JPH0826159B2 - Polysiloxane-amide block polymer having alkenyl group in side chain and method for producing the same - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel polysiloxane-amide block copolymer and a method for producing the same, and more particularly, it has excellent processability and has an alkenyl group in the side chain of the copolymer.
The present invention relates to a side chain alkenyl group-containing polysiloxane-amide block copolymer having excellent reaction curability and a method for producing the same.

[Technical background of the invention and its problems]

It is already known that polyamide has its excellent mechanical properties, extremely good heat resistance and abrasion resistance, etc., and by taking advantage of its properties, electrical insulation materials, various molding materials, coating materials, impregnation materials, etc. There are many uses such as household and industrial instruments and devices, electronic industrial parts, automobile parts, and gears.

However, the processability of polyamides having this excellent property, particularly aromatic polyamides, is extremely poor, and the polymer does not melt, requires a very high temperature even when melted, or becomes soluble. There is a drawback that the organic solvent cannot be processed unless it is extremely limited because the organic solvent is extremely limited.

To solve this drawback of polyamide, Japanese Patent Publication No. 54
JP-A-21397 discloses a method for producing an aromatic polyether amide polymer having excellent moldability by polycondensing an aromatic ether diamine and an aromatic dicarboxylic acid or a reactive acid derivative thereof.

This aromatic polyether amide polymer has excellent moldability and heat resistance.

However, since this polymer is excellent in heat resistance but is thermoplastic, it has a drawback that it is melted and deformed at a temperature higher than the heat resistance allowable temperature.

[Object of the Invention]

An object of the present invention is to provide a polysiloxane-amide block copolymer and a method for producing the same, which solves the above-mentioned drawbacks of an aromatic polyetheramide polymer, has excellent processability, and has excellent reaction curability. is there.

[Structure of Invention]

As a result of earnest studies to achieve the above object, the present inventors have found that the general formula (2) (In the formula, R ¹ is a substituted or unsubstituted divalent hydrocarbon group, R ²
Is an alkenyl group or a partially non-alkenyl group-containing monovalent hydrocarbon group) or an alkenyl group-containing diaminodisiloxane represented by the general formula (3) (In the formula, R ² is a monovalent hydrocarbon group which is an alkenyl group or a partly non-alkenyl group, and Q is an integer of 3 to 8)
The alkenyl group-containing diaminopolysiloxane obtained by subjecting the alkenyl group-containing cyclic siloxane represented by (Wherein R ³ is a substituted or unsubstituted divalent aromatic hydrocarbon group and Z is a halogen atom), the polycondensation reaction is carried out by mixing and stirring the dicarboxylic acid dihalide, and the copolymer is excellent in processability. It was found that a siloxane-amide block copolymer represented by the following general formula (1), which has an alkenyl group in its side chain and can be used for a crosslinking reaction, can be cured, can be produced, and has completed the present invention. It was

That is, the present invention has the general formula (1) (In the formula, R ¹ , R ² and R ³ are as described above, and m and n are each a number of 1 or more.) The present invention relates to a polysiloxane-amide block copolymer having a side chain alkenyl group and a method for producing the same.

The polysiloxane-amide block copolymer represented by the general formula (1) includes the alkenyl group-containing diaminodisiloxane represented by the general formula (2) or the disiloxane and the alkenyl group-containing cyclic siloxane represented by the general formula (3). And a dicarboxylic acid dihalide represented by the general formula (4).

Here, R ¹ in the alkenyl group-containing diaminodisiloxane represented by the general formula (2) is a substituted or unsubstituted divalent hydrocarbon group, examples of which include a propylene group, a butylene group, a pentylene group, and a phenylene group. Group, tolylene group,
Examples of the xylene group and the like, and the group contained in R ² include a vinyl group, an allyl group, an isopropenyl group, an alkenyl group such as a 2-methylallyl group, and a methyl group, an ethyl group,
Propyl group, butyl group, pentyl group, hexyl group, 3,3,
3-trifluoropropyl group, phenyl group, tolyl group,
Examples thereof include monovalent hydrocarbon groups other than alkenyl groups such as a xylyl group, a halophenyl group, and a halotolyl group. Thus, as the diaminodisiloxane that can be used in the present invention, for example, And one or more of these are used. However, when diaminodisiloxane itself is used in the practice of the present invention, it is necessary to use the one containing an alkenyl group in its molecule.

Further, in the alkenyl group-containing cyclic siloxane represented by the general formula (3), R ² is the same as described above, and Q is an integer of 3 to 8. As the cyclic siloxane, for example, And the like, and one kind or a mixture thereof is used. The alkenyl group-containing cyclic siloxane and the diaminodisiloxane are subjected to cleavage / ring-opening polymerization using a polymerization catalyst known to those skilled in the art, such as activated clay, potassium hydroxide, tetramethylammonium hydroxide or potassium silanolate. A polysiloxane having amino hydrocarbon groups at both ends can be obtained and can be used as a raw material for use in the present invention.

Next, R ³ in the dicarboxylic acid dihalide represented by the general formula (4) is a substituted or unsubstituted divalent aromatic hydrocarbon group, and the group contained therein is a phenylene group, a naphthalene group or a diphenyl ether group. , Diphenylmethane group,
Examples thereof include a diphenyl sulfone group and a diphenyl sulfide group, and examples of the group contained in Z include halogen atoms such as chlorine, fluorine and bromine. Examples of the dicarboxylic acid dihalide include terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 3,3 '-Diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 3,3'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 3,3'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl Examples thereof include sulfide dicarboxylic acid, dichloride such as 3,3′-diphenyl sulfide dicarboxylic acid, difluoride, and dibromide, and one kind or a mixture of two or more kinds thereof is used.

In the production of the polysiloxane-amide block copolymer represented by the above general formula (1), the alkenyl group-containing diaminodisiloxane represented by the general formula (2) or the disiloxane and the alkenyl group containing the general formula (3) are contained. A cyclic siloxane and an alkenyl group-containing diaminopolysiloxane obtained by performing an equilibration reaction by cleavage / ring-opening polymerization, and then neutralizing, topping, and filtering the dicarboxylic acid dihalide represented by the general formula (4). Add it to cause polycondensation reaction, and after the reaction is completed, wash with water,
It is performed by drying.

Here, regarding the charging of the diaminodisiloxane and the alkenyl group-containing cyclic polysiloxane, the type and the charging amount thereof can be arbitrarily selected according to the desired structure of the diaminopolysiloxane.

Further, the charging amount ratio of the diaminopolysiloxane and the dicarboxylic acid dihalide thus obtained was 0.5 for the former and 0.5 for the latter.
To 2.0, preferably equimolar amounts. If it is less than 0.5, a high molecular weight copolymer cannot be obtained, and if it exceeds 2.0, a high molecular weight copolymer cannot be obtained. When it is desired to align both ends of the copolymer obtained by molecular design in the above range with amino groups, it is necessary that the former is not equimolar and the former is slightly excessive. Specifically, from 1.005 to 1 mol of dicarboxylic acid dihalide
Charge 2.0 mol of diaminopolysiloxane and react. More preferably, it is in the range of 1.01 to 1.5 mol.
If the charged amount of diaminopolysiloxane is less than 1.005 mol, both ends of the obtained copolymer do not necessarily become amino groups, and conversely, if it exceeds 2.0 mol, it will grow to a molecular weight at which the physical properties of the copolymer become good. Is difficult.

In the method of the present invention, the obtained polysiloxane-amide block copolymer having an alkenyl group in the side chain is
A wide variety of properties can be provided depending on the kind and ratio of the amount of the diaminodisiloxane and the cyclic siloxane containing an alkenyl group, and the kind and ratio of the amount of dicarboxylic acid dihalide.

However, it is desirable that the obtained side-chain alkenyl group-containing polysiloxane-amide block copolymer is excellent in processability and sufficiently has characteristics such as excellent mechanical characteristics and heat resistance which are characteristics of polyamide.

The amount of side chain alkenyl groups in the copolymer is preferably at least 1.0% or more of the silicon atom-bonded organic groups R ² . When the alkenyl group is less than 1.0%, the crosslinking efficiency and strength are not sufficient, which is not preferable. Furthermore, from the heat resistance of the obtained copolymer and the availability of raw materials,
The amount of alkenyl groups is preferably selected from the range of 1.0 to 50% in the total organic.

To describe the reaction conditions in more detail, an alkali catalyst is usually used in the cleavage / ring-opening polymerization, and the polymerization temperature is in the range of 100 to 150 ° C. A polar solvent may be used to accelerate the reaction.

Examples of the alkali catalyst include potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetra-n-butylphosphonium hydroxide, and silanolates thereof, and the polar solvent includes tetrahydrofuran and dimethyl sulfoxide. ,
Examples thereof include phosphine oxide.

Further, a neutralizing agent is required to neutralize the alkali catalyst, and the temperature during the neutralization reaction is in the range of 100 to 130 ° C. Examples of the neutralizing agent include ethylene chlorohydrin, tri (2-chloroethyl) phosphite and phosphoric acid.

The polycondensation temperature of the thus obtained diaminodisiloxane and / or diaminopolysiloxane and dicarboxylic acid dihalide is in the range of 0 to 200 ° C, preferably 10 to 100.
It is carried out in the range of ° C, and an inorganic solvent or organic solvent and a base catalyst may be used to facilitate the reaction.

Examples of the inorganic solvent include aqueous solutions of sodium hydroxide and sodium carbonate, and examples of the organic solvent include toluene, xylene, chlorobenzene, dichlorobenzene, hexane, octane, diethyl ketone, dibutyl ketone, cyclohexanone, and chloroform. 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, N, N-dimethylformamide, N, N-dimethylacetamide, N
-Methyl-2-pyrrolidone and the like are exemplified, and these 1
Types or mixtures are used. Examples of the base catalyst include triethylamine and diisopropylmethylamine.

Thus, the obtained polysiloxane-amide block copolymer has excellent processability, and the alkenyl group of the side chain is
Curing with excellent properties by curing reaction at room temperature or under heating in the presence of the added Si-H bond-containing curing agent and a catalyst such as a platinum compound, or in the presence of a vulcanizing agent such as an organic peroxide. It becomes a thing.

〔The invention's effect〕

The side-chain alkenyl group-containing polysiloxane-amide block copolymer of the present invention is conventionally excellent in workability, while polyamide resin is excellent in mechanical and chemical properties but insufficient in processability. It is a liquid or resinous engineering plastic that has a reaction curability due to the introduced alkenyl group.

Therefore, the present invention has a wide range of applications in which the applications that have been limited by the conventional difficult workability are expanded and have a wide range of applications. It can be used as a highly reliable electron-related material.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples. In the examples, all parts are by weight.

Example 1 41.7 parts (0.168 m) of diaminopropyldisiloxane of the following formula
ol) And 58.5 parts of allyl group-containing cyclic siloxane of the following formula (0.168mo
l) And were stirred at a temperature of 150 ° C. for 11 hours by cleavage / ring-opening polymerization in the presence of 0.10 part of potassium hydroxide to carry out an equilibration reaction. Next, 0.50 parts of ethylene chlorohydrin was added dropwise, and 12
The mixture was stirred at a temperature of 0 ° C. for 2 hours to carry out a neutralization reaction. Then, the obtained reaction product was topped and then filtered. From the ¹ H-NMR spectrum and infrared absorption spectrum, this product was confirmed to be an allyl group-containing diaminopropyl polysiloxane represented by the following formula.

To this product (98.0 parts, 0.164 mol) were added diisopropylmethylamine (31.5 parts), 1,2-dichloroethane (5.0 parts) and dehydrated toluene (73.7 parts), and the mixture was stirred and mixed under a nitrogen atmosphere. Then, 27.8 parts (0.137 mol) of terephthalic acid dichloride was dissolved in 73.7 parts of dehydrated toluene containing 5.0 parts of 1,2-dichloroethane, and this was added dropwise to the above-mentioned mixed liquid at room temperature under stirring. After the completion of the dropping, the mixture was stirred at room temperature for 1 hour and further at 8O 0 C for 8 hours for polymerization. The obtained polymer was washed with water several times, and then dried under reduced pressure. It was confirmed from GPC, ¹ H-NMR spectrum and infrared absorption spectrum that this product was a polysiloxane-amide block copolymer of the compound of the present invention represented by the following formula.

The properties of this copolymer are shown in Table 1.

Example 2 Diaminophenyltetravinyldisiloxane 3 of the following formula
7.1 parts (0.102mol) And vinyl group-containing cyclic trisiloxane of the following formula: 23.9 parts (0.10
2mol) And 39.0 parts (0.102 mol) of vinyl group-containing cyclic pentasiloxane of the following formula And were stirred for 11 hours at a temperature of 150 ° C. by cleavage / ring-opening polymerization in the presence of 0.09 part of potassium hydroxide to carry out an equilibration reaction. Then, 0.61 part of ethylene chlorohydrin was added dropwise,
The mixture was stirred at a temperature of 120 ° C. for 2 hours to carry out a neutralization reaction. Then, the obtained reaction product was topped and then filtered.
From the ¹ H-NMR spectrum and infrared absorption spectrum, this product was confirmed to be a vinyl group-containing diaminophenylpolysiloxane represented by the following formula.

To 98.0 parts (0.1 mol) of this product, 1 part of triethylamine was added.
6.8 parts and dehydrated xylene 57.4 parts were added, and the mixture was stirred and mixed under a nitrogen atmosphere. Next, 16.8 parts (0.083 mol) of isophthalic acid dichloride was dissolved in 57.4 parts of dehydrated xylene containing 1.7 parts of N-methyl-2-pyrrolidone, and this was added dropwise to the above-mentioned stirred liquid mixture at room temperature. After completion of dropping, the mixture was stirred at room temperature for 1 hour, and further stirred at 80 ° C. for 1 hour to polymerize. The obtained polymer was washed with water several times, and then dried under reduced pressure. This product is GPC, ¹ H
From the NMR spectrum and infrared absorption spectrum, it was confirmed that the compound of the present invention represented by the following formula was a polysiloxane-amide block copolymer.

The properties of this copolymer are shown in Table 2.

Example 3 Vinyl group-containing diaminopropyldisiloxane of the following formula 10
0 part (0.338mol) 59.7 parts of anhydrous sodium carbonate and ion-exchanged water 140.6
In addition to the parts, stirring and mixing were performed. Then chloroform
57.2 parts of isophthalic acid dichloride in 453 parts (0.282 mol)
Was dissolved, and this was added dropwise at room temperature to the previously mixed mixture. After completion of dropping, polymerization was carried out by stirring at room temperature for 8 hours. Then, the obtained polymer was washed with water several times and then dried under reduced pressure. It was confirmed from GPC, ¹ H-NMR spectrum and infrared absorption spectrum that this product was a polysiloxane-amide block copolymer of the compound of the present invention represented by the following formula.

The properties of this copolymer are shown in Table 3.

Claims (4)

[Claims] 1. A general formula (1) (In the formula, R ¹ is a substituted or unsubstituted divalent hydrocarbon group, R ²
Are both alkenyl groups or partially non-alkenyl monovalent hydrocarbon groups, R ³ is a substituted or unsubstituted divalent aromatic hydrocarbon group, and m and n are each a number of 1 or more) A polysiloxane-amide block copolymer having an alkenyl group in its side chain. 2. General formula (2) (In the formula, R ¹ is a substituted or unsubstituted divalent hydrocarbon group, R ²
Is an alkenyl group or a partially non-alkenyl group-containing monovalent hydrocarbon group) or an alkenyl group-containing diaminodisiloxane represented by the general formula (3) (In the formula, R ² is a monovalent hydrocarbon group which is an alkenyl group or a partly non-alkenyl group, and Q is an integer of 3 to 8)
The alkenyl group-containing diaminopolysiloxane represented by the formula (4) is obtained by subjecting the alkenyl group-containing cyclic siloxane represented by the formula (4) to chain extension by ring-opening polymerization with a known acid or basic polymerization catalyst. (Wherein R ³ is a substituted or unsubstituted divalent aromatic hydrocarbon group, Z is a halogen atom), and a dicarboxylic acid dihalide is reacted with the polysiloxane represented by the general formula (1). -A method for producing an amide block copolymer. (In the formula, R ¹ , R ² , and R ³ are as described above, and m and n are each a number of 1 or more) 3. The method for producing a polysiloxane-amide block copolymer according to claim 2, wherein the dicarboxylic acid dihalide is phthalic dichloride. 4. The method for producing a polysiloxane-amide block copolymer according to claim 2, wherein the dicarboxylic acid dihalide is isophthalic acid dichloride.