JPH0343418A - Polysiloxane-polyamide-based block copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polysiloxane-boriad block copolymer.

[Conventional technology]

Polyamide resins are used in many fields, such as films, wire coatings, adhesives, paints, and laminated products, due to their excellent properties such as heat resistance. It has the disadvantage of poor properties and therefore lacks workability. In order to solve this drawback, various modified polyamides have been widely developed in which ether bonds, ester bonds, siloxane bonds, etc. are introduced into the main chain of polyamide.

In particular, regarding polysiliconamide, various polysiliconamide resins using various diaminosiloxanes have been proposed.

[Problem that the invention seeks to solve]

However, these modified polysiliconamide resins are heat resistant,
Although flexibility etc. are good, adhesion to resin films etc. is insufficient. Therefore, in order to balance these advantages and disadvantages, compounding with other reactive resins is being considered, but the situation is still insufficient. The main cause is
Because these modified polysilicon ad resins and other reactive resins are not uniformly mixed in the desired composition, the expected properties are not expressed.

Therefore, the object of the present invention is to provide a polysiloxane which is soluble in organic solvents, has reactive active sites for other reactive resins, and can be uniformly mixed with other reactive resins in a desired composition.
An object of the present invention is to provide a polyamide block copolymer.

[Means to solve the problem]

The present invention is based on the general formula (wherein R1 is an aliphatic, aromatic, or alicyclic divalent organic group, R2 is a divalent organic group having 30 or less carbon atoms, and m and n are integers. ) is a polysiloxane-polyamide block copolymer characterized by having a repeating unit represented by:

The divalent organic group for R2 is preferably a C1-C6 alkylene group, such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and the like.

m is an integer of 1Jf to 200, preferably 10 to 100.

The compound of formula (1) is a polysiloxane having amine 7 groups at both ends represented by the general formula (wherein R2 and m have the above meanings), and the compound has the general formula (wherein R1 and n have the above meanings). It can be obtained by polycondensation reaction with a polyamide having carboxyl groups at both ends represented by (having).

The polysiloxane having amino groups at both ends represented by formula (2) used in the present invention may be produced by any method of introducing amino groups at both ends of the polysiloxane molecule.

Commercially available products can also be used as the compound of formula (2).

In addition, the polyamide having carboxyl groups at both ends of formula (3) is obtained by polycondensing a diamine compound represented by the general formula % formula % (4) (in the formula has the meaning of R' It theory) with an aromatic dicarboxylic acid. It can be manufactured by a known method.

Examples of the diamine compound (4) include the following compounds. N, t-bis(2-aminophenyl)isophthalamide, N, N'-bis(3-annophenyl)inphthalamide, N, "-bis(4-annophenyl)inphthalamide, N, " -bis(2-aminophenyl) terephthalamide, N, ibis(6-aminophenyl) terephthalamide, N, t-bis(4-aminophenyl) terephthalamide, N, "-bis(2-aminophenyl) phthalamide, N, rr-bis(6-aminophenyl) phthalamide, N, I-bis(4-aminophenyl) phthalamide, N, N'-bis(2-aminophenyl) phthalamide, N, Ebis(3-aminophenyl) phthalamide , N, N'-bis(4-aminophenyl)phthalamide, N, "-bis(4-amino-
6,5-dimethylphenyl)isophthalamide, N,
pr-bis(4-amino-6,5-dimethylphenyl)terephthalamide, N,I-bis(4-amino-3,5-
dimethylphenyl)phthalamide, N, “-bis(4-
Amino-6,5-dimethylphenyl)phthalamide, N
, 1subis(4-a□)n-butyl)diisophthalamide, N, ``-bis(4-amino n-hexyl)isophthalamide, N,N'-bis(4-amino n-dodecyl)isophthalamide m-phenylenediamine, p-phenylenediamine, metatolylenediamine, 4,4'-
Diaminodiphenyl ether, 3,6'-dimethyl-4
, 4'-diaminodiphenyl ether, 6.6'-diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4.4'-diaminodiphenyl thioether, 3.3'-dimethyl-4,4'-diaminophenyl thioether, 6 , 6'-jethoxy-4,4'-diaminophenylthioether, 6,6'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 6.3 '-Diaminodiphenylmethane, 4.4'
-diaminodiphenylmethane, 6,3-dimethoxy-4
, 4'-diaminodiphenylmethane, 2,2'-bis(
4-aminophenyl)propane, 2,2'-bis(6-
aminephenyl)furopane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, 3,5'-dimethylbenzidine, 5,5'-dimethyl Benzidine(4-(4-aminophenoxy)phenyl)propane, 2,2-bis[6-methyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[6-chloro-4-( 4-aminophenoxy)phenyl]propane,
2.2-bis(3,5-dimethyl-4-(4-aminoneenoxy)phenyl)propane, 1,1-bis(4-(
4-aminophenoxy)phenyl]ethane, 111-bisc 3-1oo-4-(4-aminophenoxy)phenyl]ethane, bisC4-(4-aminophenoxy)phenylcomethane, bis[6-methyl-4- (4-Aminephenoxy)phenylcomethane, piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylenediamine, m-xylenediamine, 6-methylhebutamethylenediamine, 1.3-
Bis(4-aminophenoxy)benzene 2.2-bis(
4-aminophenyl) -1,1,1,3゜6.6-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl:] -1+L1.3,3.3
- Heki? Fluoropropane etc.

Examples of aromatic dicarboxylic acids having a hydroxyl group include t,
6-hydroxyphthalic acid, 4-hydroxyphthalic acid, 2
-Hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 6-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 6-hydroxyterephthalic acid and the like.

Polycondensation reaction between polysiloxane having amino groups at both ends of formula (2) and polyamide having carboxyl groups at both ends of formula (3) to form the polysiloxane-polyamide block copolymer of the present invention This can be performed using a known method.

In the present invention, the polymerization reaction is carried out in the presence of a condensing agent.
Performed in a non-reactive organic solvent such as dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoric triamide, etc. be exposed.

If necessary, inorganic salts such as lithium chloride and calcium chloride, triethylamine hydrochloride, tetrabutylammonium chloride, and cetyl trimethyl may be added to activate the catalytic action to increase the degree of polymerization and to prevent pseudo-crosslinking of the resulting polymer. Organic salts such as ammonium chloride can also be added to the reaction system.

As a condensing agent, ring triphenyl phosphate, diphenyl phosphite, tri-tolyl-sulfite, di--
Tolyl, phosphite tri-m - Tolyl, phosphite di-m
-tolyl, tri-p-)lyl phosphite, di-p-)lyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-p-lyl phosphite
o phenyl, dicyclohexylcarbodiimide, triphenyl phosphate, diphenyl phosphonate, etc. are used.

The reaction temperature is preferably 60 to 140°C.

The reaction time varies greatly depending on the reaction temperature, but is usually from several minutes to 20 hours. It is preferred to stir the reaction system until a maximum viscosity is obtained, meaning the highest degree of polymerization.

After the reaction is complete, the reaction mixture is poured into a poor solvent such as methanol or hexane to separate the produced polymer, and further purification is performed using a reprecipitation method to remove byproducts, salts, etc. to obtain a purified polymer. can be obtained. The viscosity of the obtained polymer is 0.1 to 3. Od/g preferably 0.2-1
．． 0 cll/g.

〔Effect of the invention〕

The polysilicon amide resin of the present invention has excellent heat resistance and solvent solubility, and can be uniformly mixed with other reactive resins in a desired composition. The polyamide □ resin of the present invention is a very useful material for applications such as films used at high temperatures, wire coatings, adhesives, paints, and laminates.

Example 1 3.41-sia□nodiphenyl ether 20g (100
mmol), 5-hydroxyinphthalic acid 27.3,
A mixed solution of F (150 mmol), 25 Qml of pyridine, 62 g (200 mmol) of triphenyl phosphite, and 10.6 g (250 mmol) of lithium chloride was added to 100
Stirred at °C for 4 hours. Poly(dimethylsiloxane)diamine 1 having an average molecular weight of 6880 was added to the obtained polymer solution.
94 g (50 mmol) was added, and the mixture was further stirred at the same temperature for 4 hours. After cooling, the reaction mixture was diluted with methanol 5000 ml.
mg, stirred at room temperature for 1 hour, and the precipitated solid matter was collected from house to house. The obtained solid was washed with hot methanol, dried, and had an intrinsic viscosity of 0.51 cn, Q (N
- in methyl-2-pyrrolidone, 5&/l concentration, 30°
A polysiloxane-polyamide block copolymer of C1 and below) was obtained.

Example 2 27.39 (150 mmol) of 5-hydroxyisophthalic acid was mixed with 27.3 g (150 mmol) of 4-hydroxyisophthalic acid.
Polysiloxane with an intrinsic viscosity of 0.28 cn/g was prepared in the same manner as in Example 1 except for
A polyamide block copolymer was obtained.

Example 3 27.3 g (150 mmol) of 5-hydroxyisophthalic acid was mixed with 27.3 g (150 mmol) of 2-hydroxyterephthalic acid.
50 mi! A polysiloxane-polyamide based block copolymer having an intrinsic viscosity of 0.30617 g was obtained by replacing it with J mole) and otherwise operating in the same manner as in Example 1.

Example 4 20g (100g) of 3.4'-diaminodiphenyl ether
mmol) to 3,3'-diaminodiphenylsulfone 2
4.8g (100 mmol), other than Example 1
A polysiloxane-polyamide block copolymer having an intrinsic viscosity of 0°25 dl/E/ was obtained in the same manner as above.

Example 5 3147-dia□nodiphenyl ether 20.9 (1
00 mmol) was replaced with 29.29 (100 mmol) of 1,3-bis(4-aminophenoxy)benzene, and otherwise operated in the same manner as in Example 1 until the intrinsic viscosity was 0.30 d.
A polysiloxane-polyamide block copolymer having a ratio of 1/9 was obtained.

Example 6 Poly(dimethylsiloxane) with an average molecular weight of 6880
Diamine 1949C50 mmol) with an average molecular weight of 17
20 poly(dimethylsiloxane) diamine 861 (5
A polysiloxane-polyamide block copolymer having an intrinsic viscosity of 0°35 d1/g was obtained by performing the same procedure as in Example 1 except for using 0 mmol).

The repeating units of the polyamide resins obtained in Examples 1 to 6 are shown below. Z in the formula is CHs CHs CHs, CH.

shows. In addition, p is 50. in Examples 1 to 5. In Example 6, it is 21.

Example 1: Example 2: Example 6: Example 4: Example 5: Example 6:

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R^1 is an aliphatic, aromatic, or alicyclic divalent organic group, and R^2 is the number of carbon atoms. is a divalent organic group m and n having 30 or less
is an integer) A polysiloxane-polyamide block copolymer having a repeating unit represented by: