JPH049171B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for making a block copolymer having a hydride segment of a diene polymer, such as hydrogenated polybutadiene, and a polyester segment, such as polyethylene terphthalate. Thermoplastic polyesters such as polyethylene terephthalate are used in fibers, films, bottles, and electrical and electronic parts, but they are often insufficient to impart the desired properties to each molded product, so other polymers are often used. The balance of physical properties is adjusted by blending or adding inorganic fillers. For example, attempts have been made to blend other polymers, particularly elastomers and polyolefins, in order to improve the impact resistance of polyester, but these polymers do not necessarily have good compatibility with polyester and have poor dispersibility. In many cases, it is difficult to achieve modification by mixing due to non-uniformity caused by poor quality and peeling between different phases. On the other hand, the use of hydrogenated diene polymers having hydroxyl or carboxyl groups at both ends as comonomers for polyester
No. 49-30710, it is said that a soft polyester with an extremely high elongation rate can be obtained. However, in this method, the efficiency of copolymerizing the hydrogenated diene polymer having hydroxyl or carboxyl groups with other copolymerizable monomers such as terephthalic acid or ethylene glycol is extremely low;
This is not a desirable manufacturing method. The present inventors investigated the possibility of modifying polyester by copolymerizing polyester with a hydrogenated diene polymer such as hydrogenated polybutadiene, and found that polyolefin and polyester with polylactone introduced into the terminal and/or side chain were used. The present invention has been achieved by discovering that the copolymer is copolymerized with an oligomer thereof, and that the resulting copolymer has excellent mechanical properties. That is, the present invention provides a hydrogenated diene polymer having a polylactone segment at the terminal and/or side chain (A), a polyester or its oligomer (B) composed of an aromatic dicarboxylic acid, and an aliphatic or alicyclic glycol. The present invention relates to a method for producing a hydride copolymerized polyester of a diene polymer, which is characterized by reacting under heating. Various methods can be employed to produce the diene polymer hydride (A) having a polylactone segment at the terminal and/or side chain. The diene polymer used as a raw material is exemplified by a diene homopolymer or a copolymer of two or more types, but diene polymers and hydrides of diene polymers are particularly preferred, such as 1,3
There are homopolymers or copolymers obtained by polymerizing at least one monomer selected from -butadiene, 1,3-pentadiene, chloroprene, isoprene, etc., and hydrogenated products thereof. For producing the diene polymer as a raw material, radical, cation, anion, coordination anion, and other polymerization methods can be used without particular limitation. Examples include a living anionic polymerization method using an initiator such as organic lithium, and a radical polymerization method 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 about 40 mol % or less, preferably about 10 mol % or less, based on the total monomers. Other copolymerizable monomers include styrene, α-methylstyrene, o- or p-vinyltoluene, vinylxylene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Examples include vinyl monomers such as vinylpyridine. In addition, a polyfunctional coupling agent, which couples the same or different living polymers together in the presence of the initiator,
For example, methylene chloride, xylylene dibromide,
Linear, branched, and radial diene polymers coupled with terephthalic acid dichloride, silicon tetrachloride, and the like can also be used. Among these, polybutadiene or polyisoprene is preferably used. Furthermore, diene polymers that are partially or completely hydrogenated are preferably used. Preferred hydrogenated diene polymers are those whose average degree of unsaturation has been reduced to about 30% 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. As the hydrogenation catalyst, catalysts such as nickel, porous diatomaceous earth, Raney nickel, finely ground platinum, palladium, and carbon-supported palladium can be used.
The hydrogenation conditions are not particularly limited,
For example, from atmospheric pressure to about 300 atmospheres, usually about 5 to about
Hydrogenation can be carried out at a temperature of 200 atm and normal pressure to about 320°C for about 0.1 to about 24 hours, preferably about 0.2 to about 10 hours. As a method for introducing a polylactone segment into the raw material polyolefin, for example, the following method is suitably used. A method of ring-opening polymerization of cratons in the coexistence of living polymers of diene compounds. A living polymer of a diene compound is reacted with ethylene oxide or the like to hydroxylate the terminal, and then a compound having multiple, preferably two acyl halide groups such as terephthaloyl dichloride or phosgene is reacted to form acyl at the terminal. A method in which a halide group is introduced and then reacted with polylactone. A method in which a diene polymer with hydroxyl groups introduced at its ends is reacted with a base such as sodium hydride to activate the ends, and then lactone is ring-opened and polymerized from these ends. A method in which a diene polymer with carboxyl groups introduced at its ends is treated with a halogenating agent such as thionyl chloride to convert the ends into acyl halide groups, and then reacted with polylactone. A method in which a carboxyl group or a hydroxyl group is introduced at the terminal and ring-opening polymerization of lactone is carried out in the presence of a diene polymer. Compounds with multiple acyl halide groups that may be used in these methods include oxalic acid dihalide, malonic acid dihalide, succinic acid dihalide, glutaric acid dihalide, adipic acid dihalide, sebacic acid dihalide, cyclohexanedicarboxylic acid dihalide, Examples include terephthalic acid dihalide, isophthalic acid dihalide, xylylene dicarboxylic acid dihalide, 2,6-naphthalenedicarboxylic acid dihalide, and bis(4-carboxyphenyl) ether dihalide. In addition, lactone has the following general formula () (where n is a positive integer of 2 to 7, R ¹ and R ² are hydrogen or lower alkyl groups) It is a compound represented by β-propiolactone, β-butyrolactone, δ-valerolactone,
Examples include ε-caprolactone. Among these, ε-caprolactone, which is industrially produced in large quantities and is economically advantageous, is particularly preferably used. The diene polymer used in the method exemplified above may be hydrogenated in advance, or may be hydrogenated after introducing the polylactone segment. In addition, commercially available polybutadiene homopolymers or copolymers having a hydroxyl group or carboxyl group at the terminal, or hydrogenated polymers thereof can be used as diene polymers that serve as raw materials for introducing polylactone segments. Examples of such polymers include the following. Nisso PB G-1000 Nippon Soda G-2000 〃 〃 G-3000 〃 〃 GI-1000 〃 〃 GI-2000 〃 〃 GI-3000 〃 〃 C-1000 〃 〃 CI-1000 〃 Polytail H Mitsubishi Kasei 〃 HA 〃 Poly -BD Arco Butarez HT Philipp Hycar-HTB Gutdrich Telogen HT General Tire Co. Polyolefins having polylactone segments at the terminal and/or side chains used in the present invention
In (A), a polylactone segment having a molecular weight of usually about 300 to about 200,000, particularly preferably about 500 to about 100,000, is added to the hydride of the diene polymer in (A).
An example is a diene polymer hydride (A) in a proportion of usually about 1 to about 500 parts by weight, particularly preferably about 2 to about 400 parts by weight, per 1000 parts by weight. A more preferred embodiment of the diene polymer hydride (A) having a polylactone segment uses a diene monomer as a raw material monomer, and the diene polymer or its hydrogen compound segment has a molecular weight of about 300 to about 700,000, particularly preferably about 500
and about 500,000, and has a polylactone segment at at least one end, particularly preferably two ends, and each of the lactone segments has a molecular weight of about
300 to about 200,000, particularly preferably about 500 to about 100,000, and the total amount of polylactone segments is about 1 to about 500 parts by weight, particularly preferably about 2 parts by weight, per 100 parts by weight of the diene polymer or its hydride segments. and about 400 parts by weight of diene polymer hydride (A). If the molecular weight of the segment of the diene polymer or its hydride is less than about 300, the excellent properties of the diene polymer or its hydride will not be exhibited. Also, when the molecular weight exceeds about 700,000,
There are disadvantages such as poor compatibility between the diene polymer or its hydride and the polyester or its oligomer, resulting in a decrease in copolymerization efficiency. Moreover, when the molecular weight of the polylactone segment is less than 300, the efficiency of copolymerization of the diene polymer or its hydrogen compound and the polyester or its oligomer decreases. Moreover, if the molecular weight exceeds about 200,000, there is a disadvantage that the heat resistance of the polyester, which is a copolymer component, decreases. Furthermore, if the total amount of polylactone segments is less than about 1 part by weight with respect to 100 parts by weight of the diene polymer or its hydroxide segments,
The efficiency of copolymerization with the polyester component decreases.
If the amount is more than 500 parts by weight, there are disadvantages such as a decrease in the excellent properties of the polyester component to be copolymerized, such as heat resistance. The aromatic dicarboxylic acids constituting the polyester or its oligomer (B) include terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid,
Examples include bis(p-carboxylphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and ester-forming derivatives thereof. If the proportion of the acid component is approximately 40 mol% or less, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, etc.
1,3-cyclohexanedicarboxylic acid, 1,4-
Dicarboxylic acids other than aromatic dicarboxylic acids such as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and ester-forming derivatives thereof may be substituted. In addition, as glycol monomer components, aliphatic glycols having 2 to 20 carbon atoms, namely ethylene glycol, propylene glycol, 1,4-
Butanediol, neopentyl glycol, 1,
5-pentanediol, 1,5-hexanediol, decamethylene diglycol, etc., alicyclic diols such as cyclohexanediol, tricyclodecane dimethylol, diethylene glycol, triethylene glycol, or polyethylene glycol with a molecular weight of 10,000 or less, Examples include poly-1,3-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, polycyclohexylene dimethylene terephthalate, polyethylene-2,6
Examples include -naphthalate and oligomers thereof, among which 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 polymers or copolymers with a high degree of polymerization. In the present invention, the diene polymer hydride (A) into which the polylactone segment has been introduced and the polyester or its oligomer (B) are mixed under heating, and if necessary, the reaction system is reduced in pressure to produce a polyester. A copolymer having a diene polymer hydride segment and a polyester segment is produced by an ester or transesterification reaction between the lactone segment and the polyester component. The mixing under heating may be carried out in the absence of a polymerization catalyst, but it is preferably carried out in the presence of a polymerization catalyst.As the polymerization catalyst, those generally used for polyester production can be used, such as manganese acetate,
Acetate metal salts such as zinc acetate, germanium oxide,
Examples include metal oxides such as antimony trioxide and organic titanates such as tetrabutyl titanate. Further, other additives such as colorants, stabilizers, inorganic fillers, etc. can be added during the reaction at the initial stage, intermediate or final stage. The charging ratio of diene polymer hydride (A) and polyester or its oligomer (B) to be mixed is not particularly limited, and may vary depending on the type of both components used (molecular weight, proportion of polylactone segments, etc.), heating temperature, types of other additives present,
It can be changed as appropriate depending on the ratio. Usually, the weight ratio of diene polymer hydride (A) to polyester or oligomer thereof (B) is from about 0.5/99.5 to about 98/2. In addition, when using a diene polymer hydride (A) consisting of hydrogenated polybutadiene having a polylactone segment at the end and polyethylene terephthalate or its oligomer (B), the diene polymer hydride (A) vs. polyester or its oligomer (B) is used. ) is preferably from about 0.5/99.5 to about 98/2, particularly from about 1/99 to about 95/5. If the weight ratio is less than about 0.5/99.5, the properties of the copolymer will be similar to that of polyester without the diene polymer hydride, and if the weight ratio is greater than about 98/2, the properties of the copolymer will be Both are unfavorable because the properties are almost the same as those of the diene polymer hydride alone. To mix the mixture of both components under heating, a kneading device such as a conventionally known device such as a reaction device with stirring blades, a single-screw or twin-screw extruder, a kneader, a Banbury mixer, a mixing roll, a Henschel mixer, etc. can be used alone. Can be used alone or in combination. Although the hydride component of the diene polymer and the polyester component can be reacted while being melt-mixed in the above apparatus, it is also possible to complete the reaction in the solid phase of the melt-mixed product. Heating temperature is about 100℃~400℃, preferably 150℃
℃~350℃. For example, when using a diene polymer hydride (A) consisting of hydrogenated polybutadiene having a caprolactone segment at the end and polyethylene terephthalate or its oligomer (B), it is usually about 150
from about 350°C, particularly preferably from about 180°C to about 350°C
The temperature is preferably 300°C. If the temperature is less than about 150°C, the reaction between the hydride component of the diene polymer and polyethylene terephthalate or its oligomer is extremely slow, and if it exceeds 350°C, the hydride component of the diene polymer will deteriorate, which is undesirable. When the reaction system of the hydride component of the diene polymer and the polyester or its oligomer component is subjected to reduced pressure, the reaction is usually carried out at a pressure of about 5 mmHg or less for about 0.2 hours to about 50 hours, particularly preferably for about 0.5 hours at a pressure of about 2 mmHg or less. It is preferred to maintain the temperature under reduced pressure for about 20 hours. By mixing under heating and, if necessary, reducing the pressure of the reaction system, a block copolymer having a hydride segment of a diene polymer and a polyester segment can be obtained. In the production method of the present invention, it is not necessary to react all the components, and the unreacted diene polymer hydride (A) and/or polyester (B)
The reaction may be terminated with the remaining. In this case, unreacted substances can be separated and removed if necessary. In addition, the polyolefin copolyester obtained in the present invention has a combination of the hydride segment (a) of the diene polymer and the polyester segment (b), b-a b-a-b b-(a-b)- _j a a -(b) _ka {-(-b-a) _-l b} _n , etc. can be exemplified. However, j, k,
l and m are arbitrary positive integers, and each a or each b may be the same or different. The diene polymer hydride copolyester polyester obtained in the present invention has excellent mechanical properties, and is a resin with particularly excellent impact resistance and elongation properties, and can be used alone or in combination with other additives. used. The copolymer provided by the present invention can be used alone or, if necessary, as a composition partially mixed with a terminally reacted diene polymer hydride (A) and/or polyester (B). 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 is 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 has the property of dissolving or swelling the diene polymer hydride (A) or polyester (B), does not have a negative effect on the mixed components, and is easily removed from the system by drying or other methods. Liquids that can be removed, such as hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-octane, ethylbenzene, cumene, methylcyclohexane, and ethylcyclohexane, ketones such as methyl isobutyl ketone, phenol, and o-chlorophenol. , phenol derivatives such as p-chlorophenol, aprotic polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, halogenated carbonization such as trichloroethane, tetrachloroethane, etc. Examples include hydrogen, benzyl alcohol, nitrobenzene, ether, etc. Among these, toluene, o-
Chlorphenol, trichloroethane, benzyl alcohol and nitrobenzene are preferred. Examples of additives in the present invention include colorants, stabilizers, and inorganic fillers. More specifically, examples of colorants include dyes such as etrosine, cadmium sulfide, phthalocyanine, and pigments such as carbon black. Stabilizers include antioxidants and heat stabilizers such as hindered phenols, hydroquinones, thioethers, phosphites, and substituted products and combinations thereof, ultraviolet absorbers such as resorcinol, salicylates, benzotriazoles, benzophenones, and stearic acid. , various lubricants and mold release agents including higher fatty acids such as montanic acid and their metal salts, esters, half esters, stearyl alcohol, derivatives such as stearamide, flame retardant aids such as antimony oxide, dodecylbenzenesulfonic acid Examples include antistatic agents such as sodium and polyalkylene glycol, crystallization promoters, and silane coupling agents. Examples of inorganic fillers include fibrous materials such as glass fiber, carbon fiber, and ceramic fiber, and mica. , glass beads, silica, barium titanate, hydrotalcite, zeolite, etc., which are plate-shaped, powdered, or granular. Furthermore, polymers used as additives include
Polybutadiene, polyisoprene or their hydrides, ethylene propylene rubber, ethylene propylene diene rubber, styrene butadiene rubber, hydrogenated styrene butadiene rubber, or modified rubbers obtained by graft copolymerizing these with acrylic acid, maleic anhydride, etc., polyethylene, polypropylene , α-olefin resin such as ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, 4-methyl-1-pentene-decene copolymer, or elastomer, polymethacrylic acid, Acrylic resins such as ethylene-ethyl acrylate copolymer, ionomer resins such as zinc salt of ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, polyamide such as nylon 6, polyacetal, polycarbonate, polysulfone, polyphenylene oxide,
Examples include fluororesins, phenolic resins, melamine resins, unsaturated polyester resins, silicone resins, and epoxy resins. The amount of the above-mentioned additives to be blended is appropriately determined in consideration of 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) Terephthalic acid 540 parts, ethylene glycol 242 parts
and 0.164 parts of triethylamine were placed in an autoclave and stirred at 240℃ and 2.7Kg/ ^cm2 gauge pressure.
The reaction was carried out for 8 hours while removing the produced water, and at the end of the reaction, 0.15 part of trimethyl phosphate was added. In this way, a polyethylene terephthalate oligomer with an esterification rate of 92% was synthesized. (Production of hydride of diene polymer having a polycaprolactone segment at the end) Anionic polymerization of ε-caprolactone was performed in a toluene solvent using n-butyllithium as an initiator to synthesize poly ε-caprolactone with a molecular weight of 2000. . A reactor containing 61 parts of terephthalic acid dichloride and 500 parts of toluene was charged with hydrogenated polybutadiene GI having hydroxyl groups at substantially both ends.
-3000 (manufactured by Nippon Soda, KOH value: 28) and 52 parts of pyridine dissolved in 1500 parts of toluene were added dropwise using a dropping funnel, and reacted for 2 hours at 50°C in a nitrogen atmosphere. Next, a solution prepared by dissolving 600 parts of the poly-ε-caprolactone in 1000 parts of toluene was added dropwise, and the mixture was reacted at 50° C. for 2 hours in a nitrogen atmosphere. The reaction solution was filtered to remove most of the pyridine hydrochloride, and then precipitated into methanol. After dissolving the precipitate in hexane and washing with water, it was precipitated in acetone and the insoluble portion was collected. The above purification operation was repeated until the insoluble portion became transparent, and hydrogenated polybutadiene having poly ε-caprolactone segments at both ends was isolated. As a result of elemental analysis (quantification of oxygen) of the hydrogenated polybutadiene whose terminals were modified in this way, it was found that approximately 51% of the hydrogenated polybutadiene contained polyε-caprolactone.
It was found that it was included. This result corresponds to 104 parts by weight of poly ε-captolactone segments per 100 parts by weight of hydrogenated polybutadiene. Note that in the above reactions, substantially anhydrous reagents and solvents were used. (Production of copolymer of polyester and diene polymer hydride) 85 parts of polyethylene terephthalate oligomer synthesized by the above method, 15 parts of hydrogenated polybutadiene having a poly-ε-caprolactone segment at the end, and 0.02 part of antimony trioxide. was charged into a reactor and heated at 270℃ for 1 hour while stirring under a nitrogen atmosphere.
Allowed time to react. The pressure of the reaction system was reduced over 20 minutes, and the polycondensation reaction was finally carried out for 4 hours at a reduced pressure of 0.6 mmHg or less. GPC the molecular weight of the produced polymer
(Apparatus: Waters model 150C, conditions: o-chlorophenol at 70°C)
The number average molecular weight in terms of polyethylene terephthalate was 29,300. The resulting polymer was pulverized using a rotor speed mill (Puluverisette 14 manufactured by Fritsch), then placed in a Soxhlet extractor and extracted with toluene for 8 hours. The ratio of the diene polymer used in the reaction of the extracted polymer to the hydride component (hereinafter referred to as toluene extraction rate) was 26%.
Press the extracted residual polymer into a press molding machine (molding temperature: 290
°C) 15cm x 15cm x 0.05cm under nitrogen seal
(), 15cm x 15cm x 0.2cm (), and the following measurements were made. Tensile test: A dumbbell-shaped test piece with a total length of 5 cm and a parallel part width of 0.5 cm was punched out from the sheet in (), and using an Instron tensile tester, the tensile speed was measured.
The test was carried out at a speed of 50 mm/min and a temperature of 23°C. Izot impact test: Two sheets of () were stacked and measured at 23°C according to the method of JIS K7110. The results are shown in Table 1. Example 2 In Example 1, instead of using polyethylene terephthalate oligomer when producing the copolymer of polyester and diene polymer hydride, polyethylene terephthalate (manufactured by Kanebo Gosen Co., Ltd., Velpette FEG
The same reaction as in Example 1 was carried out except that -7) was used. However, the polycondensation was carried out at 275°C and 0.5 mmHg or less for 2 hours. The results are shown in Table 1. Example 3 In Example 1, when producing a copolymer of polyester and diene polymer hydride, polybutylene terephthalate resin (Toyobo Co., Ltd.) was used instead of polyethylene terephthalate oligomer.
The same reaction as in Example 1 was carried out except that 0.02 part of tetrabutyl titanate was used instead of antimony trioxide. However, the polycondensation reaction was carried out at approximately 250° C. and 0.5 mmHg or less for 3 hours. The results are shown in Table 1. Example 4 75 parts of hydrogenated polybutadiene having poly ε-caprolactone segments at both ends synthesized by the same method as in Example 1, 25 parts of oligomer of polyethylene terephthalate, and tetrabutyl titanate.
0.05 part was charged into a reactor, and a polycondensation reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1. Example 5 (Production of hydride of diene polymer having a polycaprolactone segment at the end) In a reactor equipped with a condenser, a stirrer, and a dropping funnel, 61 parts of GI-3000 used in Example 1 and dehydrated toluene were added. 500 parts of sodium hydroxide and 1.4 parts of 50% oil dispersion were charged, and the mixture was reacted for 1 hour at 130°C under an argon atmosphere while refluxing toluene. After cooling the reactor to room temperature,
30 parts of anhydrous ε-caprolacum was added dropwise from the dropping funnel and allowed to react at room temperature for 3 hours. A large excess of methanol was added to the reaction solution, and the precipitate was separated. This precipitate was dissolved in hexane and then precipitated in a large excess of acetone to isolate hydrogenated polybutadiene having poly ε-caprolactone segments at the ends. (Production of copolymer of polyester and diene polymer hydride) Polycondensation was carried out under the same conditions as in Example 1, except that 15 parts of hydrogenated polybutadiene having a polyε-caprolactone segment at the end synthesized by the above method was used. The reaction was carried out. The results are shown in Table 1. Example 6 (Production of hydride of diene polymer having a poly ε-caprolactone segment at the end) 700 parts of anhydrous benzene and 136 parts of isoprene were charged into a reaction equipment equipped with a cooler and a stirrer, and sec- A hexane solution containing 0.64 parts of butyllithium was added dropwise, and the mixture was reacted for 5 hours at room temperature under an argon atmosphere. Next, 40 parts of ε-caprolactam was added dropwise and reacted at room temperature for 3 hours. The reaction solution was dropped into a large excess of methanol, and the resulting precipitate was extracted with methyl ethyl ketone to isolate a polyisoprene-poly ε-caprolactone block copolymer. As a result of GPC measurement using THF solvent,
The number average molecular weight was approximately 15,000 in terms of polyisoprene. The results of elemental analysis revealed that about 25% by weight of poly ε-caprolactone was contained in the copolymerization. This copolymer was mixed with 30 parts of cyclohexane, 700 parts of palladium on a carbon carrier (5 parts
% loading) into an autoclave, and hydrogen pressure
The reaction was carried out at 140° C. for 4 hours at a cage pressure of 100 Kg/cm ² . The reaction solution was filtered and washed with water, and then precipitated into methanol to isolate a hydrogenated polyisopre-poly-ε-caprolactone copolymer. The iodine value of this copolymer was 7. (Production of copolymer of polyester and diene polymer hydride) In Example 1, instead of hydrogenated polybutadiene having poly ε-caprolactone segments at both ends, poly ε-
A polycondensation reaction was carried out under the same conditions as in Example 1 using hydrogenated polyisoprene having caprolactone segments. The results are shown in Table 1. Comparative Example 1 When producing a copolymer of polyester and diene polymer hydride in Example 1, instead of using hydrogenated polybutadiene having poly ε-caprolactone segments at both ends, hydrogenation having hydroxyl groups at both ends was used. Polybutadiene, GI−
Polycondensation reaction was carried out under the same conditions as in Example 1 except that 3000 was used. The toluene extraction rate of the reaction product is
It was found that only 80% and 20% of the charged polyolefin was incorporated into the copolymer. Table 1 shows the results of measuring the physical properties. 【table】

Claims (1)

[Scope of Claims] 1. A polyester or its oligomer (B) composed of a hydride of a diene polymer having a polylacto segment at the terminal and/or side chain (A), an aromatic dicarboxylic acid, and an aliphatic or alicyclic glycol. ) and a method for producing hydride copolymerization of a diene polymer and polyester, the method comprising reacting them under heating. 2. The production method according to claim 1, which is a hydrogenated diene polymer having a poly ε-caprolactone segment at the terminal and/or side chain.