JPH0141650B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a block copolymer and a method for producing the same. More specifically, the present invention relates to a novel block copolymer having a hydrocarbon chain block and a polyester block, and a method for producing the same. A main saturated or partially saturated hydrocarbon polymer having at least one hydroxyl group is
Since it has good compatibility with non-polar polymers such as polyolefins, it is used as a material that imparts reactivity to non-polar polymers, or as a urethane elastomer by reacting with polyisocyanate. However, the hydrocarbon polymer has poor compatibility with polar polymers, and the tensile strength and elongation of urethane elastomers obtained by reacting with polyisocyanates are also insufficient. The present inventors have conducted intensive studies to provide a new polymer that is compatible with both polar and non-polar polymers and exhibits excellent physical properties when reacted with polyisocyanate, and a method for producing the same. As a result, the present invention has been completed. Reached. That is, the gist of the present invention is that the number average molecular weight is
A hydrogenated conjugated diene polymer with a hydrogenation rate of 80% or more in the main chain and at least one hydroxyl group in the range of 400 to 48,000 and ε-caprolactone are added to the hydroxyl group 1 in the hydrocarbon polymer. A method for producing a block copolymer, characterized in that the reaction is carried out at a ratio of 2 moles or more of ε-caprolactone per equivalent. To explain the present invention in more detail below, the block copolymer obtained by the production method of the present invention is a hydrogenated conjugated diene polymer (hereinafter simply referred to as hydrocarbon) having a hydrogenation rate of 80% or more in the main chain. (abbreviated as polymer)
A block consisting of and a formula

It is a block copolymer consisting of a polyester block represented by the formula: (in the formula, n is a number of 2 or more), and from its structure, the hydrocarbon polymer has a substituent group represented by the polyester block at the end. It is a polymer with A block made of hydrocarbon polymer

[expression] or

The structure of the block copolymer of the present invention is exemplified as follows, where the polyester block is represented by B. The preferred structure of the block copolymer of the present invention is:
It has a structure in which the hydrocarbon polymer has an average of one or more substituents, preferably an average of 1.5 to 4 substituents, represented by the above polyester blocks, at the terminal end thereof. The hydrocarbon polymer has a saturated or mostly saturated main chain, and specifically, a hydrogenated conjugated diene polymer having a hydrogenation rate of 80% or more in the main chain is used. Examples of the conjugated diene polymer include homopolymers of conjugated dienes such as butadiene-1,3 and isoprene, or conjugated dienes 70 and 70 of these conjugated dienes.
Examples include copolymers of at least 30% by weight of vinyl monomers such as styrene, methyl acrylate, methyl methacrylate, acrylonitrile, acrylic acid, 2-vinylpyridine, vinyl chloride, and vinyl acetate. The main chain of such a conjugated diene polymer is preferably hydrogenated by 80% or more, preferably 95% or more.
The number average molecular weight of the block copolymer of the present invention is
600 to 60,000, preferably 1,000 to 10,000. If the number average molecular weight is too small, the weather resistance will not be sufficient, and if it is too large, the fluidity will decrease, making handling difficult. In addition, the number average molecular weight (A) of the block made of hydrocarbon polymer is 400 to 4800, and the number average molecular weight (B) of the polyester block is 200 to 3000.
and (B)/(A) is in the range of 0.01 to 10. Note that the number average molecular weight (B) of the polyester block is 1
If there are multiple polyester blocks per molecule, it is the sum of them. If the value of (B)/(A) is too small, the compatibility of polar polymers will not be improved, and (B)/(A)
When the value of is large, the compatibility with the nonpolar polymer becomes insufficient. To produce the block copolymer of the present invention, at least one polymer having a number average molecular weight in the range of 400 to 48,000 is required.
Hydrogenated conjugated diene polymers with a main chain hydrogenation rate of 80% or more (hereinafter referred to as "hydrocarbon polymers having hydroxyl groups") and ε
- Caprolactone is reacted in a ratio such that 2 moles or more of ε-caprolactone per equivalent of hydroxyl group in the hydrocarbon polymer. As the hydrocarbon polymer having hydroxyl groups, those having a number average molecular weight in the range of 400 to 48,000, preferably 1,000 to 10,000 are used. If the number average molecular weight is too small, the weather resistance will not be sufficient, and if it is too large, the fluidity will decrease, making handling difficult. The average hydroxyl group per molecule is 1 or more, preferably 1.5 to 3.0
It is. The hydroxyl group is preferably located at the end of the main chain or at the end of a long chain branch. The main chain used is saturated or mostly saturated. Mostly saturated means that the hydrocarbon polymer has 1,
When referring to the hydrogenation rate of 4-polybutadiene, specify one in which the hydrogenation rate of the double bonds in the main chain is 80% or more. As the hydrocarbon polymer, hydrogenated products of conjugated diene polymers as described above are preferred. However, such a hydrocarbon polymer having a hydroxyl group is a conjugated diene polymer or a conjugated diene polymer manufactured from a conjugated diene or a conjugated diene and a vinyl monomer by a well-known method such as a radical polymerization method or an anionic polymerization method. It is usually obtained by hydrogenating a diene copolymer. In the case of radical polymerization, if the polymerization is carried out using hydrogen peroxide as a polymerization initiator, a conjugated diene polymer or copolymer having a hydroxyl group at the terminal can be obtained directly, but in the case of anionic polymerization, an alkali metal is first added to the terminal using an anionic polymerization catalyst. A living polymer with a bonded structure is produced and then reacted with a monoepoxy compound, formaldehyde, etc. As the raw material conjugated diene, isoprene, chloroprene, etc. can also be used, but butadiene-1,3 is preferred. Examples of the copolymerization component include vinyl monomers as described above. The amount of the copolymer component used is preferably 30% by weight or less of the total monomer amount. Hydrogenation may be carried out in a conventional manner under hydrogen using a catalyst such as nickel, cobalt, platinum, palladium, ruthenium, rhodium or the like alone or supported on a carrier. Other methods for producing hydrocarbon polymers having hydroxyl groups include a method in which a copolymer of α-olefin and another monomer is oxidized and decomposed, and then reduced. For example, polyhydroxypolyisobutylene can be obtained by subjecting a butyl rubber-based polymer obtained by cationic polymerization of isobutylene and butadiene or 1,3-pentadiene to an ozone decomposition treatment and then reducing it with lithium aluminum hydride. A block copolymer can be produced by reacting a hydrocarbon polymer having a hydroxyl group with ε-caprolactone in the following manner. A conventional reactor is sufficient as the reactor.
The reaction was carried out by charging a predetermined amount of a hydrocarbon polymer with hydroxyl groups and ε-caprolactone into a reactor.
It is carried out for 30 minutes to 15 hours at a temperature of ℃ to 250℃. A more preferred temperature range is 130-230°C. When the temperature is lower than 10°C, the reaction rate decreases, which is disadvantageous from an industrial standpoint. Furthermore, temperatures higher than 250°C are not preferred because the polymer deteriorates. The amount of ε-caprolactone used in the present invention is not particularly limited, but it is generally preferred to use 2 moles or more per equivalent of hydroxyl group in the hydrocarbon polymer having hydroxyl groups. A particularly preferred range is 5 mol to 100 mol. This is because if the amount is less than 2 moles, the objective of improving compatibility with polar polymers may not be fully achieved. During the reaction, a blocked catalyst can be used if necessary, but it is generally preferable to use it because the reaction time can be shortened. Effective catalysts include organotin compounds such as tetraoctyltin, diphenyltin dilaurate and dilauryltin oxide, lead salts such as lead acetate, lead salicylate and lead 2-ethylhexanoate, tetrabutyl titanate and isopropyl titanate. Examples include catalysts for ring-opening polymerization such as organic titanium compounds such as . The amount of catalyst used is not particularly limited, but is usually 0.005% to 5% by weight based on the amount of ε-caprolactone. A more preferred amount is 0.05% to 1% by weight. If the amount of catalyst is too large, the obtained block copolymer may change color, so it is preferable to carry out the reaction within the above range as much as possible. A solvent can be used as necessary. Usable solvents are those that do not contain active hydrogen such as hydroxyl groups and carboxyl groups, and examples include hydrocarbons such as toluene, xylene, benzene, heptane, and cyclohexane, ethyl acetate,
Examples include esters such as butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. Since the block copolymer of the present invention obtained as described above has at least one hydroxyl group at the end, it can be made into a three-dimensional cured product by reacting with a polyisocyanate, and the cured product is It has excellent physical properties such as tensile strength and elongation. Furthermore, since the block copolymer of the present invention is composed of a hydrocarbon polymer block having a hydroxyl group and a polyester block, it is well compatible with both non-polar polymers and polar polymers, and can be used as a reactive modifier for these polymers. You can also. Furthermore, it is an extremely useful material because it can be used as a variety of modifiers after the terminal hydroxyl group has been modified in advance. Next, the block copolymer of the present invention will be explained with reference to Examples, Application Examples, and Reference Examples.
We are not intended to be bound by these examples unless they go beyond their gist. The mechanical properties of the cured product were measured according to JISK-6301. In addition, the number average molecular weight is VPO manufactured by Hitachi PerkinElmer
(Vapor Pressure Csmometer) using type 115,
Measured in toluene solution at 40°C. Reference Example 1 Production of a hydrocarbon polymer whose main chain is saturated and has a hydroxyl group at the end; Polyhydroxypolybutadiene (R-45HT manufactured by Arco Chem., [-
OH] = 0.82 meq/g, cis-1,4: 15%, trans-1,4: 58%, vinyl: 27%) 3 kg, cyclohexane 3 kg and carbon-supported ruthenium (5
After charging 300 g of catalyst (manufactured by Nippon Engelhard Co., Ltd.) and replacing the inside of the system with purified argon gas, high-purity hydrogen gas was started to be supplied into the autoclave.
Start heating at the same time. It takes about 30 minutes to reach steady conditions inside the autoclave (internal temperature 100℃, internal pressure 50Kg/cm ² ).
reached. After 15 hours under these conditions, the hydrogenation reaction was stopped, and the polymer was purified and dried according to a conventional method. As a result of analysis by infrared absorption spectrum, the obtained polymer was found to be a hydrocarbon polymer containing almost no double bonds. -OH group of hydrogenated
It was 0.81meq/g, and the number average molecular weight measured by vapor pressure method was 3000. Example 1 494 g of a hydrocarbon polymer with a saturated main chain having at least one hydroxyl group at the end obtained by the method of Reference Example 1 and 456 g of ε-caprolactone were placed in a three-necked flask (No. 2) at 180°C. The temperature rose to .
After raising the temperature, 0.35 g of tin octylate was added as a catalyst, and the mixture was reacted at 180 to 190°C for 6 hours. After the reaction, unreacted ε-caprolactone was distilled off under reduced pressure.
Only a small amount of ε-caprolactone was distilled off (approximately 5
g), and the reaction was almost 100%. The infrared absorption spectrum of the obtained polymer showed an absorption of the terminal OH group at 3500 cm ^-1 and a large absorption of the ester group at 1730 cm ^-1 . This absorption intensity did not change even after washing with acetone many times. In addition, gel permeation chromatography (GPC) of this polymer
In the analysis, the peak shifted to the higher molecular weight side than the peak of the raw material hydrocarbon polymer. The number average molecular weight measured by vapor pressure method was 4800. From the above, the reaction product is a block polymer produced by ring-opening polymerization of ε-caprolactone using the terminal OH group of a main chain saturated hydrocarbon polymer having at least one hydroxyl group at the terminal. So, the number average molecular weight of the hydrocarbon polymer block is about 3000, and the formula

It is a block copolymer with a total number average molecular weight of about 1800 for the polyester block represented by the formula. Next, Table 1 shows the results of examining the compatibility of this block copolymer with polar polymers. 80℃
The two were mixed and left at 70°C for one hour, and then the mixed system was evaluated. The polar polymers used were Asahi Denka Co., Ltd.'s polypropylene glycol P-1000 (average molecular weight approximately 1000) and Chitsuso Co., Ltd.'s polycaprolactone.
PCP-0240 (average molecular weight approx. 2000), and Quaker Oats' polytetramethylene ether glycol POLYEG-2000 (average molecular weight approx.
2000POLYMEG is a trademark). For comparison, the compatibility of the hydrocarbon polymer used as a raw material was also examined in the same manner.

[Table] Application example 1 250g of the block copolymer obtained in Example 1 was
The mixture was placed in a 500 ml flask and placed in a hot air dryer at 80°C to dissolve. Add 16.8g of diphenylmethane diisocyanate to this and mix quickly with a spatula.
C. and 150 kg/cm ² for 20 minutes to obtain a transparent cured sheet with a thickness of 2 mm. Table 2 shows the mechanical properties of the cured sheet. For comparison, at least 1
Table 2 also shows the mechanical properties of a cured sheet obtained by curing a hydrocarbon polymer with a saturated main chain having 2 hydroxyl groups in the same manner as above. It can be seen that the tensile strength and elongation are significantly improved by using a block copolymer.

[Table] Example 2 Example 1 except that 482 g of a hydrocarbon polymer with a saturated main chain having at least one hydroxyl group at the end obtained by the method of Reference Example 1 and 228 g of ε-caprolactone were used. A wax-like block copolymer was obtained in exactly the same manner as above. The number average molecular weight of the block copolymer measured by vapor pressure method was 3900. Therefore, it is a block copolymer in which the hydrocarbon polymer block has a number average molecular weight of about 3,000 and the polyester block has a total number average molecular weight of about 900. Example 3 301 g of a hydrocarbon polymer with a saturated main chain having at least one hydroxyl group at the end obtained by the method of Reference Example 1 and 1140 g of ε-caprolactone
A white solid block copolymer was obtained in exactly the same manner as in Example 1, except that . The number average molecular weight of the block copolymer measured by vapor pressure method was 11,000. Therefore, this block copolymer consists of a hydrocarbon polymer block with a number average molecular weight of about 3,000 and a polyester block with a number average molecular weight of about 8,000. Example 4 150 g of 1,3-butadiene, 70 g of isopropyl alcohol, and 10 g of 60% hydrogen peroxide were placed in a 500 ml autoclave at room temperature in an argon atmosphere.
Polymerization was carried out at 90°C for 5 hours, and after cooling, the monomer was removed and the polymer was dried. Determined from the hydroxyl value of the polymer,
The OH group was 0.34 meq/g, and the number average molecular weight measured by vapor pressure method was 4700. This polymer was hydrogenated in the same manner as in Reference Example 1, and the number average molecular weight was 5000.
A hydrogenated polymer with a viscosity of 0.34 meq/g of OH groups and a hydrogenation rate of 95% or more was obtained. 882g of the above hydrogenated polymer and ε-caprolactone
A wax-like block copolymer was obtained in exactly the same manner as in Example 1, except that 342 g was used. The number average molecular weight of the block copolymer measured by vapor pressure method is 6700.
It was hot. Example 5 NISSO-PBG-1000 manufactured by Nippon Soda Co., Ltd. ([-OH]=
1.22meq/g, trans 1.4=8.9%, vinyl 91.1
%, NISSO-PB is a trademark) is used as reference example 1.
Hydrogenation was carried out in exactly the same manner as -OH group 1.21meq/
g, and the number average molecular weight measured by vapor pressure method is 1400
A hydrogenated polymer was obtained. 496 g of this hydrogenated polymer and 684 g of ε-caprolactone were placed in No. 2 three-necked flask and heated to 180°C. After raising the temperature, 0.3 g of dibutyltin dilaurate was added, and the mixture was reacted at the same temperature for 7 hours. The number average molecular weight of the obtained block copolymer was 3,500.

Claims (1)

[Claims] 1. A hydrogenated conjugated diene polymer having a number average molecular weight in the range of 400 to 48,000 and having at least one hydroxyl group and a hydrogenation rate of 80% or more in the main chain, and ε-caprolactone. A method for producing a block copolymer, which comprises reacting ε-caprolactone in a proportion of 2 moles or more per 1 equivalent of hydroxyl group in the hydrogenated conjugated diene polymer. 2. Claim 1, wherein the hydrogenated conjugated diene polymer whose main chain has at least one hydroxyl group has a hydrogenation rate of 80% or more is a hydrogenated polyhydroxydiene polymer. A method for producing a block copolymer.