JPS5827722A - Preparation of polyimidoamide acid siloxane, polyimide siloxane copolymer and/or polyimide isoindoloquinazolinedione siloxane copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having improved heat resistance, by reacting a specific diaminosiloxane with a diaminoamide and a diamine, an aromatic tetracarboxylic acid dianhydride, and reacting further an aromatic diisocyanate with the product of the first reaction. CONSTITUTION:(A) A diaminosiloxane of formulaI(R is bifunctional hydrocarbon; R' is monofunctional hydrocarbon; m is an integer >=1) is reacted with (B) a diaminoamide of formula II (Y is SO2 or CO, and one amino group and the Y-NH2 group are at the o-position to each other), (C) a diamine, e.g. 4,4'-diaminodiphenyl ether, and (D) pyromellitic acid dianhydride, and the reaction product is then reacted with (E) an aromatic diisocyanate in an amount of almost equivalent to the acid anhydride group in the reaction product at 50-100 deg.C while removing the liberated and generated CO2 from the reaction system to afford the aimed copolymer. The amount of the component (D) is 1.5-2.0mol based on one mole components (A) and (B) and/or component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyimidoamic acid siloxanes and polyimidosiloxane copolymers and/or polyimidoisoindoquinazolinedione siloxane copolymers.

The present invention relates to a repeating unit composed of an imide ring, an isoindoroquinazoline region, and a ring of the same type.

This is a method for producing a new polymer that has excellent adhesion to substrates and moisture resistance by including a siloxane structure in the bone core. The present invention provides a method for producing a polyimidosiloxane copolymer and/or a polyimidoisoindoquinazolinedione siloxane copolymer, and a polyimidoamic acid siloxane+j/ as a precursor thereof.

The polyimidosiloxane copolymer and/or polyimidoisoindoroquinazolinedione siloxane copolymer obtained by the present invention is stable to heat, has excellent heat resistance, moisture resistance, and abrasion resistance, and has the stretchability of polyimide. sex,
It has effective properties such as heat resistance stability of polyisoindoroquinazoline, adhesiveness of silicone and 9M humidity, and is used for molded products, films, adhesives, cast materials, and composite materials.

Fes, cover, 11! It can be used in food compositions, etc.

In the present invention, in the presence of an inert solvent, the general formula (11 (R is 2
valent hydrocarbon group R/ is a monovalent hydrocarbon group, R,
R' may be the same or different (, m is an integer of 1 or more and is represented by diaminosiloxane (1) general formula fl) (Ar is an aromatic hydrocarbon group, Y is Sow or CO, , one amino group and Y-NHz group are ortho-positioned in diaminoamide (group), diamine (I
) and aromatic tetracarboxylic dianhydride (5) to 1.0 mol of diaminosiloxane+11, diaminoamide (1) and/or diamine flill, aromatic tetracarboxylic dianhydride WIl r 1. 5 to 20 mol of aromatic diisocyanate is added to the reaction product in a linear equivalent amount to the acid anhydride group of the reaction product.
A polyimide amide r characterized in that the reaction is carried out while removing carbon dioxide gas, which is liberated and generated at ~100°C, from the reaction system.
a-iI2xane production method and in the presence of an inert solvent General formula (1) (B is a divalent hydrocarbon group R/ is a monovalent hydrocarbon group, R and R' may be the same) Diaminosiloxane (, m is an integer of 1 or more)
1) Diaminoamide (H) represented by the general formula +1> (Ar is an aromatic hydrocarbon group, Y is SCh or CO, and the 1m amino group and the Y-N& group are ortho to each other).

Cyanide and aromatic tetracarboxylic dianhydride are combined with diaminosiloxane (Il and diaminoamide (it)).
) and/or diamine (1) for 1.0 mol.

Aromatic tetracarboxylic dianhydride (conversion)'k 1.5~
20 mol of aromatic diincyanate is added to the reaction product in an amount equivalent to the acid anhydride group of the reaction product at 50 to 100°C while removing the generated carbon dioxide from the reaction system. The present invention relates to a method for producing a polyimidosiloxane copolymer and/or a polyimidoisoindoquinazolinedione siloxane copolymer by dehydrating and ring-closing a polyiodoamic acid siloxane obtained by reaction.

The above reaction products are:

However, Arl is an aromatic tetracarboxylic residue e Ar.

m is the same as above. For the acid anhydride group of this reaction product, 11 has an equivalent amount of aromatic diisocyanate of 50 to 1
Polyimide amide carboxylic acid siloxane is obtained by reacting at 00° C. while removing free R acid gas from the reaction system.

In the production method of the present invention, first, a greborimer of amide-carboxylic acid siloxane, which is a reaction product having acid anhydride groups at both ends of the molecule, is produced.

Thereafter, a cypolyimidoamide acid siloxane is obtained by an imidization reaction between the acid anhydride group and an aromatic diisocyanate as shown in the following formula.

The multiplication table Ar represents an and-carbo/acid siloxane residue, X represents an aromatic diisocyanate residue, and l is approximately 1
It is an integer from 0 to 20.

The diaminosiloxane represented by the above general formula (11) used in the present invention is as follows.

C) h CHs 1 CsH4CMs 1 Compounds such as

Diaminosiloxanes are 9 e.g. U.S. Pat.
It is synthesized by the method shown in No. 719.

As the diaminoamide represented by the above general formula (I[).

Compounds such as Two or more of these can also be used in combination.

+1) ~ (conversion) In the formula, Y indicates 80 wealth or CO,
X represents 0, CH*, 80m, S, CO, etc., and one 7-mino group and Y-Nl- are located at the ortho position to each other. Specific examples include 4,4'-diaminodiphenyl ether-3-sulfone, 3.4'-diaminodiphenyl ether-4-sulfonamide, and 3,4'-diaminodiphenyl ether-3'-sulfone. amide, 3,3'-diaminodiphenyl ether-4-sulfonamide)', 4,4'-diaminodiphenylmethane-3-sulfonamide.

3.4'-diaminodiphenylmethane-4-sulfonamide, 3.4'-diaminodiphenylmethane-3'-sulfonamide, a,a'-cyainodiphenylmethane-
4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide.

3.4'-diaminodiphenylsulfo/-4-sulfonamide, turtle 4'-diaminodiphenylsulfone-3'-
Sulfonamide, 3'-diaminodiphenylsulfone-4-sulfona <)',44'-diaminodiphenylsulfide-3-sulfonand,3.4'-
Diaminodiphenyl sulfide-4-sulfonamide, &3'-diaminodiphenyl sulfide-4-sulfonamide.

44'-diaminodiphenyl sulfide-31-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 44'-diaminodiphenyl ether-3-calphonamide, mi-4'-diaminodiphenyl ether-
4-Carbonamide.

Tortoise 4'-diaminodiphenyl ether-3'-carbonamide, Tortoise 3'-diaminodiphenyl ether-4-carbonamide, 4.4'-diaminodiphenylmethane-
3-Carbonamide, 4'-diaminodiphenylmethane-4-carbonamide.

314'-diaminodiphenylmethane-3'-carbonamide, 3.3'-diaminodiphenylmethane-4-carbonando, 44'-cya2nodiphenylsulfone-
3-Carbonand, 44'-diaminodiphenylsulfone-4-Carbonand.

λ4'-diaminodiphenylsulfone-3'-carbonand, 43'-diaminodiphenylsulfone-4-carbonamide, 4.4'-diaminodiphenylsulfide-3-calphonamide, 3゜4'-diaminodiphenylsulfide-゛4- Carbonamide, turtle 3'-
Diaminodiphenyl sulfide-4-carbonamide, 3.4'-diaminodiphenyl sulfide-3'
-Sulfonamide or 1,4-diaminobenzene-
Examples include 2-carbonate.

Two or more types of these diaminoamides can also be used in combination.

Examples of diamine include 44'-cyanodiphenyl ether and 44'-diaminodiphenylmethane.

44'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfide, benzidine.

Metaphenylene diamine, paraphenylene diamine, 1
．． Examples include 5-su7thalene diamine and slonaphthalenecyamine, and two or more types can also be used in combination.

Examples of the tetracarboxylic dianhydride include 2.

Pyromellitic dianhydride, :(&'44'-diphenyltetracarboxylic dianhydride, &L'4.4'-benzophenonetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2, 5.6-7-talentetracarboxylic dianhydride, 7-7-talentetracarboxylic dianhydride.

λ16-pyridinetetracarboxylic dianhydride.

1, 4.5.8-7talenetetracarboxylic dianhydride, 3,4,9.10-perylenetetracarboxylic dianhydride or 44'-sulfonylsiphthalic dianhydride; One or more of these may be used.

When reacting aromatic tetracarboxylic dianhydride, diaminosiloxane and diaminoamide and/or diamine (
If the amount of aromatic tetracarboxylic dianhydride is less than L5 mol per 1.0 mol of diamine component, 91
The content of carboxyl groups in the molecules of the reaction product is low.

Chiku, if the amount of aromatic tetracarboxylic dianhydride exceeds 20 moles, unreacted aromatic tetracarboxylic dianhydride will remain, so aromatic tetracarboxylic dianhydride is added per 1.0 mole of diamine component. is set to be 1.5 to 20 moles.

(92) The inert solvent used in carrying out the present invention does not necessarily need to dissolve all of these monomeric compounds, but (1) for example, N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone,
, N-dimethylacedo, N,N-dimethylformamide, N,N-diethylformamide, dimethylsulfoxide.

hexamethylphosphoramide, tetramethylsulfo/,
One or more types of cresol etc. are used.

The reaction between the diamine component and the aromatic tetracarboxylic dianhydride can be carried out by, for example, dissolving the diamine component in an inert solvent as much as possible, then adding the aromatic tetracarboxylic dianhydride, preferably at a temperature of 80° C. or lower, Particularly preferably, stirring is carried out while maintaining the temperature at around room temperature or lower, but there is no particular restriction on the method of adding the diamine component, the aromatic tetracarboxylic dianhydride, and the inert solvent. As a result, the reaction proceeds quickly and the viscosity of the reaction system increases.

Note that 9 reactions were monitored using water/pyridine (10/2 weight ratio).
Add 217 to a sample of 0.11, heat and stir at 60°C for 1 hour, then determine the phosphoric acid value by the method shown in JI8 K 6911, and continue until the acid value becomes constant. At the beginning of the reaction, the acid value shows a high value).

To the acid anhydride group of the above-mentioned reaction product thus obtained, tl equivalent (equivalent ratio in the range of 0.95 to 1.05)
The aromatic diisocyanate to be reacted with is &3'
-diphenyl ether diincyanate, 3.3'-
One or more of diphenylmethane diisocyanate, (4-tolylene diisocyanate), 2,6-tolylene diisocyanate, and the like are used.

In addition to the imide reaction with cyanate, the reaction between carboxylic acid and incyanate also occurs, forming urea bonds and facilitating gelation. Therefore, in order to selectively imidize, for example, benzyldimethylamine is preferably used at a temperature of 60 to 90°C. It is preferred to use tertiary amines such as tertiary amines as imidization catalysts. Preferably, the polyimidoamide acid siloxane is heat-treated at a temperature of 100 to 350°C for 30 minutes to 5 hours to cause dehydration and ring closure, thereby obtaining a polyimide siloxane copolymer or a polyimide isoindoxazolinedione siloxane copolymer.

This dehydration and ring closure reaction uses acetic anhydride as a dehydrating agent.

It may also be carried out using phosphoric acid or the like. The above polyimidoamic acid siloxane solution was poured onto a glass substrate, dried to form a film, and dehydrated.

Even if you close the ring, it will still be a storm.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 Into a 500117 four-necked flask equipped with a temperature needle, a stirrer, calcium chloride, and a nitrogen inlet tube, 1.3 bis(amitubuvir)tetramethyldisilose 2, Of(αOOS) was added.
mole), 44'-diannodi7-enyl ether 145P
(0,0725 mol) and N-methyl-2-pyrrolidone 300? and stirred for 15 minutes. Pyromellitic dianhydride 2&4P (0.12075 mol) was gradually added to this and reacted at 20°C for 2 hours to obtain a compound with an acid value (ring-opening acid value) of 384. Add 3.3'-diphenylmethane diisocyanate to this in an equivalent amount lα06 to the acid anhydride group.
P (0,04025 mol) was added and the temperature was raised to 75°C to form benzylmethylamine αl? was added and the reaction was allowed to proceed for 2 hours while removing liberated carbon dioxide gas.

Next, a part of this reaction solution was collected, poured into water to precipitate it, dried, and its reduced viscosity η, p/c was measured.
s ztu/l (solution [dimethyl sulfoxide, concentration α
1 t7100cc, temperature 25℃). The reaction solution was then applied onto a glass plate and treated at 300° C. for 2 hours to obtain a polyimide siloxa/copolymer. This film was difficult to peel off from the glass substrate due to poor adhesion to the glass substrate. Also, the lead wire fI
! It showed excellent adhesion and abrasion resistance with no scratches up to 6H when measured by a hardening method. On the other hand, this film did not lose weight in air up to 450°C and had excellent heat resistance.

Example 2 1.3bis(aminopropyl)tetramethyldisiloxane 1.7086)(0,
00687 mol), 4,4'-diaminodiphenyl ether-3-carbonamide 1.67081 (α0068
8 mol), 44'-diaminodiphenyl ether 11.
0011' (0,055 mol) and N-methyl-2-
300f of pyrrolidone was added and stirred for 15 minutes. To this, add pyromellitic dianhydride (11.9917) (0,055 mol) to 3. '4.4'-Benzophenonetetracarboxylic dianhydride 2a5688) (0,0825 mol) was gradually added and reacted at 20°C for 2 hours. Acid value (ring-opening acid value)
655 compounds were obtained. To this, 3.3'-diphenylmethane isocyanate was added to the acid anhydride group in an equivalent amount of 17.1875
) (0.06875 mol) was added, the temperature was raised to 75°C, benzylmethylamine (0.1) was added, and the reaction was allowed to proceed for 2 hours while removing liberated carbon dioxide gas. Next, a part of this liquid was collected, poured into water to precipitate it, and after drying, its reduced viscosity η was measured and found to be α61a/? (measured under the same conditions as Example 1).

Next, the reaction solution was applied onto a glass plate and heated at 300 ml.
After treatment at .degree. C. for 2 hours, a poly-2-doin-indolo-nasilindione siloxane copolymer was obtained. Further, this film exhibited excellent adhesion, abrasion resistance, and heat resistance similar to those obtained in Example 1.

Comparative Example 1 Using the same apparatus as in Examples 1 and 2, 73501% of N-methyl-2-pyrrolid was added, and 26.11' (0.12 mol) of 4.4'-dianhydride was added thereto at 15°C. A viscous reaction solution was obtained by reacting the reaction species for 8 hours.

The reduced viscosity measured according to Example 1 was 0.60 #/P
Met. After that, this reaction solution was applied on a glass plate and 3
It was treated at 00°C for 2 hours. This polyimide film can be easily combed onto glass substrates.

According to the present invention, it has the stretchability (1) toughness of polyimide, the heat resistance stability (7) of polyindoquinazoline, and the adhesiveness (7) of recon, etc., and has substrates such as glass, silicone urethane, etc. Polyimidosiloxane copolymer or polyimidoisoindoquinazolinedionesiloxane copolymer with significantly improved adhesion and heat resistance with
A union is obtained.

Claims (1)

[Claims] L In the presence of an inert solvent, general formula〇} (R is a divalent hydrocarbon group, R/ is a monovalent hydrocarbon group, and IR' may be the same or different, respectively. (, m is 1
diaminosiloxane (■
) Diaminoamide ( H), diamine (
III) and aromatic tetracarboxylic dianhydride (converted) to 1.0% of diaminosiloxane {1} and diaminoamide (It) and/or diamine (1). The substance (y) is 1.5 to 2.
React as 0 mol. This reaction product. For the acid anhydride group of the reaction product.
tl equivalent of aromatic diincyanate at 50-100℃
Polyimideamide acid siloxane whose purpose is to react while removing the carbon dioxide gas liberated from the reaction system.
manufacturing method. 2 In the presence of an inert solvent, the general formula m (R is a divalent hydrocarbon group, R/ is a monovalent hydrocarbon group, and C, R, and R' may be the same or different (, m is 1 diaminosiloxane (which is an integer greater than or equal to
11 General formula (Il) (Ar is an aromatic hydrocarbon group, Y is Son or CO, and one amino group and Y-NHx group are positioned ortho to each other. Diaminoamide (n), Diamine (11) and aromatic tetracarboxylic dianhydride (1.0 mol of diaminosiloxane (I) and diamino oxide (11) and/or diamine (11), aromatic tetracarboxylic dianhydride) GVI is reacted with 1.5 to 2.0 mol. This reaction product has 9
#1 equivalent of aromatic diisocyanate at 50-100℃
A polyimide siloxane copolymer and/or a polyimide isoindoquinazolinedione siloxane copolymer, characterized in that a polyimide acid siloxane is dehydrated and ring-closed to a polyimide obtained by the reaction while removing carbon dioxide gas liberated from the reaction system. Coalescence manufacturing method.