JPS5876425A - Preparation of polymer containing imide ring - Google Patents

Abstract

PURPOSE:To obtain the titled resin, soluble in general-purpose solvents, having improved heat resistance and flexibility, and easily separable from the solvents, by reacting a diamine having a specific structure with a tetracarboxylic acid derivative and a dicarboxylic acid anhydride. CONSTITUTION:(A) A diamine, e.g. 4,4'-di(m-aminophenoxy)diphenyl sulfone, of the formula (X is O, SO2, CH2 COO, etc.) is reacted with (B) a tetracarboxylic acid derivative, e.g. pyromellitic acid dianhydride, and (C) a dicarboxylic acid anhydride, e.g. maleic anhydride, in a solvent preferably at 0-80 deg.C, and a dehydrating agent, e.g. acetic anhydride, is added to dehydrate, carry out the ring closure preferably at 20-60 deg.C and give the aimed polymer. Preferably, the amounts of the components are as follows: 0.005-100mol component (A), 1.005- 101mol component (B) and 2mol component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention a relates to a method for producing an electrolyte containing an imide ring.

Conventionally, bismaleimide compound tubes represented by N,N'-p,p'-diphenylmethane bismaleimide have been used.
It is well known that the heat resistance of the cliff coalescence obtained when ,kX@ is damaged and deteriorated.

However, when used alone, this l-coalescence has the disadvantage that the crosslinking density is low and brittle. Therefore, bismaleimide ft
Addition reactions such as diamine to the substance can reduce the brittleness.Additionally, the brittleness can be ameliorated by adding diamine to the substance, but the problem arises that the heat resistance is reduced. The punishment wA @ blame is that it can only be melted in a confucian solvent with a low boiling point, so it also has the disadvantage of being too lazy to remove the 7AI heat of the solvent ◎ This invention was made to eliminate the above ml disadvantages. ,
The purpose is to provide a readily embossed cliff coalescence that has excellent solubility in a general-purpose M solvent, is heat resistant, and has nine-pot properties. (Here % X is 0. Son, C) I proverb, coo,
51 co, C(CHs)s s C(CF)quake, each X is very different from the other. Also, hydrogen ζ halogen atom of aromatic ring, alkyl 4.
Diamines represented by (optionally substituted with allyl group ◆), tetracarboxylic derivatives, and dicarboxylic acid anhydrides *1
% mold to react.

The imide ring-containing polymer produced by the invention has the following general formula: (In the formula, X is 0.SOm, C&, α illusion, S, Co.

C(CHs)*h C(CFs)m k, and each X may be the same or J4. Tetracarboxylic acid in R! ! 4ibs z is a divalent group representing vertical wood-charcoal dielectric combination, n is a positive number) 0 1 containing this imide ring in the presence of a catalytic acid catalyst or When heated to 100-300'C in the absence of water, a heat-resistant, non-bathable polymer is obtained.

When the polymer containing the imide ring is soaked in a general-purpose organic solvent, heat removal of 7111I from the catalyst is easier than with a high boiling point polar catalyst. Therefore, there is no residual catalyst during the primary reaction, which causes problems such as the formation of voids in the molded product.

M as a molding material, adhesive, laminate, -insulating material, etc.
It is for use.

To explain the history of the present invention in detail, a diamine, a tetracarboxylic derivative, and dicarboxylic anhydride 111 are reacted in a solvent preferably at a temperature of 0 to 80°C to obtain an amic acid intermediate, which is then treated with a dehydrating agent such as acetic anhydride. 'tJi1i7
111L, preferably react at 20 to 60°C, and prepare the imide ring-containing polymer by Lv dehydration closed system. In what order do you react the diamine, tetracarboxylic fR spindle, and dicarbonyl anhydride @? Even L.

That is, the three components may be added to the inert S medium at 111% L, or the three components may be added first and the solvent may be added later. Alternatively, the diane may be dissolved in a solvent, then the tetracarboxylic derivative is added, and then the dicarboxylic acid anhydride is added. The molar ratio of the above five components is
5 to 100 mole diamine 1.005 to a decrease, and when it is large, it causes a decrease in solubility.

As the diamine, those shown by the following general formula can be used.
COO1S, CO.

C(C)1j)-1C(CFm)m11-, respectively (ZJX is one lees and may be different by t.

(The hydrogen atom of the primary aromatic ring may be substituted with a halogen, an alkyl group, an allyl group, etc.) Specific examples of diamines represented by the above general formula include:
4.4'di(m-aminoenoxy)diphenylsulfone, 4.4'-') (p-amino2enoxy)diphenylsulfone, 4.4'-di(m-amino2enoxy)diphenyl ether, 4.4 '-di<p-aminophenoxy)diphenyl ether.

4.4'-di(m-aminophenoxy)diphenylpropane, 4. di(p-aba)2enoxy)diphenyl 10pan, 4.4'-di(m-7minophenylsulfonyl)diphenyl ether, 4.4'=')(p-
7minophenylsulfonyl) diphenyl ether 14.
4'-di(m-7mi/phenylthioether) Schiff, Nilsulf 4F's'4e4'-di(p-7mino2
(enyltheoether) di2enylsulnide s 4.4
'-di(m-aminophenoxy)diphenylketone,
Examples include 4.4'-di(p-7minophenoxy)diphenylketone, 4.4'-di(m-amino2enoxy)diphenylmethane, and 4.4'-di(p-ynoneenoxy)diphenylmethane.

17' (However, to the extent not included in the present invention, known diamines may also be used. Specific examples thereof include 4,4'-diaminodiphenyl ether.

4,4'-cya di-2enylmethane, 4,4'-
Diaminodi2menylgppan, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone)', 5,5'-cyami/diphenylsulfone, meta-2enylenediamine, p-2enylenepiazene, 1, 5
-diaminonaphthalene, 2,6-diaξnonaphthalene,
2,6-diamitspyridine, 1,4-di(p-aminophenoxy)benzene, 1,6-di(p-amino2enoxy)benzene, etc.Obut2carboytsh conductors include tetracarboxylic acid,
There are dicarboxylic acid diester, tetracarboxylic diester dihalide, and tetracarboxylic dianhydride.An example of these is tetracarboxylic dianhydride, which is pyromellitic dianhydride s 3 t 3'= 4 t
4'-benzo2enonetetotsucarboxylic dianhydride, cyclobencunato2carboxylic dianhydride, s, s', <
, 4'-diphenylnato 2-carboxylic dianhydride, 1,2
, 5.6-S2 Talin Tetra-Rubon Anhydrous #% 2
, 5,6.7-naphthalenetetracarboxylic dianhydride,
2,3,5.6-viridi/tetracarboxylic dianhydride,
1,4,5.8-Naphthalenetetracarboxylic anhydride-
s 6e4-9.10-Berylenetetoxycarboxylic acid anhydrous.

4a4'-sulfonylsiphthalic anhydride, butanetetracarboxylic dianhydride, s2,3.3-4'-di2-dibutanetetracarboxylic dianhydride, etc.

Dicarbo 7 enemy anhydrous as rtm water maraine song.

Anhydrous Itacon Ei, Anhydrous Citracon enemy, Anhydrous Jiku cil:
I malein, anhydrous tetrahydrophthal, anhydrous methertet, 2-hydrophthal, 5-norbornene-2,3-dicarvone #R anhydrous, endobicyclo-(2,2,2)
-Octo-5-ene-2,3-jitorubon sales anhydrous q! I
Only unsaturated dicarbonyl IIR anhydrides such as tJ are used.

Since the diamine used in the present invention has poor bath dissolubility with respect to organic solvents, it is convenient to use a general-purpose and inexpensive solvent. A crosslinking reaction occurs at 100 to 300°C in the presence of aom%, resulting in a non-bathable polymer.

As the catalyst, a radical "JIL" catalyst can be used.

Specific examples include 1jtert-butyl peroxybenzoate, dicumyl peroxide, p-menthane hydroperoxide, methyl ether ketone peroxide, azobisisobutyronitrile, etc. Furthermore, the terminal imide ring has two bellows, which are anionic polymers. Because they are easily sweetened, 6th class amines, alkalis, izeta'zole, etc. can also be used as catalysts.

The compound 1 of the present invention can also be used as a filler, parrot, m-type agent, etc.

Next, an example of the present invention will be shown.0 Implementation? 11゜Thermometer, calcium chloride tube, stirring bar w: 300m
11,644 g of s, s:4,4'-benzo2enonetetracarboxylic dianhydride was placed in a four-ringed flask.

4.4'-di(m-aminophenoxy)diphenylsulfo/9.504 g% anhydrous maleic llffiA 92 g
2? 100 g of dimethylformamide was added thereto, and the mixture was stirred at 15° C. for 2 hours. Then, 2 g of sodium acetate and 10 gr of anhydrous vinegar were added, and the mixture was allowed to react at 50° C. for 3 hours. The precipitate formed in the water is filtered and dries up to form a constant electric charge. Medium OT
It is melting.

The above generation process was performed at 170°C for 1 hour, and at 280°C for 6 minutes.
jJD Atsato did not lose weight until 450℃.

ffc, the above-mentioned product*'k) The molded product was made by applying 7Jl of heat and pressure, and the molded product did not develop any clumps even after being soaked in a jig for 1 minute, and the OT cylindrical properties were good.
t-.

Company Example 2 92 g of black water maleic acid was added to the same equipment as in Example 1, and 4
．． Add 11.232 g of 4'-di(p-aminone enoxy) diphenylsulfone, 1.932 g of 3.3',4.4'-benzophenone tetracarboxylic dianhydride and 100 gk of dimethylformamide.

The reaction was carried out at 15°C for 2 hours. Next, 1°g of acetic anhydride and sodium acetic acid ZgQ were added, and after reacting at 50°C for 3 hours, the mixture was poured into water, and the resulting precipitate was filtered and dried.

Generation '121'lf'' at 200℃ for 1 hour, 6 hours at 280℃
A cured product insoluble in organic solvents was obtained by heating for 1 hour.◇This product did not lose weight up to 460°C.

In addition, the molded product heated and pressurized did not crack even after being immersed in the sample for 1 minute. 4,4'-benzo2enonetetracarboxylic anhydride α322 g.

4. Added 92 g of 4'-di(m-aminone enoxy) benzo dipropylene, 1528 g of anhydrous maleic acid, and 50 g of dimethylformamide, and reacted at 15°C for 2 hours.
After that, 1941 g of acetic acid 1 a of anhydrous vinegar! 7 gl: and reacted at 50°C for 3 hours. The resulting precipitate was filtered, thoroughly washed with water, and dried. The product was soluble in common inexpensive solvents such as acetone, methyl ethyl ketone, cyclohexanone, and dioxane. Product t2
When heated at 00°C for 1 hour and 270°C for 3 hours, an insoluble gR pre-cured product was obtained. This did not reduce at 450°C. The product was heated and pressed to obtain a molded product. No cracks occurred in this molded product even after it was immersed in donated wood for 1 minute.

English 21ait/lJ4゜夾Mshio l11 and the same device as s, 6', 4, 4'
- Benzophenonetetracarboxylic anhydride? 6.44
g, 4,4'-di(p-aminone enoxy) benzo 2-functional non-a712g, anhydrous maleic acid A92gs? Add 100 gk of dimethylformamide and react at 15°C for 2 hours. Add 10 g of water vinegar and 2 gk of sodium acetate.
and reacted at 50°C for 6 hours. The reaction product was poured into water, treated with the resulting precipitate, washed with water, and dried.

The formed product was placed in a 10-degree cylinder and was pressurized to obtain a molded product.
t270"Cte5##jtko7=-rutfc.

This one didn't smack at 470 degrees Celsius ◎ Again. It was soaked in liquid nitrogen for 1 minute and did not become sticky at all.
-benzo2enoneteto2carboxylic acid dianhydride 5.22
g, 4,4'-di(P-amino-2-enoxy)dinenylnoroban a 2 g mm water maleic fN 1.96 g h engineered dimethylformamide 100 g 7 was added and reacted at 15°C for 6 hours 0 To this was added acetic anhydride 1 (Ig and sodium acetate). 2
g1e71111 and mJ6 for 6 days at 50°C. The product was poured into water and the resulting precipitate tF21i4 was washed with water and dried.

Formed qIlak - 200°C, heated for 1 hour, 27°C, 6 hours to crosslink and cure.This product did not lose weight at 430°C, 1y, lIl! y11- Even when the molded product obtained by heating and pressing was immersed in liquid water for 1 minute, no cracks occurred.

Comparative example N, N, 4.4'-cyenylmethane bismaleimito t
The mixture was placed in a cylinder and heated at 210°C to obtain a molded product. Take out this molded product from the cylinder.

Annealed at 280℃ for 5#j to 470℃
C7) Although the award was not reduced in the cabinet, it was immersed in liquid nitrogen.
A slight rack occurred.

Furthermore, %N, N, 4,4-di-2-enylmethane bismaleimide itself is indestructible to general-purpose low-boiling point melts such as acetone and methyl ether ketone. Initial J [coalescence is soluble in general-purpose 4f organic solvent,
The cured product is directly heat sensitive.

Claims (1)

[Claims] (CC”C*
C(X), S. C01C(CHs)*, C(CFs)g k, son
, zon. X may be the same or different, the aromatic ring may be substituted with a halogen atom, an alkyl group, an allyl group, etc. A method for producing an imide ring kttrli support by reacting it with a derivative and a dicarboxylic anhydride*.