JPH0288675A - Imide oligomer composition - Google Patents

Abstract

PURPOSE:To obtain imide oligomer composition having excellent heat resistance and moldability and suitable for molded article of fiber reinforced cross-oriented laminated, etc., by blending specific two kind of functionalizing agents with alkenyl phenols. CONSTITUTION:The aimed composition obtained by blending (A) imide oligomer obtained by reacting A1: aromatic tetracarboxylic acid (derivative) (e.g., pyromellitic acid) with A2: condensed product of o-ethylaniline with formaldehyde and A3: maleic acid (derivative) and (B) imide oligomer obtained by reacting B1: component A1 with B2: component A2 and B3: nadic acid (derivative) or (C) polynadinimide obtained by C1: condensed product of o-ethylaniline with formaldehyde with C2: component B3 and (D) alkenyl phenol in equivalent ratio of the component A to the component B or component C of 40:60-90:10 and ratio of component D to 1 equivalent component A of 0.1-10.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to imide oligomer compositions.

Specifically, the present invention provides an imide oligomer composition comprising a specific imide oligomer (A), imide oligomer (B) or polynadimide (C), and alkenylphenol, which improves heat resistance and moldability by heating and curing. The present invention relates to an imide oligomer composition that produces a polyimide resin having excellent properties.

[Conventional technology]

Conventionally, composite materials, so-called fiber-reinforced composite materials, are known, which are composed of a resin such as epoxy resin or polyimide resin as a matrix and reinforced with fibers such as glass fiber, aramid fiber, carbon fiber, silicon carbide fiber, etc. .

To mold a fiber reinforced composite material, first, a resin film is prepared on release paper and impregnated into the fibers using the so-called true melt method, or the fibers are pre-impregnated with a varnish prepared by dissolving the resin in a solvent. This is left in a semi-dry state to remove the solvent, and then sandwiched between release paper to produce a prepreg. This prepreg is laminated in an arbitrary number or at a lamination angle, and then placed in an autoclave.
The resin is cured at a constant temperature and pressure to obtain a molded fiber-reinforced composite material.

[Problem to be solved by the invention]

When a polyimide resin is used, the resulting fiber-reinforced composite material has good heat resistance, but it requires molding at high temperatures and high pressures, and has other drawbacks, such as being susceptible to voids.

Therefore, the present inventors aimed at producing a polyimide resin with excellent heat resistance and moldability, and developed a polyimide oligomer, which is a precursor thereof, from an aromatic tetracarboxylic acid or its derivative, a condensation product of 0-ethylaniline and formaldehyde. He invented an imide oligomer obtained by reacting three components:
No. 167369 Publication 9 was carried out.

However, when molding a fiber-reinforced composite material using the imide oligomer of the above invention, for example, when prepregs are laminated with cross orientation, curing shrinkage of the resin,
Alternatively, it has been found that molding cracks occur in the resulting molded product due to thermal stress due to the difference in thermal expansion coefficients between the resin and the fibers.

On the other hand, alkenylphenol and/or polyimide containing at least one group represented by the following formula CI A method of producing a crosslinked polymer containing an imide group by reacting it with an alkenylphenol ether, optionally in the presence of a polymerization catalyst (Japanese Patent Application Laid-Open No. 2003-120003 is known). .

However, this method for producing crosslinked polymers containing imide groups improves mold cracking during molding;
It has the disadvantage that the heat resistance of the cured product decreases.

An object of the present invention is to provide an imide oligomer composition that improves mold cracking without reducing heat resistance after heat curing.

A further object of the present invention is to provide an imide oligomer composition that can be cured at relatively low temperatures and has good moldability.

[Means to solve the problem]

That is, the gist of the present invention is an imide oligomer composition comprising the following imide oligomer (A), imide oligomer (B), or polynadimide (C), and alkenylphenol.

(a) Aromatic tetracarboxylic acid or derivative thereof, 0-
A condensate of ethylaniline and formaldehyde, and
Imide oligomer (A) obtained by reacting three components of maleic acid or its derivatives (01 aromatic tetracarboxylic acid or its derivatives, a condensate of 0-ethylaniline and formaldehyde, and three components of nadic acid or its derivatives) Imide oligomer (B) obtained by reacting the components (C) Polynadimide obtained by reacting the condensate of 0-ethylaniline and formaldehyde with nadic acid or its derivative (C) In the present invention, the imide oligomer is The constituent aromatic tetracarboxylic acids include pyromellit e L 3+3', ll+yt-benzophenone tetracarboxylic acid, 3', 4t+41'-diphenyl ether tetracarboxylic acid, L?11?'
, q, q'-biphenyltetracarboxylic acid, , 2
．． 3. A, 7-naphthalenetetracarboxylic acid, λ, a,
ty-, s-thiophenetetracarvone p, 3. tt,
Examples include q, lo-perylenetetracarboxylic acid, λ9.2-bis(,?, 4t-dicarboxyphenyl 9-propane, etc.), and isomers thereof, and a plurality of these can be used.

These tetracarboxylic acid components are lower alkyl esters,
It can also be used in the form of derivatives such as dianhydrides.

In addition, as a method for producing a condensate of 0-ethylaniline and formaldehyde, which constitutes the imide oligomer and polynadimide, there is a method in which the reaction is carried out at 10 to 700°C in the presence of a strong inorganic acid such as hydrochloric acid or sulfuric acid in an aqueous medium (Unexamined Japanese Patent Publication No. Showa 9
Publication No. 731961 9 and the like can be mentioned.

In this method, in addition to the diamines 3,3'-diethyluk and ri'-diaminodiphenylmethane, triamines, tetraamines, etc. are produced as by-products, but in the present invention, these by-products can be used in the production of imide oligomers without being separated. I can do it.

It is also possible to add aniline during the condensation reaction between 0-ethylaniline and formaldehyde. At this time, instead of aniline, it is also possible to use a condensate of 0-ethylaniline to which an aniline derivative without a substituent at the p-position, such as 0-toluidine or 0-chloroaniline, is added.

The terminal functionalizing agent used in the imide oligomer (A) is maleic acid or a derivative thereof;
) and the terminal functionalizing agent used in polynadiimide (C) is nadic acid (S-norbornene-2,3-dicarboxylic acid) or a derivative thereof.

Imide oligomers (A) and (B) are prepared by heating the three components of the above-mentioned aromatic tetracarboxylic acid or its derivative, a condensate of 0-ethylaniline and formaldehyde, and a terminal functionalizing agent in the following solvent, or It can be produced by reacting in the presence of an imidization catalyst and a dehydrating agent, if necessary. Polynadimide (C) can also be produced by reacting a condensate of 0-ethylaniline and formaldehyde with a terminal functionalizing agent in the following solvent by heating or in the presence of an imidization catalyst and a dehydrating agent if necessary. can be manufactured.

Solvents used in the reaction include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, as well as phenols such as m-cresol, dimethyl sulfoxide, etc. can be mentioned.

The proportions of the three components, the aromatic tetracarboxylic acid, the condensate of 0-ethyl IJ and formaldehyde, and the terminal functionalizing agent, are appropriately determined depending on the purpose and in relation to the physical properties. For example, when the condensate of 0-ethylaniline and formaldehyde is a diamine, the molar ratio of each component (
The condensate of aromatic tetracarboxylic acid 10-ethylaniline and formaldehyde/terminal functionalizing agent] is generally n
/(n+/)/2, but if an excess amount of the terminal functionalizing agent is used to ensure the introduction of the terminal functional group, the excess amount can be purified and removed after the reaction. good. However, since the molecular weight of the imide oligomer produced is determined by the value of n, it is preferable to strictly adjust the molar ratio of tetracarboxylic acid and diamine.

Normally, the value of n can be in the range of 1 to /S. As the value of n increases, the molecular weight of the oligomer produced increases, and the viscosity of the solution increases, making it difficult to manufacture prepregs. Therefore, preferably the value of n is /~10, and the molecular weight of the oligomer is AOOθ or less. can be mentioned.

In the imide oligomer composition of the present invention, the equivalent ratio of the imide oligomer (A) to the imide oligomer (B) or polynadimide (C) can be in the range of 0:2 o-qo2io. If this equivalent ratio is larger than the above range, the heat resistance of the cured product will decrease, and if this ratio is too small, the reactivity will decrease and a higher molding temperature will be required, which is not preferable.

The alkenylphenol used in the present invention is mono-, di- or polyallylphenol, preferably dialkenylphenol.

Representative examples of dialkenylphenols include compounds represented by the following general formula CI).

(In the formula, -CH2-1C(CHs)2-1-S
O,, -8O-5-S-, -0-1-CH (C6H5)
- or -C(CHJ 2(Ca H5) C(C1(s
)2-, and n represents 0 or l. 9 Examples of alkenylphenols include co-allylphenol, haco-bis(cu-hydroxy-3-allylphenyl)propane[diallylbisphenol A], bis(q
-Hydroxy-3-allylphenyl 9-sulfone [diallylbisphenol S], gu, gu'-dihydroxy-, ?
,,? Examples include '-diallyldiphenyl, bis(cuhydroxy-3-allylphenylramethane, etc.) and methallyl compounds corresponding thereto, and a plurality of these may be used.

The alkenylphenol used in the present invention can be produced by a known method using Claisen rearrangement of alkenyl ether.

In the imide oligomer composition of the present invention, as the amount of alkenylphenol, the imide oligomer (A)
/ equivalent, 0. /~10, preferably 0.3~3
．． A range of 0 equivalents may be mentioned. If the amount is less than this range, the effect of improving mold cracking in the molded product will be small, whereas if it is more than this range, the heat resistance of the cured product will decrease, which is not preferable.

The imide oligomer composition of the present invention differs depending on the structure of its constituent components, imide oligomers (A) and (B), polynadimide (C), and alkenylphenol, and the molecular weight of the oligomer, but N,N-dimethylacetamide , N,N-dimethylformamide, amide solvents such as N-methyl λ-pyrrolidone, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran,
It is soluble in ethers such as dioxane and dimethoxyethane, and halogenated solvents such as methylene chloride and 8-1 dichloroethane.

The prepreg produced from the imide oligomer composition of the present invention can be produced by impregnating a reinforcing fiber into a solution having a weight ratio of 20-g O and drying the solution.

〔Example〕

Hereinafter, the imide oligomer composition of the present invention will be specifically illustrated by Examples, but the present invention is not limited to these Examples.

In addition, the molding crack evaluation of the molded product is [90210□/q
o] After curing the cross-oriented laminated material of 10 layers in an autoclave, post-curing was performed in an open environment, the cross section of the molded product was observed with a microscope, and the number of cranks in the center 900 layers was determined by the number of cranks per unit length equivalent (number of cranks per unit length equivalent). /crfL).

Further, the glass transition temperature (Tg) was determined by the TMA method based on the change in the thermal expansion curve. The results are shown in Table 1.

Reference Example 1 Synthesis of maleimide-terminated imide oligomer (1
) 0-ethylaniline/formaldehyde condensate (manufactured by Nippon Kaisha, trade name: Kayahard A-A) in a Gutsuro flask.
J+3'-diethyl-p4'-diaminodiphenylmethane (3,3'-EDDM) obtained by distilling under reduced pressure 5.3
．． 3! After uniformly dissolving 0.21 mol of N,N-dimethylformamide (DMF) in 43.g of N,N-dimethylformamide (DMF), 3.J,4t,ll'-benzophenonetetracarboxylic dianhydride (BTDA)33. 71 (O0/θS mol) was dispersed in DMF/Li/, and added to the above diamine solution. After stirring at room temperature for 1 hour, maleic anhydride (
MA) λλ, Alt' (0.23 mol) was added and stirred at room temperature for 7 hours to produce an amic acid oligomer. Next, acetic anhydride g s, sir as a dehydrating agent and sodium acetate as an imidization catalyst were added. Add 32 and raise the temperature, 7
The imidization reaction was carried out at 0°C for 7 hours.

After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was gradually poured into a large amount of water to precipitate an imide oligomer.

Next, the imide oligomer was separated, neutralized with suspended soda water, washed with a large amount of water, and vacuum dried at 60° C. for 60 hours. Yield is almost quantitative, number average molecular weight 9SS
A maleimide-terminated imide oligomer was obtained.

Reference example Synthesis of maleimide-terminated oligomer (2) 3.
Reference Example 1 using 3'EDDM/52.71 (0,10 mol9, BTDA/2 g, ir' (o, 70 mol), MAAs2corr (o, <t q mol) A maleimide-terminated imide oligomer having a number average molecular weight/S00 was obtained in the same manner as above.

Reference Example 3 Synthesis of maleimide-terminated imide oligomer (3
) 3.3'-E D DM / 52.62 (0,60
Malt, pyromellitic anhydride (PMD) instead of BTDA
A) 65.4' r (0.30 mol), MAA7.7
A maleimide-terminated imide oligomer having a number average molecular weight gso was obtained by using ii' (0.66 mol 9) and performing almost the same operation as in Reference Example/.

Reference example 1 Synthesis of nasiimide-terminated imide oligomer (1
) 3,,? 'E D D Mgt, g y (o, i
g mol), BTDA, gr (o, 07 mol, nadic acid (NA), ?J, -? (0,20 mol),
N-methyl-corbyrolidone (NMP)2 as a solvent
An amic acid oligomer was produced in the same manner as in Reference Example 1 using gj and g7. After being left at room temperature overnight, imidization reaction was carried out at 200°C for 2 hours.

After the reaction was completed, it was cooled to room temperature, and the homogeneous reaction solution was poured into an aqueous S-hyridine solution to precipitate the imide oligomer, which was then dispersed in water and washed, followed by vacuum drying at 100° C. for 10 hours. The yield was quantitative, and a pear-terminated imide oligomer having a l number average molecular weight/100 was obtained.

Reference example S Synthesis of nasiimide-terminated imide oligomer (2
) 3.3'-EDDMrit,gg (0.1 g mol), BT
PMDA co0 instead of DA. /r (0.09 mol, NA 33.2 g (o, 20 mol)) was used, and a pear-terminated imide oligomer having a number average molecular weight of 1000 was obtained in the same manner as in the reference example.

Reference Example 6 Synthesis of bisnadimide (3) 3,. 3'-
E D D M 2 s, Fugu (o, io mole), NA
Using 3A, /f (0.22 mol), a bisnadiimide having a number average molecular weight of SSO was obtained in the same manner as in Reference Example G.

15 Example/Reference Example/Maleimide-terminated imide oligomer 32, g?
and reference example nashiimide-terminated imide oligomer 3o,o
t and diallylbisphenol A [BPA-CA manufactured by Mitsui Toatsu Fine Co., Ltd.] / 7. /g [MA/NA/allyl = 2///2 equivalent ratio] to dorofuran (THF
)λ33. /l to prepare a varnish. This was impregnated into carbon fiber trading card T-yoo (9 manufactured by Toshisha Co., Ltd.) to prepare a prepreg.
10 layers were laminated in a 3s configuration, and 7 layers were laminated in an autoclave.
The cross-oriented laminate was molded by curing at -30°C for a period of time under kg/cr&pressure. Further, post-curing was performed in an open environment at 250°C for 1 hour, at 270°C for 1 hour, and at 0°C for 6 hours. The Tg of the cured product was 292°C, and no cracks, voids, or mold cracks were observed.0 Maleimide-terminated imide oligomer of Example/Reference Example 1 33.2t
and reference example G's nasiimide-terminated imide ribomer 209 and diallylbisphenol S (manufactured by Nippon Kayaku Co., Ltd.)/MU2G [
MA/NA/allyl-2//72 equivalent ratio] in THF
/ jT 7. ．． A varnish was prepared by dissolving it in 2F.

A prepreg was produced and cured in the same manner as in Example.

The cured product had a Tg of 320° C., and there were no voids or mold cracks in the molded product.

Example 3 Maleimide-terminated imide oligomer J'1. of Reference Example 3. A
f and pear imide-terminated imide oligomer of Reference Example S, 20
f? and diallylbisphenol A, A? ,THF
/ 5 A, g f? Yosiwanis was prepared. Example/
A prepreg was prepared in the same manner as above and cured. As a result, the cured product had a T g of 3/A° C. and a very small amount of microcracks were observed.

Maleimide-terminated imide oligomer 3'1.9 of Example/Reference Example/
ff and bisnadiimide of Reference Example B, 2Of and sialylbisphenol S/λ, /f, THF/, 33.0 g were prepared. A prepreg was produced and cured in the same manner as in Example 1. As a result, the cured product had a Tg of 30 g°C, and the molded product had no voids or mold cracks.

Example S Maleimide-terminated imide oligomer ss, oy of Reference Example
And reference example 10 of nashiimide-terminated imide oligomer? and reference example B) -s, or and diallylbisphenol A/F/2, THF/9/, A? Yosiwanis was prepared. As a result of producing and curing a prepreg in the same manner as in Example 1, the Tg of the cured product was 2 g! There were no molding defects, no voids, and no molding cracks.

Comparative Example 1 Maleimide-terminated imide oligomer soy of Reference Example/
A varnish was prepared by dissolving it in HF/2. After impregnating carbon fiber with varnish, prepreg was laminated as in Example 7.
Curing was carried out at 2SO° C. for 1 hour under a pressure of kg/cfI. As a result, molding cracks occurred in the molded product. Further, in the oven at 270℃ for 1 hour, 2W OOC for 7 hours, 320℃
As a result of post-curing at ℃ for 6 hours, Tg was 3θO ℃.

Comparative Example - Maleimide-terminated imide oligomer gua, g?
and reference example d's nasiimide-terminated imide oligomer left group, 4
7? A varnish was prepared by dissolving 3g and 3g of THFλ. In the same manner as in Example, carbon fibers were impregnated with varnish, prepregs were laminated, and cured at 0° C. for 7 hours under a pressure of 7 kg/d. As a result, molding cracks occurred in the molded product. Furthermore, after curing in the open air at θ℃ for 1 hour, 290℃ for 7 hours, and 3λ0℃ for 2 hours, the result was a Tg of 3λ.
The temperature was 0°C.

Comparative Example 3 Maleimide-terminated imide oligomer f of Reference Example 2.
9? and diallylbisphenol A/7. / S'
[MA/Allyl-///equivalent ratio] was dissolved in THFλ332 to prepare a varnish. Prepregs were laminated in the same manner as in Example 1, and cured at 220=19-°C under pressure of 7 kg/cr to obtain a molded product. Furthermore, 1 at λ3゜℃
Time, 1 hour at 2Sθ℃, 7 hours at 270℃, Kota 0℃
As a result of post-curing at 320 °C for 7 hours and 2 hours at 320 °C,
There were no molding cracks in this molded product, and the Tg was 3°C.

Table 1 20~ [Effects of the Invention] The present invention uses two specific types of functionalizing agents and alkenylphenols, and when used as a raw material for a fiber-reinforced cross-oriented laminate molding. It has been discovered that an imide oligomer composition can be obtained that exhibits no molding cracks and exhibits excellent heat resistance.

The imide oligomer composition of the present invention can be heat-cured to yield a fiber-reinforced composite material having excellent heat resistance. Furthermore, mold cracking does not occur during heat curing.

When the imide oligomer composition of the present invention is dissolved in the above-mentioned solvent, the viscosity of the resulting solution is low, so impregnation into reinforcing fibers is good, and prepreg production is easy.

Furthermore, the imide oligomer composition of the present invention is soluble in organic solvents, and contains various additives, reinforcing materials, such as reactive diluents such as diallyl phthalate, triallyl isocyanurate, and divinylbenzene, carbon powder, various metals, It is easy to mix metal oxides, silicate materials, asbestos, etc., and can be used not only for fiber-reinforced composites but also for producing adhesives, coating materials, molded products, etc. with good heat resistance.

Out wish Man Director of Industrial Technology Agency

Claims (1)

[Claims] (1) An imide oligomer composition comprising the following imide oligomer (A), imide oligomer (B) or polynadimide (C), and alkenylphenol. (a) Imide oligomer obtained by reacting three components: aromatic tetracarboxylic acid or its derivative, a condensate of o-ethylaniline and formaldehyde, and maleic acid or its derivative (A) (b) Aromatic tetracarboxylic acid or its derivative Imide oligomer (B) obtained by reacting three components: carboxylic acid or a derivative thereof, a condensate of o-ethylaniline and formaldehyde, and nadic acid or a derivative thereof (c) Condensation of o-ethylaniline and formaldehyde Polynadimide (C) obtained by reacting a compound with nadic acid or a derivative thereof