), of the bonding positions of the amino group and oxygen with respect to the isopropylidene group, the higher the ratio of the meta position, the lower the softening point of the obtained polyimide and the better the solubility in an organic solvent, but the softening If the points become too low, the strength of the polyimide molded article at high temperature tends to decrease, so it is preferable to determine the ratio of the meta position according to the purpose. From such a viewpoint, the diamine component in the present invention has the general formula (IV) (However, X and Y are the same as those in the general formula (II)) are particularly preferable.

The compound represented by the general formula (II) is preferably used as a partner of the reaction of the acid dianhydride in an amount of 50 mol% or more, particularly preferably 75 mol% or more. When the amount of the compound represented by the general formula (II) is too small, the obtained polyesterimide tends to have a high softening point and is likely to be hardly soluble in an organic solvent.

Among the compounds represented by the general formula (I), diamines in which the group Y is an amino group include 4,4′-bis [3- (4-
Amino-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone, 4,4'-bis [3- (4-amino-
α, α′-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α′-dimethylbenzyl) phenoxy] diphenylsulfone, 4,
4'-bis [4- (4-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone, 4- [3- (4
-Amino-α, α'-dimethylbenzyl) phenoxy]
-4 '-[4- (4-amino-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone, 4- [3-
(4-Amino-α, α'-dimethylbenzyl) phenoxy] -4 '-[4-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [3-
(3-Amino-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone, 4,4'-bis [3- (3-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone, 4,4'- Bis [2- (4-amino-α,
α'-Dimethylbenzyl) phenoxy] diphenyl sulfone, 4,4'-bis [2- (4-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone, 3,3 '
-Bis [3- (4-amino-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone, 3,3'-bis [3- (4-amino-α, α'-dimethylbenzyl) phenoxy] benzdiphenone, etc. And these may be mixed and used.

When the compound represented by the general formula (II) is a diamine, other diamines that may be used together as a reaction partner of the acid dianhydride include diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone,
Diaminodiphenyl ketone, diaminodiphenylpropane, phenylenediamine, toluenediamine, bis (anilinoisopropylidene) benzene, bis (aminophenoxy) benzene, diaminodiphenylsulfide, bis (aminophenoxyphenyl) propane, bis There are (aminophenoxyphenyl) sulfone, bis (aminophenoxyphenyl) ketone, bis (aminophenoxyphenyl) hexafluoropropane, diaminodiphenylhexafluoropropane, diaminodialkyldiphenylmethane, etc. You may use together 1 or more types.

Among the compounds represented by the general formula (II), the diisocyanate in which the group Y is an isocyanate group is 4,4′-
Bis [3- (4-isocyanato-α, α'-dimethylbenzyl) phenoxy] diphenyl ketone, 4,4'-bis [3- (4-isocyanato-α, α'-dimethylbenzyl) phenoxy] diphenyl sulfone In addition, among the compounds represented by the general formula (I), in the diamine in which the group Y is an amino group, there is a compound in which the amino group is replaced with an isocyanate group. Examples of the diisocyanate which may be used in combination with such an isocyanate include diphenyl methane diisocyanate, toluylene diisocyanate and the like, in which the amino group of the other diamine is replaced with an isocyanate group.

In the present invention, the polyester imide can be manufactured as follows.

When a diamine is used as a reaction partner of the acid dianhydride, these are used in an organic solvent in the presence of a catalyst such as tributylamine, triethylamine, triphenyl phosphite, etc., if necessary, 100 ° C or higher, preferably 180 ° C or higher A method for directly obtaining a polyesterimide by heating the mixture to imidization (catalyst is 0 to 15 relative to the total amount of reaction components)
% By weight, particularly preferably 0.01 to 15% by weight), the acid dianhydride and diamine are reacted in an organic solvent at less than 100 ° C. to form a polyamic acid varnish which is a precursor of polyesterimide. When the varnish is prepared, the varnish is heated to imidize it, or acetic anhydride,
Chemical ring closure (imidization) by addition of acid anhydrides such as propionic anhydride and benzoic acid anhydride, ring-closing agents such as carbodiimides such as dicyclohexylcarbodiimide, and ring-closing catalysts such as pyridine, isoquinoline, trimethylamine, aminopyridine and imidazole as necessary. The method (ring-closing agent and ring-closing catalyst are each 1 to 8 per 1 mol of acid anhydride).
It is preferable to use it within a molar range).

As the organic solvent, N-methyl-pyrrolidone (NM
P), N, N-dimethylacetamide, N, N-dimethylformamide (DMF), dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-
Aprotic polar solvents such as 2-imidazolidone, phenol-based solvents such as phenol, cresol, xylenol, p-chlorophenol, and the like.

Benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve,
Solvents such as cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichlene, and tetrachloroethane can be mixed and used within a range that does not impair the solubility of polyimide or polyamic acid.

In the production of the above-mentioned polyimide and polyamic acid which is a precursor thereof, solid phase reaction, melting reaction at 300 ° C. or lower, etc. can be used depending on the case.

When a diisocyanate is used as a reaction partner of the acid dianhydride, it can be carried out according to the method for directly obtaining the polyesterimide. However, it is sufficient if the reaction temperature is room temperature, especially 60 ° C. or higher.

In the present invention, the acid dianhydride and the partner of the reaction are preferably used in approximately equimolar amounts, but an excess of either one is allowed to be 10 mol%, particularly preferably up to 5 mol%.

The polyesterimide obtained in the present invention is soluble in aprotic polar solvents such as N, N-dimethylformamide, dioxane, ether solvents such as tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, and the like. Can be formed into a film or the like. Further, the softening point can be easily adjusted to 100 to 250 ° C.

The polyesterimide obtained in the present invention can be used as a molded product, an adhesive, a structural material, and the like.

The polyesterimide obtained in the present invention can be appropriately produced from its precursor and used.

The diamine in which the group Y of the compound represented by the general formula (I) is an amino group is 4,4′-difluorobenzophenone or 4,4′- with respect to 2 mol of the corresponding hydroxyphenylaminophenylpropane. It can be produced by heating 1 mol of dichlorodiphenyl sulfone in a polar organic solvent in the presence of a base such as potassium hydroxide or anhydrous potassium carbonate to 100 ° C. or higher.

Further, the diisocyanate in which the group Y of the compound represented by the general formula (I) is an isocyanate group can be produced by reacting the diamine thus obtained with phosgene according to a conventional method. it can.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these ranges.

Production Example 1 2- (3-hydroxyphenyl) -2-in a 4-necked flask equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen gas introduction pipe.
After adding 45.4 g of (4'-aminophenyl) propane, 100 ml of dimethyl sulfoxide and 120 ml of chlorobenzene and dissolving at room temperature, an aqueous solution of 13 g of potassium hydroxide in the same water was added. The mixture was heated and stirred while flowing nitrogen gas to distill water. After the water had stopped distilling, the temperature was lowered to 100 ° C, 21.8 g of 4,4'-difluorobenzophenone was added, and 16
The reaction was carried out at 5 ° C for 4 hours. After cooling to room temperature and filtering out the precipitate, it was poured into water to obtain a crude product. The crude product was recrystallized from a mixed solvent of toluene-hexane to obtain the target compound 4,4'-bis [3- (4-amino-α, α'-dimethylbenzyl) phenoquine] diphenyl ketone. Yield 45.5g, melting point 107-111 ° C Liquid chromatography (column: Tosoh Corp. TSK Gel G2000H and G3000H are connected,
The purity was 99.0% (area ratio) with the eluent tetrahydrofuran).

The analysis result of this diamine is as follows.

(1) Elemental analysis value (%) C ₄₃ H ₄₀ N ₂ O ₃ C H N calculated value 81.65 6.33 4.43 Measured value 81.57 6.41 4.32 (2) Infrared absorption spectrum IR absorption position (KBr tablet method,
cm ^-1 ) 3460,3390 (amino group) 2970,2870 (methyl group) 1600 (carbonyl group) 1250 (ether group) (3) Nuclear magnetic resonance spectrum NMR spectral position (DMS
O-d ₆ , ppm) 1.57 (12H singlet) 4.86 (4H singlet) 6.4 to 7.8 (24H multiplet) Note) DMSO means dimethyl sulfoxide.

Production Example 2 In a four-necked flask equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen gas introduction pipe, 2- (3-hydroxyphenyl) -2-
(4'-Aminophenyl) propane 68.1 g, dimethyl sulfoxide 150 ml, chlorobenzene 180 ml, 4,4'-dichlorodiphenyl sulfone 40.75 g, anhydrous potassium carbonate 20.5
g was charged, and the mixture was heated and stirred under aeration of nitrogen gas to distill water. After reacting at 165 ° C. for 4 hours, it was cooled to room temperature. The reaction solution was poured into water to obtain a crude product. Benzene
The desired compound 4,4'-bis [3- (4-amino-α, α'-dimethylbenzyl) was recrystallized from a mixed solvent of hexane.
71.1 g of phenoxy] diphenyl sulfone was obtained. Melting point 67
The purity by liquid chromatography at ~ 70 ° C was 99.4%.

The analysis result of this diamine is as follows.

(1) Elemental analysis value (%) C ₄₂ H ₄₀ N ₂ O ₄ S C H N S calculated value 75.45 5.99 4.19 4.79 measured value 75.18 6.03 4.02 4.66 (2) IR absorption position (KBr tablet method, cm ^-1 ). 3450,3390 (amino group) 2970,2870 (methyl group) 1290,1110 (sulfonyl group) 1250 (ether group) (3) NMR spectral position (DMSO-d ₆ , ppm) 1.55 (12H singlet) 4.87 (4H Single line) 6.4 to 8.0 (24H multiple line) Example 1 4,4'-bis [3 obtained in Production Example 1 in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a downward cooling tube. -(4-Amino-α, α'-dimethylbenzyl) phenoxy] benzophenone 3.16 g, bisphenol A bis trimellitate dianhydride 2.88 g, N-methylpyrrolidone 15 ml, and triphenyl phosphite 0.2 g were charged, and nitrogen gas was added. A polyimide varnish was obtained by reacting at 200 ° C. for 5 hours while flowing. This varnish was poured into water, reprecipitated, pulverized and dried to obtain a polyimide powder. In DMF, concentration 0.1g / dl, temperature 30
The reduced viscosity measured at ℃ was 0.47 dl / g, the load was 10 kg / cm ² , the softening point was 165 ℃, and the 5% weight loss temperature was 437 ℃. In addition, in a solubility test (adding polyimide powder to an organic solvent to a concentration of 5% by weight and observing the dissolved state at room temperature), the polyimide powder showed that DMF, NMP, dioxane, tetrahydrofuran (THF) and It was soluble in methylene chloride.

Example 2 4,4'-bis [3- (4-amino-α, α'-) obtained in Production Example 2 was placed in a four-necked flask equipped with a stirrer, a thermometer, a calcium chloride tube, and a nitrogen gas introducing tube. Dimethylbenzyl)
3.34 g of phenoxy] diphenyl sulfone and 20 ml of N, N-dimethylformamide (DMF) are added and dissolved. 2.88 g of bisphenol A bis trimellitate dianhydride was added little by little while cooling to 5 ° C. or lower, and then reacted at 5 ° C. or lower for 3 hours and at room temperature for 1 hour to form a polyimide precursor varnish of polyamic acid. Obtained. To this varnish, 1.3 g of acetic anhydride and 1.0 g of pyridine were added and reacted at room temperature for 3 hours to obtain a polyimide varnish. This varnish was poured into water, reprecipitated, pulverized and dried to obtain a polyimide powder. The reduced viscosity was 0.33 dl / g in DMF at a concentration of 0.1 g / dl and a temperature of 30 ° C, and the softening point was 162 ° C as measured by a Koka type flow tester under a load of 10 kg / cm ² .

This polyimide powder was soluble in DMF, dioxane, tetrahydrofuran and methylene chloride in the solubility test. The 5% weight loss temperature was 432 ° C.

Example 3 A polyimide powder was obtained in the same manner as in Example 1, except that 2.67 g of 0,0′-bisphenol bistrimellitate dianhydride was used instead of bisphenol A bistrimellitate dianhydride. The reduced viscosity of this polyimide is 0.
It was 52 dl / g, the softening point was 140 ° C, the 5% weight loss temperature was 445 ° C, and it was soluble in DMF, NMP, dioxane, THF and methylene chloride in the solubility test.

Example 4 A polyimide powder was obtained in the same manner as in Example 2, except that 3.47 g of a dianhydride represented by the following formula (V) was used in place of the bisphenol A bistrimellitate dianhydride. This polyimide had a reduced viscosity of 0.35 dl / g, a softening point of 165 ° C and a 5% weight loss temperature of 450 ° C, and was soluble in DMF, NMP, dioxane, THF and methylene chloride in a solubility test.

[Effect of the Invention] According to the present invention, a polyesterimide having excellent solubility and a relatively low softening point can be produced.

Claims (5)

[Claims] 1. A general formula (I) (Wherein Ar represents a divalent aromatic group) and the general formula (II) (However, in the formula, X represents C = O or SO ₂ , and Y
Is a amino group or an isocyanate group), and a compound represented by the formula (1) is reacted. 2. The compound represented by the general formula (II) is a compound represented by the general formula (II), wherein the group Y and oxygen are bonded to the para-position or the meta-position with respect to the isopropylidene group. Item 2. A method for producing a polyesterimide according to Item 1. 3. The compound represented by the general formula (II) is the compound according to claim 2, and in the general formula (II), 2
The method for producing a polyesterimide according to claim 2, wherein at least one of the group Y and the two oxygens is bonded to the isopropylidene group in the meta position. 4. The compound represented by the general formula (II) is the compound according to claim 3, and the group Y is para to the isopropylidene group in the general formula (II). The method for producing a polyesterimide according to claim 3, wherein oxygen is bound to the meta position. 5. The method for producing a polyesterimide according to claim 1, 2, 3 or 4, wherein the group Y in the general formula (II) is an amino group.