JPH0481428A - Thermosetting compound and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful for a laminated board, etc., having excellent processability and especially excellent heat resistance by using trimellitic acid anhydride as a starting monomer and using a p-toluene sulfonyl chloride/pyridine-based reaction solvent. CONSTITUTION:A reaction system is kept below room temperature in an inert gas atmosphere and trimellitic acid anhydride dissolved in an aprotic polar solvent (e.g. dimethylformamide) is added to a mixed solution of p-toluene sulfonyl chloride and pyridine, then previously dissolved diol is added to said polar solvent, thus reacted. Next, dissolved diamine is added to said polar solvent and reacted, then dissolved acid anhydride is added to said solvent, thus a non-solvent is added to thermally perform ring closure and dehydration to afford the aimed compound expressed by the formula (Ar1 to Ar3 are bifunctional organic group; m is 1-30).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application 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 particularly excellent heat resistance and optimal reactivity for lamination and molding, and a method for producing the same.

[Prior Art and Issues to be Solved] Thermosetting resins have been used as casting, impregnating, laminating, and molding materials for various electrical insulation materials, structural materials, and the like. In recent years, the conditions for using materials in each of these applications have become increasingly strict. In particular, the heat resistance of materials has become an important characteristic. Conventionally, thermosetting polyimide resins and heat-resistant epoxy resins have been used for such purposes.

Among these, the thermosetting polyimide resin used is kerimide, which is mainly composed of a combination of bismaleimide compounds and diaminodiphenylmethane [Embryoswa Sample, Plastinx, Vol. 34, No. 7, 75 Page, 1983
Year〕. However, thermosetting polyimide resins have the drawback of requiring a high temperature and long heating process during processing. Furthermore, diaminodiphenylmethane is harmful to the human body, which poses a hygiene problem in handling. In addition, in recent years, acetylene-terminated polyimide has been applied as thermid [Gulf R&D, JP 531198]
65 mag]. However, since the organic solvent solubility is relatively low, a high-boiling organic polar solvent such as dimethylformamide or dimethylacetamide must be used, and there are problems in its handling.

In order to solve these problems with polyimide, many methods for improving resins have been proposed, and among these, various polyesterimide resins have been proposed from the viewpoint of processing characteristics [
For example, 1. lSP No. 4757118, 4,362
．． No. 861, No. 3,852,246, etc. or JP-A No. 1
-123819 etc.].

However, for boat fishing, it has been pointed out that although polyesterimide has a lower thermal softening point and superior resin flow characteristics than polyimide, it is inferior to polyimide in terms of heat resistance [Keisuke Kurita et al., Polymer Processing, Vol. 37, No. 2, pages 22-26 (I989)).

Furthermore, as in the present invention, a new acid dianhydride having an ester bond is synthesized using trimellitic anhydride as a starting material and a chlorinated balatoluenesulfonic acid/pyridine reaction solvent, and then a diamine etc. Only some knowledge is known regarding the synthesis of polyesterimide in the same reaction system by introducing
H. Tanaka et al., Proceedi
ngs/Abstracts of Th1rd 1n
International Conference on
Polyimides, 656811p (I98
8)), and no knowledge has been reported regarding polyester imides having reactivity such as thermosetting type or photoreactivity.

[Means for Solving the Problems] In view of the above circumstances, the inventors of the present invention have made extensive studies to solve these technical problems, and as a result, they have arrived at the present invention.

That is, the first aspect of the present invention is the general formula (I) (wherein Arz Arz, Ari are divalent organic groups, and Ar++ Arz+ Ar, may be the same or different. Good. m is an integer from 1 to 30.

) is dissolved in an aprotic polar solvent in a mixed solution of paratoluenesulfonic acid chloride and pyridine while maintaining the reaction system below room temperature in an inert gas atmosphere. After adding Trino'J acid anhydride, a diol pre-dissolved in an aprotic polar solvent is added and reacted.
Next, the diamine dissolved in an aprotic polar solvent is reacted by adding the necessary amount to obtain an oligoester amic acid at both ends with amino groups, and then an acid anhydride dissolved in an aprotic polar solvent is added to terminate the terminal terminals. Each content is a method for producing a thermosetting compound, which is characterized by stopping the reaction, and then adding a non-solvent to thermally ring-close and dehydrate the compound.

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

First, in an inert gas atmosphere such as argon or nitrogen, the required amount of para-toluenesulfonic acid chloride (hereinafter referred to as TsCl) is
It is written as ) was weighed out, the reaction system was cooled to room temperature or lower, preferably 10°C or lower, and more preferably water-cooled, and then pyridine was added dropwise from a syringe while exhaling due to the exotherm. After sufficient reaction, a calculated amount of trimellitic anhydride (hereinafter referred to as T-A) is dissolved in an aprotic polar solvent and then added. Thereafter, the diol [1] HO-Arz-OH (II) [1] represented by the general formula (II) (in the formula, Ar2 represents a divalent organic group) was treated with the same aprotic solution as above under cooling with water. Add after dissolving in polar solvent. In order to complete the reaction, the reaction is appropriately carried out at room temperature. Here, in order to obtain a copolymer, the general formula (III
) etc. It is also possible to add an organic tetracarboxylic dianhydride [2] [2] (wherein Ar represents a tetravalent organic group). Next, the reaction system was ice-cooled again, and the general formula (IV
) Diamine [3] Aromatic acid anhydride represented by the general formula (V) dissolved in a polar solvent [4] [4] (wherein, Ar represents a divalent organic group. ) is added to the oligoester amic acid represented by the general formula (■) (in the formula, Ar represents a divalent organic group).

At this time, it is important to add a calculated amount of diamine in advance so as to obtain a telechelic oligoester amic acid solution terminated with amino groups at both ends. After the oligoester amic acid solution is sufficiently reacted, the reaction is continued while the reaction system is heated to 60°C.

After that, the terminal amine group is attached to the same abrogate as above (wherein, Ar1.Ar2 is a divalent organic group, Ar3 is a monovalent organic group, Arz, Arz, and Arz may be the same type or different types. Also, m may be 1 to 30
is an integer. ).

Finally, in order to thermally ring-close and dehydrate the amic acid/8 solution, a non-solvent is added thereto, and the mixture is converted into an ester imide oligomer represented by the general formula (I) under reflux and azeotropy.

Here, the nonsolvent to be used can be aromatic hydrocarbons such as xylene, toluene, and Hensen without any particular restriction, but Hensen is preferably used. In the reaction, water to be azeotropically distilled off is refluxed using a Dean-Stark reflux device until the stoichiometric amount of water for the reaction is collected. After the reaction, the polyimide solution is poured into a water or alcohol solvent with vigorous stirring to precipitate the polyimide as a powder. 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, organic tetracarboxylic dianhydride having any structure can be used, but the Ar group in the above general formula (III) is a tetravalent organic group. , is preferably an aromatic group.

Specific examples of this Ar4 group include the following.

It is preferable that the main component is at least one or more of the following.

The diol used in the present invention is -C formula (II) HOA
rz OH(II) [Top] These organic tetracarboxylic dianhydrides may be used alone or in combination of two or more. More specifically, in terms of the balance of properties, Arz is represented by (wherein Ar2 is a divalent organic group), and Arz of the diol compound [earth] can essentially be any divalent organic group. Possible, specifically CF.

1+CH2→1− CF2 The diamine used in the present invention is General formula (N゛) H2N'-Ar [3] Nl(.

(8') (In the formula, y is a divalent organic group) Ar in the diamine compound [i] can be any divalent organic group, and specifically, the following may be mentioned. However, aromatic groups are desirable, and specifically, it is preferable that the main component is at least one or more of the following.

CH.

It is preferable that the main component is at least one type of CF□.

The aromatic acid anhydride used in the present invention for terminal termination is General formula (V) [4] It is expressed as The aromatic acid anhydride [4] An example of Ar3 is Then, CF Yu etc., but Aromatic groups are preferred; in particular, degree etc., but In terms of cost and handling, particularly preferred teeth, It is.

Examples of the abrotic polar organic solvent used in the production reaction of the polyamic acid solution include sulfoxide-based solvents such as dimethyl sulfoxide and dimethyl sulfoxide, formamide-based solvents such as N' dimethylformamide and N N' diethylformamide, N, N ' -dimethylacetamide,
Examples include acetamide solvents such as N,N'-diethylacetamide. These solvents can be used alone or as a mixed solvent. Furthermore, it can also be used as a mixed solvent with a non-solvent for polyamic acid such as methanol, ethanol, isopropyl, benzene methyl cellosolve, etc. together with these aprotic polar solvents. Preferably, dimethylformamide (hereinafter referred to as
It is written as DMF. ) is desirable from the viewpoint of the color tone of the produced polymer, yield, etc.

Although the mechanism for producing a cured product with particularly high heat resistance from the reactive ester imide oligomer according to the present invention is not clear, the formation of a benzene skeleton by thermal curing (trimerization) of acetylene or the opening of a Nazick ring This is said to be an effect of thermal polymerization [for example, Riki Takeichi, Polymer Processing, Vol. 37, No. 7, p. 347, 19
1988].

In addition, the number average degree of polymerization [DP; P, J, Flory, Pr
1nciples of Polymer Chemi
stry: Cornellllniversity
Press: Ithaca, NY, 91 pages,
1953], the polymerization ratio n was set to 1.
-30, preferably 1-25, more preferably 1-20
Good. If it exceeds the above range, there will be a drawback that solubility in organic solvents will decrease. Moreover, if it is smaller than the above range, problems will arise in terms of mechanical strength.

When obtaining a cured product from the esterimide oligomer of the present invention, an epoxy resin, an epoxy resin curing agent, a curing accelerator, a filler, a flame retardant, a reinforcing agent, a surface treatment agent,
Pigments, various elastomers, etc. can be used in combination.

Epoxy resin is a compound that has two or more epoxy (glycidyl) groups in its molecule, and examples include bisphenol A1 bisphenol F1 hydroquinone, resorcinol, furylglycine, tris-(4-hydroxyphenyl)methane, 1.1° Glycidyl ether compounds derived from divalent or trivalent or higher valent phenols such as 22-tetrakis(4-hydroxyphenyl)ethane, or halogenated polyphenols such as novolak derived from tetrabromobisphenol A and brominated polyphenols; Novolanc epoxy resin, which is a reaction product of phenols such as phenol and orthocresol and formaldehyde, aniline, para-aminophenol, meta-aminophenol, 4-amino-metacresol, 6-
Amino-metacresol, 4,4'-diaminodiphenylmethane, 8,8'-diaminodiphenylmethane, 4.
4'-diaminodiphenyl ether, 34'-diaminodiphenyl ether, 1.4bis(4-aminophenoxy)benzene, 14-bis(3-aminophenoxy)benzene, 13-bis(3-aminophenoxy)benzene, 22-bis( 4-amine phenoxyphenyl) propane, para-phenylene diamine, meta-phenylene diamine, 24-toluenediamine, 2,6 toluenediamine,
Para-xylylene diamine, meta-xylylene diamine, 1
．． 4-Cyclohexanebis(methylamine), 1.4-
Cyclohexane-bis(methylamine), 5-amino-
1(4'-aminophenyl)-1, 88-trimethylindane, 6-amino-1-(4-aminophenyl)-1
, 8,8-1-limethylindane, etc., glycidyl ether compounds derived from aromatic carboxylic acids such as paraoxybenzoic acid, terephthalic acid, isophthalic acid, etc., 5,5-dimethylhydantoin, etc. Hydantoin-based epoxy resin derived from 2.
2bis(3,4-epoxycyclohexyl)propane,
Cycloaliphatic epoxy resins such as 2,2-bisC4-(2,3-epoxypropyl)cyclohexyl]propane, vinylisochlorohexene dioxide, 3,4-epoxyisochlorohexanecarboxylate, and others, triglycidyl isocyanurate , 2,4.6-) liglycidoxy S-
Examples include triazine, and these may be used alone or in combination of two or more.

Examples of epoxy curing agents include amine curing agents such as aromatic amines and aliphatic amines such as xylylene diamine, polyphenol compounds such as phenol novolak and cresol novola, and hydrazide compounds.
It can be used as a species or in combination of two or more species.

As a curing accelerator, benzyldimethylamine, 2 4
64 Lis(dimethylaminomethyl)phenol, 1.8
- Amines such as diazabicycloundecene, imidazole compounds such as 2-ethyl-4-methylimidazole,
Examples include boron trifluoride amine complexes, which may be used alone or in combination of two or more.

Addition of elastomers to improve mechanical strength is also effective. Specifically, the elastomer can be exemplified by the following.

5ilastic CH3C5F7CH=C
H2-”yhaQ5-5i -0-5i-0-5i-0-
^J Summer He CH3C3F7 CL 8TBN F (X+Y=3) CI(, CH.

R-CHzCHzCHCHzCtoCHCHz9nchH,
cH bracket c-CHzCHz-RCN
CN CNR: -COOH(
CTBN, CTB) COOCHzCtlCHzOCOC
H=CHz (VTBN)H The elastomer described above is 5ilastic (LS
-420), Sylgard (I84) from Dow Corning, Hiker ATBN (I300X1
6 etc.), CTB (2000X162), CTBN
(I300X13.1300X8.1300X31)
, VTBN (I300X23) is from ■Ube Industries, 3
F is manufactured by Monsando.

Examples of fillers include aluminum hydroxide, antimony trioxide, and red phosphorus. Reinforcing materials include woven fabrics, nonwoven fabrics, mats, and vapor made of carbon fibers, glass fibers, aramid fibers, liquid crystal polyester fibers such as Vectra, polyhenji thiazole (PBT) fibers, alumina fibers, etc.
These may be used alone or in combination of two or more.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, the abbreviations of seven symbols used in the examples are summarized below.

Aromatic diol compound represented by general formula (II) [earth] The organic group Ar2 is C.F.

It is.

-i Aromatic diamine compound represented by formula (IV) [and] HzN-Ar+-Nl2 (IV) The organic group Ar, is It is.

Furthermore, acid anhydride [earth] (4) represented by general formula (V) The organic group Art is shall be.

Example 1 A 40 liter flask was equipped with a three-way stopcock, a Dean Stark retainer, a Dimroth reflux condenser, and a syram canop. The reactor was dried under reduced pressure. 14.9g (
After adding 78 mmol of TsCl to the reaction system, the reaction system was sufficiently purged with argon. The reaction system was ice-cooled, and 30 milliliters of dry pyridine was added, being careful not to generate heat. 15g (7
8 mmol) of TMA to 110 ml of dry DM
After completely dissolving in F, it was added for 30 minutes. After continued reaction at that temperature, 30 ml of dry DMF
13.1 g (39 mmol) of an aromatic diol dissolved in water was added dropwise under water cooling. After 30 minutes, the ice bath was removed, and the reaction was continued for 1 hour at room temperature. After that, the reaction system was ice-cooled again, and 50 ml of dry DI'l was added.
22.8 g (78.0 mmol) of aromatic diamine was added to F. After 30 minutes, the ice lotus was removed, and the reaction system was heated to 60°C with an oil bath, and then heated again for 3
The reaction continued for 0 minutes. 12.8 g (78.0 mmol) of aromatic acid anhydride 4 in 10 ml of dry DMF
a was added and reacted for 2.6 hours. Thereafter, 200 ml of dry benzene was added, and 1.4 ml (theoretical amount; 1.4 ml) of reaction water was distilled off azeotropically at 145°C (lotus salt). After the reaction, the reaction solution was poured into 1000 methanol to precipitate the ester imide oligomer. The precipitated ester imide oligomer 5a was filtered under reduced pressure and dried in vacuo at 80°C for 48 hours to obtain 60°5g (yield: 97.1%) of pale yellow powder 39°5.

Using 4.5 g of this ester imide oligomer 5a,
Press molding was carried out at 30°C, 10 kg/cffl, and 1.5 hours to obtain a casting plate measuring 12 cm (width) x 12 cm (length), and 3 cm (thickness). Esterimide oligomer 5a
The results of measuring various physical properties of the cast plate are summarized in Tables 1 and 2.

Example 2 A 1 Lindl 40 flask was equipped with a three-way cock, a Dean Stark distiller, a Dimroth reflux condenser, and a ram cap. The reactor was dried under reduced pressure. 14.9g (
After adding 78 mmol of TsCl to the reaction system, the reaction system was sufficiently purged with argon. The reaction system was ice-cooled, and 30 milliliters of dry pyridine was added, being careful not to generate heat. 15g (7
8 mmol) of TMA was mixed with 110 ml of dry [I
After completely dissolving in MF, it was added for 30 minutes. After continued reaction at that temperature, 30 ml of dry DM
9.76 g (39 mmol) of aromatic diol IL dissolved in F was added dropwise while cooling with water. After 30 minutes, the ice bath was removed, and the reaction was continued for 1 hour at room temperature. After that, the reaction system was cooled with water again, and 50 ml of dry DMF was added.
26.1 g (78.0 mmol) of aromatic diamine ■
added. 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 another 30 minutes. 13 in 10ml dry DMF
．． 4 g (78.0 mmol) of aromatic acid anhydride was added and reacted for 2.6 hours. Thereafter, 200 milliliters of dry Hensen's water was added, and 1.1 milliliters (theoretical amount: 1.4 milliliters) of reaction water was distilled off azeotropically at 145° C. (lotus temperature). After reaction, methanol 100
0-Reaction during? 8 liquid was added to precipitate the ester imide oligomer. Precipitated ester imide oligomer 5
After filtering under reduced pressure and drying in vacuo at 80°C for 48 hours, 57°6 g (yield: 92.5%) of a pale yellow powder was obtained.

Using 4.5 g of this ester imide oligomer 5b,
Press molded at 30'C, 10kg/cM, 1.5 hours, 12cm (width) x 12cm (length), 2III
A casting plate having a thickness of 11 (thickness) was obtained. The results of measuring various physical properties of the esterimide oligomer 5b and its casting plate are summarized in Tables 1 and 2.

Example 3 A 1 liter 40 flask was equipped with a three-way condenser, a Dainstark Mfg vessel, a Dimroth reflux condenser, and a sylum cap. The reactor was dried under reduced pressure. 14.9g
After adding (78 mmol) of TsCI to the reaction system, the reaction system was sufficiently replaced with argon. The reaction was ice-cooled and 30 milliliters of dry pyridine was added optionally to the exotherm. 15g
(78 mmol) of TMA was completely dissolved in 110 milliliters of dry DMF and then added over 30 minutes. After continued reaction at that temperature, 30 ml of dry D
20.3 g (39 mmol) of aromatic diol lc dissolved in MF was added dropwise while cooling with water. After 30 minutes, the ice bath was removed, and the reaction was continued for 1 hour at room temperature. After that, the reaction system was cooled with water again, and then dried with 50 milliliters D)
19.3 g (78.0 mmol) of aromatic diamine 3c was added to the IF. After removing the ice lotus after 30 minutes,
After heating the reaction system to 60°C in an oil bath, continue
The reaction continued for 0 minutes. 12.8 g (78.0 mmol) of aromatic acid anhydride was added to 10 ml of dry DMF and reacted for 2.6 hours. Thereafter, 200 milliliters of dry Hensen's water was added, and 1.2 milliliters (theoretical amount: 1.4 milliliters) of reaction water was distilled off azeotropically at 145° C. (lotus temperature). After the reaction, the reaction solution was poured into 1000 d of methanol to precipitate the ester imide oligomer. The precipitated ester imide oligomer m was filtered under reduced pressure and dried in vacuo at 80'C for 48 hours to obtain 58.3 g (yield: 88.3%) of a pale yellow powder.

Using 4.5g of this ester imide oligomer 2,
Press molding at 0°C, 10 kg/cal, 1.5 hours resulted in 12IaI11 (width) x 12cm (length)
A casting plate of 5 m (thickness) was obtained. The results of various physical property measurements of oligomer 5c and its stamp plate are summarized in Tables 1 and 2.

Comparative Example 1 4.5 g of commercially available imide type thermosetting imide oligomer
When press-molded for 1.5 hours at 230°C and 10 kg/cn using
A casting plate having a thickness of 1.3 mm was obtained. The results of measuring various physical properties of the imide oligomer and its casting plate are summarized in Tables 1 and 2.

[Effects of the Invention] By using the reactive ester imide oligomer according to the present invention, it is possible to obtain a cured product that has excellent processing properties due to high resin fluidity and has extremely high heat resistance that has never been seen before.

Furthermore, 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 that has excellent solubility in solvents, adhesion to other substances, and flexibility, and is less likely to cause voids or cranks in molded products.

As described above, the reactive ester imide oligomer of the present invention has many characteristics as described above, and therefore is extremely suitable for a wide range of applications such as laminates, heat-resistant paints, polymeric materials for electronic devices, and molding materials. It is possible to provide a material with high industrial value, and its usefulness is extremely large.

Patent applicant Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, Ar_1, Ar_2, Ar_3 are divalent organic groups, and Ar_1, Ar_2, Ar_3 are The thermosetting compound may be the same type or different types. m is an integer of 1 to 30. 2. The thermosetting compound according to claim 1, wherein Ar_1 is selected from the following groups; Compound; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 4. The thermosetting compound according to claim 1, in which Ar_3 is selected from the following groups; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 5. In an inert gas atmosphere Keep the reaction system below room temperature at
After adding trimellitic anhydride dissolved in an aprotic polar solvent to a mixed solution of paratoluenesulfonic acid chloride and pyridine, a diol previously dissolved in an aprotic polar solvent is added and reacted, and then dissolved in an aprotic polar solvent. The obtained diamine is reacted by adding the necessary amount to obtain a telechelic oligoester amic acid terminated with amino groups at both ends, and then an acid anhydride dissolved in an aprotic polar solvent is added to terminate the ends, and then the non-solvent is removed. In addition, a method for producing a thermosetting compound characterized by thermally ring-closing and dehydration. 6. The production method according to claim 5, wherein the aprotic polar solvent is dimethylformamide. 7. The manufacturing method according to claim 5 or 6, wherein an organic tetracarboxylic dianhydride is copolymerized.