JPS6144877B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an organosilicon-modified compound.

The following formula: [In the formula, m each independently represents the number 1 or 2, and R ₂ represents a benzene or benzophenone group, but the acid amide group and carboxyl group in formula () are bonded to different ring-constituting carbon atoms. and each carboxyl group is in the ortho position to the acid amide group, Q each independently represents a methyl group, phenyl group or -OY group (Y represents the following meaning), and Y is Each independently represents an alkyl group or phenyl group having 1 to 6 carbon atoms, and R ₁ has the following formula: (-CH ₂ ) _-x , (in the above formula, x represents a number from 1 to 4). ) represents a group represented by ] The organosilicon modified compound represented by the following formula: (In the formula, R ₂ represents the above meaning.) 1 mol of dicarboxylic acid dichloride represented by the following formula: (In the formula, R ₂ represents the above meaning.) 1 mol of tricarboxylic acid anhydride monochloride represented by the following formula: (In the formula, R ₂ represents the above meaning.) 1 mole of tetracarboxylic dianhydride represented by the following formula: (In the formula, R ₁ , Y and Q each represent the above-mentioned meanings.) By reacting with 2 moles of aminosilane represented by You can get it by twisting it.

The logarithmic viscosity number ηinh. is calculated by the following equation: [wherein, ln = natural logarithm, η = viscosity of the solution (viscosity of a solution of 0.5% by weight of the polymer in a suitable solvent. The solvent may be N.N.-dimethylacetamide, N.N.-dimethylformamide or N-methylpyrrolidone, ) ηo=viscosity of the solvent, c=concentration of the polymer solution in grams of polymer in 100 ml of solvent. ] Calculated from.

The above viscosity measurements are carried out at 25°C. As is well known, the logarithmic viscosity number is a measure of the molecular weight of a compound.

Examples of C1-C6 alkyl groups represented by Y include the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl group, n-hexyl group.

Each Y is preferably an ethyl or propyl group, particularly preferably an n-propyl group. Furthermore, when Y is an ethyl group, Q is preferably an ethoxy group, and when Y is a propyl group, it is preferably a methyl group.

The following compounds are particularly preferred compounds: In formula (), all m are 1;
Each of R ₁ represents a (-CH ₂ ) _-3 group, R ₂ represents a 1,4-phenylene group or a 1,3-phenylene group, Q represents a methyl group, and Y represents a propyl group, or a compound in which Q represents an ethoxy group and Y represents an ethyl group; in formula (), all m are 2;
Each of R ₁ represents a (-CH ₂ ) _-3 group, R ₂ represents a benzene ring or a benzophenone ring, Q represents a methyl group, and Y represents a propyl group, or Q represents an ethoxy group; And Y
represents an ethyl group and its corresponding cyclized derivative; In the formula (), one m represents the number 1, the other m represents the number 2, and each of R ₁ is (-CH ₂ )- ₃ groups, R ₂ represents a benzene ring, Q represents a methyl group and Y represents a propyl group, or Q represents an ethoxy group,
and compounds in which Y represents an ethyl group, and cyclized derivatives corresponding thereto.

The starting materials that can be used in the present invention are known compounds or can be produced by methods known per se.

Examples of dicarboxylic acid dichloride compounds of the formula that can be used as starting materials include terephthalic acid dichloride and especially isophthalic acid dichloride. As the tricarboxylic acid anhydride chloride represented by the formula, trimellitic acid 1,2-anhydride chloride (1,3-dioxo-benzo[c]oxalane-5-carboxylic acid chloride) can be used in particular.

Examples of tetracarboxylic dianhydrides of the formula that can be used as starting materials include: pyromellitic dianhydride, 3.
3', 4, 4'-benzophenone-tetracarboxylic dianhydride, 2, 3, 3'-4'-benzophenone-tetracarboxylic dianhydride, 2, 2', 3, 3'-benzophenone-tetracarboxylic dianhydride Acid dianhydride.

Preferred dicarboxylic acid derivatives, tricarboxylic acid derivatives, or tetracarboxylic acid derivatives for the above reaction are isophthalic acid dichloride, trimellitic acid 1,2-anhydride-chloride, pyromellitic acid dianhydride, and benzophenonetetracarboxylic dianhydride. It is.

The aminosilanes of the formula V as defined are known or can be prepared by known methods.

Examples of suitable aminosilanes of the formula are shown below:
Aminomethyl-di-n-propoxy-methylsilane, (β-aminoethyl)-di-n-propoxy-
Methylsilane, (β-aminoethyl)-diethoxy-phenylsilane, (β-aminoethyl)-tri-
n-propoxysilane, (β-aminoethyl)-dimethoxy-methylsilane, (γ-aminopropyl)-di-n-propoxy-methylsilane, (γ-
(aminopropyl)-di-n-butoxy-methylsilane, (γ-aminopropyl)-trimethoxysilane, (γ-aminopropyl)-triethoxysilane, (γ-aminopropyl)-di-n-pentoxy-phenylsilane, ( γ-aminopropyl)-methoxy-n-propoxy-methylsilane, (δ-aminobutyl)-dimethoxy-methylsilane.

Preferred aminosilanes include (γ-aminopropyl)-triethoxysilane, [γ-(4-aminophenyl)-propyl]-di-n-propoxy-methylsilane and (γ-aminopropyl)-di-
Among them, (γ-aminopropyl)-di-n-propoxy-methylsilane is particularly preferred.

The reaction of the starting material according to the above definition with 2 moles of aminosilane of the formula is carried out using a method known per se, preferably in an anhydrous organic solvent, at about -20
to +50°C, particularly preferably about -15 to +25
It can be carried out at a temperature of °C. As an organic solvent, N/N-dimethylacetamide (DMA),
N・N-diethylacetamide, N・N-dimethylformamide, N・N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-methyl-s-caprolactam, hexamethylphosphoric triamide [ Hexametapol], N・N・N′・
N'-tetramethylurea, tetrahydrofuran,
Cyclohexanone, tetrahydrothiophene dioxide (Sulpholane) and dimethyl sulfoxide are suitable.

This reaction can also be carried out in a mixture of the above organic solvents. On the other hand, these preferred organic solvent systems can be combined with other neutral organic solvents, such as aromatic, cycloaliphatic or aliphatic hydrocarbons or their chlorinated derivatives (e.g. benzene, toluene, xylenes, cyclohexane, pentane, hexane). , petroleum ether and methylene chloride) or diluted with dioxane.

In the reaction with the aminosilane of the formula, it is preferred to use at least twice the molar amount of the aminosilane of the formula. However, in order to obtain compounds with asymmetric formulas, either mixtures of corresponding molar amounts of the compounds are used, or the reaction is carried out in stages, with 1 mole of aminosilane of a different formula being used in each step. You can also do that.

After the reaction is completed, the solvent can be removed by conventional methods, if desired. This includes, for example, solvents,
If necessary, a method of distilling off under reduced pressure is used.

The chemical cyclization of the compounds according to the invention is also carried out using reaction methods known per se. For example, there is a method of treating under mild conditions using a dehydrating agent alone or a mixture thereof with a tertiary amine. Examples of dehydrating agents or mixtures thereof used in this method are acetic anhydride, propionic anhydride, or dicyclohexyl-carbodiimide,
or a mixture of acetic anhydride and triethylamine or pyridine. In order to avoid cross-linking reactions occurring, this reaction is carried out at as low a temperature as possible, preferably below 50°C, especially from about -20 to +25°C.
must be carried out at a temperature between

The organosilicon-modified compound obtained by the method of the present invention can be used for industrial products such as fibers, thin films, thick films, coating compositions, foams, laminated resins, laminates, compression molding powders, and compression molded bodies. It can be used for the production of For its production, 50%
A method of heating to a temperature of 350°C to 350°C is used. The crosslinked compound having siloxane bonds produced in this way is insoluble in organic solvents.
What characterizes this crosslinked compound is its excellent mechanical, electrical and thermal properties, in particular its improved thermal stability and excellent mechanical properties at low temperatures. In particular, acyclic compounds of the formula or a are characterized by their processability, in that they are generally processed using known moldings even at low temperatures of about 160°C, in particular industrial products such as laminates, foams or compression moldings. give.

Example 1 Organosilicon modified compound of the following formula Preparation of 12.9 g (0.04 mol) of finely powdered 3,3',4,4'-benzophenonetetracarboxylic dianhydride in a 200 ml container equipped with a stirrer, a dropping funnel and an internal temperature measuring device.
Suspend in 50 ml of anhydrous DMA in a sulphonation flask under a stream of nitrogen. Reaction mixture from 0 to
It is cooled to 5 DEG C. and then 17.5 g (0.08 mol) of (.gamma.-aminopropyl)-di-n-propoxy-methylsilane are added dropwise under stirring. After stirring the reaction mixture for 1 hour at room temperature, a clear solution of prepolymer forms; η _ioh of prepolymer 0.044 dl/g
(0.5% in DMA at 25°C).

Example 2 Organosilicon modified compound of the following formula Production of isophthalic acid dichloride 8.12g (0.04mol)
is dissolved in 60 ml of anhydrous DMA at −15° C. under a stream of nitrogen in a 200 ml sulphonation flask equipped with a stirrer, addition funnel, and thermometer.
There, 17.5 g of (γ-aminopropyl)-di-n-propoxy-methylsilane was added in 40 ml of anhydrous DMA.
(0.08 mol) and triethylamine 8.08 g (0.08
mol) is added dropwise under stirring at a temperature of -10°C to -15°C. The reaction mixture is then stirred for 2 hours at 0°-5°C and then for a further 2 hours at room temperature (20-25°C). After separating the precipitated triethylamine hydrochloride on a glass frit, a solution of the prepolymer [η _ioh 0.04 dl/g; DMA at 25°C
0.5%], which is suitable for example for the production of laminates.

Example 3 Organosilicon modified compound of the following formula Production method of trimellitic acid 1,2-anhydride chloride 12.63g
(0.06 mol) is dissolved in 60 ml of anhydrous DMA at −15° C. under a stream of nitrogen in a 350 ml sulphonation flask equipped with a stirrer, addition funnel and thermometer.

26.32 g (0.12 mol) of (γ-aminopropyl)-di-n-propoxymethylsilane and 6.07 g (0.06 mol) of triethylamine in 37 ml of anhydrous DMA.
is added dropwise to the above solution while stirring so that the reaction temperature does not exceed -15°C. After the addition was complete, the reaction mixture was kept at 0 °C for 1 h and then at room temperature (20 °C).
~25°C) for 1 hour, then the precipitated triethylamine hydrochloride is separated off. A clear 30% strength solution of the prepolymer of the above formula is obtained, which is suitable for example for the production of laminates.

Example of use The glass fiber fabric is impregnated with the prepolymer by soaking it in the prepolymer solution obtained in Example 2. The impregnated fabric is then dried in a vacuum dryer for 50 minutes.
Dry easily at ℃/300mmHg. This operation is 7
Repeat several times to thoroughly apply the resin to the fabric. Next, the fabric was heated at 50℃/300mmHg for 1 hour, and then at 50℃/300mmHg for 1 hour.
Dry at 10 ^-2 mmHg for 1 hour. Some of the dried prepregs obtained in this way were piled on top of each other and pressed at 165°C and 400kp/cm ³ in a platen press.
Pressed for 7 hours under pressure of 200℃/
Post-cure for 16 hours at 10 ^-1 mmHg. A laminate with good bond strength is obtained.

The prepolymer solution obtained in Example 3 can be similarly processed to obtain laminates with similar properties.

Claims (1)

[Claims] Primary formula (): [In the above formula, m each independently represents the number 1 or 2, and R ₂ represents a benzene or benzophenone group, but the acid amide group and carboxyl group in formula () are different ring-constituting carbon atoms. and each carboxyl group is in the ortho position to the acid amide group, and Q each independently represents a methyl group, a phenyl group, or an -OY group (Y represents the following meanings), Y each independently represents an alkyl group or phenyl group having 1 to 6 carbon atoms, and R ₁ each independently represents the following formula: (-CH ₂ )- _x (in the above formula, x is 1 to 4 represents the group represented by ). ] In the method for producing an organosilicon-modified compound represented by the following formula and its corresponding cyclized derivative: (In the formula, R ₂ represents the above meaning.) 1 mol of dicarboxylic acid dichloride represented by the following formula: (In the formula, R ₂ represents the above meaning.) 1 mol of tricarboxylic acid anhydride monochloride represented by the following formula: (In the formula, R ₂ represents the above meaning.) 1 mole of tetracarboxylic dianhydride represented by the following formula: (In the formula, R ₁ , Y and Q each have the above-mentioned meanings.) Reacting with 2 moles of aminosilane represented by the following formula, and optionally chemically cyclizing the obtained organosilicon-modified compound. A method for producing an organosilicon-modified compound characterized by: