JPH0436177B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a polysiloxane-polyamide multi-block copolymer and a method for producing the same, and more specifically, it has particularly high mechanical strength, excellent heat resistance, and gas selective permeability. This invention relates to a novel polysiloxane-polyamide multi-block copolymer that provides excellent molded films and a method for producing the same. (Prior Art) Polysiloxane has a flexible molecular structure, and polysiloxane-based block copolymers such as polysiloxane-polycarbonate block copolymers are known as excellent gas permeable membranes. In such polysiloxane-based block copolymers, the polysiloxane component plays an important role in developing gas permeability, and the polycarbonate component plays an important role in developing gas permeability.
It is thought that the bonate component plays a role in imparting the mechanical properties of the film. However, the intermolecular forces of polycarbonate are not necessarily strong;
Its mechanical properties are problematic. Methods for obtaining polysiloxane-polyamide or polysiloxane-polyimide block copolymers include, for example, (1) a method in which a lactam such as pyrrolidone and caprolactam is subjected to ring-opening polymerization, and then reacted with an amino group-containing polysiloxane ( Japanese Patent Application Publication 1973
(2) A method of copolymerizing the above-mentioned lactam and a polysiloxane containing a similar lactam structure or an element that initiates or promotes the ring opening of the lactam in the presence of an anionic polymerization catalyst (Japanese Patent Laid-Open Publication No. 46−6148
(3) A method of reacting an aromatic polyether having a tetracarboxylic acid residue with a disiloxane or silphenylene containing an amino group, (4) A method of reacting an aromatic diaminoamide compound with an amino group-containing polysiloxane, a diamine and Method of reacting aromatic tetracarboxylic acid (JP-A-57-42731, 57-
42732 and 58-27722) are known. However, the main purpose of (1) and (2) above is to improve the adhesion of polyamide to glass, and since the polyamide part is aliphatic, excellent heat resistance cannot be expected. The problem is that it cannot be done. In addition, method (3) is aimed at liquid crystal alignment films, and ring opening and complete curing are required.
Requires high temperature of 280℃ or higher. Furthermore,
Since the siloxane chain is short, it cannot be expected to exhibit the characteristics of a polysiloxane copolymer as a gas permeable membrane. Method (4) can form a film with excellent adhesion, heat resistance, and abrasion resistance on a glass substrate, but it requires a high temperature of 300°C to obtain the copolymer, and the reaction is difficult. However, it is complicated and difficult to control, and has the problem that it is not suitable for obtaining a copolymer with a controlled structure such as a gas permeable membrane. (Objective of the Invention) As mentioned above, polysiloxane membranes exhibit excellent gas selective permeability, but none have sufficiently high mechanical properties, which poses a major problem in the commercial use of these membranes. It is a point. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polysiloxane-polyamide multiblock copolymer that provides a molded film with excellent gas selective permeability and excellent mechanical properties, and a method for producing the same. (Summary of the Invention) The present inventors focused on the fact that polyamide has strong intermolecular forces, and decided to design and synthesize a new polymer having a polysiloxane-polyamide multi-block copolymer skeleton. Thus, the present invention has been completed. That is, the present invention is a polysiloxane-polyamide multiblock copolymer represented by the following general formula [] or []. [In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, R ³ is a hydrocarbon group, and the two hydrocarbon groups are an ether bond or a thioether bond. , a divalent group selected from groups bonded to each other via a carbonyl group or a sulfonyl group, R ⁴ is an aromatic hydrocarbon group, and the two aromatic hydrocarbon groups are an alkylene group, an ether bond, a thioether bond, A divalent aromatic hydrocarbon group selected from carbonyl groups or groups bonded to each other via a sulfonyl bond, R ⁵ and R ⁶ are each a divalent hydrocarbon group, Y is

[Formula] or (In the formula, R ¹ , R ⁵ and R ⁶ have the same meanings as above,
m represents a number from 1 to 200, and q represents a number from 1 to 10, respectively. ), m has the same meaning as above, n represents a number from 1 to 100, and p represents a number from 2 to 50, respectively. ] Furthermore, the method for producing a polysiloxane-polyamide multi-block copolymer of the present invention involves mixing a polysiloxane having carboxyl groups at both ends and a polyamide having aminoaryl groups at both ends with an aromatic phosphite ester. It is characterized by polycondensation in the presence of pyridine or a pyridine derivative. In the following, the invention will be explained in more detail. In the above general formula [ ] or [ ], p is 2 to 50, preferably in the range of 10 to 30. When p is less than 2, the characteristics of a multi-block copolymer cannot be obtained, and the mechanical properties and film-forming properties are not sufficient. Moreover, those with p exceeding 50 are difficult to synthesize and have poor solubility in solvents, making them inconvenient to handle. The polysiloxane having carboxyl groups at both ends used in the production of the polysiloxane-polyamide multi-block copolymer of the present invention includes:
Those represented by the following general formulas [] and [] are representative, and it is preferable to use at least one of these from the viewpoint of ease of synthesis. (In the formula, R ¹ , R ² and m have the same meanings as above.) (In the formula, R ¹ , R ⁵ , R ⁶ , Y and m have the same meanings as above.) In the above formula, R ¹ is a methyl group, an ethyl group,
Alkyl groups such as propyl, butyl, pentyl, hexyl, octyl, and decyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl groups; 2-phenylethyl group and 2-phenylpropyl group aralkyl groups such as; and chloromethyl groups, 3,3,3-trifluoropropyl groups,
Examples include halogen atom-substituted hydrocarbon groups such as a chlorophenyl group, but a methyl group is preferred because it is easy to synthesize and the resulting polymer has good heat resistance, mechanical properties, and gas permeability. R ² and R ⁶ are methylene group, ethylene group,
Examples include trimethylene group, tetramethylene group, hexamethylene group, decamethylene group, and phenylene group, but in R ² , due to ease of synthesis,
A divalent hydrocarbon group in which two or more carbon atoms are present between the silicon atom and the carboxyl group is preferred. R ⁵ is an ethylene group, a tetramethylene group,
Examples include hexamethylene group, octamethylene group, and phenylene group. m is from 1 to 200, preferably from 1 to 100. When m exceeds 200, the strength of the film obtained from the multi-block copolymer decreases. q is 1~
10, but a range of 1 to 3 is preferred. Examples of such polysiloxanes include the following. In order to simplify the description, the following abbreviations will be used below. Me: methyl group, Ph: phenyl group. (In the formula, m represents a number from 1 to 200 on average.) The polyamide having aminoaryl groups at both ends used in the present invention is represented by the general formula [ ]. (In the formula, R ³ , R ⁴ and n have the same meanings as defined above.) When n exceeds 100, the moldability of the multi-block copolymer decreases. Such a polyamide can be obtained, for example, by reacting an excess amount of an aromatic diamine represented by the general formula [] with a dicarboxylic acid represented by the general formula [] or a derivative thereof. H ₂ NR ⁴ NH ₂ [] (In the formula, X is a hydroxyl group, an alkoxy group,
It represents an aryloxy group, an alkylthio group, an arylthio group, or a halogen atom, and R ³ and R ⁴ have the same meanings as above. ) In the above formula, R ³ is a divalent group selected from a hydrocarbon group and a group in which two hydrocarbon groups are bonded to each other via an ether bond, a thioether bond, a carbonyl group, or a sulfonyl group, such as , alkylene groups such as ethylene group, trimethylene group, tetramethylene group, hexamethylene group and octamethylene group; cycloalkylene groups such as cyclohexylene group; aromatic hydrocarbon groups such as phenylene group, diphenylene group and naphthylene group; and methylene methylmethylene group, dimethylmethylene group, and ethylene group, or two aromatic hydrocarbon groups such as phenylene group, which are bonded to each other via an ether bond, thioether bond, carbonyl group, or sulfonyl group. It will be done. Further, ^R4 forms a hard segment in the multi-block copolymer of the present invention, and also imparts excellent heat resistance and mechanical properties to the copolymer. Examples of such R ⁴ include aromatic hydrocarbon groups such as phenylene group, diphenylene group, triphenylene group, and naphthylene group; alkylene groups such as methylene group, methylmethylene group, dimethylmethylene group, and ethylene group, or ether bond and thioether bond. , two aromatic hydrocarbon groups such as a phenylene group bonded to each other via a carbonyl group or a sulfonyl group. Examples of X include a hydroxy group; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group, an alkylthio group such as an ethylthio group; an arylthio group such as a phenylthio group; and a halogen atom such as chlorine. Examples of the aromatic diamine represented by the above formula [] include metaphenylenediamine, paraphenylenediamine, 4,4'-diaminobiphenyl,
3,3'-methylene dianiline, 4,4'-methylene dianiline, 4,4'-ethylene dianiline, 4,
4'-isopropylidene dianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 4,
4'-thiodianiline, 3,3'-carbonyldianiline, 4,4'-carbonyldianiline, 3,3'-
Sulfonyl dianiline, 4,4'-sulfonyl dianiline, 1,4-naphthalenediamine, 1,5-
Examples include naphthalene diamine and 2,6-naphthalene diamine. Among these, 3,4'-oxydianiline is preferred because it provides a copolymer with a melting point of the polyamide portion of around 200° C. and has a good balance between heat resistance and moldability. The dicarboxylic acid represented by the above formula [] and its derivatives may be any dicarboxylic acid such as aliphatic or alicyclic aromatic, but for example,
succinic acid, fumaric acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 1,3-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-
Methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-oxydibenzoic 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,
Examples include dicarboxylic acids such as 1,5-naphthalene dicarboxylic acid and 2,6-naphthalene dicarboxylic acid and derivatives thereof. Production of a polyamide having aminoaryl groups at both ends represented by the above formula [] by reacting an excess amount of the aromatic diamine represented by the above formula [] with a dicarboxylic acid represented by the above formula [] or a derivative thereof is as follows: Any known method may be used. Here, the average degree of polymerization n of the polyamide represented by the above formula [] produced from the combination of these two reaction components is usually 1 to 100, preferably 1 to 30. When n exceeds 100, the moldability of the multi-block copolymer decreases. Examples of the aromatic phosphite used in the present invention include triphenyl phosphite, diphenyl phosphite, tri(o-tolyl) phosphite,
Di(o-tolyl) phosphite, tri(m-tolyl) phosphite
Tolyl), di(m-tolyl) phosphite, tri(p-tolyl) phosphite, di(p-tolyl) phosphite, tri(o-chlorophenyl) phosphite, di(o-tolyl) phosphite chlorophenyl), tri(p-chlorophenyl) phosphite, and di(p-chlorophenyl) phosphite. Examples of pyridine or its derivatives used in the present invention include pyridine, 2-picoline,
Examples include 3,3-picoline, 4-picoline, 2,4-lutidine, 2,6-lutidine, and 3,5-lutidine. In the present invention, a polysiloxane having a carboxyl group at both ends represented by the above formula [] and/or [] and a polyamide having an aminoaryl group at both ends represented by the above formula [] are used as an aromatic compound. Polycondensation is carried out in the presence of a group phosphite and pyridine or a derivative thereof,
In this reaction, it is usually preferable to employ a solution polymerization method using a mixed solvent containing pyridine or a derivative thereof. The organic solvent used here is limited in that it does not substantially react with both components and the aromatic phosphite, but it must also be a good solvent for both reaction components and be a solvent for the reaction products. It is desirable that it is a good solvent for multi-block copolymers. Typical examples of such organic solvents include amide solvents such as N-methylpyrrolidone and N,N-dimethylacetamide. In order to obtain a multi-block copolymer with a high degree of polymerization, inorganic salts such as lithium chloride and calcium chloride, and organic salts such as triethylamine hydrochloride, tetrabutylammonium chloride, and cetyltrimethylammonium chloride are added to this reaction system. It is also possible to add. The method for producing a multi-block copolymer according to the present invention will be explained in more detail. The polycondensation reaction is carried out, for example, between a polysiloxane having carboxyl groups at both ends represented by the above formula [] and/or [] and a polyamide having aminoaryl groups at both ends represented by the above formula []. Equimolar amounts are heated and stirred in a mixed solvent containing an organic solvent represented by N-methylpyrrolidone in the presence of an aromatic phosphite and pyridine or its derivative under an inert atmosphere such as nitrogen. This is easily done by The amount of aromatic phosphite used here is usually at least an equimolar amount with respect to the carboxyl group of the polysiloxane represented by the above formula [] and/or [].
It is not economically advisable to use more than twice the molar amount. In addition, the amount of pyridine or its derivative used here needs to be at least equimolar to the carboxyl group of the polysiloxane shown in [] and/or [] above, but in reality, it is necessary to It is preferable to use it in large excess, including its role as a solvent. In the reaction, a mixed solvent consisting of pyridine or its derivative and an organic solvent represented by N-methylpyrrolidone is preferably used, but the amount of the mixed solvent used is usually 5 to 30% by weight of the reaction components. Preferably, only that amount is used. The reaction temperature is usually 60~
140°C is preferred. The reaction time is greatly influenced by the reaction temperature, but in any case it is preferred to stir the reaction system until the maximum viscosity, meaning the highest degree of polymerization, is obtained, often from a few minutes to 20 hours. The average degree of polymerization p of the multi-block copolymer represented by the above formula [] or [] to be produced is the same as the polysiloxane having carboxyl groups at both ends represented by the above formula [] or [] and the above formula. It is limited by the amount of polyamide having aminoaryl groups at both ends, which is indicated by [ ]. Under the above reaction conditions, when both reaction components are used in equimolar amounts, a multi-block copolymer having an average degree of polymerization p of around 10 can be produced. Using an excess of either of the reaction components limits the average degree of polymerization, which is undesirable for normal purposes; however, for specific purposes, it may be necessary to use an excess of either one to reduce the average degree of polymerization. It is also possible to do so. After the reaction is complete, the reaction mixture is poured into a solvent that does not dissolve the multi-block copolymer, such as methanol or hexane, to separate the produced polymer, and further purified by reprecipitation to remove by-products, salts, etc. By doing so, a purified polymer can be obtained. (Examples of the Invention) The present invention will be described below with reference to Examples. In the examples, all parts represent parts by weight. The present invention is not limited to these examples. The average molecular formula of the polysiloxane having carboxyl groups at both ends used in the examples is as follows. Example 1 4.4 parts of 3,4'-oxydianiline, 3.50 parts of isophthalic acid, 14.2 parts of triphenyl phosphite,
11.7 parts of pyridine and 2.4 parts of cetyltrimethylammonium chloride were placed in a flask, and the reaction was carried out with stirring at 100° C. for 2 hours under a nitrogen stream. 12.4 parts of dioxane and 1.34 parts of polysiloxane S-1 were added to the resulting solution, and
Polymerization was carried out by stirring for 4 hours while maintaining the temperature at 100°C.
A colorless and transparent polymer was obtained. Add this polymer solution to 400
The precipitated polymer was separated by filtration. Next, it was washed with hot methanol to obtain white flaky polymer 11. Polymer 11 in dimethylacetamide (concentration
0.5g/dl), intrinsic viscosity at 30℃ is 0.44d1/g
It was hot. Similarly, as shown in Table 1, Polymers 12 to 15 were obtained by changing the mixing ratio of raw materials and solvents.
Regarding Polymers 11 to 15, the blending ratios of raw materials and solvents, and the intrinsic viscosity and glass transition point of the obtained polymers are shown in Table 1. The specific gravity of Polymers 11 and 13 was 1.260 and 1.235, respectively. When polymer 11 was subjected to infrared spectroscopic analysis, its characteristic absorption was as follows.
Incidentally, an infrared spectroscopic analysis diagram of the polymer 11 is shown in FIG. 3300cm ^-1 (N-H) 1080cm ^-1 (Si-O
-Si) 1655cm ^-1 (C=O) 1010cm ^-1 (Si-O
-Si) 1250cm ^-1 (Si-C) Furthermore, when thermogravimetry was performed on Polymer 11, it showed almost no weight loss up to 350°C in air. Further, as a result of measuring the mechanical properties of a film obtained by casting a dimethylacetamide solution of Polymer 11, the following results were obtained. Tensile strength 63MPa Elongation at break 9% Tensile modulus 810MPa Polymers 11 to 15 obtained in this way
is represented by the following formula, and the values of n in Polymers 11 to 15 are shown in Table 1. (In the formula,

One of the formulas is the meta position and the other is the para position. The expressions of Examples 2 to 5 are also the same. )

[Table] Example 2 The procedure was the same as in Example 1 except that polysiloxane S-2 was used instead of polysiloxane S-1, but the blending ratios of raw materials and solvents were changed as shown in Table 2. Polymers 21 to 25 were obtained. Table 2 shows the blending ratio of raw materials and solvents and the intrinsic viscosity of the obtained polymer. Polymers 21 to 25 thus obtained are
It is expressed by the following formula, and the values of n in Polymers 21 to 25 are shown in Table 2.

【table】

[Table] Example 3 Polymers 31 to 3 were prepared in the same manner as in Example 1 except that adipic acid was used instead of isophthalic acid, and the blending ratios of raw materials and solvents were changed as shown in Table 3.
Got 5. Table 3 shows the blending ratio of raw materials and solvents, the intrinsic viscosity of the obtained polymer, the glass transition point, and the melting point of the polyamide part. The specific gravity of Polymers 32 and 34 was 1.236 and 1.210, respectively. still,
The infrared spectroscopy diagrams of the polymers 31, 32 and 33 are shown in FIG. Polymers 31 to 35 obtained in this way are
It is expressed by the following formula, and the values of n in Polymers 31 to 35 are shown in Table 3.

【table】

[Table] Example 4 The procedure was the same as in Example 3 except that polysiloxane S-2 was used instead of polysiloxane S-1, and the blending ratio of raw materials and solvents was changed as shown in Table 4. Polymers 41-45 were obtained. Table 4 shows the blending ratio of raw materials and solvents and the intrinsic viscosity of the obtained polymer. Polymers 41 to 45 obtained in this way are
It is expressed by the following formula, and the values of n in Polymers 41 to 45 are shown in Table 4.

[Table] Example 5 Polymer 51 was obtained in the same manner as in the synthesis of polymer 31 in Example 3, except that 3.12 parts of polysiloxane S-3 was used in place of polysiloxane S-1. Intrinsic viscosity of polymer 51 (measurement method is the same as Example 1)
was 0.37. The polymer 51 thus obtained is represented by the following formula. (Effects of the Invention) According to the method of the present invention, the polycondensation reaction proceeds at low temperatures, so high temperatures are not required, and transamide reactions and decomposition reactions of polysiloxane chains can be avoided. Furthermore, since it is possible to use an easily handled carboxylic acid as it is instead of an unstable carboxylic acid chloride, a multi-block copolymer with a controlled structure can be easily produced. On the other hand, in the method using carboxylic acid chloride, the number of functional groups decreases due to hydrolysis of the acid chloride, and side reactions occur, making it impossible to obtain a block copolymer with a controlled structure. Furthermore, the polysiloxane-polyamide multi-block copolymer obtained by the present invention can have a wide range of physical properties, from an elastic body to a tough resin-like substance, by selecting the molecular structure, molecular weight, etc. of both reaction components. It can be obtained as a polymer and is useful as a material for fibers and films.
In addition, it has excellent heat resistance and solvent resistance, and mechanical properties and gas permeability can be set arbitrarily by controlling the structural ratio of polysiloxane and polyamide.
It is highly useful as a gas selective permeation membrane, etc.

[Brief explanation of drawings]

FIG. 1 shows polymer 11, and FIG. 2 shows polymer 3.
1, 32, and 33, respectively, show infrared spectroscopic analysis diagrams.

Claims (1)

[Claims] 1. A polysiloxane-polyamide multi-block copolymer represented by the following general formula [] or []. [In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, R ³ is a hydrocarbon group, and the two hydrocarbon groups are an ether bond, a thioether bond, A divalent group selected from groups bonded to each other via a carbonyl group or a sulfonyl group,
R ⁴ is a divalent aromatic carbide selected from an aromatic hydrocarbon group and a group in which two aromatic hydrocarbon groups are bonded to each other via an alkylene group, an ether bond, a thioether bond, a carbonyl group, or a sulfonyl bond. Hydrogen group, R ⁵ and R ⁶ are each divalent hydrocarbon groups, Y is [Formula] or (In the formula, R ¹ , R ⁵ and R ⁶ have the same meanings as above,
m represents a number from 1 to 200, and q represents a number from 1 to 10, respectively. ), m has the same meaning as above, n represents a number from 1 to 100, and p represents a number from 2 to 50, respectively. 2. The multi-block copolymer according to claim 1, wherein R ¹ is a methyl group. 3. The multi-block copolymer according to claim 1, wherein ^R2 is an alkylene group having 2 to 20 carbon atoms. 4. The multi-block copolymer according to claim 1, wherein R ⁴ is a bisphenylene ether group. 5 Claim 1 in which R ⁶ is a methylene group
The multi-block copolymer described in . 6 General formula: (In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, and m is 1
Represents the number ~200. ) and/or [In the formula, R ¹ has the same meaning as above, R ⁵ and R ⁶
are each a divalent hydrocarbon group, Y is, [Formula] (In the formula, R ¹ , R ⁵ and R ⁶ have the same meanings as above,
m represents a number from 1 to 200, and q represents a number from 1 to 10, respectively. ), where m has the same meaning as above. ] Polysiloxane and general formula: (In the formula, R ³ is a divalent group selected from a carbon hydrogen group and a group in which two hydrocarbon groups are bonded to each other via an ether bond, a thioether bond, a carbonyl group, or a sulfonyl group, and R ⁴ is an aromatic a divalent aromatic hydrocarbon group selected from group hydrocarbon groups, and groups in which two aromatic hydrocarbon groups are bonded to each other via an alkylene group, an ether bond, a thioether bond, a carbonyl group, or a sulfonyl bond, and n
represents a number from 1 to 100. ) is polycondensed with an aromatic phosphite in the presence of pyridine or a pyridine derivative. Method for producing block copolymer. (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m and n
has the same meaning as above, and p represents a number from 2 to 50. ) 7 Aromatic phosphites include triphenyl phosphite, diphenyl phosphite, tri(o) phosphite,
-tolyl), di(o-tolyl) phosphite, tri(m-tolyl) phosphite, di(m-tolyl) phosphite,
Triphosphorous acid (p-tolyl), diphosphorous acid (p-tolyl)
tolyl), tri(o-chlorophenyl) phosphite,
Di(o-chlorophenyl) phosphite, tri(p-chlorophenyl) phosphite and di(p-chlorophenyl) phosphite
7. The method for producing a multi-block copolymer according to claim 6, wherein the multi-block copolymer is selected from the group consisting of chlorophenyl. 8 Pyridine or pyridine derivative is pyridine,
The multi-block combination according to claim 6, which is selected from 2-picoline, 3,3-picoline, 4-picoline, 2,4-lutidine, 2,6-lutidine and 3,5-lutidine. Method for producing polymers.