JPH10306145A - Production of polyphenylene oxide/polyester multiblock copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a multiblock copolymer for use as e.g. an engineering plastic by reacting a polyphenylene oxide with a hydroxy acid or its lower alkyl ester or by reacting a polybasic carboxylic acid or its lower alkyl ester with a polyhydric hydroxyl compound. SOLUTION: The polyphenylene oxide used has a carboxyl at one end and has a hydroxyl group on the other end. Such a compound is one represented by formula I (wherein R<1> is a substituent; m is the number of substituents and is 0-4; and n is a degree of polymerization and is a number (desirably 10-1,000) which gives a molecular weight of 500-1,000,000. The hydroxy acid or its alkyl ester is desirably one represented by formula II (wherein R<2> is a divalent aliphatic or aromatic group; and R<3> is H or a lower alkyl). The polybasic carboxylic acid or its lower alkyl ester is desirably one represented by formula III (wherein R<4> is a divalent aliphatic or aromatic group; and R<5> an R<6> are each H or a lower alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to polyphenylene oxides useful as engineering plastics, heat-resistant polymer materials, coating film forming materials, compounds for recording materials, antioxidants, photosensitive polymer materials, liquid crystal materials, and ink coating materials. The present invention relates to a method for producing a polyester multi-block copolymer.

[0002]

BACKGROUND OF THE INVENTION The synthesis of polyphenylene oxide is described in 1957.
It was first synthesized by ASHay by oxidative coupling of 2,6-dimethylphenol using a copper amine complex (J. Polymer Sci., 58, 581), and in 1965 Gen
Commercialized by eral Electric. However,
There is no example of synthesizing polyphenylene oxide in which one end is a carboxy group and the other end is a hydroxyl group, and polyphenylene comprising reacting an oxyacid with this polyphenylene oxide or reacting a polycarboxylic acid with a polyhydric alcohol. There is no report on a method for producing a multiblock copolymer of an oxide and a polyester. In addition, synthesis of various polyesters has been studied in the synthesis of condensation polymers, but the reaction of polyphenylene oxide with an oxyacid or the reaction of a polyhydric carboxylic acid and a polyhydric alcohol with a polyphenylene oxide and a polyester There is no report on a method for producing a multi-block copolymer.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a polyphenylene oxide and polyester multi-use useful as engineering plastics, coating film forming materials, recording material compounds, antioxidants, photosensitive polymer materials, liquid crystal materials, and ink coating materials. An object of the present invention is to provide a method for producing a block copolymer.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, according to the present invention, a polyphenylene oxide having one terminal having a carboxy group and the other terminal having a hydroxyl group is reacted with an oxyacid or a lower alkyl ester thereof, or a polycarboxylic acid or a lower alkyl ester thereof is reacted with a polycarboxylic acid or a lower alkyl ester thereof. A method for producing a polyblock copolymer of polyphenylene oxide and polyester, characterized by reacting a polyvalent hydroxyl compound with a polyvalent hydroxyl compound.
In the present specification, the molecular weight of polyphenylene oxide is a value obtained by converting the molecular weight at the peak of a chromatogram by gel permeation chromatography into the molecular weight of polystyrene. Also,
The number average molecular weight referred to herein with respect to the multiblock copolymer means a number average molecular weight in terms of polystyrene.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyphenylene oxide used in the present invention has a carboxyl group at one end and a hydroxyl group at the other end. As such a polyphenylene oxide, those represented by the following general formula (1) can be used.

Embedded image In the above formula, R ¹ represents a substituent, m represents the number of substituents, and is an integer of 0 to 4. n represents the degree of polymerization, and
It is a number giving a molecular weight of 1,000,000, preferably 10-1,000. The substituent R ¹ includes, for example, a hydroxyl group, a carboxyl group, a mercapto group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, a halogen group, an ether group,
An ester group, an acyl group, an amino group, a substituted amino group and the like are included.

Specific examples of the substituent R ¹ include the following. As the alkyl group, one having 1 to 2 carbon atoms
2, preferably 1 to 12, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 1 -Methylbutyl group, 2-ethylbutyl group, isopropyl group, isobutyl group, sec
-Butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, cyclohexyl group and the like. As the alkenyl group, those having 2 to 22 carbon atoms, preferably 2 to 12 carbon atoms,
For example, vinyl group, allyl group, 1-propenyl group, 1,
Examples thereof include a 3-butadienyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a 2-pentenyl group. Examples of the alkynyl group include those having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as an ethynyl group. Examples of the aryl group include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a cumenyl group, and a naphthyl group. Examples of the arylalkyl group include benzyl, phenethyl and the like. As the halogen group, a fluoro group,
Chloro, bromo, iodo, iodosyl, iodoyl and the like. Examples of the ether group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a phenoxy group, and a benzyloxy group. Examples of the ester group include a methoxycarbonyl group, an ethoxycarbonyl group, a formyloxy group, an acetoxy group, a benzoyloxy group, and an acyl group. Formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, octanoyl, lauroyl, palmitoyl, stearoyl, oleoyl, acryloyl, methacryloyl, chloro Examples include a formyl group, a pyrvoyl group, an oxalo group, a methoxyallyl group, an ethoxyallyl group, a cyclohexylcarbonyl group, a benzoyl group, a toluoyl group, a cinnamoyl group, and a naphthoyl group. Examples of the substituted amino group include a methylamino group, a dimethylamino group, an anilino group,
Examples include a toludino group, a xylidino group, a hydroxyamino group, an acetamido group, and a benzamide group.

Specific examples of the polyphenylene oxide of the present invention include poly (2,6-dimethoxy-) having a carboxyl group at one end and a hydroxyl group at the other end.
1,4-oxyphenylene), poly (2,6-dimethyl-1,4-oxyphenylene), poly (2,6-diethyl-1,4-oxyphenylene), poly (2,6-dipropyl-1, 4-oxyphenylene), poly (2,6-
Dibutyl-1,4-oxyphenylene), poly (2,6
-Diethoxy-1,4-oxyphenylene), poly (2,6-dihydroxy-1,4-oxyphenylene)
And the like.

The polyphenylene oxide used in the present invention can be synthesized from syringic acid or 4-hydroxy-3,5-dimethylbenzoic acid using, for example, an enzyme catalyst (Macromolecules, 29, 305).
3 (1996)).

The molecular weight of the polyphenylene oxide used in the present invention may be from 500 to 1,000,000, and particularly from 1,000 to 100,000.
00 can be preferably used.

The oxy acids or lower alkyl esters thereof used in the present invention include aliphatic oxy acids, aromatic oxy acids and lower alkyl esters thereof. As the oxyacid or its lower alkyl ester, for example, those represented by the following general formula (2) are preferably used.

## STR2 ## ^{HO-R 2 -COOR 3 (2} ) ( wherein, R ² is a divalent aliphatic group or an aromatic group, R ³
Is hydrogen or a lower alkyl group.) The aliphatic group has 1 to 22 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 6 alkyl groups and cycloalkyl groups. The aromatic group has a benzene nucleus of 1 to
Those derived from three-containing aromatic compounds are shown. Examples of the aromatic compound in this case include benzene, naphthalene, tetralin, anthracene, phenanthrene, biphenyl, diphenylmethane, and their methylated or ethylated products. Examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like.
To 4 alkyl groups. A substituent may be bonded to the aliphatic group or the aromatic group. As such a substituent, various substituents represented by R ¹ in the general formula (1) can be shown. Preferred specific examples of the oxy acids and lower alkyl esters thereof used in the present invention include glycolic acid, lactic acid, glyceric acid, hydroxypivalic acid, malic acid, tartaric acid, hydroxyhexanoic acid, hydroxycaproic acid, gallic acid and benzylic acid , P-hydroxybenzoic acid, m-hydroxybenzoic acid, o
-Hydroxybenzoic acid and its methyl ester, ethyl ester, propyl ester, butyl ester and the like.

The polycarboxylic acid or lower alkyl ester thereof used in the present invention includes an aliphatic polycarboxylic acid or lower alkyl ester thereof and an aromatic polycarboxylic acid or lower alkyl ester thereof. As the polyvalent carboxylic acid or its lower alkyl ester, those represented by the following general formula (3) are preferably used.

## STR3 ## ^{R 6 OOC-R 4 -COOR 5} (3) ( wherein, R ⁴ represents a divalent aliphatic group or an aromatic group, R ⁵
And R ⁶ represent hydrogen or a lower alkyl group.) As the aliphatic group and the aromatic group, those represented by the general formula (2)
Are shown. As the lower alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group can be preferably used. A substituent may be bonded to the aliphatic group and the aromatic group. Specific examples of such a substituent include those described for the general formula (1). Preferred specific examples of the polycarboxylic acid and the lower alkyl ester thereof used in the present invention include adipic acid, oxalic acid, diglycolic acid, ketohimeric acid, succinic acid, glutaric acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Decanedicarboxylic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, o-phthalic acid, benzenetetracarboxylic acid, trimellitic acid, naphthalenedicarboxylic acid,
Anthracene dicarboxylic acid, naphthalene tetracarboxylic acid and their methyl ester, ethyl ester, propyl ester, butyl ester and the like can be mentioned.

The polyhydric hydroxyl compound used in the present invention includes an aliphatic polyhydric hydroxyl compound and an aromatic polyhydric hydroxyl compound. As this polyvalent hydroxyl compound, a compound represented by the following general formula (4) is preferably used.

Embedded image HO—R ⁷ —OH (4) (wherein, R ⁷ represents a divalent aliphatic group or an aromatic group) As the divalent aliphatic group and the aromatic group, What was shown about (2) can be mentioned. Further, these aliphatic groups and aromatic groups may have various substituents shown in the general formula (2). Specific examples of the polyhydric hydroxyl compound used in the present invention include resorcinol, hydroquinone, catechol, 4,4-biphenol, naphthalene diol, bisphenol A, 4,4′-thiobiphenol, and 4,4 ′.
-Oxydiphenol, 4,4'-carbonyldiphenol, 4,4'-sulfonyldiphenol, phenolphthalein, 4,4'-dihydroxytetraphenylmethane, 1,5-isoquinolinediol, ethylene glycol, neopentyl glycol , Pentaerythritol, butanediol, diethylene glycol, hexanediol, propylene glycol, cyclohexanediol, octanediol, dodecamethylene glycol,
Hexamethylolmelamine and the like can be mentioned.

The multi-block copolymer of the present invention is obtained by reacting the polyphenylene oxide with an oxyacid or a lower alkyl ester thereof, or by reacting a polycarboxylic acid or a lower alkyl ester thereof with a polyhydric hydroxyl compound. be able to.

The reaction in the present invention can be carried out according to a conventionally known esterification method or exchange esterification method. In this reaction, when polyphenylene oxide is reacted with an oxyacid or a lower alkyl ester thereof, 0.01 mol per mol of polyphenylene oxide is used.
The oxyacid or its lower alkyl ester is used in a proportion of 10 to 10 mol, preferably 0.1 to 5 mol. The reaction temperature is -50 to 300C, preferably -10 to 100.
° C. Further, in this reaction, when polyphenylene oxide is reacted with a polyvalent carboxylic acid or a lower alkyl ester thereof and a polyvalent hydroxyl compound, 0.01 to 10 mol, preferably 0.1 to 5 mol, per mol of the polyphenylene oxide. And a polyvalent carboxylic acid or a lower alkyl ester thereof is used. The proportion of the polyhydric hydroxyl compound used is 0.1 to 5 mol, preferably 0.5 to 1.5 mol, per 1 mol of the polycarboxylic acid or the lower alkyl ester thereof. The reaction temperature is-
The temperature is 50 to 300C, preferably -10 to 100C.
The reaction is carried out in the presence of a catalyst. In this case, a catalyst customary for an esterification reaction or a transesterification reaction can be used. Examples of such a catalyst include alkali metals such as lithium and potassium, alkaline earth metals such as magnesium, calcium, and barium; typical metals such as tin, antimony, and germanium;
Various compounds of transition metals such as lead, zinc, bismuth, cadmium, manganese, cobalt, nickel, zirconium, titanium and iron, lanthanoid metals such as niobium and lanthanum, for example, carboxylate, carbonate, borate and oxide , Hydroxides, hydrogen compounds, alcoholates, acetylacetonate chelates and the like. Further, a nitrogen-containing basic compound, boric acid, a borate ester, a phosphorus compound and the like are also used. The use ratio of the catalyst is 10 moles per 1 mole of the oxycarboxylic acid component or the polycarboxylic acid component.
^-7 to 10 mol, preferably 10 ^{-6 to} 5 mol is used.

[0015] The reaction is carried out in the presence of an organic solvent, if necessary. Examples of such a solvent include dimethylformamide, pyridine, a pyridine / hexachloroethane mixed solution, and carbon tetrachloride.

Catalyst preferably used in the present invention
Specific examples of combinations of organic solvents include tosyl chloride-dimethylformamide, chlorophosphoric acid diphenyl-dimethylformamide, triphenylphosphine dichloride (and / or thionyl chloride) -pyridine, picryl chloride-pyridine, and hexachlorocyclotriphosphazene-pyridine. , Phosphorus trichloride-pyridine, triphenylphosphine-hexachloroethane-pyridine, triphenylphosphine-carbon tetrachloride-pyridine, triphenylphosphine-carbon tetrabromide-pyridine, triphenyl phosphite-pyridine, triphenyl phosphite -Lithium chloride (and / or
Or phosphorus trichloride, phosphorus oxychloride, thionyl chloride, etc.). In particular, a combination of triphenylphosphine-hexachloroethane-pyridine can be preferably used.

In the above reaction, water or a hydroxyl compound is produced as a by-product of the condensation reaction. In order to accelerate the reaction, it is preferable to quickly remove this by-product from the reaction system. In order to remove such by-products from the reaction system, a condition in which the by-products are present in a vapor state is used as the reaction condition, and the vapor-like by-products are discharged from the reaction system together with the inert gas, or a distillation column is used. Can be distilled out of the reaction system.

The multi-block copolymer of the present invention comprises a polyphenylene oxide portion and an ester portion bonded to both ends thereof, and comprises an oxyphenylene-bonded portion A represented by the formula (OAr) (Ar represents a phenylene group). , Expression (OR
² CO) (R ² has the same meaning as described above) or (OCR
⁴ COOR ⁷ O) (R ⁴ and R ⁷ have the same meaning as described above). In this copolymer, the content of the oxyphenylene bond A is:
The molar fraction is 10 to 90%, preferably 35 to 65%, and the content of the ester bond B is 10 to 9 in terms of the molar fraction.
0%, preferably 35-65%. The number average molecular weight of the copolymer of the present invention is from 800 to 1,200,000, especially from 1600 to 120,000.

The multi-block copolymer of the present invention comprises a resin component such as a rosin-modified phenol resin, an alkyd resin, a polyester resin, and a polyamide resin; a coloring agent such as a pigment or dye such as yellow, red, indigo, or black;
Auxiliary agents such as leveling improvers, thickeners, plasticizers, ultraviolet inhibitors, antioxidants, antistatic agents and the like can be appropriately added and used for various applications.

[0020]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 1.32 g (5 mmol) of triphenylphosphine having a carboxyl group at one end and a hydroxyl group at the other end having a molecular weight of 13700 and having a molecular weight of 13700.
0.5 g of 1,4-oxyphenylene) and 0.69 g (5 mmol) of p-hydroxybenzoic acid were dissolved in 5 ml of pyridine. While stirring the solution, 1.19 g (5 mmol) of hexachloroethane was added. The reaction was performed at room temperature. After 30 minutes, the reaction solution was poured into a large excess of methanol, and the precipitate was isolated by centrifugation. The precipitate was washed with methanol and water and dried. The product is 0.
863 g. The product is a IR measurement of the copolymer derived from esters 1738cm ^-1, 1227cm ^-1
Was observed. TGA and DS of the obtained copolymer
C measurements were made under nitrogen. The temperature that gives 5% weight loss is 372 ° C, the residual ratio at 1000 ° C is 28.2%,
Tg was observed at 153 ° C. Poly (2,6)
-Dimethoxy-1,4-oxyphenylene) at a temperature of 321 ° C. to give a weight loss of 5%, and a residual ratio at 1000 ° C. of 22.7%. Therefore, the multi-block copolymer of polyphenylene oxide and polyester is heat-resistant. Characteristic improved.

Example 2 1.32 g (5 mmol) of triphenylphosphine having a carboxyl group at one end and a hydroxyl group at the other end having a molecular weight of 13700 and having a molecular weight of 13700.
1,4-oxyphenylene) 0.5 g, m-hydroxybenzoic acid 0.700 g (5 mmol), pyridine 5 m
1 and 1.19 g (5 mmol) of hexachloroethane, and an experiment was conducted in the same manner as in Example 1 to obtain a multiblock copolymer of polyphenylene oxide and polyester 0.56.
2 g were obtained. The product is a IR measurement of the copolymer derived from esters 1738 cm ^-1, absorption of 1227cm ^-1 were observed. TGA and DSC measurements of the resulting copolymer were performed under nitrogen. The temperature giving 5% weight loss is 36
The residual ratio at 9 ° C. and 1000 ° C. was 32.0%, and the Tg was observed at 156 ° C.

Example 3 0.525 g (2 mmol) of triphenylphosphine,
One end is a carboxyl group and the other end is a hydroxyl group, having a molecular weight of 1700 and having a molecular weight of 1700.
0.20 g of 1,4-oxyphenylene), 0.116 g (0.7 mmol) of isophthalic acid, 0.1% of bisphenol A
An experiment was conducted in the same manner as in Example 1 using 160 g (0.7 mmol), 6 ml of pyridine, and 1.19 g (5 mmol) of hexachloroethane to obtain 0.301 g of a polyphenylene oxide / polyester multiblock copolymer. From GPC measurement of the obtained copolymer, the number average molecular weight was 7,800 in terms of polystyrene.

Example 4 0.525 g (2 mmol) of triphenylphosphine,
One terminal is a carboxyl group and the other terminal is a hydroxyl group.
0.20 g of 1,4-oxyphenylene), 0.097 g (0.7 mmol) of m-hydroxybenzoic acid, 0.097 g (0.7 mmol) of p-hydroxybenzoic acid, 6 ml of pyridine, 10.413 g of hexachloroethane (2 mm
ol) in the same manner as in Example 1 to obtain 0.225 g of a polyphenylene oxide / polyester multiblock copolymer. According to IR measurement of the product copolymer, 1738 cm ⁻¹ , 1227 c derived from the ester
An absorption of m ^-1 was observed. The obtained product was soluble in pyridine and insoluble in dimethyl sulfoxide. Polyester obtained by using m-hydroxybenzoic acid or p-hydroxybenzoic acid as a monomer is insoluble in pyridine. Further, since the raw material polyphenylene oxide is soluble in dimethyl sulfoxide, the product may be a multi-block copolymer of a polyphenylene oxide part and a polyester part formed from m-hydroxybenzoic acid and p-hydroxybenzoic acid. It became clear. From GPC measurement of the obtained copolymer, the number average molecular weight was 7,400 in terms of polystyrene.

Example 5 1.32 g (5 mmol) of triphenylphosphine having a carboxyl group at one end and a hydroxyl group at the other end having a molecular weight of 1700 and having a molecular weight of 1700.
0.5 g of 1,4-oxyphenylene), 0.49 g (5 mmol) of 1,4-butanediol, 0.4 of isophthalic acid
An experiment was conducted in the same manner as in Example 1 using 2 g (2.5 mmol), 5 ml of pyridine, and 1.19 g (5 mmol) of hexachloroethane to obtain 0.825 g of a polyblock copolymer of polyphenylene oxide and polyester. G
According to the PC measurement, the number average molecular weight of the obtained copolymer was 7,500 in terms of polystyrene.

Example 6 1.32 g (5 mmol) of triphenylphosphine having a carboxyl group at one end and a hydroxyl group at the other end having a molecular weight of 1700 and having a molecular weight of 1700
(1,4-oxyphenylene) 0.5 g, hydroquinone 0.5 g
28 g (2.5 mmol), 0.42 g of isophthalic acid
(2.5 mmol), 5 ml of pyridine and 1.19 g (5 mmol) of hexachloroethane were subjected to the same experiment as in Example 1 to obtain 0.675 g of a polyphenylene oxide / polyester multiblock copolymer. GPC
From the measurement, the number average molecular weight of the obtained copolymer was 7,200 in terms of polystyrene.

Example 7 1.32 g (5 mmol) of triphenylphosphine having a carboxyl group at one end and a hydroxyl group at the other end having a molecular weight of 1700 and having a molecular weight of 1700.
1,4-oxyphenylene) 0.5 g, bisphenol A 0.57 g (2.5 mmol), adipic acid 0.36 g
(2.5 mmol), 5 ml of pyridine and 1.19 g (5 mmol) of hexachloroethane were subjected to the same experiment as in Example 1 to obtain 0.767 g of a polyphenylene oxide / polyester multiblock copolymer. In the IR measurement of the product copolymer, 17
Absorption of 38cm ^-1 1,1227cm ^-1 was observed. G
According to the PC measurement, the number average molecular weight of the obtained copolymer was 8,500 in terms of polystyrene.

Example 8 1.32 g (5 mmol) of triphenylphosphine having a carboxyl group at one end and a hydroxyl group at the other end having a molecular weight of 1700 and having a molecular weight of 1700 (poly (2,6-dimethoxy))
0.5 g of lactic acid, 0.45 g of lactic acid
(5 mmol), 5 ml of pyridine, and 1.19 g (5 mmol) of hexachloroethane were used to conduct an experiment in the same manner as in Example 1. The product weighed 1.20 g. In the IR measurement of the product copolymer, 1738 derived from the ester was determined.
cm ^-1, absorption of 1227cm ^-1 was observed. According to GPC measurement, the number average molecular weight of the obtained copolymer was 5,400 in terms of polystyrene.

Example 9 1.32 g (5 mmol) of triphenylphosphine having a carboxyl group at one end and a hydroxyl group at the other end having a molecular weight of 1700 and having a molecular weight of 1700
1,4-oxyphenylene) 0.5 g, pyridine 5 m
1 and 1.19 g (5 mmol) of hexachloroethane, and an experiment was carried out in the same manner as in Example 1 to obtain a multi-block copolymer of polyphenylene oxide and polyester 0.35.
0 g was obtained. According to GPC measurement, the number average molecular weight of the obtained copolymer was 14,700 in terms of polystyrene. TGA and DSC measurements of the resulting copolymer were performed under nitrogen. The temperature giving 5% weight loss is 371 ° C., 1000
The residual ratio at 32 ° C was 32%, and the Tg was observed at 153 ° C.

[0030]

According to the present invention, a multi-block copolymer of polyphenylene oxide and polyester can be produced under mild conditions and in high yield. The resulting copolymer is useful as a material exhibiting intermediate properties between amorphous polyphenylene oxide having excellent thermal properties and polyester having excellent thermal properties and having high crystallinity. Also, the obtained copolymer is
Excellent in thermal properties, chemical resistance and mechanical strength and useful as engineering plastics, and also useful as coating film forming materials, compounds for recording materials, antioxidants, photosensitive polymer materials, liquid crystal materials, ink coating materials It is.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Uyama 6-5-7-205 Koriyama, Taishiro-ku, Sendai City, Miyagi Prefecture (72) Inventor Ryohei Ikeda 2-10-20 Higashi Tsukuba City, Ibaraki Prefecture 102 Sun Life Ohno

Claims (4)

[Claims] An oxyacid or a lower alkyl ester thereof is reacted with a polyphenylene oxide having one terminal being a carboxyl group and the other terminal being a hydroxyl group, or a polycarboxylic acid or a lower alkyl ester thereof and a polyhydric hydroxyl. A method for producing a multiblock copolymer of polyphenylene oxide and polyester, which comprises reacting a compound. 2. The polyphenylene oxide moiety has a molecular weight in the range of 500 to 1,000,000.
The described method. 3. The multiblock copolymer according to claim 1, wherein the number average molecular weight is in the range of 800 to 1,200,000.
The described method. 4. The polyphenylene oxide is poly (dialkoxy-oxyphenylene) or poly (dialkyl-oxyphenylene) having a carboxyl group at one end and a hydroxyl group at the other end. the method of.