JPH04126719A - Polyamide-polysiloxane block copolymer and method for producing the same - Google Patents

Abstract

PURPOSE:To obtain the objective copolymer at a relatively low temperature without causing a side reaction, having excellent heat resistance and high mechanical strength as well by subjecting a specific polysiloxane and a polyamide to polycondensation in the presence of an aromatic phosphorous ester and a pyridine derivative. CONSTITUTION:(A) A polysiloxane shown by formula I [R is alkylene; R1 and R2 are alkyl or (alkyl-substituted) phenyl; n is average degree of polymerization and is 2-10] and (B) a polyamide shown by formula II and formula III (R3 is bifunctional organic group; R4 is hydroxyl group-substituted arylene; Ar is bifunctional aromatic group shown by formula IV to formula VI), a random polycondensation product of a phenolic OH group-containing dicarboxylic acid, a dicarboxylic acid not containing the OH group and a diamine are subjected to polycondensation in the presence of an aromatic phosphorous ester and a pyridine derivative to give the objective copolymer comprising 2-20 block units shown by formula VII and 2-20 block units of the component B which are mutually linked through -NHCO- bond.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel block copolymer and a method for producing the same, and more particularly to a polyamide-polysiloxane copolymer and a method for producing the same.

[Conventional technology]

Polysiloxane is an industrially useful material in fields that have recently been attracting attention, such as selectively permeable membranes, such as oxygen enrichment membranes, and peripheral materials for electronic components, such as photoresist materials. It is. Therefore, various attempts have been made to take advantage of the heat resistance characteristic of polysiloxane and to further improve its functionality. For example, polymer blending, which involves blending different types of polymers, is often used. Although polymer blending is very convenient from the perspective of increasing functionality and added value, it is difficult to achieve compatibility. From this point of view, there are many problems.

Therefore, as a method for solving the compatibility problem, it has been proposed to graft or block polymers, and various polysiloxane graft copolymers and block copolymers have been proposed. It is technically quite difficult to make composite materials using these methods, and from the viewpoint of production costs, they are not necessarily satisfactory, and at present they are only used for limited applications. Among these methods, block copolymerization can be cited as a relatively low-cost method.

To give a few examples, for example, as a method for producing a polysiloxane-aramid block copolymer by the phosphite method, a method using an aliphatic amine-terminated polysiloxane is known (Japanese Patent Application Laid-open No. 81-293224), a polysiloxane-aramid block copolymer with a high degree of polymerization and high strength has a problem in that it is difficult to produce. Therefore, for the production of high-strength polysiloxane-aramid block copolymers, a low-temperature interfacial polycondensation method using dicarboxylic acid chloride and the above-mentioned aliphatic amine-terminated polysiloxane has been proposed (Tokikai, 1982).
-257933).

[Problem to be solved by the invention]

However, the previously proposed method for producing polysiloxane-aramid block copolymers using the above-mentioned low-temperature interfacial polycondensation method requires purification of the monomers used during synthesis, and also requires reaction control during production and Treatment of by-product hydrochloric acid gas, protection of reactive functional groups, deprotection, etc.
There were various problems, and it could not be said to be an easy synthesis method.

The present invention has been made in view of the above-mentioned problems in the conventional technology.

Therefore, an object of the present invention is to provide a novel polyamide-polysiloxane copolymer that does not require consideration of the above-mentioned manufacturing problems. Another object of the present invention is to provide a method for easily producing a novel polyamide-polysiloxane copolymer.

[Means to solve the problem]

As a result of studies, the present inventors have discovered that when producing a polyamide-polysiloxane block copolymer using the phosphite ester method, a macromonomer having an aminophenyl group at the end of polysiloxane is used, and a phenolic The inventors have discovered that the above problems can be solved by using a dicarboxylic acid having a hydroxyl group, and have completed the present invention.

The first polyamide-polysiloxane block copolymer of the present invention is a random polycondensate of a dicarboxylic acid having a phenolic hydroxyl group, a dicarboxylic acid having no phenolic hydroxyl group, and a diamine, and has carboxyl groups at both ends. A polycondensate of a polyamide having a group and a polysiloxane having an aminophenyl group at both ends,
A block unit (A) represented by the following formula (I), (wherein R represents an alkylene group, R1 and R2 each represent an alkyl group, a phenyl group, or an alkyl-substituted phenyl group, and n is an average degree of polymerization and indicates a number from n-2 to 100.) A block unit (B) in which structural units represented by the following general formulas (n) and (DI) are randomly arranged in a range of 1 to 30, respectively. -(N11-^r-NIICO-R3-COh
(IF)→N11-Ar-NIICO-Ra −
coh (III) (wherein R3 represents a divalent organic group, R4 represents a hydroxyl group-substituted arylene group, and Ar represents a divalent aromatic group represented by (1) to (8) below). ) F3 The block unit (A) and the block unit (B) are each present in a range of 2 to 20, and are bonded to each other through an -NHCO- bond.

The first polyamide-polysiloxane block copolymer of the present invention comprises a polysiloxane having aminophenyl groups at both ends represented by the following general formula (■'), (wherein R, R,, R2 and n each have the same meaning as defined above.) A random polycondensate of a dicarboxylic acid having a phenolic hydroxyl group, a dicarboxylic acid having no phenolic hydroxyl group, and a diamine, which has the following general formula ( -(Nll-Ar-NIICO-Ri
-GO)-(IT)-(N11-^r-NIICO
-R4-CO)-(I[r) (wherein R6, R4, and Ar each have the same meaning as defined above) Direct polycondensation in the presence of an aromatic phosphite and a pyridine derivative It can be manufactured by

The second polyamide-polysiloxane block copolymer of the present invention is a polycondensate of a polysiloxane having aminophenyl groups at both ends, an aromatic diamino compound, and a dicarboxylic acid, and is a polycondensate of the following formula (I ) and the structural unit (C) represented by the following formula (IV).
), the IR structural unit D) represented by the following formula (V), and the structural unit (E) represented by the following formula (VT) are -CON
It is randomly bonded by H-bonds, (NH-Ar-NH? (■) GO GO (wherein, R represents an alkylene group, and R and R2 are
Each represents an alkyl group, a phenyl group, or an alkyl-substituted phenyl group, R9 represents a divalent organic group, and R4 represents a hydroxyl-substituted arylene group. Ar is the following (1)
In the divalent cp3 represented by ~(8), n is an average degree of polymerization, and represents a number from n=2 to 100.

) and the block unit (A) is present in a range of 2 to 20,
It is characterized in that the number of structural units (C) is present in a range of 2 to 600, and the total number of structural units (D) and structural units (E) is present in a range of 2 to 600.

The second polyamide-polysiloxane block copolymer of the present invention comprises a polysiloxane having aminophenyl groups at both ends represented by the following general formula (1'), (wherein RSR, , R, and n each has the same meaning as defined above.) An aromatic diamino compound represented by the following general formula (■') and R2N Ar NR2 (IV' ) (wherein -Ar
has the same meaning as above. ) A dicarboxylic acid represented by the following general formula (V') and HOOC-R, -COOH(
V') (R3 has the same meaning as above.) The following general formula (
HOOC-R4-COOH(Vl') (wherein, R4 has the same meaning as above) aromatic phosphite and pyridine derivative It can be produced by polycondensation in the presence of.

The present invention will be explained in more detail below.

In the present invention, the polysiloxane having aminophenyl groups at both ends used to constitute the block unit (A) can be synthesized, for example, by a method represented by the following general formula.

(In the formula, X represents 3 or 4, R1' and R2' each represent a methyl group, an ethyl group, or a phenyl group, and n
' represents 5 to 20, and p represents 3 to 5. ) Catalysts used in the above reaction include platinum-based catalysts,
Examples include platinum black (Pt/C), chloroplatinic acid, and silver thread catalysts such as silver halide. Further, the degree of polymerization of the polysiloxane is in the range of 2 to 100, preferably 5 to 20. If the degree of polymerization is less than 2, the heat resistance will be poor, and if it is greater than 100, various problems will occur, such as a decrease in the reactivity of the polysiloxane. When the degree of polymerization is in the range of 5 to 20, it has excellent heat resistance,
It is particularly useful as a highly reactive macromolecule.

The polyamide having carboxyl groups at both ends used in the production of the first polyamide-polysiloxane block copolymer of the present invention comprises an aromatic diamino compound represented by the above general formula (■') and an aromatic diamino compound represented by the above general formula (■'). A dicarboxylic acid represented by (V') or a functional derivative thereof and the general formula (■
It can be produced by reacting a hydroxyl group-substituted aromatic dicarboxylic acid represented by ') or a functional derivative thereof by a known method. The reaction proceeds according to the reaction formula below.

oo　　　　o.

1100cmY+ -CONII R2)-NIICO
Y2-COOII (wherein, , A r % R3, R4 and □ each have the same meaning as described above, and Z is represented by the following general formula (IV
), (V) and (Vl) are randomly bonded together by carbonamide bonds, -eNH-A r-NH) (IV
) The structural units of formulas (II) and (III) are randomly arranged and represent a group having CO at both ends, Yl and Y2 may be the same or different, each represents R3 or R4, m5l ) and q are numbers from 1 to 30, m+1
=N+Q. ) In this case, the polyamide obtained has an intrinsic viscosity in the range of 0.1 to 2.0 dll/g, taking into consideration the mechanical properties such as tensile strength and tensile modulus of the finally obtained block copolymer. Preferably.

The aromatic diamino compounds represented by the above general formula (■') used in the present invention include ■-phenylenediamine, p-phenylenediamine, 3°4'-oxydianiline, 4,4' -oxydianiline, bis(3-aminophenyl) sulfone, bis(4-aminophenyl) sulfone, 1,3-bis(S-aminophenyl)-1,1
, 3,3-tetramethyldisiloxane, 1゜3-bis(
p-aminophenyl)-1,1,,3,3-tetramethyldisiloxane, 3,4'-diaminobenzophenone,
4.4'-diaminobenzophenone, 3.3'-diaminobenzophenone, bis(3-aminophenyl) sulfide, 2.2-bis(ρ-aminophenyl)hexafluoropropane, 4.4'-diaminodiphenylmethane, etc. can give.

Further, as the dicarboxylic acid represented by the above general formula (V') used in the present invention, any carboxylic acid such as aliphatic, alicyclic, araliphatic, aromatic, etc. can be used. Specifically, for example, isophthalic acid, terephthalic acid, 4.4'-biphenyldicarboxylic acid, R8'-methylene nibenzoic acid, 4.4'-methylene nibenzoic acid, 4.
, 4'-oxynibenzoic acid, 4,4'-thiodibenzoic acid, 3.3'-carbonyl dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid,
1.4-naphthalene dicarboxylic acid, 1.5-naphthalene dicarboxylic acid, 2.6-naphthalene dicarboxylic acid, succinic acid, glutaric acid, superric acid, azelaic acid, sebacic acid, undecanniic acid, 1,3-cyclohexanedicarboxylic acid, ■.

4-Cyclohexanedicarboxylic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, adipic acid, l.

IO-decanoic acid, phenylmalonic acid, benzylmalonic acid, phenylsuccinic acid, 3-phenylglutaric acid, homophthalic acid, ■, 3-phenylenediacetic acid, ■.

4-phenylenediacetic acid, 4-carboxyphenylacetic acid,
Examples include 4-carboxyphenylacetic acid, 5-bromo-N-(carbomethyl)anI.ranilic acid, and -monocarboxycinnamic acid. These can be used as functional derivatives. , Further, as the carboxylic acid represented by the above general formula (■') used in the present invention, 2,5-dihydroxy-1,4
-Benzenediacetic acid, 5-hydroxyisophthalic acid, 4-
Examples include hydroxyisophthalic acid and 4,6-cyhydroxyisophthalic acid. These can be used as functional derivatives.

In the present invention, in order to obtain the first polyamide-polysiloxane block copolymer, the above general formula (I')
The polysiloxane having aminophenyl groups at both ends as shown in the formula is polycondensed with the polyamide having carboxyl groups at both ends, and the polycondensation is carried out in the presence of an aromatic surface phosphate and a pyridine derivative. As a result, the advantage arises that the polycondensation reaction can be carried out at relatively low temperatures without side reactions.

In addition, in the present invention, in order to obtain the second polyamide-polysiloxane block copolymer, the general formula (
A polysiloxane having aminophenyl groups at both ends represented by 1'), an aromatic diamino compound represented by the above general formula (■'), a dicarboxylic acid represented by the above general formula (V'), and the above general formula A hydroxyl-substituted aromatic dicarboxylic acid represented by formula (■') is polycondensed, and the polycondensation reaction is carried out using the three raw materials in the presence of an aromatic phosphite and a pyridine derivative. .

Phosphite esters used in the production of these block copolymers include triphenyl phosphite, diphenyl phosphite, tri-tolyl phosphite, and di-0- phosphite.
Tolyl, tri-tolyl phosphite, di-tolyl phosphite, tri-11-)lyl phosphite, di-p-tolyl phosphite, di-0-lylorophenyl phosphite, tri-p-chlorophenyl phosphite, phosphorous acid Examples include, but are not limited to, p-chlorophenyl. Furthermore, the pyridine derivatives used together with phosphite in the present invention include pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4
-lutidine, 2,6-lutidine, 8,5-lutidine and the like.

In the present invention, the above polycondensation reaction is carried out in the presence of a phosphite and a pyridine derivative, but during the reaction,
Usually, a solution polymerization method using a mixed solvent containing a pyridine derivative is employed. The organic solvent used here is limited in that it must be a solvent that does not substantially react with the reaction components or phosphite, but it must also be a good solvent for the reaction components and be reactive. It is desirable that the solvent be a good solvent for the block copolymer product. Typical organic solvents that can be used include amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide.

In the present invention, when obtaining a block copolymer with a high degree of polymerization, inorganic salts such as lithium chloride and calcium chloride can be added to the reaction system, but preferably an amine-based cationic surfactant is added. It is desirable to add Examples of the amine-based cationic surfactant include trialkylammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, cetyltrimethylammonium chloride, cetyltriethylammonium bromide and chloride. However, the combination of inorganic salts and l-realkylammonium salts is not preferred.

The manufacturing method of the present invention will be explained in more detail.

In order to obtain the first polyamide-polysiloxane block copolymer, an aromatic diamino compound represented by the above general formula (■'), a dicarboxylic acid represented by the general formula (V'), and a general formula ( (ii) a hydroxyl group-substituted aromatic dicarboxylic acid represented by ()) in the presence of a phosphite ester and a pyridine derivative in a ratio such that the total amount of these dicarboxylic acids is in excess of the aromatic diamino compound; N
- Reaction by heating and stirring in an organic solvent such as methyl-2-pyrrolidone under an inert atmosphere such as nitrogen,
The above polyamide is synthesized. A polysiloxane having aminophenyl groups at both ends is further added to the obtained polyamide-containing solution, and heated to perform a polycondensation reaction with the polyamide.

In addition, in order to obtain the second polyamide-polysiloxane block copolymer, an aromatic diamino compound represented by the above general formula (■'), a dicarboxylic acid represented by the general formula (V'), A hydroxyl-substituted aromatic dicarboxylic acid represented by the general formula (■') and a polysiloxane having aminophenyl groups at both ends are mixed in an organic solvent such as N-methyl-2-pyrrolidone, The polycondensation reaction is carried out in the presence of an ester and a pyridine derivative.

The amount of phosphite used in these polycondensation reactions in the present invention is usually at least an equimolar amount to the carboxyl group, but it is not economically advisable to use more than 30 times the molar amount. In addition, it is necessary that the amount of pyridine derivatives is equal to or more than the equivalent molar amount to the carboxyl group.
It is preferred to use a large excess amount, including its role as a reaction solvent. In the present invention, especially when using a mixed solvent of a pyridine derivative and an organic solvent such as N-methyl-2-pyrrolidone, the amount used should be such that it contains 5 to 30% by weight of the reaction component. is preferred.

In the present invention, the reaction is preferably carried out by stirring the reaction system until the highest viscosity, meaning the highest degree of polymerization, is obtained. The reaction temperature is generally preferably in the range of 60 to 140°C. Also, the reaction time is greatly influenced by the reaction temperature, and in any case it is preferable to stir the reaction system until the highest viscosity, meaning the highest degree of polymerization, is obtained.
In most cases, the reaction is complete within a few minutes to 20 hours.

After the reaction is completed, the reaction mixture is poured into a non-solvent such as methanol or hexane to separate the produced block polymer, and further purified by reprecipitation method to remove by-products and inorganic salts to obtain a purified block. It is possible to obtain a copolymer.

In the case of the first polyamide polylinoxane block copolymer of the present invention, the polycondensation ratio of polysiloxane having aminophenyl groups at both ends and polyamide is 2 in molar ratio.
- It is in the range of 3 to 3.2 and is determined by the amount of each raw material component. Furthermore, when the reaction components are used in equimolar amounts under the above reaction conditions, the intrinsic viscosity is 0. O1~4.0dl
/g, preferably in the range of 0.1 to 2.0 dl/g, and is it possible to produce a block copolymer with an average degree of polymerization of 2 to 20? If the average degree of polymerization exceeds 20, processability etc. I don't like it.

In the case of the second polyamide-polysiloxane block copolymer of the present invention, polycondensation of a polysiloxane having aminophenyl groups at both ends, an aromatic diamino compound, a dicarboxylic acid, and a hydroxyl group-substituted aromatic dicarboxylic acid The molar ratio of all carboxyl groups to gold amino groups is 1:1.
It is sufficient if the ratio is such that It is determined by the amount of each raw material component. The block copolymer to be purified has an intrinsic viscosity of 0.01 to 4.0 dl/g, preferably 0.1 to 2.0 dl/g.
It is in the range of 0 dl/g, and the block unit (A) is 2 to 2
Exists in the range 0.

In the first and second polyamide-polysiloxane block copolymers of the present invention synthesized as described above, the aromatic dicarboxylic acid having a phenolic hydroxyl group is Since it is formed by containing a dicarboxylic acid, this hydroxyl group can be modified by reacting with another compound or a different type of reactive polymer. Compounds that can be used to modify the polyamide-polysiloxane block copolymer of the present invention include amino groups, carboxyl groups,
Examples include compounds having an epoxy group, an acid chloride group, an isocyanate group, a chlorosulfonic acid group, or an acid anhydride. By being transformed by those things,
It is possible to improve solvent resistance and adhesion, as well as reactivity and handling properties.

The first and second polyamide-polysiloxane block copolymers of the present invention synthesized as described above have both high heat resistance and high mechanical strength, and can be used in a wide range of fields. For example, gas selective permeation membranes such as oxygen enrichment membranes, epoxy resin modified materials that utilize phenolic hydroxyl groups, photoresist materials that utilize the reactivity of phenolic hydroxyl groups, for example, pendant phenolic hydroxyl groups with naphthoquinone diazide. What was replaced,
Furthermore, it has various potential uses such as insulating films and coating film forming materials.

〔Example〕

The present invention will be described in detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 Synthesis of polysiloxane having aminophenyl groups at both ends.

1 mole of bisH-(p-aminophenyl)propyl]disiloxane and 2 moles of dimethylsiloxane cyclic tetramer were mixed in a 1 g 33-bottle flask under a nitrogen atmosphere, heated to 80°C, and the total amount was added as a reaction catalyst. Trifluoroacetic acid equivalent to 14% was gradually added dropwise, and the reaction was continued for 24 hours. After the reaction was completed, the crude oligomer was sufficiently purified with distilled water to remove excess acid catalyst. Subsequently, the oligomer was extracted from the aqueous suspension by an ether extraction method, and the ether was further distilled at atmospheric pressure.
The unreacted cyclic oligomer was removed by distillation under reduced pressure at 10° C. and 100° C. Yield 9I% 'H-NMR: aromatic protons and amino protons 6.3-7.4 flpm (II1) 1211 Si-methyl group 0.1 ppm (s) 4811 methylene protons 2
, 1 ppm (s)I 2111 RCA1'R method) :5i-0-3i 1008-1079cm-
'-0-CH2-1156cm'Ar-0-1183cm-' -3t-CI3 1257cm-1,2910cm-'
Synthesis of polyamide having carboxyl groups at both ends: Isophthalic acid 0.536 g (4+I1wol), 5
-Hydroxyisophthalic acid 0. BOOg (4ouao
l), 1.401 g of 3,4'-oxydianiline (
7ml), cetyltrimethylammonium chloride 1.2g, triphenyl phosphite 6.2g, N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 2
0 IIIB and pyridine 6III were placed in a 100-Mitsuro round bottom flask and reacted at 100° C. for 2 hours under a nitrogen stream to prepare a solution of polyamide having aminophenyl groups at both ends. This polyamide contains structural units (n-1) and (I[[-1) of the following formula in a ratio of 2=1, has a degree of polymerization of about 7, and has an intrinsic viscosity of 0°21 dll/g.
It had

(II-1) Synthesis of block copolymer: A solution prepared by dissolving 1 g of polysiloxane having aminophenyl groups at both ends in 5 g of NMP was added dropwise to the obtained polyamide solution, and after the completion of the dropwise addition, 4 g of NMP was added. Let the time react,
A reaction solution containing an aramid-polysiloxane block copolymer was obtained. After the reaction is complete, lj! The above reaction solution was poured into methanol to precipitate a block copolymer. After filtration, unreacted monomers and cetyltrimethylammonium chloride were removed in hot methanol, and the unreacted polysiloxane was further removed in hot carbon tetrachloride. After filtration, vacuum drying yields purified aramid with a yield of 92%.
A polysiloxane block copolymer was obtained.

The intrinsic viscosity of this aramid-polysiloxane block copolymer was 0.34 dN 7 g at 30°C in N,N-dimethylacetamide. In addition, when we measured the IR spectrum (KBr tablet method) and confirmed the structure, we found that there was an absorption based on the aminocarbonyl group near 1650an-' and an absorption of the methyl group, which is a substituent on silicon, at 2850an-'. (Absorption based on siloxane skeleton was observed from 110 to HOO mark-1.

Example 2 8,4'-auxidianiline 1.4 in Example 1
A polyamide was obtained by replacing 01 g (7 gaol) with 1.485 g (7 m5 ol) of 3,4'-diaminobenzophenone.

This polyamide has structural units (■-2) and (
m-2) in a ratio of 2:1, with a degree of polymerization of about 7 and an intrinsic viscosity of 0.18 dR/g.

(II-2) H (II[-2) Except for using this polyamide, the same procedure as in Example 1 was carried out to obtain a polyamide-polysiloxane block copolymer in a yield of 88%. Intrinsic viscosity is 0.24 dR
It was 7g.

As a result of IR spectrum analysis, in addition to the absorption in Example 1, a new absorption based on the ketone carbonyl group was observed at 1710 cm-'.

Example 3 8,4'-oxydianiline in Example 1 1.40
A polyamide was obtained by replacing 1 g (75 sol) with 1.513 g (7 allol) of bis(3-aminophenyl) sulfide. This polyamide contains the structural units (IF-3) and (m-3) of the following formula in a ratio of 2:1, has a degree of polymerization of about 7, and an intrinsic viscosity of 0.24 dN/
It had g.

Margin below (n-3) OH (m-3) The same procedure as in Example J was carried out except that this polyamide was used to obtain a polyamide-polysiloxane block copolymer at a yield of 90%. Intrinsic viscosity is 0.351dD
It was 7g.

As a result of the IR spectrum analysis, in addition to the absorption in Example 1, a new absorption based on the -8- group was observed at 1425 cm-'.

Example 4 3,4'-oxydianiline in Example 1 1.40
A polyamide was obtained by replacing 1 tr (7 smog) with 1.839 g (7 mmol) of bis(3-aminophenyl)sulfone. This polyamide contains structural units (■-4) and (III-4) of the following formula in a ratio of 2=1, has a degree of polymerization of about 7, and an intrinsic viscosity of 0.0. I6 d,Q
/g.

(II-4) (m-4) A polyamide-polysiloxane block copolymer was obtained in a yield of 87% by carrying out the same operation as in Example 1 except for using this polyamide. Intrinsic viscosity is 0.32 dl
/g.

As a result of IR spectrum analysis, in addition to the absorption in Example 1, 1217 crn~! Nearby and at 1388 cm-',
Absorption based on the -802- group was newly observed.

Example 5 3,4'-oxydianiline in Example 1 1.40
A polyamide was obtained by replacing 1 g (7a+gol) with 1.387 g (7 gaol) of bis(4-aminophenyl)methane. This polyamide contains structural units (II-5) and (m-5) of the following formula in a ratio of 221,
Degree of polymerization: about 7, with an intrinsic viscosity of 0.12 djll 7g.

(II-5) (■~5) The same procedure as in Example 1 was carried out except that this polyamide was used, and a polyamide-polysiloxane block copolymer was obtained in a yield of 94%. Intrinsic viscosity is 0.21 dN
/g.

As a result of IR spectrum analysis, absorptions other than those in Example 1 could not be clearly observed separately.

Example 6 3,4'-oxydianiline in Example 1 1.40
1 g<11+aol) and 2.339 g of 2.2-bis(4-aminophenyl)hexafluoropropane (
7■5ol)1. : Polyamide was obtained instead. This polyamide has structural units (II-6) and (III
-6) in a ratio of 2:1, degree of polymerization: approximately 7, and intrinsic viscosity 0.22 dll! /g.

(m-6) Except for using this polyamide, the same procedure as in Example 1 was carried out to obtain a polyamide-polysiloxane block copolymer in a yield of 89%. Intrinsic viscosity is 0.311 d
It was 7g.

As a result of IR spectrum analysis, in addition to the absorption in Example 1, a new absorption corresponding to -C-F was observed around 1300 am −'.

Example 7 8,4'-oxydianiline in Example 1 1.40
A polyamide was obtained by replacing 1 g (7 m5 ol) with 2.215 g (7 ml 1 ol) of 1.3-bis(p-aminophenyl) 1,1,3.3-tetramethyldisiloxane. This polyamide has a structural unit (U-
7) and (I[l-7) in a ratio of 2:1, the degree of polymerization was about 7, and the intrinsic viscosity was 0.10 djll/g.

Except for using this polyamide, the same procedure as in Example 1 was carried out to obtain a polyamide-polysiloxane block copolymer with a yield of 79%. Intrinsic viscosity is 0.19617
It was g.

As a result of IR spectrum analysis, no new absorption other than the absorption in Example 1 was observed.

Example 8 Block unit (A) Structural unit (C) Structural unit (D) Structural unit (E) Isophthalic acid 0.538 g (4 m5 ol), 5-hydroxyisophthalic acid o, eoo g (4 mog 101),
3.4'-oxydianiline 1.401 g (7m5
ol), 1g of polysiloxane having aminophenyl groups at both ends as in Example 1, 1.2g of cetyltrimethylammonium chloride, 6.2g of triphenyl phosphite, 20d of NMP, 6-pyridine.
, placed in a Q 30 round bottom flask and heated at 100°C under a nitrogen stream.
The mixture was reacted for 4 hours to obtain a solution containing an aramid-polysiloxane random Pro-Nc copolymer. After the reaction was completed, the reaction solution was poured into 1 g of methanol to precipitate a block copolymer. After filtration, unreacted monomers and cetyltrimethylammonium chloride were removed in hot methanol, and the unreacted polysiloxane was further removed in hot carbon tetrachloride. After filtration, vacuum dry
A purified aramid-polysiloxane random block copolymer was obtained with a yield of 92%.

The intrinsic viscosity of this aramid-polysiloxane random block copolymer is 30% in N,N-dimethylacetamide.
°C, it was 0.40 dN/g.

In addition, when we measured the IR spectrum (KBr tablet method) and confirmed the structure, we found that there was an absorption based on the aminocarbonyl group near 1650 cm-', an absorption of the methyl group which is a substituent on silicon at 2850c+n-', and an absorption of 1010 cm-' due to the methyl group, which is a substituent on silicon. ~1l1
Absorption based on the siloxane skeleton was observed at 00a-', and the same measurement results as in Example 1 were obtained.

〔Effect of the invention〕

The polyamide-polysiloxane block copolymer of the present invention is a thermoplastic elastomer with excellent heat resistance and at the same time has high mechanical strength, and is useful as a material with a wide range of applications.

Furthermore, according to the method of the present invention, the polycondensation reaction can proceed at a relatively low temperature, so the polyamide-polysiloxane block copolymer can be easily synthesized without side reactions. can.

Claims (4)

[Claims] (1) A polyamide having carboxyl groups at both ends, which is made of a random polycondensate of a dicarboxylic acid having a phenolic hydroxyl group, a dicarboxylic acid having no phenolic hydroxyl group, and a diamine, and having an aminophenyl group at both ends. It is a polycondensate with polysiloxane, and has a block unit (A) represented by the following formula (I), and ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (wherein, R represents an alkylene group, R_1 and R_2
each represents an alkyl group, a phenyl group, or an alkyl-substituted phenyl group, n is the average degree of polymerization, and n=2 to
Shows the number 100. ) It consists of a block unit (B) in which structural units shown by the following general formulas (II) and (III) are arranged randomly in the range of 1 to 30, respectively, and there are ▲mathematical formulas, chemical formulas, tables, etc.▼( II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_3 represents a divalent organic group, R_4 represents a hydroxyl group-substituted arylene group, and Ar represents the following (1) to
This represents a divalent aromatic group represented by (8). ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (
3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(7) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (8) The block units (A) and block units (B) each exist in the range of 2 to 20, and -NHCO
- A polyamide-polysiloxane block copolymer characterized in that the polyamide-polysiloxane block copolymer is bonded by a bond. (2) A polysiloxane having aminophenyl groups at both ends represented by the general formula (I') below, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I') (In the formula, R, R_1, R_2 and n have the same meanings as above, respectively.) A random polycondensate of a dicarboxylic acid having a phenolic hydroxyl group, a dicarboxylic acid not having a phenolic hydroxyl group, and a diamine, which has the following general formula (II) and (
▲Mathematical formulas, chemical formulas, tables, etc. are available▼(II) ▲Mathematical formulas, chemical formulas, There are tables etc. ▼ (III) (In the formula, R_3, R_4 and Ar each have the same meaning as above.) Characterized by polycondensation in the presence of an aromatic phosphite and a pyridine derivative. A method for producing a polyamide-polysiloxane block copolymer according to claim 1. (3) A polycondensate of a polysiloxane having an aminophenyl group at both ends, an aromatic diamino compound, and a dicarboxylic acid, the block unit (A) represented by the following formula (I) and the following formula ( IV) a structural unit (C) shown in
A structural unit (D) represented by the following formula (V) and the following formula (V
Structural units (E) shown in I) are randomly bonded by amide bonds, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) (In the formula, R represents an alkylene group, R_1 and R_
2 represents an alkyl group, a phenyl group, or an alkyl-substituted phenyl group, R_3 represents a divalent organic group, and R
_4 represents a hydroxyl group-substituted arylene group, and Ar represents a divalent aromatic group shown in (1) to (8) below. There are tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼ (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (7) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (8) n is the average degree of polymerization, and n = 2 to 100 Indicates the number of ) and the block units (A) are present in a range of 2 to 20, the structural units (C) are present in a range of 2 to 600, and the total of the structural units (D) and structural units (E) is 2 to 20. A polyamide-polysiloxane block copolymer, characterized in that the polyamide-polysiloxane block copolymer is present in a range of 600%. (4) A polysiloxane having aminophenyl groups at both ends represented by the general formula (I') below, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I') (In the formula, R, R_1, R_2 and n each has the same meaning as defined above.) An aromatic diamino compound represented by the following general formula (IV') and H_2N-Ar-NH_2(IV') (wherein Ar has the same meaning as defined above) .) A dicarboxylic acid represented by the following general formula (V') and HOOC-R_
3-COOH(V') (R_3 has the same meaning as described above.) HOOC-R_4-COOH(VI') ( (In the formula, R_4 has the same meaning as defined above.) The polyamide-polymer according to claim 3, which is polycondensed in the presence of an aromatic phosphite and a pyridine derivative. A method for producing a siloxane block copolymer.