JPS62256820A - Production of polyether-polyamide block copolymer - Google Patents

Abstract

PURPOSE:To obtain a block copolymer excellent in transparency, impact strength and solvent resistance by a simple reaction process, by copolymerizing a specified aromatic diisocyanate with a specified dicarboxylic acid and a specified telechelic polyether oligomer. CONSTITUTION:At least one aromatic diisocyanate (a) of the general formula: OCN-Ar-NCO (wherein Ar is a bivalent aromatic residue of -C6H4-X-C6H4- or tolylene and X is -CH2- or -O-) is copolymerized with at least one dicarboxylic acid (b) of the general formula: HOOC-R-COOH (wherein R is a bivalent aromatic or aliphatic hydrocarbon residue of phenylene or -(CH2)n- and n is an integer of 2-12) and a telechelic polyether oligomer (C) terminated with diol groups, diamino groups or dicarboxylic groups.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a novel polyether-polyamide block copolymer.

[Conventional technology and its problems]

Various methods have been studied for the production of polyamide block copolymers. For example, in British Patent No. 1,243,238, a polyether oligomer having a terminal diol group is reacted with a diisocyanate. A method has been proposed in which a polyether oligomer having a diisocyanate group at both terminals is synthesized, and this is reacted with a polyamide having a diamino terminal group synthesized in advance.

However, the above method has problems in that the reaction is complicated and involves multiple steps, and a high molecular weight product cannot be obtained.

Also, in the specification of Japanese Patent Publication No. 46-26979, α, ω
A method has been proposed for producing a polyether-polyamide plotter copolymer by reacting -diaminopolyalkylene oxide, dicarboxylic acid, and diamine at a high temperature of 250° C. or higher for a long period of time. However, this method has problems such as coloration due to high reaction temperature, and cannot necessarily be said to be an industrially preferable method, and also has the disadvantage that a high molecular weight product cannot be obtained.

Additionally, U.S. Pat.
420.602, the terminal hydroxyl group of a polyether oligomer and an aliphatic dicarboxylic acid are reacted,
A method has been proposed for producing a polyether-polyamide plotter copolymer containing an ester group using the obtained polyether oligomer of terminal dicarboxylic acid containing an ester group. However, since the polymer obtained by this method contains an ester group, there are problems with hydrolysis resistance, thermal stability, etc.

In addition, dicarboxylic acid and an excess amount of diamine relative to the dicarboxylic acid are reacted using triphenyl phosphite and pyridine as condensing agents to synthesize a polyamide oligomer of terminal diamine, which is then reacted with a polyether oligomer of terminal dicarboxylic acid. A method for producing a polyamide-polyether block copolymer has been proposed. However, this method requires an equivalent amount of condensing agent to the substrate, is difficult to recover and recycle, and has problems such as the condensing agent remaining in the polymer. It was hard to say that it was the preferred method.

An object of the present invention is to overcome the problems of the prior art described above and to provide an industrially advantageous method for producing a novel polyether-polyamide plotter copolymer containing no ester group.

[Means for solving problems]

The present invention is based on (a) general formula: % formula % () (Ar in the formula is a divalent aromatic residue represented by -C6H4-X-C,H4- or tolylene, and X is -CH2
- or -〇-), one or more aromatic diisocyanates (bl general formula: % formula % () (R in the formula is phenylene or -+ GHz +- one or more dicarboxylic acids represented by (n is an integer of 2 to 12), and (C) at the terminal This is a method for producing a polyether-polyamide block copolymer, which comprises copolymerizing a telechelic polyether oligomer having a diol group, diamino group or dicarboxylic acid group.

That is, according to the present invention, one or more aromatic diisocyanates represented by the general formula (1) and one or more dicarboxylic acids represented by the general formula (■) are used as the polyamide segment. Using a telechelic polyether oligomer that has a polyamide component obtained by reaction and has a terminal diol group, diamino group, or dicarboxylic acid group as a polyether segment,
A polyether-bolyamide block copolymer can be obtained by copolymerizing with the above polyamide component.

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

Preferred examples of aromatic diisocyaner (I) used in the present invention include diphenylmethane-4゜4゛-diisocyanate, diphenyl ether-4,4''-diisocyanate, 2.4-)lylene diisocyanate, 2.
6-) lylene diisocyanate or a mixture thereof, among which diphenylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate,
2.6-Tolylene diisocyanate is particularly preferred.

Dicarboxylic acids used in the present invention include isophthalic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid,
pimelic acid, speric acid, azelaic acid, sebacic acid,
Undecanniic acid, dodecanniic acid, tridecanniic acid, tetradecanniic acid, or a mixture thereof, with isophthalic acid, adipic acid, and azelaic acid being particularly preferred.

Telechelic polyether oligomers having terminal diol groups used in the present invention include polyoxymethylene, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide random copolymer, and polyethylene glycol-polymer. Poly(alkylene ether) diols typified by propylene glycol prosocopolymer or mixtures thereof are used.

Telechelic polyether oligomers having terminal diamino groups used in the present invention include polyoxyethylene diamine (α, ω-diaminopolyoxyethylene),
Polyoxypropylene diamine (α, ω-diaminopolyoquine propylene), polyoxytrimethylene diamine (α, ω-diaminopolyoxytrimethylene), polyoxytetramethylene diamine (α, ω-diaminopolyoxytetramethylene), α , ω-diaminopolyoxyethylene-polyoxypropylene block copolymer, α,
Poly(alkylene ether) diamines such as ω-diaminoethylene oquine dopropylene oxide random copolymers or mixtures thereof are used.

Furthermore, the telechelic polyether oligomers with terminal dicarboxylic acids used in the present invention include polyoxyethylene dicarboxylic acid (α, ω-dicarboxyl polyoxyethylene), polyoxypropylene dicarboxylic acid (α, ω-dicarboxylic acid),
dicarboxylic polyoxypropylene), polyoxytrimethylene dicarboxylic acid (α, ω-dicarboxyl polyoxytrimethylene), polyoxytetramethylene dicarboxylic acid (α, ω-dicarboxyl polyoxytetramethylene), α, ω-dicarboxylic acid (α, ω-dicarboxyl polyoxytetramethylene), Poly(alkylene ether)dicarboxylic acids such as carboxylpolyoxyethylene-polyoxypropylene block copolymers, α,ω-dicarboxylethylene oxide-propylene oxide random copolymers, or mixtures thereof are used.

In the present invention, diol-, diamino-, and dicarboxylic acid-terminated polyether oligomers are usually used alone, but different terminal types can also be used simultaneously.

The average molecular weight of the telechelic polyether oligomer used in the present invention is preferably from 500 to 6,000, more preferably from 1,000 to 5,000.

The catalyst used in the present invention includes 1-phenyl-3-
Methyl-2-phosphosine-1-oxide, 1,3-dimethyl-2-phosphosine-1-oxide, 1-phenyl-3-methyl-2-phosphosine-1-sulfide, 1
, phosphorus compounds such as 3-dimethyl-2-phosphosine-1-sulfide, tertiary amines such as triethylenediamine, hexamethylenetetramine, 1-ethylpiperidine, 1,8-diazabicyclo(5,4,0)-7-undecene, etc. alkaline alcoholades such as lithium methylate, sodium methylate, potassium methylate, lithium t-butyrate, sodium L-butyrate, potassium t-7' tylate, and sodium ferulate;
Alkali metal sectorates such as sodium probiolaphtamate, potassium propiocyclomate, lithium probiolatamate, sodium pyrrolidone, potassium pyrrolidone, and lithium pyrrolidone, alkali metal salts of acetic acid, etc. are used, and among these, 1= Phoenix Lou 3
-Methyl-2-phosphosine-1-oxide is particularly preferred.

The amount of the catalyst used is preferably 0.05 to 20 mol%, more preferably 0.1% by mole based on the aromatic diisocyanate.
It is used in a range of 10 mol%. Further, when a telechelic polyether oligomer having a terminal diol is used as the polyether oligomer, a tertiary amine, alcoholate, ferlate, organometallic compound, etc. are used in combination with the above-mentioned catalyst as a catalyst. Specific examples of these catalysts include lithium methylate, sodium methylate, potassium methylate, lithium-t-butyrate,
Sodium t-butyrate, potassium t-butyrate, sodium ferulate, lithium acetate, sodium acetate, potassium acetate, alkali metal alcoholate of 2-ethylhexanol, alkali metal salt of 2-ethylcaproic acid, lead octoate, tin octoate , nickel octoate, nickel acetylacetonate, dibutyl-tin-dilaurate, ethylamine, 1-ethylpiperidine, l,8-diazabicyclo(5,4,0)-7-undecene, etc. Among these, dibutyl -tin-dilaurate is preferred. These catalysts are preferably used in an amount of 0.01 to 5 mol%, more preferably 0.05 to 1 mol%, based on the aromatic diisocyanate.

The molar ratio of the aromatic diisocyanate component to the total of the dicarboxylic acid component and polyether oligomer used in the present invention is preferably in a chemical Ha1, ie, equivalent relationship, but is 0.9 to 1.10 (di The reaction can be carried out within the range of molar ratio of isocyanate component/dicarboxylic acid component to polyether oligomer. In order to obtain a high molecular weight polyether-polyamide plotter copolymer, this ratio is preferably 1.0 or more, and 1.0 to 1.0.
It is particularly preferred to carry out the reaction at a molar ratio of 0.08.

In the present invention, tetramethylene sulfone (sulfolane) or diphenyl sulfone is used as the reaction solvent. So-called amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphorotriamide, which are generally considered to be good solvents for aromatic polyamides. reacts with diisocyanate-1- during the reaction, according to Ulrich, N. Journal of Polymer Science (J, Polyn+, Sci.
Macrosolecular Reviews, 11
．． 93 (1976)), and because of these side reactions, it is extremely difficult to obtain high molecular weight polyether-polyamide block copolymers in these amide solvents.

In the present invention, the reaction is preferably carried out at 60-200°C,
More preferably, the temperature range is 120 to 200°C. If the temperature exceeds 200°C, the trimerization reaction of the diisocyanate will occur in advance during polymerization, resulting in a gel-like polymer, which is not preferred. Furthermore, at temperatures below 60°C, the polymer will precipitate during the polymerization reaction, making it difficult to obtain a high polymer.

The reaction time is usually 1 to 4 hours.

The polyamide-polyether block copolymer can be preferably produced by the following two methods.

The first method is a one-step polymerization method in which an aromatic diisocyanate component, a dicarboxylic acid component, and a telechelic polyether oligomer component are simultaneously mixed and a polymerization reaction is carried out.

The second method involves first reacting a dicarboxylic acid component with an aromatic diisocyanate component in an excess amount relative to the dicarboxylic acid component to produce a polyamide oligomer having isocyanate groups at both ends in a solution. This is a two-step polymerization method in which a polyether oligomer component is added and reacted.

When polymerization is carried out by a two-step polymerization method, the chain length of the polyamide segment in the block copolymer can be controlled to the desired chain length by adjusting the amount of aromatic diisocyanate in excess of the dicarboxylic acid component. It is possible.

In this case, the molecular weight of the polyamide segment is generally 2
A range of 00 to 30,000 is used, but 300 to 2
A range of 0,000 is particularly preferred.

When polymerization is carried out by a one-step polymerization method, it is possible to obtain a block copolymer in which polyamide segments and polyether segments are more randomly distributed than by a two-step polymerization method.

Depending on the purpose of use of the block copolymer, any of the above polymerization methods can be adopted, and a high molecular weight polyether-bolyamide block copolymer can be produced using any of the polymerization methods. is possible.

For separation and purification of the block copolymer obtained after completion of polymerization, methods generally used for separation and purification of this type of polymer can be used.

For example, the polymer can be isolated by a method in which the obtained polymer solution is added to a non-solvent such as water or alcohol to precipitate the polymer, or a method in which the solvent is distilled off together with water vapor.

The polyether-polyamide copolymer produced according to the present invention can be used as a heat stabilizer, ultraviolet absorber, antioxidant (antiaging agent), mold release agent, antistatic agent, pigment, glass fiber, carbon, etc., depending on the purpose of use. Fibrous fillers such as fibers, asbestos, polyaramid fibers, etc. or powdered fillers such as calcium carbonate, silica, talc, titanium oxide, etc. can be added.

The block copolymer obtained by the present invention can be molded into various articles by known molding techniques depending on the purpose of use. Suitable molding methods include injection molding, extrusion, pressure molding and similar molding methods. - It is also possible to dissolve this block copolymer in various solvents and create films from this solution.

The block copolymer obtained by the present invention has excellent transparency, impact strength, and solvent resistance, and can be used in a wide temperature range. As molded products, it can be used for various hoses, wires, cables, belts, gaskets, diaphragms, etc. The film is also used for lining various tanks,
Used for various bags, etc.

Further, the block copolymer obtained by the present invention can be blended with various plastics and used as an impact modifier for various plastics. Blended plastics include polyethylene, polypropylene, polyvinyl chloride, polymethylmethacrylic resin, acrylic resin, acrylonitrile-styrene resin (
AS), high impact polystyrene (HIPS), polystyrene (PS), ABS (acrylonitrile-butadiene-styrene) resin, AAS (acrylonitrile-acryl-styrene) resin, MS (methyl methacrylate-styrene) resin, styrene-maleic anhydride (
Styrenic resins such as SMA) resins, nylon 6, 6.6
．． 4.6゜11, 12 etc. nylon resin, PET,
It can be blended with polyesters such as PBT, polyarylates, polycarbonates, polyacetal resins, polyphenylene oxides, polysulfones, polyethersulfones, polyphenylene sulfides, polyetheretherketones, polyetherimides, polyamideimides, and the like.

〔Effect of the invention〕

According to the present invention, the reaction process is extremely simple in one or two steps, the desired molecular weight substance can be obtained by changing the reaction conditions, and transparency, impact strength, solvent resistance, and hydrolysis resistance are It is possible to provide a block copolymer that has excellent properties and can be used in a wide temperature range. Further, by the production method of the present invention, block copolymers with polyamide and polyether segments of various lengths can be produced, and block copolymers with a wide range of properties can be obtained.

Further, the production method of the present invention does not have the problem of condensing agents remaining in the polymer, and the polymer purification process can be simplified, making it excellent as an industrial production method.

〔Example〕

The present invention will be specifically explained below using Examples and Comparative Examples.

In addition, in the examples and comparative examples, the logarithmic viscosity (η8,
) has a polymer concentration of 0.5 g/100m at 30°C.
An N,N-dimethylacetamide solution of / was prepared and measured at 30° C. using a Cannon-Fenske viscometer, and calculated using the following formula.

Lo・Outflow time of solvent (seconds) 1.・Outflow time of polymer solution (seconds) C=Concentration of polymer solution (grams of polymer per solution Loom It) Oxyethylenedicarboxylic acid (both terminal carboxyl groups, v7=3,900)
A polyether-polyamide plotter copolymer was synthesized using a one-step polymerization method.

4.8 mmol of isophthalic acid, 4.8 mmol of azelaic acid, polyoxyethylenedicarboxylic acid (M.

=3,900) 0.4 mmol, 1-phenyl-3
-Methyl-2-phosphosine-1-oxide 0.025
Stir millimoles of tetramethylene sulfone 15m/
The samples were placed in a flask equipped with an AM, a nitrogen introduction tube, and a dropping funnel, and heated to 200° C. to dissolve each sample.

Diphenylmethane-4,4'-diisocyanate 10.
A solution was prepared by dissolving 0.05 mmol in 10 mA of tetramethylene sulfone, and this was added dropwise from the dropping funnel to the tetramethylene sulfone solution of the dicarboxylic acid and polyether oligomer.

All of the above operations were performed under a nitrogen atmosphere.

Simultaneously with the dropwise addition of the diisocyanate component, CO□ (carbon dioxide) began to be generated, the reaction progressed, and the viscosity of the solution gradually increased.

After finishing dropping the diisocyanate component, heat to 200℃ for 3 hours.
Stirring was continued. The obtained polymer solution was poured into a large amount of water and solidified.

After the coagulated polymer was filtered, it was added to about 300 ml of methanol, and the methanol was heated under reflux for about 1 hour to purify the polymer. After heating and refluxing methanol, the polymer was filtered off and dried. η1nh= 0.76 d
l/g of polymer was obtained with a yield of 91%.

The result of IR (infrared) analysis of the obtained polymer was 1650"
” (shi c-o), 3300 cm-' (νNi1).

Elemental analysis results: Actual value C68,87X I+ 7.00 AN
5.83% Calculated value C69,40X H7,10X
It was N5.81X.

Polymer N,N-dimethylacetamide? A transparent and strong film could be obtained by film casting from a liquid solution.

叉旌■ The main polyether oligomer is polyoxyethylene dicarboxylic acid (both terminal carboxyl groups, rich.

A polyether-polyamide plotter copolymer was synthesized by a two-step polymerization method using 3,900).

4.8 mmol of isophthalic acid, 4.8 mmol of azelaic acid, 1-phenyl-3-methyl-2-phosphosine-
1-oxide 0.025-9 methylene sulfone 15m
j! into a flask equipped with a stirrer, nitrogen inlet tube, and dropping funnel:. ．． Each sample was dissolved by heating to 20°C.

Diphenylmethane-4,4'-diisocyanate 10.
A solution was prepared by dissolving 0.05 mmol in 10 ml of tetramethylene sulfone, and this solution was dropped into the tetramethylene sulfone solution of the dicarboxylic acid described above from the dropping funnel.

All of the above operations were performed under a nitrogen atmosphere.

At the same time as the diisocyanate component was added dropwise, CO2 (carbon dioxide) began to be generated. When the generation of CO2 was almost completed and the theoretical amount of CO□ had been generated, 0.4 mmol of polyoxyethylene dicarboxylic acid (M. = 3,900) was added. The timing of addition of polyoxyethylene dicarboxylic acid was 15 minutes after the start of polymerization by dropping diisocyanate. After addition of the polyoxyethylene dicarboxylic acid, stirring was continued at 200° C. for 4 hours. The obtained polymer solution was poured into a large amount of water and solidified.

The coagulated polymer was filtered and then added to methanol at about 300 mA, and the methanol was heated under reflux for about 1 hour to purify the polymer. After heating and refluxing methanol, the polymer was filtered off and dried. η,.

= 0.92 dl/g of polymer was obtained with a yield of 94%.

Results of IR (infrared) analysis of the obtained polymer 1650c
m-' (shi, 8.), 3300cm-'(1'-)
Met.

Results of elemental analysis: Actual value C 69.36χ H 7.16χ N S
．． 83χ calculated value C 69.40χ H 7.10χ
N was 5.81χ.

A transparent and strong film could be obtained by dissolving the polymer in N,N-dimethyl-acetamide and then using a film casting method.

4.5 mmol of isophthalic acid and 4.5 mmol of azelaic acid were used as the main dicarboxylic acid components, and 1.0 mmol of polyoxyethylene dicarboxylic acid (M, = 3,900) was used.
Polymerization, purification, and isolation were carried out in the same manner as in Example 1, except that mmol was used.

η8. ．． A yield of 87% of polymer with h·0.53 dl/g was obtained.

A film was made from the polymer thus obtained by a film casting method using N,N-dimethylacetamide as a solvent, and from this film 1. OcmX5. Q
cm, thickness approximately 0. Cut out the IH film and make 20z
The tensile test was conducted at a tensile speed of /min.

As a result, TM=47MPa STS (at break)=21
MPa, and elongation at break was 510't.

Example 2 except that 4.9 mmol of isophthalic acid, 4.9 mmol of azelaic acid, and 0.2 mmol of polyoxyethylene dicarboxylic acid (M,...3,900) were used as dicarboxylic acid components. Polymerization, purification, and isolation were performed in the same manner.

89% polymer with ηrnh = 0.83 di/g
was obtained in a yield of .

A film was made from the polymer thus obtained by a film casting method using N,N-dimethylacetamide as a solvent, and from this film 1. QcmX5
．． Cut out a film with an o mark and a thickness of approximately 0.11, and
The tensile test was conducted at a tensile speed of /min.

As a result, TM=1. I GPa, TS (at rupture)
=47 MPa, and elongation at break was 160χ.

Examples 5 to 7 Polymerization, purification, and isolation were carried out in the same manner as in Example 1, except that the composition ratio of the dicarboxylic acid component and the polyoxydiethylenedicarboxylic acid component was varied.

The polymerization results are summarized in Table 1.

Examples 8 to 10 Polymerization, purification, and isolation were carried out in the same manner as in Example 2, except that the composition ratio of the dicarboxylic acid component and the polyoxyethylene dicarboxylic acid component was varied.

The polymerization results are summarized in Table 2.

Using polytetramethylene ether glycol (-〇H groups at both ends, DuPont Company "Teratane 2000", Kawa, = 2,000) as a polyether oligomer, polyether-bolyamide broth copolymerization was performed by a one-step polymerization method. Synthesized the union.

3.6 mmol of isophthalic acid, 3.6 mmol of azelaic acid, polytetramethylene ether glycol (“Teratane 2000”, M,, = 2,000) 2.8
0.025 mmol of -phenyl-3-methyl-2-phospholene-1-oxide, 0.02 mmol of dibutyl-tin-dilaurate, and 15 mj2 of tetramethylene sulfone were placed in a flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel. and heated to 200°C to dissolve each sample.

diphenylmethane-4,4'-diisocyaner) 10
．． 05 mmol to 10m of tetramethylene sulfone! !
A solution was prepared by dissolving the above dicarboxylic acid and polyether oligomer into the tetramethylene sulfone solution from the dropping funnel.

All of the above operations were performed under a nitrogen atmosphere.

Simultaneously with the dropwise addition of the diisocyanate component, CO□ (carbon dioxide) began to be generated, the reaction progressed, and the viscosity of the solution gradually increased.

After finishing dropping the diisocyanate component, heat to 200℃ for 3 hours.
Stirring was continued for m. The obtained polymer solution was poured into a large amount of water and solidified.

After the coagulated polymer was filtered, it was added to about 300 ml of acetone, and the acetone was heated under reflux for about 1 hour to purify the polymer. After heating with acetone, the polymer was filtered off and dried.

η+,, h = 1.09 dl/g of polymer is 97
% yield.

Results of TR (infrared) analysis of the obtained polymer 1650c
m-' (c=o), 3300cm-' (νNH)
Met.

Results of elemental analysis: Actual value C69, 11% H9, 21% N 3
．． 27% Calculated value C69,32X H9,232N
3.20! Met.

A transparent and strong film could be obtained by film casting from a solution of the polymer in N,N-dimethylacetamide.

A polyether-polyamide plotter copolymer was synthesized by a two-step polymerization method using polytetramethylene ether glycol (Dupont Co., Ltd. "Teratane 2000", wealth, = 2.000) as a polyether oligomer.

3.6 mmol of isophthalic acid, 3.6 mmol of azelaic acid, l-phenyl-3-methyl-2-phosphosine-
1-oxide 0.025 mmol, dibutyl-tin-
dilaure) 0.02 mmol, tetramethylene sulfone 15IllI! was placed in a flask equipped with a stirring device, a nitrogen introduction tube and a dropping funnel, and heated to 200°C to dissolve each sample.

Diphenylmethane-4,4'-diisocyaner day 0.0
A solution was prepared by dissolving 5 mmol of the dicarboxylic acid in 10 ml of tetramethylene sulfone, and this solution was dropped into the tetramethylene sulfone solution of the dicarboxylic acid described above from the dropping funnel.

All of the above operations were performed under a nitrogen atmosphere.

At the same time as the diisocyanate component was added dropwise, Cot (carbon dioxide) began to be generated. When the generation of CO□ has almost finished and the theoretical amount of CO□ has been generated, polytetramethylene glycol (“Teratane 2000”, 87.2,00%
0) 2.8 mmol was added. Polytetramethylene ether glycol was added 13 minutes after the start of polymerization by dropping diisocyanate. After addition of the polytetramethylene ether glycol, stirring was continued at 200° C. for 4 hours.

After the reaction was completed, the resulting polymer solution was poured into a large amount of water and solidified.

After the coagulated polymer was filtered, it was added to about 300 ml of acetone, and the acetone was heated under reflux for about 1 hour to purify the polymer. After heating and refluxing the acetone, the polymer was filtered off and dried.

ηi, h = 1.04 dl/g polymer 95%
was obtained in a yield of . Results of IR (infrared) analysis of the obtained polymer: 1650 cm-' (c-o), 3300 cm
-' (v14.).

Results of elemental analysis: Actual value C69,32χ II 9.20χ N 3
．． 34χ calculated value C69, 32χ H9, 23χ N
It was 3.20χ.

A transparent and strong film was obtained by film casting from a solution of the polymer in N,N-dimethylacetamide.

5 U of blood, using 4.6 mmol of isophthalic acid and 4.6 mmol of azelaic acid as the dicarboxylic acid components, -polytetramethylene ether glycol (“Teratane 2,000”)
Polymerization, purification, and isolation were carried out in the same manner as in Example 11, except that 0.8 mmol of the compound was used.

η,, h・0.95 dl/g polymer is 100%
was obtained in a yield of .

A film was made from the polymer thus obtained by a film casting method using N,N-dimethylacetamide as a solvent, and from this film 1.0 CllX5
．． Cut out a film with a thickness of about 0.1 mm,
Tensile tests were conducted at a tensile rate of 20x/min.

As a result, TM=420MPa, TS (at break) =
28 MPa.

The elongation at break was 140χ.

Using 4.6 mmol of isophthalic acid and 4.6 mmol of azelaic acid as dicarboxylic acid components, polytetramethylene ether glycol (“Teratane 2.000” 1
Polymerization, purification, and isolation were carried out in the same manner as in Example 12, except that 0.8 mmol of M7.2.000) was used.

ηinh = 0.72 dl/g polymer 95%
was obtained in a yield of .

A film was made from the polymer thus obtained by a film casting method using N,N-dimethylacetamide as a solvent, and from this film 1.0 co+X
5. Q am, cut out a film about 0.1 mm thick,
Tensile tests were conducted at a tensile rate of 20x/min.

As a result, TM=480 MPa, TS (at break)
=35 MPa.

The elongation at break was 18 oz.

Polymerization, purification, and isolation were carried out in the same manner as in Example 11, except that the composition ratio of the dicarboxylic acid component for removal and polytetramethylene ether glycol was varied.

The polymerization results are summarized in Table 3.

Polymerization, purification, and isolation were carried out in the same manner as in Example 12, except that the composition ratio of the dicarboxylic acid component and polytetramethylene ether glycol was varied.

The polymerization results are summarized in Table 4.

Large-scale flame ■ Using bis-(3-aminopropyl)-polyoxytetramethylene (-NH, group, 2,540 at both ends) as a polyether oligomer, a polyether-polyamide plotter was created using a one-step polymerization method. A polymer was synthesized. Isophthalic acid 4.4 mmol, azelaic acid 4.4 mmol, bis-(3-aminopropyl)-polyoxytetramethylene 1.2 mmol, -phenyl-3-methyl-2-phospholene-1-oxide 0.025 mmol, 15ml of tetramethylene sulfone in a stirring device,
Pour into a flask equipped with a nitrogen introduction tube and dropping funnel,
Each sample was dissolved by heating to 160°C.

Diphenylmethane-4,4'-diisocyanate 10.
A solution was prepared by dissolving 0.05 mmol in 10 ml of tetramethylene sulfone, and this solution was dropped into the tetramethylene sulfone solution of the dicarboxylic acid and polyether oligomer from the dropping funnel.

All of the above operations were performed under a nitrogen atmosphere.

Simultaneously with the dropwise addition of the diisocyanate component, CO□ (carbon dioxide) began to be generated, the reaction progressed, and the viscosity of the solution gradually increased.

After dropping the diisocyanate component, heat to 160°C for 3 hours.
Stirring was continued. The obtained polymer solution was poured into a large amount of water and solidified.

After the coagulated polymer is filtered out, it is about 300m 7! The polymer was purified by adding it to methanol and heating and refluxing the methanol for about 1 hour. After heating and refluxing methanol, the polymer was filtered off and dried. ηi+th= 0.51
dl/g of polymer was obtained with a yield of 90%.

Results of IR (infrared) analysis of the obtained polymer 1650c
m-' (ν.,.), 3300cm-' (νN+4)
Met.

As a polyether oligomer, bis-(3-aminopropyl)-polyoxytetramethylene (both terminals -N Hz
A polyether-polyamide plotter copolymer was synthesized by a two-step polymerization method using M, .2,540).

Isophthalic acid 4.4 mmol, azelaic acid 4.4
mmol, 0.025 mmol of 1-phenyl-3-methyl-2-phosphosine-1-oxide was placed in a flask equipped with an apparatus, a nitrogen introduction tube, and a dropping funnel, and heated to 160°C to dissolve each sample. Ta.

Diphenylmethane-4,4'-diisocyanate 10.
A solution was prepared by dissolving 0.05 mmol in 10 ml of tetramethylene sulfone, and this solution was dropped into the tetramethylene sulfone solution of the dicarboxylic acid described above from the dropping funnel.

All of the above operations were performed under a nitrogen atmosphere.

At the same time as the diisocyanate component was added dropwise, Co2 (carbon dioxide) began to be generated. When the generation of CO2 was almost complete and the theoretical amount of CO2 had been generated, 1.2 mmol of bis-(3-aminopropyl)-polyoxytetramethylene was added. Bis-(3-aminopropyl)-polyoxytetramethylene was added 20 minutes after the start of polymerization by dropping diisocyanate. Bis-(3-
After addition of the (aminopropyl)-polyoxytetramethylene, stirring was continued at 160° C. for 4 hours. The obtained polymer solution was poured into a large amount of water and solidified.

After the coagulated polymer was filtered, it was added to about 300 ml of methanol, and the methanol was heated under reflux for about 1 hour to purify the polymer. After heating and refluxing methanol, the polymer was filtered off and dried. η8,,h=0.58
dl/g of polymer was obtained with a yield of 92%.

Results of IR (infrared) analysis of the obtained polymer 1650c
m-'(L'c-o), 3300 cm-' (ν□).

Claims (3)

[Claims] (1) (a) General formula: OCN-Ar-NCO (I) (Ar in the formula is a divalent aromatic residue represented by -C_6H_4-X-C_6H_4- or tolylene, and X is -CH_2- or -O-), (b) General formula: HOOC-R-COOH(II) (R in the formula is phenylene or -(CH_2)- one or more dicarboxylic acids represented by _n (where n is an integer of 2 to 12), and (c ) A method for producing a polyether-polyamide block copolymer, which comprises copolymerizing a telechelic polyether oligomer having a diol group, diamino group, or dicarboxylic acid group at the terminal. (2) The manufacturing method according to claim 1, wherein (a) the aromatic diisocyanate, (b) the dicarboxylic acid, and (c) the telechelic polyether oligomer are reacted simultaneously. (3) The aromatic diisocyanate of (a) and the dicarboxylic acid of (b) are reacted using an excess amount of the aromatic diisocyanate with respect to the dicarboxylic acid component, and after the substantial completion of the reaction, , (c) is reacted with the telechelic polyether oligomer according to claim 1.