JPH03195732A - New polyesterimide - Google Patents

Abstract

PURPOSE:To obtain a new polyesterimide containing a specific unit, having excellent solubility to organic solvent and molding properties in low temperature. CONSTITUTION:For example, an acid dianhydride (e.g. catecholbistrimellitate dianhydride) and diamine {e.g. 4,4.-bis[3-(4-amino-alpha,alpha'-dimethylbenzyl) phenoxy]diphenylsulfone} which are used in equimolar amounts are heated to >=100 deg.C in an organic solvent such as phenol in the presence of a catalyst such as tributylamine and imidized to provide the aimed polyesterimide containing an unit expressed by formula I [A is bivalent group expressed by formula II (Ar is bivalent aromatic group); Z is bivalent group expressed by formula III (X is formula IV or formula V].

Description

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

[Conventional technology]

Polyimide resins have excellent heat resistance, but many have poor moldability because they are insoluble and infusible. Therefore, in order to form a film or the like, a varnish prepared by dissolving the precursor polyamic acid in an organic solvent was used. However, polyamic acid varnishes have to be stored at low temperatures because their molecular weight decreases due to hydrolysis. Furthermore, since the solvent easily absorbs moisture, there were problems such as resin precipitation due to moisture absorption. Furthermore, after being molded into a film or the like, condensed water is generated during imidization, resulting in the problem that voids remain in the molded product.

Furthermore, since it is necessary to raise the temperature to a high temperature of 300° C. or higher during imidization, there is a problem that it cannot be used for heat-sensitive base materials.

In order to solve this problem, polyimides that have a softening point and can be molded have been developed.

For example, in Japanese Patent Application Laid-Open No. 62-10051, -Adult (
) A polyimide consisting of a diamine and pyromellitic acid represented by the formula % () (where X' represents C=O or S02) is disclosed, but this polyimide has a softening point and is difficult to mold. It is possible.

Furthermore, in order to solve the above problems, polyester imides soluble in organic solvents have been developed.

For example, the polyesterimide made of alkylene bistrimelitate and diisocyanate shown in Japanese Patent Publication No. 43-22120 and the polyesterimide made of aromatic bistrimelitate and diamine shown in Japanese Patent Publication No. 47-30437 are soluble in cresol. be.

[Problem 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 and must be molded at a temperature exceeding 300°C.

In addition, since the polyimide is poorly soluble in organic solvents, in order to form it into a film, it is formed into a film using a varnish in which polyamic acid, which is the front piece, is dissolved in an organic solvent.
This must be heated to a high temperature to be imidized, which poses the problems described above.

The polyesterimide disclosed in Japanese Patent Publication No. 43-22120 has an alkylene chain in its main chain, so it has extremely poor heat resistance. It is necessary to mold at temperatures exceeding

[Means to solve the problem]

The present invention represents a divalent group represented by -adult (1) (in the formula, Ar represents a divalent aromatic group), and Z represents the general formula (3) % formula % (3) The present invention relates to a polyesterimide comprising a divalent group represented by the following formula)].

The above-mentioned polyesterimide is an acid dianhydride represented by -adult (1) (wherein Ar represents a divalent aromatic group) and -adult (II)...(II), and Y is It can be produced by reacting a compound represented by (representing an amino group or an isocyanate group).

The acid dianhydride represented by general formula (1) will be explained next.

In general formula (1), examples of Ar include divalent groups represented by (a) or (b) below.

(a) (In the formula, R is a lower alkyl group such as a methyl group, an ethyl group, or a propyl group, a halogen such as chlorine, bromine, or fluorine, an alkoxy group such as a methoxy group or an ethoxy group, a trifluoromethyl group, or a penta It represents a fluorine-substituted alkyl group such as a fluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc., where p is the number of R bonded to the benzene ring and is 0 or 1 to 3. When p is an integer and is 2 or more, the plurality of R's may be the same or different.

and m is an integer of 1 or more. RL and R2 each independently represent 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,
Alkoxy groups such as ethoxy groups.

It represents a fluorine-substituted alkyl group such as trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl group, etc., and q and r are the number of bonds of R1 and R2 to the benzene ring, respectively, and O or represents an integer from 1 to 4, n represents an integer of 1 or more, and when there are multiple R'', Y, and R2, the multiple R1, Y, and R2 may be the same or different in each case. A specific example of the acid dianhydride represented by the general formula (1) is catechol bistrimelitate dianhydride.

Resorcinol bistrimelitate dianhydride, dihydroxybenzene bistrimelitate dianhydride.

Bisphenol A bistrimelitate dianhydride.

Tetrachlorobisphenol A bistrimelitate dianhydride, tetrabromobisphenol A bistrimelitate dianhydride, biphenyl bistrimelitate dianhydride,
Examples include bistrimelitate dianhydride represented by the following adult (m).

-adult (III) υ In the present invention, the reaction partner of the acid dianhydride is -adult (III)
The compound represented by II) is an essential component.

The compound represented by the general formula (n) includes -adult (I
Among I), those in which an amino group and oxygen are bonded to the isopropylidene group at the para or meta position are preferred, and in particular, at least one of the two amino groups and the two oxygens is bonded to the isopropylidene group.
Preferably, the isopropylidene group is meta to the isopropylidene group.

- In adult (II), the higher the proportion of the meta-position among the bonding positions of the amino group and oxygen to the isopropylidene group, the lower the softening point of the obtained polyimide and the better the solubility in organic solvents, but the softening If the point becomes too low, the strength of the polyimide molded product at high temperatures tends to decrease, so it is preferable to determine the ratio of the meta position according to the purpose. From this viewpoint, the diamine component in the present invention is particularly preferably a compound represented by the general formula (IV) (IV) (where X and Y are the same as the general formula (n)).

The compound represented by the general formula (II) is preferably used in an amount of 50 mol% or more, particularly preferably 75 mol% or more, as a reaction partner for the acid dianhydride.

If the amount of the compound represented by the general formula (II) is too small, the resulting polyesterimide tends to have a high softening point and is likely to be poorly soluble in organic solvents.

Among the compounds represented by the general formula (II), diamines in which the group Y is an amino group include 4.4'bisC3-(4
-amino-α,α′-dimethylbenzyl)phenoxydiphenylsulfone, 4゜4′-bis(3-(4-amino-α,α′-dimethylbenzyl)phenoxybenzophenone, 4゜4′-bis[4 -(4-amino-α, α
'-Dimethylbenzyl)phenoxy]diphenylsulfone, 4,4'-bis(4-(4-amino-α,α'dimethylbenzyl)phenoxybenzophenone, 4-(
3-(4-amino-α,α-dimethylbenzyl)phenoxy)-4′-(4-(4-amino-α,α′-
dimethylbenzyl) phenoxydiphenyl sulfone,
4-(3-(4-amino-α,α′-dimethylbenzyl)phenoxy]-4′-(4-amino-α,α′-
dimethylbenzyl)phenoxifbenzophenone, 4,
4'-bis(3-(3-amino-α,α-dimethylbenzyl)phenoxydiphenylsulfone, 4°4’-
Bis(3-(3-amino-α,α′-dimethylbenzyl)phenoxifbenzophenone, 4゜4′-bis(2-
(4-amino-α,α′-dimethylbenzyl)phenoxy]diphenylsulfone.

4.4'-bis(2-(4-amino-α,αdimethylbenzyl)phenoxifbenzophenone.

3.3'-bis(3-(4-amino-α,αdimethylbenzyl)phenoxydiphenylsulfone, 3,3'-
Bis(3-(4-amino-α.

Examples include α'-dimethylbenzyl)phenoxifbenzophenone, and a mixture of these may be used.

When the compound represented by the general formula (U) is a diamine, examples of other diamines that may be used in combination as a reaction partner with the acid dianhydride include diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, diaminodiphenyl ketone, and diaminodiphenyl methane. Diphenylpropane, phenylenediamine, toluenediamine, bis(anilinoisopropylidene)benzene, bis(aminophenoxy)benzene, diaminodiphenyl sulfide.

Bis(aminophenoxyphenyl)propane, bis(aminophenoxyphenyl)sulfone, bis(aminophenoxyphenyl)ketone, bis(aminophenoxyphenyl)hexafluoropropane, diaminodiphenylhexafluoropropane.

Examples include diaminodialkyldiphenylmethane, and two or more of these may be used in combination.

Among the compounds represented by general formula (II), the diisocyanate in which group Y is an isocyanate group includes 4,4
'-Bis(3-(4-isocyanato-α,α'-dimethylbenzyl)phenoxydiphenylketone, 4,4
'-bis(3-(4-isocyanato-α,α-dimethylbenzyl)phenoxydiphenylsulfone), and other compounds represented by general formula (I),
Among diamines in which the group Y is an amino group, there are diamines in which the amino group is replaced with an isocyanate group. Examples of diisocyanates that may be used in combination with such diisocyanates include those in which the amino groups of the other diamines described above are replaced with isocyanate groups, such as diphenylmethane diisocyanate and tolylene diisocyanate.

In the present invention, polyesterimide can be produced in the following manner.

When diamines are used as reaction partners with acid dianhydrides, they are heated at 100°C or higher, preferably at 180°C, in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, or triphenyl phosphite. A method of directly obtaining polyester imide by heating to above temperature and imidization (the catalyst is 0 to 10% based on the total amount of reaction components
It is preferable to use 15% by weight, especially 0.01 to 15% by weight.
A varnish of polyamic acid, which is a precursor of polyesterimide, is produced once by reacting an acid dianhydride and a diamine at less than 100°C in an organic solvent (preferably used in % by weight), and then heating this varnish. or imidize with a ring-closing agent such as an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride, or a carbodiimide such as dicyclohexylcarbodiimide, and if necessary, pyridine or isoquinoline.

A method of chemically closing the ring (imidization) by adding a ring-closing catalyst such as trimethylamine, aminopyridine, or imidazole (
The ring-closing agent and the ring-closing catalyst are each preferably used in an amount of 1 to 8 mol per 1 mol of the acid anhydride.

As the organic solvent, N-methyl-pyrrolidone (NM
P), N, N-dimethylacetamide, N, N-dimethylformamide (DMF), dimethyl sulfoxide, sulfolane, hexamethyl phosphoric acid triamide, 1,3
Examples include aprotic polar solvents such as -dimethyl-2-imidazolitone, phenolic solvents such as phenol, cresol, xylenol, and P-chlorophenol.

These solvents include benzene, toluene, and xylene.

Methyl ethyl ketone, acetone, tetrahydrofuran,
Dioxane, monoglyme, diglyme.

Solvents such as methyl cellosolve, cellosolve acetate, methanol, ethanol, inpropatol, methylene chloride, chloroform, trichlene, and tetrachloroethane can be mixed and used within a range that does not impair the solubility of the polyimide or polyamic acid.

When producing the polyimide described above and the polyamic acid that is its precursor, in-phase reaction, melt reaction at 300° C. or lower, etc. can be used depending on the case.

Further, 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 polyesterimide described above. However, it is sufficient that the reaction temperature is room temperature, particularly 60'C or higher.

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

The polyesterimide obtained in the present invention has N.

aprotic polar solvents such as N-dimethylformamide;
Ether solvents such as dioxane and tetrahydrofuran,
It is soluble in halogenated hydrocarbons such as methylene chloride,
These solutions can be formed into films and the like.

Moreover, the softening point is 1o.

The temperature can be adjusted to ~250°C.

The polyesterimide in the present invention is a molded product.

It can be used as an adhesive, a structural material, etc.

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

In addition, for the diamine in which the group Y of the compound represented by the general formula (1) is an amino group, 4.4'-difluorobenzophenone or 4.4'-dichlorodiphenylsulfone is added to 2 moles of the corresponding hydroxyphenylaminophenylpropane. 1 mol in the presence of a base such as potassium hydroxide or anhydrous potassium carbonate.

It can be produced by heating to 100'C or higher in a polar organic solvent.

Further, a diisocyanate in which the group Y of the compound represented by general formula (1) is an isocyanate group can be produced by reacting the diamine obtained as described above with phosgene according to a conventional method.

The amic acid that is the precursor of the polyesterimide described above has the general formula (4), and the amide group and carboxyl group bonded to the same benzene ring are bonded to the meta or para position with respect to A.] It has the structural unit represented by .

〔Example〕

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

Production Example 1 In a fourth flask equipped with a cooling tube, thermometer, stirrer, and nitrogen gas introduction tube, 2-(3-hydroxyphenyl)-
2-(4'-aminophenyl)propane 45.4g, dimethyl sulfoxide 100mQ, chlorobenzene 120
After mQ was added and dissolved at room temperature, an aqueous solution of 13 g of potassium hydroxide dissolved in the same water was added. Water was produced by heating and stirring while flowing nitrogen gas. After the water production stopped, the temperature was lowered to 100"C, 21.8 g of 4,4'-difluorobenzophenone was added, and the mixture was reacted at 165°C for 4 hours. It was cooled to room temperature and the precipitate was removed by filtration. After that, the crude product was obtained by pouring it into water.
Recrystallize from a hexane mixed solvent to obtain the desired compound 4,4'
-bis(3-(4-amino-α).

α'-dimethylbenzyl)phenoquine fudiphenyl ketone was obtained. Yield 45.5g, melting point 107-111℃ Liquid chromatography (column: Tosoh Corporation TSK)
Connecting Gel G2000H and G3000H, purity 99.0% (area ratio) using eluent tetrahydrofuran
Met.

The analysis results of this diamine are as follows.

(1) Elemental analysis value (%) C43H4°N,O.

CHN Calculated value 81,65 6.33 4.43 Actual value
81,57 6.41 4.32 (2) Absorption position of infrared absorption spectrum E (KBr tablet method, C!l-1) 3460.3390 (Amino group) 2970.2870 (Methyl group) 1600 (Carbonyl group) 1250
(Ether group) (3) Nuclear magnetic resonance spectrum NMR spectral position (DMSO-dct ppm) 1.57 (12H-multiplet) 4.86 (4H-multiplet) 6.4-7.8 (24H-multiplet ) Note) DMSO means dimethyl sulfoxide.

Production Example 2 2-(3-hydroxyphenyl)-2- was placed in a four-bottle flask equipped with a cooling tube, thermometer, stirrer, and nitrogen gas introduction tube.
(4'-aminophenyl)furopane 68.1g, dimethyl sulfoxide 150mM, chlorobenzene 180mQ
, 4.4'-dichlorodiphenylsulfone 40.75
g and 20.5 g of anhydrous potassium carbonate were added, and the mixture was heated and stirred under nitrogen gas flow to produce water. 165℃
After reacting for 4 hours, the mixture was cooled to room temperature. The reaction solution was poured into water to obtain a crude product. The target compound 4,4'-bis[3-(4
-amino-α,α′-dimethylbenzyl)phenoxy]
71.1 g of diphenyl sulfone was obtained. Melting point 67
~70°C, purity determined by liquid chromatography is 99.
It was 4%.

The analysis results of this diamine are as follows.

(1) Elemental analysis value (%) C42H4°N20. SCHN Calculated value 75.45 5,99 4,19 4°9 Actual value 75.18 6.03 4.02. 4゜6 (2) IR absorption position (KBrBr method, Ql-') 34
50.3390 (amino group) 2970.2870 (methyl group) 1290.1110 (sulfonyl group) 1250
(ether group) (3) NMR spectral position (DMSO-dsyPPl) 1.55 (12H
- doublet) 4.87 (4H-multiplet) 6.4 to 8.0 (24H multiplet) Example 1 Manufactured in a four-loop flask equipped with a stirrer, thermometer, nitrogen gas introduction tube, and downward cooling tube. 3.16 g of 4,4'-bis(3-(4-amino-α,α'dimethylbenzyl)phenoxy)benzophenone obtained in Example 1 and 2.88 g of bisphenol A bistrimelitate dianhydride, N-methyl Pyrrolidone 15mQ, triphenyl phosphite 0.2
g and reacted at 200° C. for 5 hours while flowing nitrogen gas to obtain a polyimide varnish. This varnish was poured into water and reprecipitated, ground and dried to obtain polyimide powder. The reduced viscosity measured in DMF at a concentration of 0-1 g/dQ and a temperature of 30°C is 0.47 dQ/g, and a load of 10 kg/a.
The softening point measured with a Koka type flow tester at J is 165℃
, the 5% weight loss temperature was 437°C. In addition, in a solubility test (polyimide powder was added to an organic solvent at a concentration of 5% by weight and the state of dissolution was observed at room temperature), the polyimide powder was found to contain DMF, NMP, dioxane, tetrahydrofuran (THF) and Each was soluble in methylene chloride. The infrared absorption spectrum of the above polyimide is shown in FIG.

Example 2 4,4'- obtained in Production Example 2 was placed in a four-loaf flask equipped with a stirrer, a thermometer, a calcium chloride tube, and a nitrogen gas introduction tube.
Bis(3-(4-amino-α.

3.34 g of α'-dimethylbenzyl)phenoxyfudiphenylsulfone and N,N-dimethylformamide (
Add 20 mA of DMF and dissolve. Bisphenol A bistrimelitate dianhydride while cooling to below 5°C2.
After adding 88 g little by little.

The mixture was reacted for 3 hours at 5°C or lower and for 1 hour at room temperature to obtain a polyamic acid varnish, which is a polyimide precursor. 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 and reprecipitated, ground and dried to obtain polyimide powder. In DMF, concentration 0.1 g/dQ, temperature 3
Reduced viscosity measured at 0°C is 0.33 dQ/g, load 10
The softening point measured with a Koka type flow tester in kg/aj is
The temperature was 162°C.

This polyimide powder was soluble in DMF, dioxane, tetrahydrofuran, and methylene chloride in a solubility test. The 5% weight loss temperature was 432°C. FIG. 2 shows the infrared absorption spectrum of the polyimide.

Example 3 A polyimide powder was obtained in the same manner as in Example 1 except that 2.67 g of 0,0'-bisphenol bistrimelitate dianhydride was used instead of bisphenol A bistrimelitate dianhydride. The reduced viscosity of this polyimide is 0.52dj2/g, and the softening point is 140T:, 5%.
The weight loss temperature was 445°C and D in the solubility test.
MF, NMP.

It was soluble in dioxane, THF, and methylene chloride. FIG. 3 shows the infrared absorption spectrum of the polyimide.

Example 4 Polyimide powder was obtained in the same manner as in Example 2, except that 3.47 g of dianhydride represented by the following formula (V) was used instead of bisphenol A bistrimelitate dianhydride. The reduced viscosity of this polyimide is 0.3
5dQ/g, softening point is 165℃, 5% weight loss temperature is 4
50"C, and in the solubility test, DMF, NMP,
Dioxane, THF.

It was soluble in methylene chloride. FIG. 4 shows the infrared absorption spectrum of the polyimide.

〔Effect of the invention〕

The polyesterimide according to the present invention has excellent solubility in organic solvents and exhibits a relatively low softening point.

[Brief explanation of drawings]

Claims (1)

[Claims] 1. General formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (1) [However, in the formula, A is general formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ …(2) (However, in the formula, Ar represents a divalent aromatic group) represents a divalent group represented by the general formula (3) ▲ Numerical formula, chemical formula, table, etc. ▼…( 3) A polyesterimide comprising a structural unit represented by (wherein, X represents a divalent group represented by ■C=O or ■SO_2). 2. The divalent group represented by the general formula (3) is represented by the general formula (3)
2. The polyesterimide according to claim 1, wherein the bond and oxygen are bonded to the isopropylidene group at the para-position or meta-position, respectively. 3. The divalent group represented by general formula (3) is the one according to claim 2, and in general formula (3), at least one of two bonds and two oxygen 3. The polyesterimide according to claim 2, wherein the isopropylidene group is bonded to the meta position of the isopropylidene group. 4. The divalent group represented by the general formula (3) is the one according to claim 3, and in the general formula (3), the bond is in the para position with respect to the isopropylidene group and the oxygen The polyesterimide according to claim 3, wherein is bonded to the meta position.