JP3022917B2 - Thermosetting compound and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel thermosetting compound and a method for producing the same. More specifically, the present invention relates to an esterimide oligomer having excellent heat resistance and optimal reactivity for lamination and molding, and a method for producing the same.

[Conventional technology and problems to be solved]

Thermosetting resins have been used as materials for casting, impregnation, lamination, and molding in various electric insulating materials and structural materials.
In recent years, the use conditions of materials in each of these applications have become increasingly severe. In particular, the heat resistance of the material has become an important characteristic. Conventionally, thermosetting polyimide resins and heat-resistant epoxy resins have been used for such purposes. Among them, as the thermosetting polyimide resin, kerimide (trade name of Lone Poulin-Schmi), which is mainly composed of a combination of a bismaleimide compound and diaminodiphenylmethane (Matsuo Fujisawa, Plastics, 34, No. 7, p. 75, 1983]. However, the thermosetting polyimide resin has a disadvantage that a high-temperature and long-time heating step is required at the time of processing. Furthermore, there is a problem in handling hygiene because diaminodiphenylmethane is harmful to the human body. Also, in recent years, acetylene-terminated polyimide has been marketed as "Thermid (trade name of Gulf R &D)" [JP-A-53-119865].
etc〕. However, since the solubility of the organic solvent is relatively low, a high-boiling organic polar solvent such as dimethylformamide and dimethylacetamide must be used, which has a problem in handling.

In order to solve such problems of polyimide, many methods for improving resins have been proposed, and among them, various polyesterimide resins have been proposed from the viewpoint of processing characteristics (for example, USP 4,757,118, 4,362,861). No. 3,852,24
No. 6, etc. or JP-A-1-123819].

However, polyesterimides generally have lower thermal softening points than polyimides and have excellent resin flow properties, but have been pointed out to be inferior to polyimides in terms of heat resistance (Kurita et al., Polymer Processing, Vol. 37, No. 2, pages 22-26 (1989)].

Furthermore, a novel acid dianhydride having an ester bond is synthesized using trimellitic anhydride as a starting monomer and a paratoluenesulfonic acid / pyridine-based reaction solvent as in the present invention, and then diamine and the like are introduced. Thus, only a few findings are known for synthesizing polyesterimides in the same reaction system (for example, H. Tanaka et al., Proceedings / Abstracts of Third
International Conference on Polyimides, 65-68 pp
(1988)], and there is no report on polyesterimides having reactivity such as thermosetting or photoreactivity.

[Means for solving the problem]

In view of such circumstances, the present inventors have made intensive studies to solve these technical problems, and as a result, have reached the present invention.

That is, the first aspect of the present invention is that the general formula (I) (Wherein, Ar ₁ , Ar ₂ , and Ar ₃ are each a divalent organic group selected from the following group, and Ar ₁ , Ar ₂ , and Ar ₃ may be the same or different. Further, m is an integer of 1 to 30.).

Ar ₁ : Ar ₂ : Ar ₃ : A second aspect of the present invention is to keep the reaction system at room temperature or lower in an inert gas atmosphere, and then add trimellitic anhydride dissolved in an aprotic polar solvent to a mixed solution of paratoluenesulfonic acid chloride and pyridine. Then, a diol previously dissolved in an aprotic polar solvent is added and reacted, and then the diamine dissolved in the aprotic polar solvent is added in an amount necessary to obtain an oligoester amic acid capable of elongating a molecular chain terminated at both terminal amino groups. The method further comprises adding an acid anhydride dissolved in an aprotic polar solvent to terminate the terminal, and then adding a non-solvent to thermally close and dehydrate the thermosetting compound. It is assumed that.

First, a method for producing the thermosetting compound of the present invention will be described.

First, a required amount of p-toluenesulfonic acid chloride (hereinafter, referred to as TsCl) is weighed and measured in an atmosphere of an inert gas such as argon or nitrogen, and the reaction system is cooled to room temperature or lower, preferably 10 mL or lower.
After cooling under ice-cooling, more preferably under ice-cooling, pyridine was added dropwise from a syringe while paying attention to heat generation. After sufficient reaction, the calculated amount of trimellitic anhydride (hereinafter referred to as TMA)
It is written. Is dissolved in an aprotic polar solvent and then added. Then, the diol [1] represented by the general formula (II) (Wherein, Ar ₂ represents a divalent organic group) is dissolved in the same aprotic polar solvent as described above under ice-cooling, and then added. The reaction is appropriately performed at room temperature to complete the reaction. Here, in order to obtain a copolymer, a compound represented by the general formula (III)
Organic tetracarboxylic dianhydride [2] (In the formula, Ar ₄ represents a tetravalent organic group.) Next, the reaction system was cooled again with ice, and the diamine represented by the general formula (IV) [3] dissolved in the same aprotic polar solvent as described above. (Wherein, Ar ₁ represents a divalent organic group). At this time, it is important to add a calculated amount of diamine in advance so as to obtain an oligoester amic acid solution in which both ends of the amino group are terminated and the molecular chain can be extended. After sufficiently reacting the oligoester amic acid solution, the reaction is continued while heating the reaction system to 60 ° C. Thereafter, the terminal amino group was dissolved in the same aprotic polar solvent as described above, and the general formula (V)
An aromatic acid anhydride represented by the formula [4] (Wherein, Ar ₃ represents a divalent organic group.) The oligoester amic acid represented by the general formula (VI) terminated with: (Wherein Ar ₁ , Ar ₂ , Ar ₃ and m are the same as those in the above formula (I)).

Finally, in order to thermally close and dehydrate the amic acid solution, a non-solvent is added, and then the mixture is refluxed and azeotropically converted into an esterimide oligomer represented by the general formula (I).

Here, the non-solvent to be used can be used without any particular limitation as long as it is an aromatic hydrocarbon such as xylene, toluene and benzene, but benzene is preferably used.
In the reaction, the azeotropically distilled water is refluxed using a Dean-Stark reflux until a stoichiometric amount of water is collected.
After the reaction, the polyimide is precipitated as a powder by pouring the polyimide solution into water or an alcohol-based solvent with vigorous stirring. The powder is collected by filtration and dried at 80 ° C. under reduced pressure for 48 hours.

As the organic tetracarboxylic dianhydride used in the present invention, an organic tetracarboxylic dianhydride having any structure can be used, but the Ar ₄ group in the general formula (III) is a tetravalent organic group. And an aromatic group. this
Specific examples of the Ar ₄ group include the following.

These organic tetracarboxylic dianhydrides may be used alone or in combination of two or more. More specifically, from the aspect of the balance of various characteristics, It is preferable that at least one or more of the above is used as a main component.

The diol used in the present invention has the general formula (II) (Wherein, Ar ₂ is a divalent organic group) is indicated by, Ar ₂ of the diol compound (1) is essentially in whatever available if the divalent organic group, specifically, Etc., but an aromatic group is preferred, and specifically, It is preferable that at least one or more of the above is used as a main component.

The diamine used in the present invention has the general formula (IV) (Wherein, Ar ₁ is a divalent organic group) is indicated by, Ar ₁ of the diamine compound [3] is available whatever divalent organic group, specifically, Etc., but an aromatic group is desirable, and specifically, It is preferable that at least one or more of the above is used as a main component.

The aromatic acid anhydride used in the present invention for terminal termination is
General formula (V) When Ar ₃ of the aromatic acid anhydride [ 4 ] is exemplified, However, in terms of cost and handling, it is particularly preferable that It is.

Examples of the aprotic polar organic solvent used in the polyamic acid solution generation reaction include, for example, dimethyl sulfoxide, sulfoxide solvents such as diethyl sulfoxide,
Examples thereof include formamide solvents such as N, N'-dimethylformamide and N, N'-diethylformamide, and acetamido solvents such as N, N'-dimethylacetamide and N, N'-diethylacetamide. These can be used alone or 2
It can also be used as a mixed solvent of more than one kind. Furthermore, with these aprotic polar solvents, methanol,
It can also be used as a mixed solvent of a polyamic acid such as ethanol, isopropanol and benzenemethyl cellosolve with a non-solvent. It is preferable to use dimethylformamide (hereinafter, referred to as DMF) from the viewpoint of the color tone, yield, and the like of the produced polymer.

Although the mechanism for providing a cured product having particularly high heat resistance from the reactive ester imide oligomer according to the present invention is not clear, the thermal curing of acetylene (3.
It is said to be the effect of benzene skeleton formation or nagic ring opening by thermal quantification) and thermal polymerization [for example, Takeichi Riki, Polymer Processing, Vol. 37, No. 7, p. 347, 1988
Year〕.

Further, the number average degree of polymerization (DP; PJ Flory, Principle
s of Polymer Chemistry: Cornell University Press: It
haca, NY, page 91, 1953], the polymerization ratio n is preferably 1 to 30, preferably 1 to 25, and more preferably 1 to 20. When it is larger than the above range, there is a disadvantage that the solubility in the organic solvent is reduced. On the other hand, if it is smaller than the above range, there is a problem in mechanical strength.

When obtaining a cured product from the ester imide oligomer of the present invention, an epoxy resin or an epoxy resin curing agent, a curing accelerator, a filler, a flame retardant, a reinforcing agent, a surface treatment agent, a pigment, various elastomers, etc. are used as necessary. I can do it.

The epoxy resin is a compound having two or more epoxy (glycidyl) groups in a molecule. Examples thereof include bisphenol A, bisphenol F, hydroquinone, resorcin, furylglycine, tris- (4-hydroxyphenyl) methane, 1,1 Derived from dihydric or trihydric phenols such as 2,2,2-tetrakis (4-hydroxyphenyl) ethane or halogenated polyphenols such as novolak derived from tetrabromobisphenol A or brominated polyphenols. Glycidyl ether compounds, phenols, novolak epoxy resins which are reaction products of phenols such as orthocresol and formaldehyde, aniline, paraaminophenol, metaaminophenol, 4-amino-metacresol, 6-
Amino-metacresol, 4,4'-diaminodiphenylmethane, 8,8'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, paraphenylenediamine, metaphenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, para Xylylenediamine, meta-xylylenediamine, 1,4-cyclohexane-bis (methylamine), 1,4-cyclohexane-bis (methylamine), 5-amino-1- (4'-
Aminophenyl) -1,8,8-trimethylindane, 6-
Amine-based epoxy resins derived from amino-1- (4-aminophenyl) -1,8,8-trimethylindane, and the like;
Glycidyl ester compounds derived from aromatic carboxylic acids such as paraoxybenzoic acid, terephthalic acid, and isophthalic acid; hydantoin-based epoxy resins derived from 5,5-dimethylhydantoin; and 2,2'-bis (3,4 -Epoxycyclohexyl) propane, 2,2-bis [4- (2,3
-Epoxypropyl) cyclohexyl] propane, vinylcyclohexene dioxide, alicyclic epoxy resins such as 3,4-epoxycyclohexanecarboxylate, and others, triglycidyl isocyanurate, 2,4,6-triglycidoxy-s-triazine and the like. These are used alone or in combination of two or more.

Examples of the epoxy curing agent include amine curing agents such as aromatic amines and aliphatic amines such as xylylenediamine, polyphenol compounds such as phenol novolak and cresol novolak, and hydrazide compounds. These may be used alone or in combination. Used in combination.

Benzyldimethylamine, 2,4,6 as curing accelerator
-Tris (dimethylaminomethyl) phenol, 1,8-
Examples thereof include amines such as diazabicycloundecene, imidazole compounds such as 2-ethyl-4-methylimidazole, and boron trifluoride amine complex, and these may be used alone or in combination of two or more.

Addition of an elastomer to improve mechanical strength is also effective. Specific examples of the elastomer include the following.

The elastomers described above include Silastic (LS-420), S
ylgard (184) is a hiker / ATB from Dow Corning
N (1300x16 etc.), CTB (2000x162), CTBN (1300x13,
1300 × 8, 1300 × 31) and VTBN (1300 × 23) are manufactured by Ube Industries, Ltd., and 3F is manufactured by Monsanto.

Aluminum hydroxide, antimony trioxide,
Red phosphorus and the like can be exemplified. As the reinforcing material, woven fabric, nonwoven fabric, mat, paper (paper) made of liquid crystal polyester fiber such as carbon fiber, glass fiber, aramid fiber, Vectra, polybenzothiazole (PBT) fiber, alumina fiber, etc.
These are used alone or in combination of two or more.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Abbreviations of the monomers used in the examples are summarized below.

Aromatic diol compound [ 1 ] represented by general formula (II) The organic group Ar ₂ of It is.

Aromatic diamine compound represented by the general formula (IV) [ 3 ] The organic group Ar ₁ of It is.

Furthermore, the acid anhydride [ 4 ] represented by the general formula (V) The organic group Ar ₃ of And

Example 1 A one-liter four-necked flask was equipped with a three-way cock, a Din Stark still, a Dimroth reflux condenser, and a seal cap. The reactor was dried under reduced pressure. 14.9g (7
(8 mmol) of TsCl was added to the reaction system, and the atmosphere was sufficiently replaced with argon. The reaction was cooled on ice and 30 milliliters of dry pyridine was added with care for the exotherm. 15 g (78 mmol)
Of TMA was completely dissolved in 110 ml of dry DMF and then added in 30 minutes. After continuing the reaction at that temperature,
13.1 g (39 mmol) of aromatic diol 1a dissolved in 30 ml of dry DMF was added dropwise under ice cooling. After 30 minutes, the ice bath was removed, and the reaction was continued at room temperature for 1 hour.
After that, the reaction system was again ice-cooled, and 22.8 g (78.0 mmol) of aromatic diamine 3a was added to 50 ml of dry DMF. After 30 minutes, the ice bath was removed, the reaction system was heated to 60 ° C. in an oil bath, and the reaction was continued for 30 minutes. 12.8 g (78.0 mmol) of aromatic anhydride 4a was added to 10 ml of dry DMF and reacted for 2.6 hours.
Then, after adding 200 ml of dry benzene, 1
1.4 ml azeotropically at 45 ° C (bath temperature) (theoretical; 1.
(4 ml) of reaction water was distilled off. After the reaction, the reaction solution was put into 1000 ml of methanol to precipitate an ester imide oligomer. The precipitated ester imide oligomer 5a was filtered under reduced pressure and dried in a vacuum at 80 ° C. for 48 hours to give 60.5 g (yield: 97.1%) of a pale yellow powder 39.5 g.
As obtained.

230 ° C using 4.5 g of this ester imide oligomer 5a
・ 10kg / cm ²・ After 1.5 hours press molding, 12mm
A casting plate of (width) × 12 cm (length) × 1.3 mm (thickness) was obtained. The measurement results of various physical properties of the ester imide oligomer 5a and its casting plate are summarized in Tables 1 and 2.

Example 2 A one-liter four-necked flask was equipped with a three-way cock, a Din Stark still, a Dimroth reflux condenser, and a seal cap. The reactor was dried under reduced pressure. 14.9g (7
(8 mmol) of TsCl was added to the reaction system, and the atmosphere was sufficiently replaced with argon. The reaction was cooled on ice and 30 milliliters of dry pyridine was added with care for the exotherm. 15 g (78 mmol)
Of TMA was completely dissolved in 110 ml of dry DMF and then added in 30 minutes. After continuing the reaction at that temperature,
9.76 g (39 mmol) of aromatic diol 1b dissolved in 30 ml of dry DMF was added dropwise under ice cooling. After 30 minutes, the ice bath was removed, and the reaction was continued at room temperature for 1 hour.
After that, the reaction system was again ice-cooled, and 26.1 g (78.0 mmol) of aromatic diamine 3b was added to 50 ml of dry DMF. After 30 minutes, the ice bath was removed, the reaction system was heated to 60 ° C. in an oil bath, and the reaction was continued for 30 minutes. 13.4 g (78.0 mmol) of aromatic acid anhydride 4b was added to 10 ml of dry DMF and reacted for 2.6 hours.
Then, after adding 200 ml of dry benzene, 1
1.1 ml azeotropically at 45 ° C (bath temperature) (theoretical; 1.
(4 ml) of reaction water was distilled off. After the reaction, the reaction solution was put into 1000 ml of methanol to precipitate an ester imide oligomer. The precipitated ester imide oligomer 5b was filtered under reduced pressure and dried in vacuum at 80 ° C. for 48 hours to obtain 57.6 g (yield: 92.5%) of a pale yellow powder.

230 ° C using 4.5 g of this ester imide oligomer 5b
・ 10kg / cm ²・ After 1.5 hours press molding, 12mm
A casting plate of (width) × 12 cm (length) × 1.2 mm (thickness) was obtained. Tables 1 and 2 summarize the measurement results of various physical properties of the ester imide oligomer 5b and its cast plate.

Example 3 A one-liter four-necked flask was equipped with a three-way cock, a Din Stark still, a Dimroth reflux condenser, and a seal cap. The reactor was dried under reduced pressure. 14.9g (7
(8 mmol) of TsCl was added to the reaction system, and the atmosphere was sufficiently replaced with argon. The reaction was cooled on ice and 30 milliliters of dry pyridine was added with care for the exotherm. 15 g (78 mmol)
Of TMA was completely dissolved in 110 ml of dry DMF and then added in 30 minutes. After continuing the reaction at that temperature,
20.3 g (39 mmol) of aromatic diol 1c dissolved in 30 ml of dry DMF was added dropwise under ice cooling. After 30 minutes, the ice bath was removed, and the reaction was continued at room temperature for 1 hour.
After that, the reaction system was again ice-cooled, and 19.3 g (78.0 mmol) of aromatic diamine 3c was added to 50 ml of dry DMF. After 30 minutes, the ice bath was removed, the reaction system was heated to 60 ° C. in an oil bath, and the reaction was continued for 30 minutes. 12.8 g (78.0 mmol) in 10 ml of dry DMF
Was added and reacted for 2.6 hours. After that, after adding 200 ml of dry benzene,
1.2 ml (theoretical amount; 1.4 ml) of reaction water was distilled off azeotropically at (bath temperature). After the reaction, methanol
The reaction solution was charged into 1000 ml to precipitate the ester imide oligomer. Precipitated ester imide oligomer 5c
Was filtered under reduced pressure and dried in vacuum at 80 ° C. for 48 hours to obtain 58.3 g (yield: 88.3%) as a pale yellow powder.

230 ° C using 4.5 g of this ester imide oligomer 5c
・ 10kg / cm ²・ After 1.5 hours press molding, 12mm
A casting plate of (width) × 12 cm (length) × 1.5 mm (thickness) was obtained. The measurement results of various physical properties of the oligomer 5c and its cast plate are summarized in Tables 1 and 2.

Comparative Example 1 When 4.5 g of a commercially available imide type thermosetting imide oligomer was press-molded at 230 ° C. and 10 kg / cm ^{2 for} 1.5 hours,
A casting plate of 12 mm (width) x 12 cm (length) x 1.3 mm (thickness) was obtained. The measurement results of various physical properties of the imide oligomer and its cast plate are summarized in Tables 1 and 2.

[Effect of the Invention] By using the reactive ester imide oligomer according to the present invention, it is possible to obtain a cured product which is excellent in processing characteristics due to high resin fluidity and has extremely high heat resistance, which has not been achieved conventionally. Further, the reactive ester imide oligomer according to the present invention has excellent mechanical strength, dimensional stability, electrical properties and the like. In particular, it is possible to obtain a polyesterimide which is excellent in solubility in a solvent, adhesion to other substances, and flexibility, and is less likely to cause voids and cracks in a molded product.

As described above, the esterimide oligomer having reactivity of the present invention has many characteristics as described above, and thus has a laminate, a heat-resistant paint, a polymer material for electronic devices,
A material having extremely high industrial value can be provided for a wide range of uses such as molding materials, and its usefulness is extremely large.

Claims (7)

(57) [Claims] 1. The compound of the general formula (I) (Wherein, Ar ₁ , Ar ₂ , and Ar ₃ are each a divalent organic group selected from the following group, and Ar ₁ , Ar ₂ , and Ar ₃ may be the same or different. And m is an integer of 1 to 30). Ar ₁ : Ar ₂ : Ar ₃ : 2. The thermosetting compound according to claim 1, wherein Ar ₁ is selected from the following groups: 3. The thermosetting compound according to claim 1, wherein Ar ₂ is selected from the following groups: 4. The thermosetting compound according to claim 1, wherein Ar ₃ is selected from the following groups: 5. The reaction system is maintained at room temperature or lower in an inert gas atmosphere, and trimellitic anhydride dissolved in an aprotic polar solvent is added to a mixed solution of p-toluenesulfonic acid chloride and pyridine. A diol previously dissolved in a polar solvent is added and reacted, and then a diamine dissolved in an aprotic polar solvent is added and reacted in an amount necessary to obtain an oligoester amic acid capable of elongating a molecular chain having both terminal amino groups terminated, Further, an acid anhydride dissolved in an aprotic polar solvent is added to terminate the terminal, and then a non-solvent is added to thermally ring-close and dehydrate, so that the ring is dehydrated. A method for producing a thermosetting compound. 6. The method according to claim 5, wherein the aprotic polar solvent is dimethylformamide. 7. The method according to claim 5, wherein an organic tetracarboxylic dianhydride is copolymerized.