JPH02225541A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance, weathering resistance, oil resistance, mechanical strengths and abrasion resistance by mixing a specified modified hydrogenated conjugated polymer with a specified block copolymer and a specified thermoplastic polyurethane elastomer. CONSTITUTION:A thermoplastic polymer composition is prepared by mixing a modified hydrogenated conjugated diene polymer (a) containing at least 30wt.% (co)polymer prepared by hydrogenating at least 60% of the unsaturated bonds of the conjugated diene part of a conjugated diene polymer and bonding an isocyanate group or a polar group derived therefrom to at least one molecular end of the polymer with a thermoplastic polyurethane elastomer (b) and a block copolymer (c) comprising a polymer block based on a vinylaromatic compound and a polymer block based on a conjugated diene compound and/or a product of hydrogenation of this block copolymer in such amounts that 0-150 pts.wt. component (c) is present per 100 pts.wt. total of 2-98wt.% component (a) and 98-2wt.% component (b).

Description

DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a thermoplastic polymer composition having excellent heat resistance, weather resistance, oil resistance, mechanical strength and abrasion resistance.

b. Conventional technology Since diene polymers having unsaturated double bonds in the polymer have poor thermal stability, weather resistance, and ozone resistance, the unsaturated double bonds are hydrogenated as a means to improve this. A method is known, which is described, for example, in Japanese Patent Application Laid-Open No. 59-13320.
No. 3, JP-A No. 56-62805, JP-A No. 43-199
No. 60, Special Publication No. 1973-39275, Special Publication No. 1971-1973
It is disclosed in No. 55, etc.

Hydrogenated polymers obtained by these methods exhibit the expected heat resistance, weather resistance, and ozone resistance, and are therefore widely used in resin modification applications.

On the other hand, thermoplastic polyurethane elastomer is a material with excellent abrasion resistance, mechanical strength, oil resistance, and cold resistance, and is widely used for sports shoe soles, hoses, tubes, etc. However, it has drawbacks such as poor weather resistance, water resistance, and moldability.

The above-mentioned hydrogenated polymers, such as the hydrogenated vinyl aromatic compound-conjugated diene compound copolymer and the thermoplastic polyurethane elastomer, each have useful properties as described above, so they can be combined to create even more useful materials. Attempts have been made to obtain However, the actual situation was that the two had poor compatibility, and the performance of the blend was extremely poor.

Therefore, many attempts have been made to improve the compatibility between the two. For example, JP-A-63-254156 discloses a composition comprising a thermoplastic polyurethane and a hydrogenated block polymer modified with maleic anhydride or the like. There is. However, in this composition, although the effect of improving compatibility was observed to some extent, it was not sufficient.

Problems to be Solved by the C0 Invention The present inventors have improved the compatibility of the above-mentioned hydrogenated vinyl aromatic compound-conjugated diene compound copolymer with a thermoplastic polyurethane elastomer to create a composition that is beneficial in terms of physical properties. As a result of intensive research into development, the present invention has been arrived at.

61 Means for Solving the Problems The present invention provides: (a) at least 60% of the unsaturated bonds in the conjugated diene moiety in the conjugated diene polymer are hydrogenated, and at least one end of the molecule of the polymer is hydrogenated; A modified hydrogenated conjugated diene polymer containing at least 30% by weight of a (co)polymer to which an isocyanate group or a polar group derived from an isocyanate group is bonded, ■) a thermoplastic polyurethane elastomer, (c) a vinyl aromatic consisting of a block copolymer consisting of a polymer block mainly composed of a group compound and a polymer block mainly composed of a conjugated diene compound, and/or a hydrogenated product of the block copolymer, and (a) component 2 to 98 (c
The present invention provides a thermoplastic polymer composition characterized in that 0 to 150 parts by weight of the component (a) to 150 parts by weight are blended.

The modified hydrogenated conjugated diene polymer (a) used as the base material in the present invention is a conjugated diene polymer or a random, block or graft copolymer of a conjugated diene compound and a vinyl aromatic compound.

The above-mentioned conjugated diene polymers include conjugated diene homopolymers, and copolymers obtained by copolymerizing conjugated dienes with each other or with at least one conjugated diene and at least one olefin monomer copolymerizable with the conjugated diene. Ru. The conjugated diene used in the production of such conjugated diene polymers is -4 to about 1 for boat fishing.
Mention may be made of conjugated dienes having two carbon atoms. A specific example is l.

3-butadiene, isoprene, 2,3-dimethyl-1,
3-butadiene, i, 3-pentadiene, 2-methyl-
1,3-pentadiene, 1,3-hexadiene, 4.5
-diethyl-1,3-octadiene, 3-butyl-1,
Examples include 3-octadiene and chlorobrene.

In order to obtain an elastomer that can be industrially advantageously developed and has excellent physical properties, 1,3-butadiene and isoprene are particularly preferred, and in the present invention, elastomers such as polybutadiene, polyisoprene, and butadiene/isoprene copolymers are particularly preferred. . In such polymers, the microstructure of the polymer is not particularly limited, but if the number of 1,2-vinyl bonds is small, the solubility of the polymer after hydrogenation decreases, and the solvents for uniform hydrogenation are limited. 1.
More preferred are polymers containing about 10% or more 2-vinyl bonds.

Suitable conjugated dienes used in the production of a copolymer obtained by copolymerizing at least one of the above conjugated dienes and at least one olefin monomer copolymerizable with the conjugated diene include the above conjugated dienes; As the olefin monomer to be polymerized, all seven monomers that can be copolymerized with a conjugated diene can be used, but vinyl-substituted aromatic hydrocarbons are particularly preferred.

Copolymers of conjugated dienes and vinyl-substituted aromatic hydrocarbons are particularly important for obtaining industrially useful and valuable elastomers and thermoplastic elastomers.

Examples of vinyl-substituted aromatic hydrocarbons used in the preparation of such copolymers include styrene, 1-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-
Examples include dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, and vinylpyridine, with styrene and α-methylstyrene being particularly preferred.

Examples of copolymers include butadiene/styrene copolymers, isoprene/styrene copolymers, butadiene/styrene copolymers,
Alpha-methylstyrene copolymers and the like are most preferred since they provide hydrogenated copolymers with high industrial value.

Such copolymers include random copolymers, tapered block copolymers, complete block copolymers, and graft copolymers in which the monomers are statistically distributed throughout the polymers.

The content of the vinyl-substituted aromatic hydrocarbon is preferably 90% by weight or less, more preferably 5% to 80% by weight.

Further, it is preferable that the 1,2-vinyl bond of the conjugated diene unit is more than 10 times more valuable than the entire conjugated diene unit because the polymer performance after hydrogenation is excellent.

The molecular weight of the polymer is not particularly limited, but from the viewpoint of ease of handling and processability, the number average molecular weight is 500 to soo,
oo.

is preferred.

The method for producing the modified hydrogenated conjugated diene polymer (a) is not limited, but since it is necessary to introduce a functional group at the end, polymerization using an organic alkali metal compound as a polymerization initiator is preferable, and in particular, polymerization using an organic lithium compound as a polymerization initiator is preferable. It is preferable to use an initiator or to carry out ping anionic polymerization.

As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used.

The block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon may be produced by any known method,
For example, Special Publication No. 36-1.9286, Special Publication No. 43-17
No. 979, Special Publication No. 1979-31951, Special Publication No. 1977-3
Examples include the method described in No. 2415. These methods are methods in which a conjugated diene and a vinyl aromatic hydrocarbon are block copolymerized in a hydrocarbon solvent using a polymerization initiator such as the above-mentioned organic alkali metal compound.
(A-B), ,A-(-B-A), ,B(-A-B
), % [In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbon, and B is a polymer block mainly composed of conjugated diene. The boundary between A block and B block does not necessarily need to be clearly distinguished. Further, n is an integer of 1 or more. ] or the general formula % formula % [In the above formula, A and B are the same as above, X represents an initiator such as a polyfunctional organolithium compound, m and n
is an integer greater than or equal to 1. ] is obtained as a block copolymer.

The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed or tapered.

Further, a plurality of uniformly distributed portions and/or a plurality of tapered portions may coexist in each block.

The block copolymer used for producing the terminal-modified block copolymer may be any mixture of block copolymers represented by the above-mentioned formula.

Particularly preferred block copolymers in the present invention are block copolymers containing at least two polymer blocks mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of conjugated dienes. .

Examples of methods for introducing polar groups derived from isocyanate groups or incyanate groups into the polymer prior to hydrogenation include the following method.

That is, this is a method in which an isocyanate group is introduced at the end of a polymer by polymerization using the above method or by reacting the active alkali metal end of a pinion anion with a polyfunctional isocyanate compound.

The polyfunctional isocyanate compound used in the present invention is not particularly limited, but for example, 2,4- and 2,6-
) lylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl diisocyanate), 1,5-naphthalene diisocyanate, 5-chloro-2,4- and 5-chloro-2,6-)rylene diisocyanates, aromatic diisocyanates such as 3°3'-dimethyl-4,4-diphenyl diisocyanate, 1,3- and 1,4-xylene diisocyanate, 1.
6-hexamethylene diisocyanate, l, 3- and l.

4-cyclohexyl diisocyanate, 1-methyl-2
, 4- and 1-methyl-2,6-cyclohexyl diisocyanate, aliphatic diisocyanates such as methylene bis(4-cyclohexyl isocyanate), 4.4'
, 4'-1-rephenylmethane triisocyanate,
Polyisocyanates such as polymethylene polyphenylisocyanate having the following structural formula and mixtures thereof are used.

n=1-8 The amount of the polyfunctional isocyanate compound added is preferably 0.2-1.5, more preferably 0.7-1.3 mol per 1 atom of alkali metal.

The number of isocyanate groups introduced into the polymer is arbitrary, but preferably 0.5 to 10 per polymer chain.

It is necessary that the isocyanate group is bonded to at least 30% by weight of the polymer molecule. 30% by weight
A sufficient improvement effect cannot be obtained below.

The isocyanate-modified polymer thus obtained may be hydrogenated as it is, or may be further reacted with at least one of the following compound groups to form an isocyanate derivative, and then hydrogenated. It may be hydrogenated while being modified and then reacted with at least one of the following compound groups to form an isocyanate derivative. Groups of compounds that should react with incyanate groups include water, alcohols, amines, amides, hydrazines, hydrazides, epoxy group-containing compounds, carboxylic acids, acid anhydrides, mercaptans, phosphoric acids,
Examples include phosphorous acids, acetylacetone, hydrogen cyanide, and an active methylene compound represented by the following formula (1).

Cx, y are -CN group or COOR group (R is an alkyl group)] (a) The modified hydrogenated conjugated diene polymer is usually dicyclopentadienyl, titanium halide, nickel organic carboxylate, cobalt organic carboxylate and hydrogenation catalysts consisting of organometallic compounds of groups I to II, nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalysts supported on carbon, silica, diatomaceous earth, etc., cobalt, nickel, rhodium, ruthenium complexes, etc. using hydrogen as a catalyst under a pressure of 1 to 100 atm, or lithium aluminum hydride, P-)luenesulfonyl hydrazide or Zr-4i-Fe-V-Cr alloy, Z
r-Ti-Nb-Fe-V-Cr alloy, LaNi
It is obtained by hydrogenating a conjugated diene-based (co)polymer having an isocyanate group or a polar group derived from an isocyanate group at its terminal in the presence of a hydrogen storage alloy such as No. 5 alloy.

These conjugated diene (co)polymers can be used in hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene, and ethylbenzene, or methyl ethyl ketone,
Hydrogenation is carried out using the hydrogenation catalyst and hydrogenation compound described above in a polar solvent such as ethyl acetate, ethyl ether, or tetrahydrofuran. Modified hydrogenated conjugated diene polymer (
A) is obtained by drying after desolvation and coagulation treatment using a direct release roll or desolvation by steam stripping, or coagulation with alcohol. The hydrogenation rate of unsaturated bonds in the conjugated diene portion of the hydrogenated polymer is 60% or more, preferably 80% or more, and more preferably 90% or more.

If the hydrogenation rate is less than 60%, heat resistance, weather resistance and ozone resistance will be poor. In order to fully exhibit these properties, the hydrogenation rate is preferably higher.

Thermoplastic polyurethane elastomer (b) is a polymer obtained through a polyaddition reaction using long-chain polyol, short-chain glycol, diisocyanate, etc. as raw materials, with urethane bonds in the molecule, and has traditionally been used in shoe soles, hoses, tubes, etc. It is used in adhesives, etc.

The long-chain polyols that are the raw materials for this thermoplastic polyurethane elastomer include poly(1,4-butylene adipate), poly(1,6-hexane adipate), polycaprolactone, polyethylene glycol, polypropylene glycol, and polyoxytetramethylene. There are glycols, etc. Further, short chain glycols include ethylene glycol, 1,4-butanediol, 1,4-hexanediol, etc., and diisocyanates include tolylene diisocyanate), 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Examples include isophorone diisocyanate. A soft segment is formed by a long chain polyol and a diisocyanate, and a hard segment is formed by a short chain glycol and a diisocyanate.

The molecular weight of the thermoplastic polyurethane elastomer (b) is
Preferably it is s, ooo to 500.00 (1), more preferably 10.000 to 300,000.

The block copolymer and/or the hydrogenated product (c) of the block copolymer preferably contains a vinyl aromatic compound in an amount of 5 to 95% by weight, more preferably 10 to 90% by weight,
Particularly preferably, it contains 15 to 70% by weight, and its structure may be straight, branched, or radial (but is not particularly limited).

Specifically, the general formula: % formula %) [In the formula, A is an aromatic vinyl compound polymer block, B is a conjugated diene compound polymer block, X is a coupling agent residue, and n is an integer of 1 or more. . ].

Here, the polymer block mainly composed of a vinyl aromatic compound means that the vinyl aromatic compound block is a vinyl aromatic compound alone, or a vinyl aromatic compound containing a vinyl aromatic compound in an amount of 60% by weight or more, preferably 80% by weight or more. It has a copolymer block structure of a group compound and a conjugated diene compound.

On the other hand, a polymer block mainly composed of a conjugated diene compound means that the conjugated diene compound block is a conjugated diene compound alone, or a conjugated diene compound containing a conjugated diene compound in an amount of 60% by weight or more, preferably 80% by weight or more, and a vinyl aromatic compound. It may be a copolymer block with vinyl aromatic compounds bonded randomly, or a copolymer block with one or more so-called tapered blocks gradually increasing in number.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert
-Butylstyrene, ethylstyrene, vinylnaphthalene, etc., and these may be used alone or in combination of two or more. Among these, styrene is particularly preferred.

Conjugated diene compounds include l,3-butadiene, 2-
Methyl-1,3-butadiene, 2,3-dimethyl-1,
3-butadiene, 2-neopentyl-1°3-butadiene, 2-chloro-1,3-butadiene, 2-cyano-1
, 3-butadiene, linear conjugated pentadiene and/or conjugated pentadiene having a substituent, linear conjugated hexadiene and/or conjugated hexadiene having a substituent, and the like. Among these, 1. 3-butadiene and 2-methyl-1,3-butadiene are particularly preferred.

The weight average molecular weight of the entire block copolymer is preferably 10.000 to soo, ooo, more preferably 2
0,000 to 300,000.

Not only one type of block copolymer may be used, but also a combination of block copolymers having different structures and different vinyl aromatic compound contents may be used. Further, as the block copolymer, a hydrogenated version of the above block copolymer can also be used, such as a styrene-ethylene-propylene block copolymer or a styrene-ethylene-butylene block copolymer.

In the thermoplastic polymer composition of the present invention, the composition ratio of the modified hydrogenated conjugated diene polymer (a) and the thermoplastic polyurethane elastomer C) is 2 to 98/98.
-2% by weight, preferably 5-95/95-5% by weight, particularly preferably 7-90/93-10! The amount is %.

If component (a) is less than 2% by weight, weather resistance will be insufficient, while if component (a) is more than 98% by weight, oil resistance and abrasion resistance will be poor.

In the present invention, the object of the present invention can be achieved by a composition consisting of component (a) and component (c).
By incorporating component () into a composition consisting of component (a) and component ('b), the elasticity, flexibility, etc. of the composition can be further improved.

Component (c) is added in an amount of 0 to 150 parts by weight, preferably 0 to 100 parts by weight, based on a total of 100 parts by weight of components (a) and (b). In order to fully obtain the effect of adding component (c), the amount is preferably 2 to 150 parts by weight, more preferably 5 to 100 parts by weight. If the blending ratio of component (c) exceeds 150 parts by weight, heat resistance, weather resistance, abrasion resistance, oil resistance and mechanical strength will deteriorate, which is not preferable.

In addition, the composition of the present invention can be modified by maleation, carboxylation, hydroxylation, epoxidation, halogenation, sulfonation, etc. and sulfur crosslinking, peroxide crosslinking, metal ion crosslinking by conventionally known methods as necessary. , electron beam crosslinking, silane crosslinking, and the like can also be carried out.

Additives used in ordinary thermoplastic resins can be added to the thermoplastic polymer composition of the present invention, if necessary. plasticizers such as phthalate compounds, fillers or reinforcing agents such as silica, talc, glass fibers,
Other antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, foaming agents, colorants, pigments, core materials, crosslinking agents, crosslinking aids, and mixtures thereof can be added.

Other rubbery polymers may be used as necessary, such as 5BR (styrene-butadiene rubber), NBR (tolyl-butadiene rubber), BR (butadiene rubber), EPT (ethylene-propylene terpolymer), EPR (ethylene-propylene rubber), NR (natural Rubber), IR (isoprene rubber), 1,2-polybutadiene, AR (acrylic rubber), CR (chlorbrene rubber), IIR (isobutyne-isoprene rubber), H5R (high styrene rubber), etc. can be added.

In addition, other thermoplastic resins may be used as necessary, such as polystyrene resins, polyethylene resins, polypropylene resins, diene resins, polyvinyl chloride resins, polyvinyl acetate resins, polycarbonate resins, polyacecool resins, and polyamide resins. Resin, polyester resin, polyether resin, polysulfone, polyphenylene sulfide, etc. can also be blended.

In the present invention, (a) component, (b) component and (c)
Mixing of the components, as well as the plasticizer, filler, rubber, resin, etc., can be carried out by conventionally known methods.

That is, it can be carried out using an extruder (single screw or two wheels), a roll, a Banbury mixer, a Niegoo mixer, a Henschel mixer, or the like.

In addition, the thermoplastic resin composition obtained by such a method can be processed into a practically useful molded article by a conventionally known method using, for example, extrusion molding, injection molding, blow molding, compression molding, calendering, etc. be able to. Furthermore, processing such as painting and plating can be applied as necessary.

The composition of the present invention has excellent heat resistance, wear resistance, processability,
flexibility, low temperature properties, temperature dependence, compatibility, paintability,
By taking advantage of printability, hot stampability, adhesiveness, deep drawability, hot water resistance, rubber elasticity, rubber feel, flexibility, slip resistance, stress crack resistance, etc., we can produce various plastic improvement materials, footwear sole materials, It can be used as a material for adhesives and clay, asphalt modification material, and vulcanized rubber modification material.

For example, sheets for meat and fresh fish trays, fruit and vegetable bags, frozen dessert food containers, molding applications, food packaging, daily goods packaging, various rubber resin products, laminates for cloth cotton and leather products, and films for stretch tapes for disposable diapers, etc. Applications, hoses
Tube/belt applications, footwear applications such as sports shoes, leisure shoes, fashion sandals, leather shoes, etc.
Materials for home appliances such as TVs, stereos, and vacuum cleaners; automotive interior and exterior parts such as bumper parts, body panels, and side seals; hot melt adhesives, pressure-sensitive adhesives, contact adhesives, and spray adhesives. It can be used in a wide range of applications, including asphalt blend materials such as road paving materials, waterproof sheets, and pipe coatings, as well as other daily necessities, leisure goods, toys, and industrial goods.

e. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Degassed and dehydrated cyclo-
\5 kg of xane and 150 g of styrene were charged, and 5 g of tetrahydrofuran and 0.8 g of n-butyllithium were added to carry out adiabatic polymerization from 30'C. After 15 minutes, 700 g of butadiene was added and polymerized for 30 minutes, and then 150 g of styrene was added and polymerized for another 15 minutes. where 4.4'-diphenylmethane diisocyanate 2.
6g was processed and the polymer terminal was modified with isocyanate.

At this time, some clumping occurred, and about 10% by weight became a coupling polymer. The remaining 90% by weight of the polymer was terminally modified with isocyanate.

The reaction solution was heated to 40°C, 0.93 g of n-butyllithium and 1.5 g of 2゜6-di-L-butyl-p-cresol were added, and further 0.5 g of bis(cyclopentagenyl)titanium dichloride and diethylaluminum chloride were added. 2
g was added thereto, and hydrogenation was carried out for 1 hour at a hydrogen pressure of 10 kg/c+a.

A hydrogenated polymer with a hydrogenation rate of 98% and a number average molecular weight of 150.000 was obtained.

The amount of bound styrene in the block copolymer before hydrogenation reaction is 30
%, 40% of the butadiene moieties were 1,2-vinyl bonds.

The amount of -NGO groups was determined by titration analysis, and the average number of isocyanate groups introduced per molecule was determined by dividing by the average number of molecules determined from the number average molecular weight, which was about 0.9.

The polymer solution after the hydrogenation reaction was dried with hot air to form a solid polymer. This is referred to as a modified hydrogenated conjugated diene polymer A.

5 kg of degassed and dehydrated cyclohexane, 200 g of styrene, 1. After charging 800 g of 3-butadiene, 5 g of tetrahydrofuran,
Polymerization was carried out by adding 0.7 g of n-butyllithium. The polymerization temperature was 30°C to 70°C. After the conversion rate reached approximately 100%, 2 g of 2,4-1-lylene diisocyanate was added to modify the polymer terminals with isocyanate.

At this time, about 20% by weight of the polymer was coupled, but the remaining 80% by weight of the polymer was modified with an isocyanate group at the end.The reaction solution was heated to 70°C, and 1g of n-butyllithium and 2,6-di -butyl-p-cresol I
Then, 0.5 g of bis(cyclopentagenyl)titanium dichloride and 2 g of diethylaluminum chloride were added, and hydrogenation was carried out at a hydrogen pressure of 10 kg/c1A for 1 hour.

A polymer with a hydrogenation rate of 95% and a number average molecular weight of 200.000 was obtained. The -NGO group was determined by titration analysis, and the average number of isocyanate groups introduced per molecule was determined by dividing by the average number of molecules determined from the number average molecular weight, which was approximately 0.
．． It was 8.

The polymer solution was removed and dried using a direct removal roll to obtain a solid polymer. This is referred to as modified hydrogenated conjugated diene polymer B.

5 g of degassed and dehydrated cyclohexane and 200 g of styrene were placed in a 102 autoclave of Ushi Diene C, followed by 5 g of tetrahydrofuran and 0.0 g of n-butyllithium. Adiabatic polymerization was carried out from 30'C by adding h. 600g of butadiene after 15 minutes
After 30 minutes of polymerization, 200 g of styrene was added and polymerization was continued for another 15 minutes. Here 4,4'4
5.2 g of #-triphenylmethane triisocyanate was added to modify the polymer terminals with isocyanate.

At this time, some clumping occurred, and about 30% by weight became a coupling polymer. The remaining 70% by weight of the polymer was terminally modified with isocyanate.

The reaction solution was heated to 40°C, 1.5 g of n-butyllithium and 1.5 g of 2°6-di-t-butyl-p-cresol were added, and further 0.5 g of bis(cyclopentagenyl)titanium dichloride and diethylaluminium were added. Chloride 2
g was added thereto, and hydrogenation was carried out for 1 hour at a hydrogen pressure of 10 kg/c4.

A hydrogenated polymer with a hydrogenation rate of 96% and a number average molecular weight of 150.000 was obtained. This is referred to as a modified hydrogenated conjugated diene polymer C.

Ox Diene A D 101 Degassed and dehydrated cyclohexa7 in an autoclave
5kg, 7100gSl, 3-butane x
After charging 7900g, add 20g of tetrahydrofuran.
0g,,n~0.7g of butyllithium was added to carry out polymerization. Adiabatic polymerization was performed at a polymerization temperature of 5°C. After the conversion rate reached approximately 100%, 2 g of 2.4=tolylene diisocyanate was added to modify the polymer terminals with isocyanate.

At this time, about 20% by weight of the polymer was coupled, but the remaining 80% by weight of the polymer was terminally modified with isocyanate groups. The reaction solution was heated to 90°C, and n-butyllithium Ig and 2,6-di-L-butyl-p-cresol 1
g, and further added 0.5 g of bis(cyclopentadienyl)titanium dichloride and 2 g of diethylaluminium chloride, and hydrogenated at a hydrogen pressure of 10 kg/c for 30 minutes.

A polymer with a hydrogenation rate of 100% and a number average molecular weight of 200,000 was obtained. The amount of bonded styrene in SBR before the hydrogenation reaction was 10%, and 80% of the butadiene moiety was 1,2-vinyl bond.

The amount of -NCO groups was determined by titration analysis, and the average number of isocyanate groups introduced per molecule was determined by dividing by the average number of molecules determined from the number average molecular weight, which was about 0.8.

This is used as a modified hydrogenated conjugated diene polymer.

5 kg of degassed and dehydrated cyclohexane and 150 g of styrene were placed in a 10J2 autoclave manufactured by Diene E, and 5 g of tetrahydrofuran and 0.7 g of n-butyllithium were added thereto, and adiabatic polymerization was carried out at 30°C. After 15 minutes, 700 g of isoprene was added and polymerized for 30 minutes, and then 150 g of styrene was added and polymerized for another 15 minutes. where 4,4'-diphenylmethane diisocyanate 2.6
g was added to modify the polymer terminals with incyanate.

At this time, some clumping occurred, and about 30% by weight became a coupling polymer. The remaining 70% by weight of the polymer was terminally modified with isocyanate.

The reaction solution was heated to 40°C, and 0.8 g of n-butyllithium and 1.5 g of 2゜6-di-butyl-p-cresol were added, followed by 085 g of bis(cyclopentagenyl) titanium dichloride and 2 g of diethylaluminium chloride.
was added and hydrogenated at a hydrogen pressure of 10 kg/cd for 2 hours.

A hydrogenated polymer with a hydrogenation rate of 98% and a number average molecular weight of 150.000 was obtained.

The amount of -NGO groups was determined by titration analysis, and the average number of isocyanate groups introduced per molecule was determined by dividing by the average number of molecules determined from the number average molecular weight, which was about 0.7.

This is referred to as modified hydrogenated conjugated diene polymer E.

After charging 5 kg of degassed and dehydrated cyclohexane and 1 kg of 1,3-butadiene into a 10F autoclave containing diene, 5 g of tetrahydrofuran and 2 g of 1,4-dilithiobutane were added to carry out polymerization. Polymerization temperature from 30"C to 70°C
The temperature-rising polymerization was carried out. After the addition rate reached approximately 100%, 15 g of 2.4-)lylene diisocyanate was added to modify both ends of the polymer with isocyanate.

At this time, approximately 10% by weight of the polymer was coupled, but the remaining 90% by weight of the polymer was modified with isocyanate groups at both ends. 1 g of t-butyl-p-cresol was added, and 1 g of bis(cyclopentadienyl) titanium dichloride and 4 g of diethylaluminium chloride were added, followed by hydrogenation at a hydrogen pressure of 10 kg/cffl for 3 hours.

A polymer with a hydrogenation rate of 100% and a number average molecular weight of 5,000 was obtained.

The amount of -NGO groups was determined by titration analysis, and the average number of isocyanate groups introduced per molecule was determined by dividing by the average number of molecules determined from the number average molecular weight, which was about 1.7.

This is referred to as a modified hydrogenated conjugated diene polymer F.

After 4.500 g of cyclohexane and 1 g of tetrahydrofuran were charged into an autoclave equipped with a washed and dried stirrer and jacket under a nitrogen atmosphere, the internal temperature was brought to 70°C.

Next, a hexane solution containing 0.4 g of n-butyllithium was added, and 120 g of styrene was further added and polymerized for 60 minutes. Then, 360 g of butadiene was added and polymerized for 60 minutes. Further, 120 g of styrene was added and polymerized for 60 minutes.

Note that during the polymerization, the temperature was adjusted to 70°C.

After the polymerization was completed, 2.6-tert-butyl-p-cresol was added, and cyclohexane was removed by heating.
A linear block copolymer was obtained. The bound styrene content in this block copolymer was 40%, and the weight average molecular weight was iso, ooo. This will be referred to as block copolymer G.

In the same manner as above, a linear block copolymer having a bound styrene content of 15% and a weight average molecular weight of 180.000 was obtained. This will be referred to as block copolymer H.

4.5 cyclohexane in the same autoclave as above for Pro Kita AI.
After charging 00 g of tetrahydrofuran Ig, the internal temperature was set to 70°C.

Next, a hexane solution containing 0.8 g of n-butyllithium was added, and then 420 g of styrene was added and polymerized for 60 minutes. Next, 180 g of butadiene was added and polymerized for 60 minutes.

Next, 0.5 g of tetrachlorosilane was added and left to stand for 30 minutes. During the polymerization, the temperature was adjusted to 70°C.

After the polymerization was completed, 2,6-di-tert-butyl-p-cresol was added and cyclohexane was removed by heating to obtain a radial block copolymer. This block copolymer has a bound styrene content of 70% and a weight average molecular weight of 220.
It was 000. This is referred to as block copolymer ①.

After carrying out the same polymerization reaction as the modified hydrogenated conjugated diene polymer A manufactured by Kita Diem JK L, a hydrogenation reaction was carried out without adding 4,4'-diphenylmethane diisocyanate.

A hydrogenated polymer with a hydrogenation rate of 98% and a number average molecular weight of 150,000 was obtained.

The bound styrene content of the block copolymer before the hydrogenation reaction was 30%, and 40% of the butadiene moieties were 1,2-vinyl bonds. The hydrogenated conjugated diene polymer obtained here is J
shall be.

After carrying out the same polymerization reaction as the modified hydrogenated conjugated diene polymer B or E, a hydrogenation reaction was carried out without adding an isocyanate compound. The hydrogenated conjugated diene polymers obtained here are referred to as K and L.

After carrying out the same polymerization reaction as the modified hydrogenated conjugated diene polymer A of Kita Diem M, the hydrogenation reaction was carried out without adding 4,4'-diphenylmethane diisocyanate.

A hydrogenated polymer with a hydrogenation rate of 98% and a number average molecular weight of 150,000 was obtained.

The bound styrene content of the block copolymer before the hydrogenation reaction was 30%, and 40% of the butadiene moieties were 1,2-vinyl bonds.

To 100 parts by weight of the hydrogenated conjugated diene polymer obtained above, 2.5 parts by weight of maleic anhydride and 0.1 parts by weight of Barhexa 25B (manufactured by NOF Corporation) were uniformly mixed. Thereafter, it was fed to a screw extruder (axle, screw diameter 40 na, L/D = 28 full-flight screw) under a nitrogen atmosphere, and a maleation reaction was carried out at a cylinder temperature of 250''C.The obtained modified block copolymer Unreacted maleic anhydride was removed under reduced pressure by heating, and 0.0% of 2,6-tert-butyl-p-cresol was added as a stabilizer.
5 parts by weight was added. The amount of maleic anhydride added was 1.3% by weight. The modified hydrogenated conjugated diene polymer obtained here is designated as M.

Using the modified hydrogenated conjugated diene polymer, block copolymer, and polyurethane obtained by the above method, the formulation shown in Table 1 was used for 5 minutes at 110 rpm + m using a 190°C blast mill (Toyo Seiki Seisakusho type). They were kneaded to obtain compression molded products, and their physical properties were measured. In addition, the following materials were used as shown in Table-1.

Hydrogenated block copolymer: Kraton G (manufactured by Shell Chemical Co., Ltd.) Polyurethane elastomer: Elastolan E180MN
AT (manufactured by Nippon Elastolan Co., Ltd.) In addition, each physical property was measured by the following method.

Vicat softening point: 8STM 01525 (load 1k
g) Tensile properties: Conforms to JIS K6301 Taper wear: ASTM 01044 (Abrasion ring 22) Transparency: Judging by visual inspection of a compression molded 1mm receipt Transparent 20, Translucent: Δ, Opaque: × Weather resistance: Compression molding The 1II11 thick sheet was tested using a shine weather meter manufactured by Suga Test Instruments (BPT63°C).
1 Humidity 68χ, rain, rain cycle 18 minutes/120 minutes) After being left in the tank for 200 hours, visually determined discoloration: Large or large Slight discoloration: Medium, Small discoloration: Small Example 1~
No. 11 is a composition of the present invention, which has excellent weather resistance, tensile properties, abrasion resistance, and transparency, and the composition aimed at by the present invention has been obtained.

On the other hand, in the compositions of Comparative Examples 1 and 2, the amount of component (a) or (b) exceeds the range of the present invention, and Comparative Example 1 has inferior heat resistance and weather resistance. Example 2 has poor abrasion resistance and mechanical strength.

In addition, the compositions of Comparative Examples 3 to 9 used unmodified hydrogenated conjugated diene polymers, and had better heat resistance, abrasion resistance, and weather resistance than Examples 1 to 11, which were the compositions of the present invention. and poor mechanical strength.

The compositions of Examples 12 to 16 are compositions in which a vinyl aromatic compound-conjugated diene block copolymer is further blended with the compositions of Examples 1 to 11, and have higher heat resistance than the compositions of Comparative Examples 12 to 15. , excellent weather resistance and mechanical strength.

Furthermore, by adding the vinyl aromatic compound-conjugated diene block copolymer, a softer and more elastic composition was obtained, although the heat resistance was slightly inferior to the composition of Example 1-11 without the addition of the vinyl aromatic compound-conjugated diene block copolymer. There is.

In addition, the compositions of Comparative Examples 10, 11 and 12 have a blending ratio of vinyl aromatic compound-conjugated diene block copolymer that exceeds the range of the present invention, and therefore have poor heat resistance and weather resistance, which are the characteristics of the present invention. and poor abrasion resistance, making it undesirable.

The compositions of Comparative Examples 13, 14, 15 and 16 are compositions consisting of components (a), This is an example of a diene polymer, which has poor mechanical strength, abrasion resistance, and weather resistance.

Comparative Example 17.1 is a composition using a hydrogenated conjugated diene polymer modified with maleic anhydride, and has good heat resistance, abrasion resistance,
Although the mechanical strength is superior to that using an unmodified hydrogenated conjugated diene polymer, it is inferior to the composition of the present invention.

The composition of the present invention, in which the effect-modified hydrogenated conjugated diene polymer of the f2 invention and the polyurethane polymer are blended, shows a marked improvement in the Vikaft softening point and is a composition with excellent heat resistance. It also has improved tensile strength and elongation, and has excellent wear resistance.

Furthermore, the composition of the present invention also has excellent transparency.

Furthermore, the composition of the present invention containing the vinyl aromatic compound-conjugated diene block copolymer is softer and more elastic than the composition containing no vinyl aromatic compound-conjugated diene block copolymer.

The composition of the present invention is a material with such excellent properties and can be suitably used for footwear, industrial parts, automobile interior and exterior parts, toys, daily necessities, films, medical products, adhesives, paints, etc. Therefore, it is a material of high industrial value.

Claims (1)

Scope of Claims: (a) At least 60% of the unsaturated bonds in the conjugated diene moiety in the conjugated diene polymer are hydrogenated, and at least one end of the molecule of the polymer has an isocyanate group or an isocyanate group. A modified hydrogenated conjugated diene polymer containing at least 30% by weight of a (co)polymer to which polar groups to be derived are bonded, (b) a thermoplastic polyurethane elastomer, and (c) a vinyl aromatic compound as the main component. and/or a hydrogenated product of the block copolymer, and contains 2 to 98% by weight of component (a) and a polymer block mainly composed of a conjugated diene compound. ) component (c
1.) A thermoplastic polymer composition comprising 0 to 150 parts by weight of the component.