JPS6176459A - Imide containing acetylene group - Google Patents

Abstract

NEW MATERIAL:The acetylene group-containing imide compound of formula I (X is group of formula II, CH2, S, O, SO2, CO, CF2, group of formula III or nil, n is 0 or 1). EXAMPLE:2,2-Bis{4-[N-(3-ethynylphenyl)phthalimid-4-oxy]phenyl}-propane. USE:Useful as a varnish for impregnation, lamination, adhesion, film, or prepreg in the form of an organic solvent solution, and useful as a molding resin by compounding with an inorganic filler, flame-retardant, pigment, etc. It can be cured under a relatively mild condition, and the cured material is an insoluble and infusible heat-resistant polymer having remarkable heat-resistance and excellent mechanical properties. PREPARATION:The compound of formula I can be prepared, e.g. by reacting the ether group-containing aromatic tetracarboxylic acid of formula IV with the acetylene compound of formula V, and imidating the reaction product.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an acetylene group-containing imide useful as a resin for prepregs, casting materials, and laminate materials.

[Prior art and its problems]

In recent years, as rotating electrical equipment, electrical wiring circuit boards, etc. have become larger in electric capacity, smaller, and lighter, there has been a demand for thermosetting resins with extremely high heat resistance as insulating materials used in these devices. has been done. In addition, as the performance of aircraft composite materials increases, there is a demand for improved heat resistance of thermosetting resins used as matrix resins of composites for structural members.

On the other hand, research has been carried out on various heat-resistant polymer materials, but in the case of heat-resistant polymer materials for multilayer plate bodies, paints, and impregnations, it has been found that no voids remain in the cured product. This is one of the important requirements. Addition-curing heat-resistant polymer materials are known as materials that meet this requirement.

As such an additive type heat-resistant polymer material,
No. 6-23250 discloses addition polymerization type polyimide resins such as bismaleimide resin (trade name: Kelimide, manufactured by Loos-Boulin). Curing by reaction (Michael addition reaction) and double bond polymerization 1~,
It becomes a cured resin that provides excellent heat resistance. However, bismaleimide resin has a slow curing speed and takes a long time to cure. Furthermore, this resin contains a structure derived from Michael addition reaction, and its long-term use is limited to 260°C at most.

Similarly, acetylene-substituted polyimide oligomers that cure by addition reaction have been proposed to avoid the release of gaseous products during curing (% opening/closing 50-53
Publication No. 48). This acetylene-substituted polyimide oligomer ij is cured at 200 to 300°C [7] The thermal decomposition onset temperature of the cured product is 460°C according to thermal loss characteristics (TGA)
It has extremely excellent heat resistance. However, this acetylene-substituted polyimide oligomer has a high melting point and
Poor moldability due to poor solubility. In addition, the price is high because the raw material synthesis is complicated, the yield is low, and the production is difficult.

As described above, this acetylene-substituted polyimide oligomer has high performance, but there are many points that need improvement.

[Problems to be Solved by the Invention] The present invention provides a heat-resistant polymer material that can be cured by heating without emitting gaseous products, the obtained cured product has a high degree of heat resistance, and has excellent moldability. This gives an acetylene group-containing imide that gives the following.

[Structure of the invention]

The present invention provides an acetylene-terminated imide containing an ether group represented by the following formula (I).

The numeral H8 is n1l (the phenyl group is directly bonded to the adjacent phenyl group), and n is 0 or 1. ] (Production method) An acetylene group-containing imidoke represented by the above formula (,1), an ether group-containing aromatic tetracarboxylic acid represented by the following formula (lI) or (I), a lower alkyl tetraester thereof,
Alternatively, the corresponding diacid anhydride and the acetylene compound represented by the general formula (■) are reacted to form an amic acid or its lower It is produced by obtaining an alkyl ester compound and imidizing it.

(v) [In formula buttons, (lIl) and (7), X and n are the same as in formula (1), and are RtiH or an alkyl group having 1 to 4 carbon atoms. ] As the ether group-containing aromatic tetracarboxylic acid represented by the above formulas (Il'l and (n), its lower alkyl tetraester, or its corresponding dianhydride, 2,
2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propanedioic anhydride, bis(4-(3,4-dicarboxyphenoxy)phenyl)methanedioic anhydride,
4.4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4.4'-bis(3,
4-dicarboxyphenoxy) diphenyl sulfide diacid anhydride, 4.4'-bis(3,4-dicarboxyphenoxy) diphenylether diacid anhydride, 4.4'-bis(3,4-dicarboxyphenoxy) diphenyl Sulfonic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)penzophenone dianhydride, bisC4-
(,3゜4-dicarboxyphenoxy)phenyl]difluoromethanedioic anhydride, 2,2-bis(4-(3,4
-dicarboxyphenoxy)phenyl) -1,1,L
.

3.3.3-hexafluoroborobanniic anhydride, 4.
4'-bis(3,4-dicarboxyphenoxy)piphenyl, 1,4-bis(3,4-dicarboxyphenoxy)benzenioic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzenioic acid anhydride, 1,2-bis(3,4-dicarboxyphenoxy)benzenic acid anhydride, 2,2-bis(4-2,3-dicarboxyphenoxy)phenyl]furopaniic acid mhydrate, bis(: 4 −
(2,3-dicarboxyphenoxy)phenyl]methanedioic anhydride, 4.4'-bis(2,3-dicarboxyphenoxy)diphenylsulfide diacid anhydride, 4.4'
-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4.4'-bis(2,3-dicarboxyphenoxy)diphenylsulfonic anhydride, 4
．． 4'-bis(2,3-dicarboxyphenoxy)penzophenone dianhydride, bis[4-(2,3-dicarboxyphenoxy)phenyl]difluoromethanedioic anhydride, 2,2-bis(4-(2 ,3-dicarboxyphenoxy)phenyl) -1,1,1,3,3,3-hexafluoropropanedioic anhydride, 4.4'-bis(2,3
-dicarboxyphenoxy)biphenyldicic anhydride, 1
, 4-bis(2,3-dicarboxyphenoxy)benzenic anhydride, 1,3-bis(2,3-dicarboxyphenoxy)benzenic anhydride, 1,2-bis(2,3
-dicarboxyphenoxy)benzenioic anhydride, etc., and the corresponding carboxylic acids or alkyl esters thereof can be used.

The aminophenylacetylene represented by the formula (translation) can be obtained by using p-aminophenylacetylene, m-aminophenylacetylene, or 0-phenylacetylene.

Containing an acetylene group represented by formula (1) (for example, 2,2-bis[a-[N-(3-ethynylphenyl)phthalimido-4-oxy]phenyl)
Flopane, bis('4''4N-(3-ethynylphenyl)phthalimido-4-,txy]phenyl)methane, 4
,4'-bis(N-(a-ethynylphenyl)phthalimido-4-oxy]diphenyl sulfide, 4.4'-
Bis(N-(')-ethynylphenyl)phthalimide-
4-oxy]diphenyl ether, 4,4'-bisCN
-<3-ethynylphenyl)phthalimido-4-oxy]diphenylsulfone, 4,4'-bis[N-(3-ethynylphenyl)phthalimido-4-oxy]benzophenone, bis(4-(N-(4-ethynyl) phenyl)phthalimido-4-oxyphphenyl)difluoromethane, 2,2-bis(4-[N-(4-ethynylphenyl)
Phthalimido-4-oxyphphenyl) -1,1,1
, 3,3,3-hexafluoropropane, 4,4'-bis[N-(3-ethynylphenyl)phthalimide-3-
oxy]biphenyl, 1,4-bis(N-(3-ethynylphenyl)phthalimido-4-oxy]benzene, 1
, 3-bisCN'-(3-ethynylphenyl)phthalimi)'-4-4xy]benzene, 1.2nibis(N-(
Examples include 3-ethynylphenyl)phthalimido-4-oxy]benzene.

In producing the novel ether group-containing acetylene-terminated amidic acid compound of the present invention, the general formula (V
) The amount of aminophenylacetylene used is
Ether group-containing diacid anhydride 1 represented by the general formula W
It is used in a range of 2.0 to 10 moles.

Preferably, 2.2 to 4.
0 mol is suitable.

As a solvent, a solvent inert to the ether-based dianhydride and aminophenylacetylene, such as dimethylformamide, dimethylacetamide, N-methyl-
Aprotic dipolar solvents such as pyrrolidone and dimethyl sulfoxide are used.

In addition, the reaction temperature and reaction time are room temperature to 200°C, 30 minutes to
The range is 5 hours. Preferably, 50°C to 100°C,
It is appropriate to react for 1 to 3 hours.

Furthermore, the acetylene-terminated imide compound containing an ether group in the present invention can be produced by imidizing the acetylene-terminated amic acid containing an ether group or its lower alkyl ester by a known method. As the imidization reaction, a method using an imidization agent such as acetic anhydride or a mixture of benzene and cresol is known. When acetic anhydride is used, the dehydration reaction is carried out using 1 to 20 equivalents of acetic anhydride per equivalent of amine group. Preferably, 2 to 10 equivalents are appropriate.

When a benzene-cresol mixture is used, the water produced is removed by azeotropic dehydration, and the reaction is allowed to proceed until no water is produced.

The acetylene-terminated imide compound containing an ether group represented by formula (1) of the present invention can be cured under relatively mild conditions. Furthermore, the obtained cured product has excellent heat resistance and provides an insoluble, infusible, heat-resistant polymeric material with excellent mechanical properties and the like.

The acetylene-terminated imide compound containing an ether group represented by formula (1) of the present invention can be used for impregnation, lamination, adhesives, films, etc. by making it into an organic solvent solution (FESS).
It is useful as a festival for prepreg. In addition, it is useful as a molding resin by blending inorganic brightening agents, flame retardants, pigments, etc.

Next, the present invention will be illustrated in more detail with examples.

All parts in the text are by weight.

Example 1 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl) was placed in a 40 flask with a capacity of 1 t equipped with a stirring device, a reflux device, a thermometer, and a dropping funnel with a nitrogen inlet tube under a nitrogen atmosphere. 52 parts of propane diM were dissolved in 400 parts of dry N,N-dimethylformamide.

Next, 29 parts of m-aminophenylacetylene was added dropwise into the flask while stirring. After that, 80℃~100℃
The reaction was carried out for 2 hours at a temperature of .degree. Further, 102 parts of acetic anhydride was added, and the mixture was reacted at reflux temperature for 3 hours.

After the reaction was completed, the reaction solution was cooled and poured into 10 times the volume of water to precipitate the reaction product, filtered and washed, and heated at 60°C under reduced pressure.
I let it dry for a day and night.

Product yield was 68 parts. When this product was analyzed by IR spectrum and NMR spectrum, 2,
It was confirmed to be 2-bis+4-[N-(3-ethynylphenyl)phthalimido-4-oxyphphenyl)propane. The yield was 95 cm. Melting point is 105-1
The temperature was 07°C.

The IR spectrum of this compound is shown in FIG.

Example 2 4.4′-bis(3,4dicarboxyphenoxy)diphenyl instead of 52 parts of 2.2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propanihydride in Example 1 Except for using 51 parts of sulfide-anhydride
[68 parts of a product were obtained in exactly the same manner as in Example 1.

When this product was analyzed by IR spectrum and NMR spectrum, it was confirmed that it was 4,4'-bis(N-(,3-ethynylphenyl)phthalimido-4-oxy]diphenylsulfur, phyto.

The yield was 96%. Also melting point 1j166-168℃
Met. The IR spectrum of this compound is shown in FIG.

Application Example 1 The novel ether group-containing acetylene-terminated imide compounds obtained in Examples 1 and 2 were
When heated at 300° C. for 4 hours, an insoluble and infusible cured product was obtained. Further, when differential thermal analysis of these novel ether group-containing acetylene-terminated imide compounds was performed, all of the compounds showed exothermic peaks around 200 to 300°C.

At this point, it is thought that a cyclization trimerization reaction or polymerization of the acetylene group occurs, and the novel ether group-containing acetylene-terminated imide compound of the present invention becomes crosslinked and networked.

=14- The heat loss characteristics (TGA) of the above two types of cured products are shown in Table 1. As shown in Table 1, it can be seen that the cured product obtained from the novel ether group-containing acetylene-terminated imide compound of the present invention has excellent heat resistance.

Table 1 Measurement in air at a heating rate of 10°C/min Application example 2 The acetylene-terminated imide compounds containing ether groups obtained in Examples 1 and 2 were dissolved at 120 to 180°C, and a release agent was applied. Pour into a metal mold and heat at 220℃.
It was cured at 250°C and 280°C for 2 hours each. When removed from the mold, a transparent brown molding material was obtained.

Application Example 3 The novel ether group-containing acetylene-terminated imide compounds obtained in Examples 1 and 2 were each dissolved in an N,N-dimethylformamide/acetone mixed solvent to prepare a solid content of about 50 Chiwanis.

A glass cloth was impregnated with the above fabric and dried at 150° C. for 10 minutes to prepare a prepreg with a resin impregnation amount of 40 to 50 inches. Next, 8 sheets of each prepreg were stacked and the pressure was 20~
4oKy/all, cured for 1 hour at a temperature of 110°C to 170°C, and further cured at 200°C, 220°C, 250°C, 280°C
Each curing was performed for 1 hour to produce a laminate with a thickness of approximately 1.6B.

The obtained laminate had no internal bubbles or peeling, and had excellent surface smoothness.

[Brief explanation of the drawing]

Figure 1 shows the IR spectrum of 2,2-bis[:4-N-(3-ethynylphenyl)phthalimido-4-oxy]phenylpropane, and Figure 2 shows the IR spectrum of 4,4-bis[N-3(3
-ethynylphenyl)phthalimide-4-oxy]diphenyl sulfide. Patent Applicant Mitsubishi Yuka Co., Ltd. Agent Patent Attorney Hidetoshi Furukawa Agent Patent Attorney Masa Hisashi Hase 171

Claims (1)

[Claims] 1) An acetylene group-containing imide represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -C
H_2-, -S-, -O-, -SO_2-, -CO-,
-CF_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or nil, and n is 0 or 1. ]