JPH059222A - Polymerization of alkenyl-substituted nadiimides - Google Patents

Abstract

PURPOSE:To provide a polymerization process wherein the polymerization and curing reaction can be effected within a short time at a relatively low temperature, a mixture of an alkenyl-substituted nadimide, its mixture or its oligomer with a catalyst can be stored for a long time, and the reaction can be further accelerated by irradiation with ultraviolet rays. CONSTITUTION:A process for polymerizing an alkenyl-substituted nadimide by using an onium compound as a catalyst for polymerizing the imide, its mixture or its oligomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing alkenyl-substituted nadiimides. More specifically, it relates to a novel catalytic polymerization method using an onium compound as a catalyst when polymerizing an alkenyl-substituted nadiimide.

[0002]

2. Description of the Related Art Materials used with the progress of science and technology are required to have higher performance and higher functions, and various materials have been developed to meet the demand. For example, various high-performance polymers called so-called super engineering plastics (engineering plastics) such as polyetherketone, polyphenylene sulfide, and polyimide are on the market, and expectations for polyimide are particularly high.

Aromatic imides having a norbornene ring at both ends (bisnadiimide) have been attracting attention as raw materials for addition type polyimide resins having extremely high heat resistance, and some of them have been put to practical use as so-called matrix for advanced composite materials. There is. However, aromatic bisnadiimide generally has a high melting point and poor solubility in a solvent, and thus is difficult to handle. Further, since nadiimide has poor reactivity, harsh reaction conditions (for example, high temperature such as 300 ° C.) are required to increase the molecular weight of the compound.

However, under such reaction conditions, in addition to the intended high molecular weight reaction, the reverse Diels-
Part of the Alder reaction occurs, and the highly volatile cyclopentadiene generated there is significant bubbles (voids) in the molded body.
It is said to cause the.

In order to suppress such foaming, the molding method is limited to a method of reacting under high temperature and pressure (for example, an autoclave molding method), or an acid anhydride (ester) as a raw material of imide and a diamine are used as a solvent. There is a drawback in that its usage is considerably limited, such as melting and oligomerization to use as a varnish.

On the other hand, in addition to adopting the above-mentioned means for suppressing the foaming, the norbornene ring is suitable so as not to generate a volatile component even if the curing reaction temperature is lowered or the Diels-Alder reaction occurs. Various methods of introducing a substituent are also under study.

As one of them, various methods of introducing an allyl group have been proposed (for example, JP-A-59-80662, JP-A-60-124619 and JP-A-60-1).
78862, JP 61-18761, JP 61-73710, JP 61-19755.
6, JP-A-62-111967, JP-A-6-6
2-253607, JP-A-63-95263, JP-A-63-150311, JP-A-63-1.
70358, JP-A-63-310884,
JP-A-63-317530 and JP-A-1-1975.
No. 16, etc.).

According to these, by introducing the allyl group, the melting point of the raw material imide is lowered, the solubility in the solvent is increased, the curing temperature can be lowered to some extent, and no volatile component is generated during curing, Moreover, it is stated that the physical properties of the obtained cured product were hardly deteriorated.

However, in such a thermal polymerization method, even though the curing temperature is low, it is lowered to 240 to 250 ° C. at the most, and the reaction time is long. A method using a catalyst has been proposed (JP-A-60-181130). In this method, the polymerization temperature is 160 to 260 ° C., and it has been disclosed that an acid or an acid-releasing acid derivative is used as a catalyst.

However, in many cases, such a typical cation catalyst has a high polymerization initiation ability, so that it is impossible to store the imide and the catalyst in a mixed state for a long time. The catalyst had to be mixed. Therefore, when the same quality is manufactured little by little, the quality is not stable, and it takes a lot of time to mix.

[0011]

The object of the present invention, which solves the above-mentioned drawbacks of the prior art, is to carry out polymerization and curing reactions in a short time at temperatures as low as those of typical cationic catalysts. In addition, the alkenyl-substituted nadiimide, a mixture thereof or a mixture of an oligomer thereof and a polymerization catalyst can be stored for a long time, and further, an alkenyl-substituted catalyst using a catalyst that further accelerates the polymerization and curing reaction by ultraviolet rays. Another object is to provide a method for polymerizing nadiimide.

[0012]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the object can be achieved by using a series of compounds commonly called onium salts as catalysts. The present invention has been completed.

That is, the gist of the present invention is a method for polymerizing an alkenyl-substituted nadiimide, which comprises using an onium compound as a catalyst when polymerizing an alkenyl-substituted nadimide, a mixture thereof or an oligomer thereof.

In more detail, the alkenyl-substituted nadiimide has the general formula (I)

[Chemical 1] [Wherein, R ¹ R ² is independently selected hydrogen or a methyl group, n represents an integer of 1 to 2, and when n = 1,
R ³ is a C _{1 to} C ₁₂ alkyl group, a C _{3 to} C ₆ alkenyl group, a C _{5 to} C ₈ cycloalkyl group, a C _{6 to} C ₁₂ aromatic group, a benzyl group, and 1 to 1 of these groups. 3 groups or substituted with a hydroxyl group hydrogen _{- {(C q H 2q O} ) t (C r H 2r O) u
C _s H _{2s + 1} } (wherein q, r and s are independently selected integers of 2 to 6, t is an integer of 0 or 1 and u is an integer of 1 to 30) group or -C ₆ H ₄
-T-C ₆ H ₅ {where T is _{-CH 2 -, - C (CH} 3) 2
-, - CO -, - O -, - S -, - SO 2 -} groups represented by or 1-3 hydrogen of these groups is a group substituted by a hydroxyl group, when n = 2, R ₃ is -C _p H _2p - alkylene group (wherein p is an integer of 2 to 20) represented by, C ₅ ~
A cycloalkylene group _{C 8, - {(C q} H 2q O) t (C r H
_{2r O) u C s H 2s} } - ( provided that q, r, s is an integer of from 2 to 6 selected independently, t is an integer of 0 or 1, u is 1
An integer of 30), a polyoxyalkylene group represented by C ₆
-C ₁₂ aromatic _{group, -C 6 H 4 -T-C} 6 H 4 - { where T
Is _{-CH 2 -, - C (CH} 3) 2 -, - CO -, - O-,
_{-OC 6 H 4 C (CH 3} ) 2 C 6 H 4 O -, - S -, - SO
₂₋ } or a group obtained by substituting 1 to 3 hydrogens of these groups with a hydroxyl group. ]] Is represented.

A typical example thereof is N-methyl-
Allylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-methyl-methallylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N-methyl-methallylmethylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (2-ethylhexyl) -allylbicyclo [2.
2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-isopropenyl-
Allylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide, N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene -2,3-Dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2'-hydroxyethyl)-
Allylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- (2'-hydroxyethyl) -allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- (2'-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(2 ', 2'-dimethyl-3'-hydroxypropyl)
-Allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 ', 3'-dihydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2', 3'-dihydroxypropyl) -allyl Methylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (3'-hydroxy-1'-propenyl) -allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (4'-hydroxy-cyclohexyl) -allylmethylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (4'-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4'-hydroxyphenyl) -allylmethylbicyclo [2.2] .1] hept-5-ene-2,
3-dicarboximide, N- (4'-hydroxyphenyl) -methallylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (4'-hydroxyphenyl) -methallylmethylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (3'-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3'-hydroxyphenyl) -allylmethylbicyclo [2.2] .1] hept-5-ene-2,
3-dicarboximide, N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2 '-(2 "-
Hydroxyethoxy) ethyl} -allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- {2 '-(2 "-hydroxyethoxy) ethyl} -allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- {2'-
(2 "-hydroxyethoxy) ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {2 '-(2" -hydroxyethoxy) ethyl}- Methallylmethylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
[2 ′-{2 ″-(2 ″ ″-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 ′
-{2 "-(2"'-hydroxyethoxy) ethoxy}
Ethyl] -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- [2 '
-{2 "-(2"'-hydroxyethoxy) ethoxy}
Ethyl] -methallylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- {4'-
(4 "-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4 '-(4"-
Hydroxyphenyl isopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- {4 '-(4 "-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-ethylene-bis (meta) Rilbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N,
N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylbicyclo [2.2. 1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide] ), N, N′-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N,
N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), 1,2-bis {3 '-(allylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximido) propoxy} ethane, 1,2-bis {3'-
(Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane, 1,2-bis {3 '-(methallylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximido) propoxy} ethane, bis [2 '-{3 "-(allylbicyclo [2.2.1] hept-5-ene-2,3 −
Dicarboximido) propoxy} ethyl] ether,
Bis [2 '-{3 "-(allylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximido) propoxy} ethyl] ether, 1,4-bis {3 '-(allylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximido) propoxy} butane, 1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) propoxy} Butane, N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), N, N'-p
-Phenylene-bis (allylmethylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) ), N, N′-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide), 2,2-bis [4'-
{4 ″-(allylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximido) phenoxy} phenyl] propane, 2,2-bis [4 '-{4 "-(allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide) phenoxy} phenyl]
Propane, 2,2-bis [4 '-{4 "-(methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenoxy} phenyl] propane, bis {4- (Allylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1]]
Hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylbicyclo [2.
2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl (Imido) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximido) phenyl} ether, bis {4-
(Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5-ene- 2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide)
Phenyl} sulfone, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis {4- (methallylbicyclo [2.2. 1] hept-5-ene-2,3-
Examples thereof include, but are not limited to, dicarboximido) phenyl} sulfone.

The onium salts used in the present invention include iodonium compounds [R ₂ I] ⁺ X ⁻ , ammonium compounds [R ₄ N] ⁺ X ⁻ , sulfonium compounds [R ₃ S] ⁺ X ⁻ , stannonium. Compound [R ₃ Sn]
⁺ X ⁻ , phosphonium compound [R ₄ P] ⁺ X ⁻ , arsonium compound [R ₄ As] ⁺ X ⁻ , stibonium compound [R ₄ S
b] ⁺ X ⁻ , an oxonium compound [R ₃ O] ⁺ X ⁻ or a selenonium compound [R ₃ Se] ⁺ X ⁻ , preferably an iodonium compound [R ₂ I] ⁺ X ⁻ , an ammonium compound [R ₄
N] ⁺ X ⁻ , a sulfonium compound [R ₃ S] ⁺ X ⁻ or a stannonium compound [R ₃ Sn] ⁺ X ⁻ (wherein R is a substituted or unsubstituted aromatic group, or a linear or branched alkyl group). Or an alkenyl group, which may be the same or different and X ⁻ represents an anion having weak nucleophilicity or non-nucleophilicity).

Examples of the substituent of the above-mentioned substituted aromatic group include C ₁ -C ₁₀ alkyl groups and halogens, and the above straight-chain or branched-chain alkyl groups are C ₁ -C.
_10, the alkenyl group is suitably one of C ₂ -C _10.
X ⁻ is an anion having weak or no nucleophilicity and is, for example, Cl ⁻ , Br ⁻ , I ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , ClO _{4
^{-, PF 6 -, CF 3}} SO 3 -, SbF 6 - or SbCl ₆ ^-,
Preferably Cl ⁻ , Br ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , Cl
O ₄ ⁻ , PF ₆ ^−, CF ₃ SO ₃ ^{− and the} like can be mentioned.

Specifically, as the iodonium compound,
For example, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium perchlorate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, (p-methoxyphenyl) phenyliodonium tetra Fluoroborate, di (2-nitrophenyl) iodonium hexafluoroarsenate, di (p
-Tolyl) iodonium hexafluorophosphate,
Examples of di (p-chlorophenyl) iodonium hexafluoroarsenate and ammonium compounds include:
Benzyltriethylammonium chloride, benzyltriethylammonium bromide, phenyltrimethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium perchlorate, tetraethylammonium tetrafluoroborate, m-trifluoromethylphenyltrimethylammonium bromide, tetra- Examples of the sulfonium compound such as n-butylammonium trifluoromethanesulfonate include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroarsinate, tri (p-methoxyphenyl) sulfonium hexafluorophosphate, tri (p-tolyl) sulfonium. Tetrafluoroborate, dimethylphenacyl sulfoni Examples of stannonium compounds such as muhexafluorophosphate and dimethylphenacylsulfonium tetrafluoroborate include triphenylstannonium chloride, triphenylstannonium bromide, tri-n-butylstannonium bromide, and benzylphenylstannonium. Examples of the phosphonium compound such as chloride include methyltriphenylphosphonium iodide, methyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, 3
Examples of the arsonium compound such as -bromopropyltriphenylphosphonium bromide and the like include benzyltriphenylarsonium chloride, tetraphenylarsonium bromide, tetra-n-butylarsonium chloride and the like, and the stibonium compound such as
Examples of oxonium compounds such as benzyltriphenylstibonium chloride and tetraphenylstibonium bromide include triphenyloxonium chloride,
Examples of triphenyloxonium bromide and selenonium compounds include triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroarsenate, triphenylselenonium hexafluoroantimonate, p- (t-butylphenyl) diphenylseleno. Examples thereof include, but are not limited to, aluminum hexafluoroarsenate and the like.

In the present invention, the amount of the onium compound used as the catalyst is not particularly limited and may be appropriately selected within a wide range, but is usually 0.001 to 10 mol%, preferably 0.01 to 1 mol%. It is better to let them do it.

As one of the methods for polymerizing and curing the alkenyl-substituted nadiimide, a mixture thereof or an oligomer thereof, the imide and the catalyst are powder-mixed or melt-mixed and then molded by casting, injection molding, compression molding or the like. Polymerization is performed by heating at a temperature of 120 to 250 ° C., preferably 150 to 240 ° C. for 0.01 to 5 hours, preferably 0.05 to 2 hours.

As another method, these imides and the catalyst are mixed without a solvent or in the presence of a solvent, and the mixture is cast or coated, and the solvent is removed if necessary.
At a temperature of 0 to 230 ° C, preferably 80 to 200 ° C,
It can be polymerized and cured by heating and irradiation with ultraviolet rays for 0.001 to 1 hour, preferably 0.005 to 0.5 hour to obtain a molded product, a thin film, or a coating film.

It is also possible to use an alkenyl-substituted nadimide as an adhesive or a filler by utilizing such curing and polymerization methods.

The molded body, thin film, coating film, and adhesive body thus obtained may be further heat-treated at a temperature of 200 to 350 ° C. for 0.5 to 30 hours, if necessary.

The catalyst can also be used for the purpose of oligomerizing an alkenyl-substituted nadiimide.

In this case, the conditions are milder than the above curing reaction, that is, the amount of the catalyst used is 0.001 to 1 mol%,
Preferably 0.001-0.5 mol%, 100-200
At a temperature of 100C, preferably at a temperature of 100-180C,
The reaction is carried out for 0.01 to 2 hours, preferably 0.01 to 1 hour. It is possible to use ultraviolet irradiation together during heating.

During the polymerization, curing and oligomerization, various fillers such as glass fiber, carbon fiber, and
Metal fibers, calcium phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay, talc, quartz powder, carbon black and the like are alkenyl-substituted nadiimides, mixtures thereof or oligomers thereof 100 10 to 500 parts may be mixed with parts.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples, but the contents of the present invention are not limited to these. Examples 1-5 Bis {4- (allylbicyclo [2.2.1] hept-5
To 5 g of -ene-2,3-dicarboximido) phenyl} methane powder, various onium compound powders of 0.
When 05 g was uniformly mixed and a part of the mixture was placed on a hot plate exposed to air at 220 ° C. and the stirring and gelling time was measured while maintaining the temperature, the results shown in Table 1 were obtained.

Comparative Example 1 The same experiment as in Example 1 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 1 were obtained.

Table 1 Onium compound gelation time Example 1 Diphenyliodonium hexafluoro 4 minutes 00 seconds Phosphate 2 Dimethylphenacylsulfonium hexa 3 minutes 30 seconds Fluorophosphate 3 Diphenyliodonium tetrafluoro 6 minutes 50 seconds Borate 4 Diphenyliodonium perchlorate 2 Minutes 00 seconds 5 benzyltri-n-butylammonium 8 minutes 30 seconds Bromide Comparative Example 1 --- 15 minutes 40 seconds

Example 6 Bis {4- (allylbicyclo [2.2.1] hept-5
0.05 g of diphenyliodonium perchlorate powder was uniformly mixed with 5 g of -ene-2,3-dicarboximido) phenyl} methane powder, and the mixture was placed on a glass plate heated to 120 ° C. and stirred to melt-mix. When the product was heated at 220 ° C. for 5 hours under exposure to air and left to stand, a cured product having a glass transition temperature of 230 ° C. was obtained.

Example 7 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane powder (5 g) was uniformly mixed with dimethylphenacylsulfonium hexafluorophosphate powder (0.05 g),
The mixture was placed on a glass plate heated to 120 ° C., stirred, melt-mixed, and heated at 220 ° C. for 5 hours while being exposed to air, and allowed to stand, whereby a cured product having a glass transition temperature of 218 ° C. was obtained.

Examples 8 to 19 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane powder (5 g) was mixed with various onium compound powders shown in Table 2.
When 05 g was uniformly mixed and a part of the mixture was placed on a hot plate exposed to air at 240 ° C. and the gel time for stirring was measured while maintaining the temperature, the results shown in Table 2 were obtained.

Comparative Example 2 The same experiment as in Example 8 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 2 were obtained.

Table 2 Onium compound gelation time Example 8 Diphenyliodonium hexafluoro 0 minutes 50 seconds Phosphate 9 Dimethylphenacylsulfonium hexa 1 minute 30 seconds Fluorophosphate 10 Diphenyliodonium hexafluoro 5 minutes 00 seconds Arsenate 11 Triphenylsulfonium hexafluoro 5 minutes 30 seconds Arsenate 12 tetra-n-butylammonium tri 4 minutes 30 seconds Fluoromethane sulfonate 13 Diphenyliodonium tetrafluoro 3 minutes 20 seconds Borate 14 Dimethylphenacylsulfonium 3 minutes 40 seconds Tetrafluoroborate 15 Tetra-n-butylammonium 4 Minutes 40 seconds Perchlorate 16 Diphenyliodonium perchlorate 0 minutes 40 seconds 17 Benzyltri-n-butylammo Um 4.5 minutes bromide 18 diphenyliodonium chloride 7 minutes 00 seconds 19 triphenyl Stan Roh chloride 7 minutes 10 seconds Comparative Example 2 --- 9 minutes 20 seconds

Example 20 Bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane oligomer previously oligomerized by heating (melting point: 150 ° C.) ) To 100 parts of powder are uniformly mixed 1 part of diphenyliodonium perchlorate powder,
A mixture obtained by heating and melting and mixing at 0 ° C. was left at 100 ° C. for 5 hours and further at room temperature for 10 days, but no gel was formed.
Next, the crushed powder is charged into a mold, and under pressure, 2
Bending strength was 8.7 when hot pressed at 20 ° C for 5 hours.
A cured product having a Kg / mm ² and a glass transition temperature of 230 ° C. was obtained.

Examples 21-23 Bis {4- (allylbicyclo [2.2.1] hept-5
To 5 g of -ene-2,3-dicarboximido) phenyl} methane powder, various onium compound powders of 0.
When 05 g was uniformly mixed and a part of the mixture was placed on a hot plate exposed to air at 200 ° C. and the gel time for stirring was measured while maintaining the temperature, the results shown in Table 3 were obtained.

Comparative Example 3 The same experiment as in Example 21 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 3 were obtained.

Table 3 Onium compound gelation time Example 21 Diphenyliodonium hexafluoro 5 minutes 00 seconds Phosphate 22 Dimethylphenacylsulfonium hexa 8 minutes 40 seconds Fluorophosphate 23 Diphenyliodonium perchlorate 4 minutes 10 seconds Comparative Example 3 ----- 30 minutes

Example 24 Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} methane powder (5 g) was uniformly mixed with dimethylphenacylsulfonium hexafluorophosphate powder (0.05 g),
The mixture was placed on a glass plate heated to 120 ° C., stirred, melt-mixed, and heated at 200 ° C. for 5 hours while being exposed to air, and allowed to stand. As a result, a cured product having a glass transition temperature of 208 ° C. was obtained.

Example 25 Bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenyl} methane powder (5 g) was added to tetra-n-butylammonium perchlorate. 0.05 g of the powder was uniformly mixed, and a part of the mixture was placed on a hot plate exposed to air at 260 ° C., and the stirring and gelling time was measured while maintaining the temperature, and it was 1 minute 00 seconds.

Comparative Example 4 The same experiment as in Example 25 was conducted without using the onium compound, and the gelation time was measured.
It was seconds.

Examples 26-28 Bis {4- (methallylbicyclo [2.2.1] hept-
5 g of 5-ene-2,3-dicarboximido) phenyl} methane powder was uniformly mixed with 0.05 g of various onium compound powders shown in Table 4, and a part of the mixture was exposed to air at 240 ° C. on a hot plate. Then, the gelation time was measured while stirring and keeping the temperature, and the results shown in Table 4 were obtained.

Comparative Example 5 The same experiment as in Example 26 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 4 were obtained.

Table 4 Onium compound gelation time Example 26 Diphenyliodonium hexafluoro 6 minutes 00 seconds Phosphate 27 Dimethylphenacylsulfonium hexa 5 minutes 50 seconds Fluorophosphate 28 Diphenyliodonium perchlorate 1 minute 30 seconds Comparative Example 5 ---> 30 minutes

Examples 29 to 31 2,2-bis [4 '-{4 "-(allylbicyclo [2.
2.1] hep-5-ene-2,3-dicarboximide) phenoxy} phenyl] propane powder in 5 g, Table 5
0.05 g of the various onium compound powders shown in 1 above were uniformly mixed, and 1 part thereof was placed on a hot plate exposed to air at 240 ° C., and the stirring and gelation time was measured while maintaining the temperature. The results were obtained.

Comparative Example 6 The same experiment as in Example 29 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 5 were obtained.

Table 5 Onium compound gelation time Example 29 Diphenyliodonium hexafluoro 2 minutes 50 seconds Phosphate 30 Diphenyliodonium tetra 12 minutes 30 seconds Fluoroborate 31 Diphenyliodonium perchlorate 2 minutes 20 seconds Comparative example 6 --- 24 minutes 00 Second

Examples 32 to 35 N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) 5 g was mixed with various onium compounds shown in Table 6. 0.1 g of the compound powder was uniformly mixed, and a part of the mixture was placed on a hot plate exposed to air at 220 ° C., and the stirring and gelling time was measured while maintaining the temperature. The results shown in Table 6 were obtained. Was given.

Comparative Example 7 The same experiment as in Example 32 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 6 were obtained.

Table 6 Onium compound gelation time Example 32 Diphenyliodonium hexafluoro 5 minutes 10 seconds Phosphate 33 Diphenyliodonium perchlorate 1 minute 20 seconds 34 Benzyltri-n-butylammonium 6 minutes 30 seconds Bromide 35 Diphenyliodonium bromide 6 minutes 00 Second Comparative Example 7 --- 8 minutes 00 seconds

Examples 36 to 38 In 5 g of N, N'-dodecamethylene-bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) are shown in Table 7. 0.1 g of the various onium compound powders shown below were uniformly mixed, and 1 part thereof was placed on a hot plate exposed to air at 220 ° C., and the stirring and gelling time was measured while maintaining that temperature. Results were obtained.

Comparative Example 8 The same experiment as in Example 36 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 7 were obtained.

Table 7 Onium compound gelation time Example 36 Dimethylphenacylsulfonium hexa 7 minutes 40 seconds Fluorophosphate 37 Dimethylphenacylsulfonium tetra 7 minutes 50 seconds Fluoroborate 38 Diphenyliodonium perchlorate 5 minutes 00 seconds Comparative Example 8 --- -10 minutes 20 seconds

Examples 39 to 41 N- (4'-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide powder 5 g was mixed with various onium compounds shown in Table 8. 0.05 g of the compound powder was uniformly mixed, 1 part of the mixture was placed on a hot plate exposed to air at 240 ° C., and the stirring and gelation time was measured while maintaining the temperature. The results shown in Table 8 were obtained. Was given.

Comparative Example 9 The same experiment as in Example 39 was conducted without using the onium compound, and the gelation time was measured. The results shown in Table 8 were obtained.

Table 8 Onium compound gelation time Example 39 Diphenyliodonium hexa 10 minutes 00 seconds Fluorophosphate 40 Dimethylphenacylsulfonium hexa 10 minutes 50 seconds Fluorophosphate 41 Diphenyliodonium perchlorate 12 minutes 10 seconds Comparative Example 9 ----- 27 Minutes 00 seconds

Example 42 N-Cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide 2.5
g, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl}
2.5 g of methane and 0.05 g of dimethylphenacylsulfonium hexafluorophosphate were uniformly mixed, and a part of the mixture was placed on a hot plate exposed to air at 220 ° C., and the gelation time was measured while stirring while maintaining the temperature. However, it was 4 minutes and 20 seconds.

Example 43 Bis {4- (allylbicyclo [2.2.1] hept-5
A MEK solution (10 ml) of 5 g of -ene-2,3-dicarboximido) phenyl} methane and 0.05 of diphenyliodonium hexafluoroarsenate was evenly applied on a copper plate, and the solvent was evaporated to obtain about 50 micron. A coating film was formed. Next, it was placed on a hot plate at 200 ° C., and the gelation time was measured by stirring and maintaining the temperature, and gelation occurred in 5 minutes and 30 seconds.

Example 44 In Example 43, when heated to 200 ° C. and irradiated with ultraviolet light from a high pressure mercury lamp of 400 W from the upper 10 cm, gelation occurred in 1 minute 30 seconds.

Example 45 Bis {4- (allylbicyclo [2.2.1] hept-5
A MEK solution (10 ml) of 5 g of -ene-2,3-dicarboximido) phenyl} methane and 0.05 of diphenyliodonium hexafluorophosphate was evenly applied on a copper plate, and the solvent was evaporated to give a coating of about 60 μm. A film was formed. Next, it was placed on a hot plate at 200 ° C., and the gelation time was measured by stirring and maintaining the temperature, and gelation occurred in 4 minutes and 40 seconds.

Example 46 In Example 45, while heating to 200 ° C. and irradiating with ultraviolet light from a high pressure mercury lamp of 400 W from an upper portion of 10 cm, the gelation time was 2:00 minutes.

Examples 47-50 Bis {4- (allylbicyclo [2.2.1] hept-5
10 g of -ene-2,3-dicarboximide) phenyl} methane and 0.1 g of the onium salt shown in Table 9 were melted by heating at 90 ° C. and mixed well, and the gelation onset temperature was measured to obtain the pot life (potable). When the time) was obtained, the results shown in Table 9 were obtained.

Comparative Examples 10 to 13 The same experiment as in Example 47 was conducted except that the catalyst shown in Table 9 was used instead of the onium compound, and the pot life (pot life) was calculated. The results were obtained.

Table 9 Catalyst Pot Life Example 47 Diphenyliodonium Hexa> 72 h Fluorophosphate 48 Dimethylphenacyl sulfonium hexa ″ Fluorophosphate 49 Diphenyliodonium Tetrafluoro ″ Borate 50 Diphenyliodonium Perchlorate ″ Comparative Example 10 β-naphthalene sulfonic acid 3 hours 11 Phosphoric acid 1 hour 12 Diphenyl phosphate 2 hours 13 Aluminum chloride 0.5 hours

[0065]

INDUSTRIAL APPLICABILITY The present invention uses an onium compound catalyst for the polymerization and curing reaction of an alkenyl-substituted nadimide, thereby allowing the polymerization and curing reaction to proceed at a relatively low temperature in a short time, and at the same time to produce an alkenyl-substituted nadimide and a catalyst. Since it was possible to store the mixture for a long time, it is possible to save the trouble of mixing the raw material imide and the catalyst each time of polymerization, and to obtain a stable quality product even when manufacturing small quantities of the same quality. It has the effect that it can be manufactured. Furthermore, since the polymerization and the curing reaction are accelerated by the irradiation of ultraviolet rays, the combined use of the irradiation of ultraviolet rays also has an effect that the polymerization and the curing temperature can be further lowered and the polymerization and the curing time can be shortened as compared with the case of using the cation catalyst. .

Claims (3)

[Claims] 1. A method for polymerizing an alkenyl-substituted nadimide, which comprises using an onium compound as a catalyst when polymerizing an alkenyl-substituted nadimide, a mixture thereof, or an oligomer thereof. 2. An onium compound is an ammonium compound [R ₄ N] ⁺ X ⁻ , a phosphonium compound [R ₄ P] ⁺ X ⁻ , an arsonium compound [R ₄ As] ⁺ X ⁻ , and a styvonium compound [R ₄ Sb] ⁺ X. ^- , Oxonium compound [R ₃ O]
⁺ X ⁻ , a sulfonium compound [R ₃ S] ⁺ X ⁻ , a selenonium compound [R ₃ Se] ⁺ X ⁻ , a stannone compound [R ₃
Sn] ⁺ X ^-, or iodonium compound [R ₂ I] ⁺ X ^-
(In the formula, R represents a substituted or unsubstituted aromatic group, or a linear or branched alkyl or alkenyl group,
And may be the same or different, and X ⁻ represents an anion having weak nucleophilicity or having no nucleophilicity)), The method for polymerizing an alkenyl-substituted nadiimide according to claim 1. 3. An anion (X
^- ) Is Cl ⁻ , Br ⁻ , I ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , ClO _{4
^{-, PF 6 -, CF 3}} SO 3 -, SbF 6 - or SbCl ₆ ^- polymerization process of claim 2 wherein the.