WO1996000741A1

WO1996000741A1 - Hydrogenated block polymer, resin composition, and block polymer

Info

Publication number: WO1996000741A1
Application number: PCT/JP1995/001259
Authority: WO
Inventors: Kouichirou Maeda; Tetuya Toyoshima; Eiji Furuno; Naoki Tanahashi; Keiko Yoshida
Original assignee: Nippon Zeon Co., Ltd.
Priority date: 1994-06-28
Filing date: 1995-06-23
Publication date: 1996-01-11
Also published as: JPH0812720A

Abstract

A block polymer having a weight-average molecular weight of 50,000 to 1,000,000 and composed of at least one polyisoprene block having a 1,4-bond content of at least 80 % and a weight-average molecular weight of 25,000 to 500,000 and at least one polyisoprene block having a 3,4-bond content of at least 30 % and a weight-average molecular weight of 25,000 to 500,000; a hydrogenated block polymer produced by hydrogenating the above polymer at a hydrogenation rate of at least 50 %; and a resin composition comprising 40-1 wt.% of the above hydrogenated polymer and 60-99 wt.% of a thermoplastic resin such as polypropylene. As compared with other resin compositions containing, for example, an elastomer, the invention composition has an excellent impact resistance which can well withstand low-temperature applications, is also excellent in mechanical strengths such as modulus of elasticity, and has a high melt flow rate, thus being excellent also in processability and moldability.

Description

Description Block copolymer hydrogenated product, resin composition, and block polymer

The present invention relates to a block polymer hydrogenated product that is a raw material of a resin composition having excellent impact resistance, the resin composition, and a block polymer used for producing a block polymer hydrogenated product. Production of thermoplastic resin having impact resistance usable, hydrogenated isoprene block polymer as a raw material of the composition, thermoplastic resin composition containing the isoprene block, and hydrogenated block polymer The present invention relates to a block polymer comprising a combination of polyisoprene blocks having a specific structure.

Background art

Polyolefins are used as molding materials in many fields. However, there was a problem with the impact resistance, and in fields where impact resistance was required, there was a problem that it had to be used as a thick molded product.

In order to improve impact resistance, it is widely used to blend ethylene (propylene) rubber with polyolefins. Polyolefin resin composition containing low molecular weight ethylene / propylene rubber has insufficient impact resistance, poor mechanical strength such as elastic modulus, and high molecular weight ethylene / propylene rubber. In the case of a polyolefin resin composition, a new problem has arisen in that the melt viscosity is too high, the fluidity is reduced, and molding / adding becomes difficult.

As a polyolefin composition excellent in both processability and moldability and impact resistance, a composition comprising a mixture of polyolefins and hydrogenated natural rubber or synthetic 1,4-polyisoprene (Japanese Patent Publication 1-2) No. 9 13 13), isoprene 'butadiene', a hydrogenated product of block copolymer, isoprene 'butadiene' random copolymer, in which 1,2 bonds and / or 3,4 bonds are 30% or less in polyolefins (Japanese Patent Laid-Open Publication No. Hei 11-68743) and the like have been proposed.

The former has excellent low-temperature brittleness and impact resistance, but in most cases The hydrogenated substances are dispersed as large particles having a particle size of 10 or more in the components, and the structure tends to concentrate stress around the particles, so that the impact resistance etc. are improved, but the elastic modulus However, there is a problem that the mechanical strength decreases. The latter improved the impact resistance, which improved compatibility, improved dispersibility in polyolefins, and improved moldability to some extent.

Heretofore, there has not been known a block polymer hydrogenated product composed of a combination of polyisoprene blocks having different contents of 3, 4 bonds, and what properties of a polyolefin composition containing the same have been known. It was not known before the present invention was completed.

Disclosure of the invention

The present inventors have conducted intensive studies to improve the properties of hydrogenated polyisoprene and to greatly improve the impact resistance by adding a small amount to a thermoplastic resin. As a polyisoprene, a polyolefin composition containing a polyisoprene block polymer combined with a polyisoprene block having a specific structure was found to be excellent in impact resistance and mechanical strength, and completed the present invention. It came to be.

BEST MODE FOR CARRYING OUT THE INVENTION

Thus, according to the present invention, a polyisoprene block having a weight average molecular weight of 25,000 to 500,000, containing 80% or more of 1,4 bonds, and 30% of 3,4 bonds, A weight average molecular weight of at least 50,000 to 1,0,0,0 having at least one polyisoprene block having a weight average molecular weight of 2,500,000 to 500,000. A block polymer hydrogenated product obtained by hydrogenating a block polymer of No. 00 to a hydrogenation ratio of 50% or more; a resin composition comprising a thermoplastic resin and the hydrogenated block polymer; and 1 Polyisoprene block having a weight average molecular weight of 25,000 to 500,000 containing not less than 80% of 2,4 bonds, and a weight average molecular weight of 25,0 containing not less than 30% of 3,4 bonds. And a weight average molecular weight of at least one polyisoprene block having a weight average molecular weight of 500, 000, 0000, 0000, 0000. Is provided.

(Block polymer) The block polymer of the present invention is a polymer of isoprene, which is a polyisoprene block containing 1,4 bonds of 80% or more (hereinafter, referred to as A block), and containing a 3,4 bond of 30% or more. Block (hereinafter referred to as B block).

When polymerizing each block, in addition to isoprene, compounds that can be copolymerized with isoprene, such as butadiene, 1,3-pentadiene, 2,3-dimethyl-11,3-butadiene, and 2-methyl-1,3 —Pentadene, 1,3-hexagene, 4,5-getyl-1,3-octadiene, etc. may be used in combination as a monomer, but at least 80%, preferably not less than 80%, of the repeating structural units in each block. At least 90%, more preferably at least 95%, of the repeating structural units derived from isoprene is used. If the amount of the repeating structural units derived from isoprene is too small, the impact resistance decreases.

A block

The A block is a polyisoprene block containing at least 80%, preferably at least 85%, more preferably at least 90% 1,4 bonds. There are two types of 1,4 bond, cis 1,4 bond and trans 1,4 bond, which may be either one or both. If there are too few 1,4 bonds in the A block, the impact resistance of the resin composition of the present invention will decrease.

The weight average molecular weight of the A block is a polystyrene equivalent value by gel 'permeation' chromatography, and the lower limit is preferably 25,000, more preferably 50,000, particularly preferably 100,000. 0, the upper limit is preferably 500,000, more preferably 300,000, particularly preferably 200,000. If the weight average molecular weight is too small, the impact resistance of the resin composition of the present invention decreases, and if the weight average molecular weight is too large, the melt viscosity of the resin composition of the present invention becomes too high, making processing and molding difficult. .

The method for producing the A block is not particularly limited, and a known method such as a method of polymerizing a monomer using a lithium-based catalyst such as alkyllithium is exemplified. In particular, alkyl lithium such as n-butyllithium, sec-butyllithium and other monovalent alkyllithiums; dilithiummethane, 1,4-dilithiobutane, and 1,6-dilithiohexane such as divalent alkyllithiums; preferable. The method described below Thereby, the block polymer of the present invention can be easily obtained.

When alkyllithium is used as the catalyst, the amount of the catalyst is determined according to the type of alkyllithium and the desired weight average molecular weight of the A block. For example, when synthesizing an A block having a weight average molecular weight of about 200,000 using n-butyllithium, usually, about 5 mmol is used per 1 kg of monomer. This is a standard when it is considered that the reaction has been completed when the weight of the polymer in the polymerization reaction solution reaches 95% or more of the weight of the charged monomers. Increasing the amount shortens the time to the end of the reaction but decreases the molecular weight. Decreasing the amount of the catalyst increases the time to the end of the reaction but increases the molecular weight. If the A block is recovered before the reaction is completed, or if the Lewis base is added and the polymerization is switched from A block polymerization to B block polymerization continuously as described below, select the appropriate amount of catalyst. There is a need.

When alkyllithium is used as a catalyst and polymerization is performed using a monomer other than isoprene, a Lewis base described later is also used as a cocatalyst. In this case, the amount of the Lewis base to be used is generally from 0.01 to 0.5 mol per 1 mol of the catalyst. When the amount of Lewis base is reduced, monomers other than isoprene are less likely to polymerize, and when the amount of Lewis base is increased, 3,4 bonds of isoprene increase and 1,4 bonds decrease.

When the alkyllithium is used as a catalyst for the polymerization reaction of the A block, the lower limit is 10 ° C, preferably 40 ° C, more preferably 50 ° C, and the upper limit is 120 ° C, preferably 100 ° C. The reaction is more preferably performed at a temperature of 80 ° C. If the reaction temperature is too low, the reaction rate is slow and the production efficiency is poor. If it is too high, the control of the reaction becomes difficult, and the production efficiency is also poor. The pressure during the reaction has no significant effect, and the polymerization usually takes place at 7 to 10 atmospheres. The production of these A blocks is usually performed in a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include hydrocarbon solvents such as pentane, heptane, n-hexane, cyclohexane, methylcyclohexane, benzene, and xylene. Is exemplified. Usually, the lower limit of the solvent is 1 part by weight, preferably 2 parts by weight, more preferably 3 parts by weight, and the upper limit is 50 parts by weight, preferably 10 parts by weight, more preferably 10 parts by weight, based on 1 part by weight of the monomer. Use in the range of 5 parts by weight. Solvent amount If the amount is too small, the reaction solution becomes highly viscous and stirring becomes difficult, so that it is difficult to uniformly control the reaction.

The ratio of 1, 4 bonds in the A block varies depending on the combination of the type and amount of the monomer used in combination and the polymerization reaction conditions, etc., and the type and amount of the monomer so that the predetermined ratio is set according to the purpose. Select polymerization reaction conditions and the like. For example, when polyisoprene is polymerized using n-butyllithium as a catalyst, the number of 1,4 bonds is usually 90 to 93%.

In the case of the preferred method for producing a block polymer described below, it is not necessary to recover the A block synthesized from the polymerization reaction solution, but if recovery is necessary, for example, a large amount of the reaction solution, preferably It is sufficient to pour it into 10 times or more volume of alcohol. By this method, the A block precipitates and can be recovered by filtration.

B block

The B block is a polyisoprene block containing at least 30%, preferably at least 35% of 3,4 bonds. If there are too few 3,4 bonds in the B block, the impact resistance of the resin composition of the present invention will be reduced. It should be noted that a polyisoprene block substantially containing 100% of 3,4 bonds may be used.

The weight average molecular weight of the B block is gel permeation. In terms of polystyrene by chromatography, the lower limit is preferably 25,000, more preferably 50,000, and particularly preferably 100,000. 0, the upper limit is preferably 500,000, more preferably 300,000, particularly preferably 200,000. If the weight average molecular weight is too small, the impact resistance of the resin composition of the present invention decreases, and if the weight average molecular weight is too large, the melt viscosity of the resin composition of the present invention becomes too high, making processing and molding difficult. .

The method for producing the B block is also not particularly limited, but a known method using an alkyl lithium as a catalyst and a Lewis base as a co-catalyst is preferable in that a block polymer can be easily obtained by a method described later. As the alkyllithium, the same ones used in the production of the A block are exemplified, and the amount used is also the same as that used in the production of the A block. Lewis bases include: Ethers such as orchid, propyl ether, ethylene glycol dimethyl ether and ethylene glycol dibutyl ether; and amines such as tetramethylethylenediamine and triptylamine. The lower limit of the amount of the Lewis base used is 1 mol, preferably 2 mol, more preferably 5 mol, and the upper limit is 40 mol, preferably 30 mol, more preferably 20 mol, per mol of alkyl lithium. It is. If the amount of the Lewis base is too small, the 3,4 bonds in the B block will be reduced. If the amount is too large, the catalytic activity of the hydrogenation reaction will be inhibited, thus requiring a Lewis base removal step, which complicates the process and costs. Get high.

The polymerization reaction conditions, the method for adjusting the solvent and the molecular weight, the method for terminating the reaction, and the method for recovering the polymer to be carried out if necessary are the same as those for the production of A-block.

Block polymer

The block polymer of the present invention has a weight average molecular weight composed of A block and B block of a lower limit of 50,000, preferably 100,000, in terms of polystyrene by gel 'permeation' chromatography. Preferably, it is a block polymer in the range of 150, 000, upper limit of 1, 000, 000, preferably 50,000, 0000, more preferably 300, 000. . If the weight average molecular weight is too small, the impact resistance of the resin composition of the present invention decreases, and if the weight average molecular weight is too large, the melt viscosity of the resin composition of the present invention becomes too high, making processing and molding difficult. .

The method for producing the block polymer is not particularly limited. As described above, the A block is synthesized using alkyllithium as a catalyst, and when the molecular weight reaches a predetermined value, a Louis base and, if necessary, a monomer are added to the reaction system to synthesize a B block having a predetermined molecular weight. This is the easiest way to do this. In addition, a B block is synthesized using alkyl lithium as a catalyst in the presence of a Lewis base, and when the molecular weight reaches a predetermined value, only the Lewis base is evaporated, or a complex is formed and precipitated to form a Lewis base. It is also possible to synthesize an A-block of a predetermined molecular weight by decreasing the concentration.

In these methods, when a monovalent alkyllithium catalyst is used, an A block-B block type AB, a B block-A block BA type, etc. can be produced. BAB type of block A block A block B block type, A block type B block type A block type ABA type can be manufactured. is there. In addition, by combining these methods, a linear block polymer in which A blocks and B blocks are alternately arranged can be produced. The terminal of the obtained linear block polymer may be either an A block or a B block, and may be a block polymer having different terminals. Furthermore, each block or block polymer that has been prepared in advance can be bonded using a coupling agent such as divinylbenzene, tetrachlorosilane, or dimethylchlorosilane. In addition to the block polymer, a star-type block polymer in which a plurality of linear block polymers are linked and branched can also be produced.

In order to obtain an AB type block polymer by the former method, a monovalent alkynolelithium may be used as a catalyst, and to obtain a BAB type block polymer, a divalent alkyl lithium may be used as a catalyst.

When the block polymer is recovered from the polymerization reaction solution as needed, the recovery method is not particularly limited. For example, a method of precipitation in a poor solvent, a steam solidification method and the like can be mentioned. Examples of the poor solvent include alcohols such as methanol, butanol, and isopropanol. Usually, the polymerization reaction solution is poured into an alcohol having a lower limit of 3 times, preferably 5 times, and an upper limit of 20 times, preferably 15 times the weight of the alcohol to cause precipitation, and the solvent is removed by volatilization. If the amount of alcohol is small, precipitation is difficult, and if too large, efficiency is poor.

Block polymer hydrogenated product

The hydrogenated block polymer of the present invention is used as a compounding agent to be added to a thermoplastic resin for the purpose of reforming. Of these unsaturated double bonds, 50% or more, preferably 80% or more, more preferably 90% or more are saturated. If the saturation ratio is small, the heat resistance and weather resistance of the hydrogenated block polymer and the resin composition using the same are reduced. The weight average molecular weight is substantially the same as the above-mentioned block polymer. Hydrogenation is carried out by contacting the block polymer with hydrogen in the presence of a hydrogenation catalyst. Usually, hydrogenation is carried out in a solvent, but the solvent used may be the same as that used for the block polymerization. When the solvent for the polymerization reaction solution is used as it is as the solvent for the hydrogenation reaction, it is not necessary to prepare the hydrogenation reaction solution after the precipitation and coagulation of the polymer. A hydrogenation catalyst can be added to the polymerization reaction solution after the reaction to obtain a hydrogenation reaction solution. In this case, before the addition of the hydrogenation catalyst, a deactivating agent for the polymerization catalyst, for example, an alcohol such as methanol, butanol, or isopropanol, or a compound having an OH group such as water is added to the polymerization reaction solution. To stop the reaction. When alcohols are used as a deactivator, 1 mol or more and 3 mol or less are usually added to 1 mol of alkyllithium. If the amount is too small, the polymerization reaction cannot be stopped.If the amount is too large, the efficiency is low.However, when a homogeneous catalyst described below is used as the hydrogenation catalyst, it may cause a decrease in hydrogenation activity. In some cases, it is more efficient to add a hydrogenation catalyst without adding a catalyst, and the use of a deactivator depends on the efficiency of the process.

The hydrogenation catalyst may be a homogeneous catalyst comprising (a) a transition metal compound and (b) a reducing metal compound, or a heterogeneous catalyst. The homogeneous catalyst is easy to disperse in the hydrogenation reaction solution, so that the addition amount may be small. In addition, since the catalyst is active even at a high temperature and a high pressure, it does not cause decomposition or gelation of the polymer, resulting in low cost. Excellent quality stability. Heterogeneous catalysts are highly active at high temperatures and pressures, can be hydrogenated in a short time, and are excellent in production efficiency, such as being easy to remove.

Homogeneous catalysts are those known in JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-11-138257 and the like. (A) As the transition metal compound, a compound of a transition metal belonging to Group I or any of Groups IV to VIII of the Deming periodic table, for example, Cr, Mo, Fe, Mn, Examples include transition metal halides such as Co, Ni, Pd, and Ru, alkoxides, acetylacetonate, sulfanates, carboxylate, naphthenate, trifluoroacetate, and stearate. Examples include chromium (III) acetylacetonate, manganese (III) acetyl acetate, iron (III) acetyl acetate, cobalt (III) acetyl acetate, bis (triphenylphosphine), cobalt dichloride. And nickel (II) acetyl acetonate, bis- (tributylphosphine) -palladium and the like. In addition, (b) the reducing metal compound may be a compound of Group IA, IIA, IIB, IIIA, or IVA metal of the Deming Periodic Table. And having at least one metal element-carbon bond or metal element-hydrogen bond, for example, an A1 compound, a Li compound, a Zn compound, a Mg compound, and the like. Aluminum, triphenylaluminum, getylaluminum chloride, ethylaluminum sesquichloride, getylaluminum hydride, methyllithium, n-propyllithium, sec-butyllithium, p-tolyllithium, xylyllithium, Examples include diphenylzinc, bis (cyclopentagenenyl) zinc, dimethylmagnesium, methylmagnesium bromide, and lithium aluminum hydride. Specific examples of the combination of the component (a) and the component (b) include: (a) an organometallic compound of Mn, Fe, Co, or Ni, a halide, an alkoxide, acetylacetonate, a sulfonate, or a naphthenate; It is preferable to use a catalyst obtained by combining an organic compound such as A, Li, Zn, Mg or the like or a hydride as the component (b) with high activity, and the influence of impurities on the inhibition of the reaction and the decrease in the activity is small. Catalysts combining (a) an organometallic compound of Mn, Fe, Co, or Ni, a halide, alkoxide, or acetyl acetonate, and (b) an alkylaluminum or alkyllithium as a component are particularly preferred. It is more preferable because it has high activity and the effect of impurity inhibition / reduction of activity by impurities is particularly small. The quantitative relationship between these components depends on the type of each component, but generally 0.5 to 50 moles, preferably 1 to 8 moles of the metal element (b) per mole of the metal element (a). Is a mole. If too much or too little, the activity of the hydrogenation reaction is insufficient. If the amount is particularly large, gelation and side reactions may occur.

Heterogeneous catalysts are also known, and examples thereof include those in which a hydrogenation catalyst metal such as Ni or Pd is supported on a carrier. In particular, when it is preferable that the amount of impurities and the like is as small as possible, it is preferable to use an adsorbent such as alumina diatomaceous earth as a carrier, and a pore volume of 0.5 cm ³ / g or more, preferably 0.7 cm. ^It is preferable to use aluminas of ³ Zg or more, preferably 250 cm ² / g or more. When such a carrier is used, transition metal atoms or the like derived from the catalyst used for the polymerization can be adsorbed, and a resin with few impurities can be obtained.

When adding a hydrogenation catalyst to the polymerization reaction solution and performing hydrogenation, The concentration of the block polymer may change due to volatilization of the solvent after the reaction. In this case, it is preferable to adjust the amount of the solvent to 1 to 100 times, preferably 2 to 20 times the weight of the block polymer.

The amount of the hydrogenation catalyst used in the hydrogenation reaction varies depending on the type and combination of each component in the case of a homogeneous catalyst. Usually, 100 g of the polymer and the transition metal compound of the component (a) are 0%. It is from 0.01 to 100 millimoles, preferably from 0.1 to 100 millimoles. Also, in the case of a heterogeneous catalyst, the amount of the hydrogenation catalyst used in the hydrogenation reaction varies depending on the type of catalyst metal, the state of being supported on a carrier, and the like. The amount of the catalyst metal is 0.1 to 20 g, preferably 1.0 to 15 g. Excessive addition of the hydrogenation catalyst to the hydrogenation reaction solution is costly, and it is difficult to carry out post-treatment such as removal of the hydrogenation catalyst. The hydrogenation reaction is carried out by introducing hydrogen into the hydrogenation reaction solution. For example, a method in which the introduced hydrogen is sufficiently brought into contact with the polymer under stirring is preferable. The reaction is usually carried out at a lower pressure of 0.1 kgZcm ² , preferably 2 kg / cm ² and an upper limit of 100 kg / cm ² , preferably 40 kg / cm ² . If the hydrogen pressure is too low, the hydrogenation reaction does not proceed, and if it is too high, control of the reaction is difficult, and side reactions and gelation may occur.

The hydrogenation reaction is usually carried out at 0 to 250 ° C, preferably at 20 to 100 ° C when using a homogeneous catalyst, and preferably at 200 to 200 ° C when using a heterogeneous catalyst. It is carried out at 40 ° C., particularly preferably at 210 to 230 ° C. If the temperature is too low, the reaction rate will be slow.If it is too high, the polymer or hydrogenated product will be easily decomposed or gelled, and energy

—The cost is also high.

The method for recovering the hydrogenated ring-opening polymer from the hydrogenation reaction solution is not particularly limited. As in the above-described recovery of the polymer, a large amount of a poor solvent, for example, alcohol, may be added to the hydrogenation reaction solution to precipitate and coagulate the polymer hydrogenated product, and the solvent may be volatilized and removed.

Resin composition

In the resin composition of the present invention, the lower limit is 60% by weight, preferably 70% by weight, more preferably 80% by weight, and the upper limit is 99% by weight, preferably 95% by weight, more preferably 95% by weight. Or 92% by weight, and the lower limit of the above-mentioned block polymer hydrogenated product is 1% by weight, preferably 5% by weight, more preferably 8% by weight, and the upper limit is 40% by weight, preferably 30% by weight. More preferably, it comprises 20% by weight. If the amount of the block polymer hydrogenated product is too small, the impact resistance becomes insufficient, and if the content is too large, the strength is reduced and it is not practical.

The thermoplastic resin is used as a molding material, and is an addition-polymerized resin such as polyolefins, polyvinyl chloride, polystyrene, polyvinylidene chloride, fluororesin, and polymethyl methacrylate; polyamide, polyester, polycarbonate, Polycondensation resins such as polyphenylene oxide; polyaddition resins such as thermoplastic polyurethane; ring-opening polymerization resins such as polyacetal and norbornene ring-opening polymers; and hydrogenated products thereof. Among them, polyolefins are preferred because the effect of improving the impact resistance by adding the hydrogenated block polymer of the present invention is large.

Examples of the polyolefin include an ethylene polymer and a propylene polymer, and a propylene polymer is preferred. The propylene polymer is not particularly limited, and a propylene polymer obtained by a known method or a commercially available propylene polymer can be used. The lower limit of melt flow index is preferably 0.1 g / 10 min, more preferably 0.1 gZlOmin, particularly preferably 0.5 gZl0min, and the upper limit force is preferably 10 g / min. It is in the range of 0 gZlO min, more preferably 50 g / in, particularly preferably 30 g / min.

Further, the propylene-based polymer is a polymer mainly composed of repeating structural units derived from propylene, the propylene-based polymer may be a copolymer of propylene and other monomers, Examples of the monomer to be copolymerized include olefins other than propylene such as ethylene, for example, ethylene, butene-11, pentene-11, and 3-methylpentene-11. In particular, a propylene polymer having a repeating structural unit derived from propylene of 85% or more and a repeating structural unit derived from a one-year-old olefin other than propylene of 15% or less is preferable.

The method of blending the block polymer hydrogenated product with the polyolefin is not particularly limited. For example, a Banbury type kneader, a neader type kneader, a single-screw extruder, a twin-screw extruder, or the like may be used. do it. The lower limit of the hydrogenated block polymer is 0.01 on average. 、 M, preferably 0.05 / zm, more preferably 0.1〃111, with an upper limit of 10/111, preferably 5〃m, more preferably 2 tzm. Disperse in resin. If the particle size is too small, the impact resistance will decrease. If the particle size is too large, the impact resistance will decrease, and the transparency will also decrease.

Further, the resin composition of the present invention may optionally contain various additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a coloring agent, and a flame retardant. Also, carbon fibers, metal fibers, glass fibers, glass flakes, blended charge塡剤which may _c molding such as talc

The resin composition of the present invention can be obtained by molding a known thermoplastic resin, such as injection molding, extrusion molding, cast molding, inflation molding, blow molding, vacuum molding, press molding, and compression molding. It can be formed by a method such as a molding method, a rotational molding method, a calendar molding method, a rolling molding method, and a cutting molding method.

Use

The resin composition of the present invention is used in a wide range of fields as a molding material. In particular, it is suitable for molding molded products that require impact resistance, such as automobile parts such as bumpers and interior materials, sporting goods, home appliances and office equipment.

As an aspect of the present invention,

(1) A polyisoprene block having a weight average molecular weight of 25,000 to 500,000 containing 80% or more of 1,4 bonds and a weight average molecular weight containing 30% or more of 3,4 bonds. A block polymer having a weight average molecular weight of 50,000 to 1,000,000 having at least one polyisoprene block having a molecular weight of 25,000 to 500,000 Block polymer hydrogenated product obtained by adding 50% or more of hydrogen,

(2) A block polymer hydrogenated product according to (1), which is a polyisoprene block containing at least 80% of 1,4 bonds and having a 85% or more of 1,4 bonds. ) A polyisoprene blocking power containing 30% or more of 3,4 bonds <<, a polyisoprene blocking power containing 35% or more of 3,4 bonds, (1) to (2),

(4) The isoprene block containing 80% or more of 1,4 bonds has a weight average molecular weight of 50,000 to 300,000 (1 :) to (3). Heavy Combined hydrogenated product,

(5) The isoprene block containing 30% or more of 3,4 bonds has a weight average molecular weight of 50,000 to 300,000, and the block weight according to (1) to (4). Combined hydrogenated product,

(6) The block polymer hydrogenated product according to (1) to (5), wherein the block polymer has a weight average molecular weight of 100,000 to 500,000.

(7) A thermoplastic resin modifying compound comprising the block polymer hydrogenated product according to (1) to (6),

(8) A resin composition comprising a thermoplastic resin and a hydrogenated block polymer according to any one of (1) to (6),

(9) The resin composition according to (8), comprising 60 to 99% by weight of a thermoplastic resin and 40 to 1% by weight of a hydrogenated block polymer,

(10) The resin composition according to any one of (8) to (9), wherein the thermoplastic resin is a polyolefin.

(11) The resin composition according to (10), wherein the polyolefin is polypropylene.

(1 2) The resin according to (8) to (: 11), wherein the hydrogenated block polymer is dispersed in the thermoplastic resin as particles having an average particle size of 0.01 βm or more and 10 m or less. Composition,

(1 3) Polyisoprene block having a weight average molecular weight of 25,000 to 500,000 and containing 1,4 bonds of 80% or more, and a weight average molecular weight of containing 3,4 bonds of 30% or more. Block weight of a weight average molecular weight of 50,000 to 1,000,000 having at least one polyisoprene block with a molecular weight of 25,000 to 500,000 Coalescing,

(14) a polyisoprene blocking force containing 80% or more of 1,4 bonds, and a block polymer according to (13), which contains 85% or more of 1,4 bonds.

(15) A polyisoprene block containing at least 30% of 3,4 bonds and having a strength of at least 35% of 3,4 bonds. The block polymerization according to (13) to (: 14). body, (16) The isoprene block containing 80% or more of 1,4 bonds has a weight average molecular weight of 50,000 to 300,000, according to (13) to (15). Block polymer as described,

(17) The isoprene block containing 30% or more of 3,4 bonds has a weight average molecular weight of 50,000 to 300,000 (13) to (16) The block polymer described in (1),

(18) The block polymer according to any one of (13) to (17), wherein the block polymer has a weight average molecular weight of 100,000 to 500,000.

(19) In the polymerization of isoprene using alkyl lithium as a catalyst, polymerization (13) The method for producing a block polymer according to (13) to (18),

(20) When polymerizing isoprene using alkyllithium as a catalyst, the polymerization is carried out continuously under the reaction conditions in which the amount of Lewis base in the reaction solution is 0.5 mol or less per 1 mol of alkyllithium, The method for producing a hydrogenated block polymer according to any one of (1) to (6), wherein

And the like.

The invention's effect

The resin composition of the present invention containing the block polymer hydrogenated product of the present invention has a higher content than the resin composition containing another elastomer or the like instead of the block polymer hydrogenated product of the present invention. Even if the amount is the same, it has excellent impact resistance, has sufficient impact resistance to withstand use even at low temperatures, has excellent mechanical strength such as elastic modulus, and has melt flow. Excellent in nature.

Example

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. The polymerization conversion ratio was determined from the weight concentration of the polymer in the polymerization reaction solution in terms of the amount of each of the 1,4-bonded isoprene-derived repeating structural unit and the 3,4-bonded isoprene-derived repeating structural unit as C ¹³ — Based on the NMR data, the hydrogenation rate was calculated based on a comparison of the H ¹ -NMR data of the polymer before hydrogenation and the hydrogenated product. —Melt 'flow

• The latet is at 230 ° C and 2.16 kg according to ASTM D-123, the Izod impact value is according to JISK710, the elastic modulus is according to JISK7203, and The particle size of the dispersed particles was measured by washing the cut surface of the resin with toluene, dissolving and removing the hydrogenated isoprene, and taking a hole with a scanning electron microscope photograph, based on the photograph.

Example 1

(A block polymerization)

To a 3-liter autoclave, add 170 g of cyclohexane, 100 g of isoprene, and 0.6 mmol of n-butyllithium, heat to 60 ° C, and initiate polymerization at 1 atm. When the polymerization was completed until the polymerization conversion reached 98%, 10 g of the polymerization reaction solution was sampled to obtain Sample 1.

(B block polymerization)

Subsequently, 5 mmol of ethylene glycol dibutyl ether and 100 g of isoprene were added to the polymerization reaction solution in the autoclave, and the polymerization was continued under the same pressure and temperature conditions. After the polymerization conversion reached 9.9% and the polymerization was substantially completed, 10 g of the polymerization reaction solution was sampled to obtain Sample 2.

(Hydrogenation)

Further, to the polymerization reaction solution in the autoclave, a solution prepared by dissolving 3.9 mmol of nickel (II) acetylacetonate and 15.6 mmol of triisobutylaluminum in 10 ml of cyclohexane was added in total, and a hydrogen pressure of 10 ml was added. A hydrogenation reaction was performed at 80 kgf / cm ² and 80 ° C. for 3 hours. After the completion of the hydrogenation reaction, the hydrogenated reaction solution was poured into 800 liters of methanol, and the precipitated resin was separated by filtration, and allowed to stand at 70 ° C for 48 hours at 0.1 t0 rr or less. Drying yielded about 180 g of hydrogenated product.

(Analysis)

The polymer contained in Sample 1 had a weight-average molecular weight of 122,000, and 93% of 1,4 bonds and 7% of 3,4 bonds among carbon'carbon bonds in the main chain. However, it could be used as an A block of the block polymer of the present invention.

The polymer contained in sample 2 had a weight average molecular weight of 241,000, and carbon in the main chain. • Of the carbon bonds, 1,4 bonds accounted for 77% and 3,4 bonds accounted for 23%.

From the comparison with the analysis results of Sample 1, only the polymerized portion of the polymer contained in Sample 2 after ethylene glycol dibutyl ether was added and before Sample 2 was sampled had a weight average molecular weight of 1 19,000, out of the carbon'carbon bonds in the main chain, 60% were 1,4 bonds and 40% were 3,4 bonds. This was the block B of the block polymer of the present invention, and it was found that the polymer contained in Sample 2 was the block polymer of the present invention.

Further, from a comparison between the polymer contained in Sample 2 and the hydrogenated product, the hydrogenation rate of the hydrogenated product was 97%, and it was found that the hydrogenated product was the block polymer hydrogenated product of the present invention.

Example 2

The hydrogenated block polymer obtained in Example 1 was added to polypropylene (produced by Chisso Corporation, polypropylene K41017 for injection molding) at 200 ° C using a twin-screw extruder so that the weight of the block polymer obtained in Example 1 became 15% by weight. To obtain a resin composition of the present invention. . The melt of the resin composition flow index is 8. 5 gZl 0m in, Izod impact value 1 6. 6 k JZm ² at 2 3 ° C, - 3 0 in ^{° C 4. 5 k J Zm 2} , elastic the rate was 1 1 7 kgfZmm ^2. The particle size of the hydrogenated block polymer in the resin composition was approximately 0.5 to l / zm.

Example 3

The resin composition of the present invention was prepared in the same manner as in Example 2 except that the amount of the hydrogenated block polymer obtained in Example 1 was changed to 10% by weight instead of 15% by weight. I got something. The melt 'flow' index of this resin composition is 8.3 g / 10 min, and the Izod impact value is 23. It was 13.5 kJ Zm ² at C, 3.8 kJ / m ² at -30 ° C, and the elastic modulus was 123 kgf / mm ² . The particle size of the hydrogenated block polymer in the resin composition was approximately 0.5 to 1 m.

Example 4

(A block polymerization)

The same procedure as in Example 1 was carried out to obtain a similar A block.

(B block polymerization) Subsequently, 13 mmol of ethylene glycol dibutyl ether and 100 g of isoprene were added to the polymerization reaction solution in the autoclave, and the weight was maintained at 50 ° C. and 1 atm. After the polymerization conversion reached 99% and the polymerization was substantially completed, 10 g of the polymerization reaction solution was sampled to obtain Sample 3.

(Hydrogenation)

Further, to the polymerization reaction solution in the autoclave, a solution prepared by dissolving 3.9 mmol of nickel (II) acetyl acetate and 15.6 mmol of triisobutylaluminum in 1 Om 1 of cyclohexane was added in total, and a hydrogen pressure of 1 O 2 O was added. The hydrogenation reaction was carried out at 80 ° C. for 3 hours at kg fZcm ² . After the completion of the hydrogenation reaction, the hydrogenation reaction solution was poured into 8000 liters of methanol, and the precipitated resin was separated by filtration, left at 70 ° C for 48 hours at 0.1 torr or less, dried, and hydrogenated. About 180 g of the product were obtained.

(Analysis)

The polymer contained in Sample 3 had a weight-average molecular weight of 246,000 and 64% of 1,4 bonds and 32% of 3,4 bonds among carbon-carbon bonds in the main chain.

From the comparison with the analysis results of Sample 1, only the polymerized portion of the polymer contained in Sample 3 after ethylene glycol dibutyl ether was added and before Sample 3 was sampled had a weight average molecular weight of 1 27,000, out of the carbon-carbon bonds in the main chain, 1,4 bonds were 45% and 3,4 bonds were 55%. This is the B block of the block polymer of the present invention, and it was found that the polymer contained in Sample 3 was the block polymer of the present invention.

Further, from a comparison between the polymer contained in Sample 3 and the hydrogenated product, it was found that the hydrogenation rate of the hydrogenated product was 97%, indicating that it was the block polymer hydrogenated product of the present invention.

Example 5

A resin composition of the present invention was obtained in the same manner as in Example 2, except that the hydrogenated block polymer obtained in Example 4 was used instead of the hydrogenated block polymer obtained in Example 1. The melt 'flow' index of the resin composition 8. 5 gZl Omi n, 1 eye shudder impact value at ^{23 ° C 6. 2 k JZm 2} , one 30 ° C with 3. 7 kJZm ^2, elastic rate It was 1 1 1 kgfZmm ² . In addition, the block polymer water in the resin composition The particle size of the additive was approximately 0.4-1 m.

Comparative Example 1

Melt-flow of polypropylene (K4 0 17) without block polymer hydrogenated, with an index of 8.0 g / 1 Omin and an Izod impact value of 5.2 kJ / m ² at 23 ° C. , — ^2.5 kJ Zm ² at 30 ° C. and an elastic modulus of 178 kgf / mm ² .

Comparative Example 2

To a 3-liter autoclave, add 170 g of cyclohexane, 200 g of isoprene, and 0.6 mmol of n_butyllithium, and heat to 60 ° C to initiate polymerization. After polymerization until the conversion reached 98%, 10 g was sampled to obtain Sample 3. The polymerization reaction solution in the autoclave was charged with 3.9 mmol of nickel (II) acetylacetonate and 15.6 mmol of triisobutylaluminum. A solution prepared by dissolving mmol in 10 ml of cyclohexane was added to the whole solution, and a hydrogenation reaction was carried out at 80 ° C. and a hydrogen pressure of 10 kgf / cm ² for 3 hours. After the completion of the hydrogenation reaction, the hydrogenated reaction solution was poured into 800 liters of methanol, and the precipitated resin was separated by filtration.The resin was allowed to stand at 70 ° C for 48 hours at 0.1 torr and dried. About 180 g of hydrogenated product was obtained.

The polymer contained in Sample 3 had a weight-average molecular weight of 240,000, and 93% of 1,4 bonds and 7% of 3,4 bonds among carbon bonds in the main chain. Was. The hydrogenated product had a hydrogenation rate of 97%.

A resin composition was obtained in the same manner as in Example 2, except that this hydrogenated product was used instead of the hydrogenated block polymer obtained in Example 1. The melt flow index of this resin composition is 5.1 gZl 0 min, the Izod impact value is 8.4 kJ Zm ^{2 at} 23 ° C, — 3.4 kJ / m ² at 30 ° C, modulus of 9 1 kg f / mm ^2. The particle size of the hydrogenated polyisoprene in this resin composition was approximately 10 to 50 μm.

Claims

The scope of the claims

1. Polyisoprene block with a weight average molecular weight of 25,000 to 500,000 and a weight average molecular weight of at least 30% containing 3,4 bonds. 25, 000 to 50,000, at least one polyisoprene block having a weight average molecular weight of 50, 000 to 1, 0000, 0000 Block polymer hydrogenated product with hydrogenation rate of 50% or more

2. The hydrogenated block polymer according to claim 1, wherein the polyisoprene block has a 1,4 bond content of 80% or more, and has a 1,4 bond content of 85% or more.

3. The block polymer hydrogenated product according to claim 1 or 2, wherein the polyisoprene blocking force containing at least 30% of 3,4 bonds is at least 35% of 3,4 bonds.

4. The isoprene block containing at least 80% of 1,4 bonds has a weight average molecular weight of 50,000 to 300,000, any one of claims 1 to 3. Block polymer hydrogenated product described in item

5. The isoprene block containing not less than 30% of 3,4 bonds has a weight average molecular weight of 50,000 to 300,000, any one of claims 1 to 4. Block polymer hydrogenated product described in Item

6. The block polymer according to any one of claims 1 to 5, wherein the block polymer has a weight average molecular weight of 100,000 to 500,000. Hydrogenated material

7. A thermoplastic resin modifying compound comprising a hydrogenated block polymer according to any one of claims 1 to 6.

8. A resin composition comprising a thermoplastic resin and a hydrogenated block polymer according to any one of claims 1 to 6.

9. The resin composition according to claim 8, comprising 60 to 99% by weight of a thermoplastic resin and 40 to 1% by weight of a hydrogenated block polymer.

10. Claim 8 or Claim 9 wherein the thermoplastic resin is a polyolefin The described resin composition

11. The resin composition according to claim 10, wherein the polyolefin is polypropylene.

12. The block polymer according to any one of claims 8 to 11, wherein the hydrogenated block polymer is dispersed in the thermoplastic resin as particles having an average particle size of not less than 0.01 / zm and not more than 1.

Resin composition according to item 1

13. Weight-average molecular weight containing more than 80% of 1,4 bonds 25,000-500,000 polyisoprene block and weight-average molecular weight containing more than 30,4% of 3,4 bonds A block polymer having a weight average molecular weight of 50,000 to 1,000,000 having at least one polyisoprene block of 25,000 to 500,000

14. The block polymer according to claim 13, wherein the block polymer has a polyisoprene blocking force containing not less than 80% of 1,4 bonds and not less than 85% of 1,4 bonds.

15. The block polymer according to claim 13 or 14, wherein the block polymer has a polyisoprene blocking ability containing 30% or more of 3,4 bonds and 35% or more of 3,4 bonds.

16. The isoprene block containing not less than 80% of 1,4 bonds having a weight average molecular weight of 50,000 to 300,000, according to claim 13 to claim 15. The block polymer according to any one of the first to third aspects.

17. The isoprene block containing at least 30% of 3,4 bonds having a weight average molecular weight of 50,000 to 300,000, 000. The block polymer according to any one of the first to third aspects.

18. The block polymer according to any one of claims 13 to 17, wherein the block polymer has a weight average molecular weight of 100,000 to 500,000.

19. When polymerizing isoprene using alkyllithium as a catalyst, polymerization is continuously performed under the reaction conditions that the amount of Lewis base in the polymerization reaction solution is 0.5 mol or less per 1 mol of alkyllithium and 1 mol or more. A method for producing a block polymer according to any one of claims 13 to 17

20. Polymerization of isoprene using alkyllithium as catalyst 7. The polymerization is carried out continuously under a reaction condition in which the amount of Lewis base in the liquid is 0.5 mol or less per mol of alkyl lithium and in a reaction condition in which the amount is 1 mol or more, and hydrogenation is further carried out. The method for producing a block polymer hydrogenated product according to any one of the above