JPS59193927A - Production of polyester copolymerized with polyolefin - Google Patents

Abstract

PURPOSE:To prepare a polyester copolymerized with polyolefin, having excellent mechanical properties, especially impact resistance and elongation characteristics, by reacting a polyolefin having NH2 group and a specific polyester (or its oligomer) under heating. CONSTITUTION:The objective compound composed of polyolefin segments and polyester segments bonded together through amide bonds, is prepared by reacting (A) a polyolefin having NH2 at the terminal and/or side chain (e.g. diene polymer, hydrogenated diene polymer, etc.) with (B) a polyester composed of (i) an aromatic dicarboxylic acid (e.g. terephthalic acid, 1,5-naphthalenedicarboxylic acid, etc.) and (ii) an aliphatic or alicyclic glycol (e.g. ethylene glycol, cyclohexanediol, etc.) (e.g. polyethylene terephthalate) or its oligomer preferably at a weight ratio (A/B) of about 1/99-95/5, under heating preferably at 150-350 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a block copolymer in which a polyolefin segment such as hydrogenated polybutadiene and a polyester segment such as polyethylene tylphthalate are connected by an amide bond.

Thermoplastic polyesters such as polyethylene terephthalate are used in fibers, films, bottles, and electrical and electronic parts.

In general, the use of a single substance is often insufficient to impart the desired properties to each molded product, so the balance of physical properties is adjusted by blending other polymers or adding inorganic fillers. things are being done.

For example, in order to improve the impact resistance of polyester, attempts have been made to blend other polymers, particularly nidistomers and polyolefins, but these polymers do not necessarily have good compatibility with polyester and are difficult to disperse. Modification through mixing is often difficult to achieve due to non-uniformity due to poor properties and separation between different phases.

On the other hand, Japanese Patent Publication No. 49-30710 discloses the use of a hydrogenated diene polymer having hydroxyl groups or carboxyl groups at both ends as a copolymerization monomer for polyester, and a soft polyester with extremely high elongation can be obtained. It is said that it will be done. However, in this method, the efficiency of copolymerizing a hydrogenated product of a diene polymer having a hydroxyl group or a carboxyl group with other copolymerizable monomers such as terephthalic acid or ethylene glycol is extremely low, and it cannot be said to be a preferable production method.

The present inventors investigated the possibility of modifying polyester by copolymerizing polyester with polyolefin such as hydrogenated polybutadiene, and found that polyolefin with amino groups introduced into the terminal and/or side chains and polyester or its oligomers were copolymerized. The present invention was achieved based on the discovery that the copolymer is copolymerized through an amide bond and that the resulting copolymer has poor mechanical properties.

That is, the present invention is directed to a polyester or an oligomer thereof consisting of a polyolefin (A) having an amine group at the terminal and/or side chain, an aromatic dicarboxylic acid, and an aliphatic or alicyclic glycol (by reacting the The present invention relates to a method for producing a polyolefin copolyester in which a polyolefin segment and a polyester segment are connected by an amide bond.

The polyolefin (A) having an amino group at the terminal and/or side chain is prepared by introducing an amine 7 group into a polyolefin by a conventionally known method. The raw material polyolefin is preferably an α-olefin such as ethylene or propylene, a homopolymer such as a diene, a copolymer of two or more types, or a hydrogenated product of a diene polymer, such as 1,3-butadiene, 1,3-pentadiene, etc. There are homopolymers or copolymers obtained by polymerizing at least one monomer selected from , chloroprene, isoprene, etc., and hydrogenated products thereof.

Diene polymers contain radicals, cations, anions,
There are polymers using catalysts such as coordinating anions, which can be used without particular limitation in the present invention. For example, it can be synthesized by a living anion polymerization method using an initiator such as organic lithium or by radical polymerization using a peroxide as an initiator. It is also possible to employ a method of copolymerizing a small amount of other monomers together with the diene monomer. In this case, the proportion of other monomers copolymerized with the diene monomer is approximately 40 mo/L of the total monomers.
/% or less, preferably about 10V% or less. Other copolymerizable monomers include styrene, α-methylstyrene, 0- or p-vinyltoluene rylonitrile, methyl acrylate, ethyl acrylate,
Examples include vinyl monomers such as butyl acrylate, methyl methacrylate, and vinylpyridine.

Also, a linear structure in which the same or different living polymers are coupled together using a polyfunctional coupling agent such as methylene chloride, xylylene dibromide, terephthalic acid dichloride, silicon tetrachloride, etc. in the presence of the initiator;
Branched and radial diene polymers are also exemplified. Among these, polybutadiene or polyisoprene is preferably used. Also preferably used is a diene polymer in which part or all of the diene polymer is hydrogenated.

Preferred hydrogenated diene polymers are those whose average degree of unsaturation has been reduced to about 60% or less of their original value, particularly those whose average degree of unsaturation has been reduced to about 10% or less of their original value. Preferably.

To hydrogenate diene polymers, methods well known to those skilled in the art are employed. Examples of hydrogenation catalysts include nickel, diatomaceous earth, Raney nickel, finely ground platinum,
Catalysts such as palladium and carbon-supported palladium can be used.

The hydrogenation conditions are not particularly limited, and for example, the hydrogenation temperature is from atmospheric pressure to about 300 atm, usually about 5 to about 200 atm, at a temperature of room temperature to about 320'C, and about 0.1 to about 2.
Hydrogenation can be carried out for 4 hours, preferably from about 0.62 hours to about 10 hours.

Examples of methods for introducing amine groups into the terminals of raw material polyolefins include the following methods.

After reacting a mono-olefin polymer or copolymer such as polyethylene, polypropylene, ethylene-propylene copolymer, or ethylene-1-butene copolymer with an anhydride of unsaturated cafrefonic acid such as maleic anhydride. , a method of reacting diamines.

After reacting a living polymer of a diene compound with ethylene oxide to make it terminally hydroxylated, it can be reacted with ammonia, or the terminally hydroxylated diene polymer can be reacted with a compound having multiple acyl-ride groups such as terephthalic acid dichloride, or An acyl leno-ride group is introduced at the end by reacting with phosgene, etc., and this is reacted with a diamino compound such as ethylenediamine, or the acyl halide group is amidated with liquid ammonia, an alkali metal amidate, etc., and then hydrogen How to convert and aminate. Compounds with multiple acyl halide groups used in this method include oxalate civalide, malonic acid civalide, succinic acid civalide, glutaric acid dino-ride, adipic acid civalide, sebacic acid civalide, cyclohexanedicarboxylic acid civalide, and terephthalic acid civalide. Examples include acid civalide, isophthalic acid civalide, xylylene dicarboxylic acid civalide, 2.6-f phthalenedicarboxylic acid civalide, bis(4-carboxylated di)L/) ether dino ride, and the like.

The above-mentioned terminal hydroxylated diene polymer is cyanoethylated with acrylonitrile and then hydrogenated, or treated with a halogenating agent such as thionyl chloride to form a halide, which is then further treated with liquid ammonia, alkali metal amides, etc. A method of amidation followed by hydrogenation.

A method in which a living polymer of a diene compound is reacted with bromomethylnitrobenzene, etc. to introduce a nitro group at the end, and then hydrogenated. During this hydrogenation, the diene polymer can also be hydrogenated simultaneously.

Another method involves reacting a living polymer of a diene compound with carbon dioxide to introduce a carboxyl group at the end, and reacting this with a diamino compound such as hexamethylene diamine.

The terminal carboxylated diene polymer is reacted with a halogenating agent such as thionyl chloride to convert the terminal into an acyl halide group, and then the end is reacted with a diamino compound such as ethylenediamine, or the acyl halide group is converted into an acyl halide group using liquid ammonia or an alkali metal. A method of amidation with an amidide or the like and then hydrogenation is also exemplified.

The diene polymer used in the method exemplified above may be hydrogenated in advance, and if possible, the diene polymer may be hydrogenated in advance.
Hydrogenation may be performed when introducing the group.

In addition, as a diene polymer that is a raw material for introducing an amine group, a commercially available polybutadiene homopolymer or copolymer having a hydroxyl group or a carboxyl group at the end, or a hydrogenated polymer thereof can be used. For example, there are the following.

N15so PB G-1 (100 Nippon Soda-2000 -3000 tt GI-1000 ttGI-2000 tt GI-3000/'〃 C-
1000 tt CI-1000 Polytail H Mitsubishi Kasei HA ttPoly-13
D Arco Butarez HT
Philip Hycar-HTB
Shoes)'Richsha Telogen HT
General Steel Co., Ltd. The polyolefin having 7 amino groups at the terminal and/or side chain used in the present invention (
A preferred example of A) is one in which the molecular weight of the olefin unit is about 600 to about 700,000, particularly preferably about 500 to about 500,000, and the ratio of amino groups is about 0.02 per 100 carbon atoms of the polyolefin (A). from about 95 pieces, particularly preferably from about 0.03 pieces to about 60 pieces.

A more preferred embodiment uses a diolefin as the raw material monomer, and the molecular weight of the diene polymer or its hydride is about 300 to about 700,000. Particularly preferably about 5
00 to about 500,000, and is a diene polymer having an amine group at both ends or at one end. If the molecular weight is less than about 600, it is not preferable because the excellent properties of the diene polymer, such as low temperature flexibility, will not be exhibited. Moreover, if the molecular weight exceeds about 700,000, the compatibility between the diene polymer and the polyester or its oligomer becomes poor, and the efficiency of copolymerization decreases, which is not preferable.

If the number of amino groups is less than about 0.02 per 1000 carbon atoms, the copolymerizability with polyester or its oligomer will decrease, and if it exceeds about 95, gel will form during the copolymerization reaction with polyester or its oligomer. oxidation may progress, both of which are undesirable.

The aromatic dicarboxylic acids constituting the polyester or its oligomer (B) include terephthalic acid, iso-7
' acid, lid)v acid, 2,6-naphthalene dicarboxylic acid-1t5-naphthalene dicarboxylic acid, bis(p-carpoxypheny)V) methane, anthracenedicarboxylic acid,
4.4'-diphenyl dicarboxylic acid, 4.4'-diphenyl ether dicarboxylic acid, or their ester-forming derivatives are considered to be cold.

In addition, if the proportion of the acid component is less than about 40% V%,
Aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dodecanedicarboxylic acid; alicyclic dicarboxylic acids such as 113-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as ester-forming derivatives thereof. Dicarboxylic acids other than acids may be substituted.

Glycol monomer components include aliphatic glycols having 2 to 20 carbon atoms, namely ethylene glycol, propylene glycol/l/, 1,4-butanediol, neopentyl glycol, and 1,5-pentanediol.
, L5-hexanediol, decamethylene diglycol, etc., alicyclic glycols such as cyclohexanediol, tricyclodecane dimethylol, diethylene glycol, triethylene glycol, or polyethylene glycol with a molecular weight of 1000 or less, poly-
Examples include 1,6-propylene glycol, polytetramethylene glycol, and mixtures thereof.

Preferred embodiments of the polyester or its oligomer (B) used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate,
Examples include polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate, and oligomers thereof, and among them, polyethylene terephthalate, polybutylene terephthalate, and oligomers thereof having appropriate mechanical strength are most preferred.

The polyester or oligomer thereof used in the present invention may range from bishydroxyethyl terephthalate to high polymerization degree polymers or copolymers, and is not particularly limited.

In the present invention, the polyolefin (A) into which the above-mentioned amide 7 groups have been introduced and the polyester or its oligomer (B
) are mixed under heating, and if necessary, the reaction system is reduced in pressure, so that the amide 7 group and the carboxyl group at the end of the polyester are connected by a condensation reaction, and the polyolefin segment and the polyester segment are connected by an amide bond. A copolymer is produced.

The mixing under heating may be carried out in the absence of the polymerization catalyst, but it is preferably carried out in the presence of the polymerization catalyst, and other additives, such as colorants, stabilizers, inorganic fillers, etc., may be added from the initial stage or in the intermediate stage. , can also be added at the final stage.

As the polymerization catalyst, those commonly used for polyester production can be used, including metal acetates such as manganese acetate and zinc acetate, metal oxides such as germanium oxide and antimony trioxide, and tetrabutyl titanate. Organic titanates can be exemplified.

The ratio of the polyolefin (A) and polyester or its oligomer (B) to be mixed is not particularly limited, and depends on the types of both components used, (molecular weight,
It can be changed as appropriate depending on the heating temperature, the type and proportion of other additives present, etc.). Usually, a weight ratio of polyolefin (A) to polyester or its oligomer CB) of about 0.5/99.5 to about 9872 is used.

In addition, when using polyolefin (A) consisting of hydrogenated polybutadiene having an amino group at the terminal and polyethylene terephthalate or its oligomer (B), polyolefin (I) vs. polyester or its oligomer (
It is preferred that the weight ratio of B) is about 0.5/99.5 to about 98/2, particularly about 1/99 to about 9575.

If the weight ratio is less than about 0.5/99.5, the properties of the copolymer will be almost the same as homopolyester that does not contain polyolefin, and if the weight ratio is greater than about 9872, the properties will be almost the same as polyolefin. None of these are desirable because it becomes

To mix the mixture of both components while heating, a kneading device such as a reaction device with stirring blades, a screw or twin screw extruder, a kneader, a Banbury mixer, a mixing roll, a Henschel mixer, etc. is used. can be used alone or in combination. Although it is possible to react the polyolefin component and the polyester component while melt-mixing them in the above-mentioned apparatus, it is also possible to complete the reaction of the melt-mixed mixture in a solid phase.

The heating temperature is about 100°C to 400°C, preferably about 150°C to 50°C.

For example, in the case of using a polyethylene terephthalate or its oligomer (B), the temperature is usually about 150 to about 350°C, particularly preferably about 18°C.
Preferably, the temperature is between 0 and about 300'C. Approximately 15
If it is less than 0°C, the reaction between polyethylene terephthalate or its oligomer (B) and the polyolefin component will be extremely slow, and if it exceeds about 650°C, the polyolefin component will deteriorate, which is not preferable.

When reducing the pressure of the reaction system between the polyolefin component and polyester or its oligomer, the pressure is usually about 5 mmHg.
from about 0.2 to about 50 hours at a pressure of less than or equal to
It is preferable to keep it under reduced pressure for 0 hours.

By mixing under heating and, if necessary, reducing the pressure of the reaction system, a block copolymer in which polyolefin segments and polyester segments are connected through amide bonds can be obtained.

In the production method of the present invention, it is not necessary to react all the components, and unreacted polyolefin (N and/or
Alternatively, a polyolefin copolyester partially containing polyester/v(B) may be produced.

In addition, the polyolefin copolyester obtained in the present invention includes combinations of polyolefin segments (a) and polyester segments (b) such as -a b -a -b b+a-b-)-, a a+b)k a-++b-a This b l.

For example, However, 3% ks I
Is m is a positive integer, and each person or person may be the same or different.

The polyolefin copolyester obtained by the present invention has excellent mechanical properties, especially impact resistance 1.
It is a resin with excellent elongation properties and is used alone or in combination with other additives.

The copolymer provided by the present invention may be used alone or as a composition containing a portion of unreacted polyolefin (A) and/or polyester (B) as required.

The copolymer provided by the present invention is also suitable for use in blending with conventional polyesters in order to modify their properties. The copolymer provided by the present invention can be blended with polyester together with additives conventionally blended as modifiers for polyester, such as various polymers such as polybutadiene, to improve polyester modification effects, such as impact resistance. There are uses for expressing it.

When blending for these uses, one or more organic diluents can be added as needed.

The organic diluent in the present invention refers to polyolefin (70%
Or, it is a liquid that has the property of dissolving or swelling polyester (B), does not adversely affect the mixed components, and can be easily removed from the system by drying or other methods, such as benzene, toluene, xylene, cyclohexane. ,n
- Hydrocarbons such as octane, ethylbenzene, cumene, methylcyclohexane, and ethylcyclohexane, ketones such as methyl isobutyl ketone, phenol, phenol derivatives such as o-chlorophenol and p-chlorophenol, N,N-dimethylformamide, and dimethyl sulfoxide. , N-methylpyrrolidone, aprotic solvents such as hexamethylphosphoramide, halogenated hydrocarbons such as trichloroethane, tetrachloroethane,
Examples include benzyl alcohol nitrobenzene, ether, etc. Among these, tehatoluene, 0-chlorophene/-
Preferred are alcohol, trichloroethane, pencil alcohol and nitrobenzene.

In addition, examples of additives in the present invention include colorants, stabilizers, inorganic fillers, etc. More specifically, as colorants,
Examples include dyes, pigments such as cadmium sulfide, phthalocyanine, and carbon black, and stabilizers include antioxidants and heat stabilizers such as hindered phenols, hydroquinones, thioethers, phosphites, and substituted products and combinations thereof. , various lubricants and mold release agents, including ultraviolet absorbers such as resorcinol, salicylate, benzotriazole, and benzophenone, higher fatty acids and their metal salts such as stearic acid and montanic acid, esters, halfesters, stearyl alcohol derivatives, etc.
Examples include flame retardant aids such as antimony oxide, antistatic agents such as F-decylbenzene, sodium sulfonate, and polyalkylene glycol, crystallization promoters, and silane coupling agents.Inorganic fillers include glass. Examples include fibrous materials such as fibers, carbon fibers, and ceramic fibers, and granular, powder, and plate materials such as mica, glass beads, silica, barium titanate, hydrotalcite, and zeolite F.

Furthermore, polymers used as additives include polybutadiene, polyisoprene, or their hydrogen ([1,
Ethylene propylene rubber, ethylene propylene diene rubber, styrene butadiene rubber, hydrogenated styrene butadiene rubber, or modified rubber obtained by graft copolymerizing acrylic acid, maleic anhydride, etc. with these, polyethylene, polypropylene, ethylene-1-butene copolymer , ethylene-
4-Methyl/-1-pentene copolymer, 4-methyl-
α-olefin resins or elastomers such as 1-pentene-decene copolymers, polymethacrylic acid, acrylic resins such as ethylene-ethyl acrylate copolymers, zinc salts of ethylene-methacrylic acid copolymers, etc. Examples include ionomer resins, ethylene-vinyl acetate copolymers, polyamides such as nylon 6, polyacetals, polycarbonates, polysulfones, polyphenylene oxides, fluororesins, phenolic resins, melamine resins, unsaturated polyester resins, silicone resins, and epoxy resins. Ru.

The amount of the above-mentioned additives to be added is determined as appropriate in consideration of the various properties of the polyester.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (Production of polyester oligomer) Terephtha/L/acid 540 parts, ethylene glycol 242
1 part and 0.164 parts of triethylamine were placed in an autoclave, stirred at 240" C12 and 7 kg/cm2 gauge pressure, and reacted for 8 hours while removing generated water. At the end of the reaction, 0.1 part of trimethyl phosphate was added to the autoclave. 15 parts were added.In this way, a polyethylene terephthalate oligomer with an esterification rate of 92% was produced.

(Production of polyolefin having 7 amino groups at the end) Three-hole flask with a condenser, dropping funnel, and stirrer (A)
66 parts of terephthalic acid dichloride and 60 parts of toluene
0 part was added under nitrogen atmosphere and stirred until the solution became homogeneous. Hydrogenated polybutadiene oI-3000 (manufactured by Nippon Soda, xoH value:
2B) 200 parts, H) 54 parts of synthetic dissolved in 700 parts of toluene was charged into a dropping funnel, and added dropwise into the flask with strong stirring using a stirrer, and the reaction was carried out at 50''C for 2 hours. Into another sealed flask, 210 parts of hexamethylene diamine and 110 parts of toluene were charged.
After dissolving, add the reaction solution in flask (A) dropwise to
The reaction was carried out for 2 hours at 50°C. After the reaction solution was filtered to remove most of the hydrochloride of pyridine, the solvent was evaporated. The obtained product was dissolved in hexane, washed with water, filtered at
The operation of removing the solvent was repeated until the product became transparent. This product was dried in a vacuum dryer for a day and night to obtain hydrogenated polybutadiene having an amine group at the end. 0.5 g of this hydrogenated polybutadiene was dissolved in 25 ml of toluene and 0.5 g was dissolved using thymol blue as an indicator. l1 of IN
As a result of titration with a m-cresol solution of l-)/reensobonic acid, the amount of terminal amine groups was 0.16 meq/g polymer. This result corresponds to a ratio of about 2 amino-7 groups per 100 carbon atoms in the hydrogenated polybutadiene. Note that substantially anhydrous reagents and solvents were used in the above reactions.

(Synthesis of copolymer of polyester and polyolefin) 85 parts of polyethylene terephthalate oligomer synthesized by the above method, 15 parts of hydrogenated polybutadiene having 7 amino groups at both ends, and 0.02 part of antimony trioxide were placed in a reactor. Prepare at 270° while stirring under nitrogen atmosphere.
The reaction was carried out at C for 1 hour. Next, the pressure of the system was gradually reduced over 15 minutes, and the reaction was finally carried out for 4 hours at a reduced pressure of 0.7 mmHg or less. Results of measuring the molecular weight of the produced polymer using GPC (0-chlorophenol solvent, 70°C
1 Waters, MODEL/L/150C) The number average molecular weight in terms of polyethylene terephthalate was 32,900. The generated polymer is rotor speed controlled.
After pulverizing the mixture using a Puluvezlette 14 (manufactured by Sch. Scholastic AG), the mixture was placed in a Soxhlet extractor and extracted with toluene for 8 hours. The ratio of the extracted polymer to the hydrogenated polybutadiene used in the reaction (hereinafter referred to as toluene extraction rate) was 27% by weight. The extracted residual polymer is heated to 15C under a nitrogen seal using a press molding machine (molding temperature: 290°C). nX 15C1nX0.05C77
1(1), 151X 15 cMX O, 2cin(I
A sheet having the shape of t) was prepared and the following measurements were performed.

Tensile test: A dumbbell-shaped test piece with a total length of 50 mm and a parallel portion width of 5 mm was punched out from the sheet (I), and a tensile tester manufactured by Instron was used at a tensile speed of 50 mm/min.

The measurement temperature was 23°C.

Izot impact test: Measured at 23°C using two sheets of (Kawa) in accordance with the JIS K71D method.

The results are shown in Table 1.

Example 2 In Example 1, when a polyolefin having an amino group at the terminal was synthesized, terephtha)V acid dichloride 10
．． 4 parts, 9.7 parts of pyridine, 2 parts of hexamethylene diamine
The same reaction as in Example 1 was carried out except that 9 parts were used.

A copolymer was synthesized under the same conditions as in Example 1 using 15 parts of the thus obtained hydrogenated polybutadiene having an amino group at the terminal and 85 parts of a polyethylene terephthalate oligomer. The results are shown in Table 1.

Example 3 In Example 1, in place of 15 parts of oligomer of polyethylene terephthalate when synthesizing the copolymer of polyester and polyolefin, 0.80 dl! /
A copolymer was synthesized by carrying out the same polycondensation reaction as in Example 1, except that 15 parts of polyethylene terephthalate-1 (Belpera EFG-7, manufactured by Kanebo Gosen Co., Ltd.) of 1.5 g was used. However, polycondensation is carried out for 2 hours at approximately 270-280°C.
The test was carried out at 0.5 mmH6 or less. The results are shown in Table 1.

Example 4 Anhydrous benzene 700 in a reactor equipped with a cooler and a stirrer
130 parts of isoprene and 5e with strong stirring.
A hexane solution containing 0.64 parts of c-butyllithium was added dropwise, and the mixture was reacted for 5 hours at room temperature under an argon atmosphere. The reactor was then cooled in a water bath and ethylene oxide
6 parts were added dropwise to the mixture and reacted at 5°C for 2 hours and then at room temperature for 12 hours. The reaction solution was precipitated into a large excess of methanol,
Polyisoprene with hydroxyl groups at the ends was isolated. THF
As a result of GPC measurement using a solvent, the number average molecular weight was approximately 10,000 in terms of polyisoprene. This polyisoprene was reacted with acetyl chloride, and the concentration of the generated ester group was determined by IR (using the absorption intensity ratio of E-R absorption due to the double bond between the carbonyl of 17401 and the carbon of 1640CIn-1). 0.013 mo/I/
%Met. 30 parts of this polyisoprene, 700 parts of cyclohexane, palladium on carbon carrier (palladium 5
% loading) into an autoclave, hydrogen pressure 10
The reaction was carried out at 140°C for 4 hours at 0 kg/cm2.

After the reaction solution was filtered and washed with water, it was precipitated in methanol to obtain hydrogenated polyisoprene having hydroxyl groups at the terminals. The iodine value of this hydrogenated polyimblene was 11. In Example 1, the same reaction as in Example 1 was carried out except that the hydrogenated polyisoprene having hydroxyl groups at both ends was used instead of the hydrogenated polybutadiene GI-3000 having hydroxyl groups at both ends. A copolymer of polyolefin and polyolefin was synthesized. The results are shown in Table 1.

Example 5 15 parts of hydrogenated polybutadiene having 7 amino groups at the end synthesized in Example 1, polybutylene terephthalate resin (
A polycondensation reaction similar to that in Example 1 was carried out using 85 parts of Toughvet N1000 (manufactured by Toyobo Co., Ltd.). However, the polycondensation reaction was carried out for 6 hours under conditions of about 250"C10.5 mmHg or less. The results are shown in Table 1.

Example 6 75 parts of hydrogenated polybutadiene having an amino group at the terminal synthesized by the same method as in Example 1, 25 parts of oligomer of polyethylene terephthalate, and 0.1 part of antimony dioxide were mixed to produce the same polymer as in Example 1. A condensation reaction was performed. The results are shown in Table 1.

Example 7 Hydrogenated polybutadiene a-1000 having carboxy p groups at substantially both ends (Nippon Soda Department, acid value: 48.2)5
0 parts, hexamethylene diamine, 50 parts, and para-toluene sulfonic acid (1 part) were dissolved in 12 parts of toluene, and the mixture was heated under nitrogen for 14 hours.
Refluxing was carried out for 8 hours while removing water produced at 0°C. The reaction product was purified to isolate hydrogenated polybutadiene with 7 terminal Q groups. A polycondensation reaction was carried out under the same conditions as in Example 6 except that 75 parts of this hydrogenated polybutadiene was used to synthesize a copolymer. The results are shown in Table 1.

Comparative Example 1 Same as Example 1 except that in the copolymerization reaction of polyester and polyolefin, hydrogenated polybutadiene having hydroxyl groups at both ends was used instead of hydrogenated polybutadiene having amino groups at both ends. The polycondensation reaction was carried out under the following conditions.

Claims (3)

[Claims] (1) A polyolefin having an amino group at the terminal and/or side chain (a polyester or its oligomer CB composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic glycol) is reacted with heating. A method for producing a polyolefin copolymerized polyester in which a polyolefin segment and a polyester segment are connected by an amide bond. (2) Claim (1) characterized in that the polyolefin (A) having an amine group at the terminal and/or side chain is a diene polymer having an amine group at the terminal and/or side chain. The manufacturing method described in. (3) Polyolefin having an amino group at the terminal and/or side chain (Claim No. 1) characterized in that the polyolefin is a hydrogenated product of a diene polymer having an amine group at the terminal and/or side chain. The manufacturing method described in section.