JPH02175705A - Modified hydrogenated conjugated diene polymer and its composition and production - Google Patents

Abstract

PURPOSE:To obtain the title polymer composition excellent in compatibility with a (non)polar resin, heat resistance, etc., by forming a block copolymer comprising an aromatic vinyl component and a conjugated diene component so that it may have a structure in which the conjugated diene part is hydrogenated and the terminals are combined with isocyanate groups (or polar groups derived therefrom). CONSTITUTION:The title polymer composition is obtained from at least 30wt.% block copolymer having a number-average MW of 1000-50000 in terms of PS, consisting of 5-90wt.% aromatic vinyl component (e.g. styrene component) and 95-10wt.% conjugated diene component (e.g. butadiene component), and having a structure in which at least 60% of the unsaturated bonds in the conjugated diene part are hydrogenated and at least one terminal of the copolymer is combined with an isocyanate group (e.g. by reaction with 4,4'-diphenylmethane diisocyanate) or a polar group derived from an isocyanate group (e.g. by reaction with an alcohol after being combined with an isocyanate).

Description

Detailed Description of the Invention a. Industrial Application Field The present invention has excellent weather resistance and heat resistance, and can improve properties such as adhesiveness and paintability. Furthermore, in a composite system, it has excellent compatibility with polar resins. The present invention relates to a modified hydrogenated conjugated diene polymer, a polymer composition, and a method for producing the same, which have high properties and excellent effects on improving impact resistance, mechanical strength, and the like.

b. Conventional technology Diene polymers with unsaturated double bonds in the polymer are:
Since thermal stability, weather resistance, and ozone resistance are poor, a method of hydrogenating unsaturated double bonds (hereinafter referred to as "hydrogenation") is known as a means to improve this. Special Publication No. 19960, Special Publication No. 1996-
No. 39275, Japanese Patent Publication No. 1983-3555, Japanese Patent Publication No. 1983-
No. 62805, JP-A-59-133203, and the like. Hydrogenated polymers obtained by these methods exhibit expected heat resistance, weather resistance, and ozone resistance.
It is widely used for modifying resins.

However, since this hydrogenated polymer does not have a polar group, it has poor compatibility with polar resins, and the blend does not exhibit satisfactory physical properties. Furthermore, blends with non-polar resins also have the drawback of poor adhesion and paintability of the blend.

Incidentally, a method of introducing an isocyanate group or a polar group derived from an isocyanate group into a copolymer of an aromatic vinyl compound and a conjugated diene compound before hydrogenation is already known, for example, as described in US Pat. No. 3,838,108. ,
US Pat. No. 4,070,344 and the like disclose amine-terminated polymers in which living polymer ends are reacted with polyisocyanate.

However, among the polar group-containing polymers obtained by these methods, the unsaturated double bonds of which are hydrogenated by conventional methods do not have a high hydrogenation rate.

That is, a highly hydrogenated polymer containing an isocyanate group or a polar group derived from an isocyanate group at the terminal has not been known.

C0 Problems to be Solved by the Invention The purpose of the present invention is to provide a material that has excellent compatibility with polar resins, can improve physical properties such as impact resistance and mechanical properties, and has good compatibility with non-polar resins. The object of the present invention is to provide a polymer with excellent heat resistance, weather resistance, and ozone resistance, which can improve properties such as impact resistance, adhesion, and paintability.

66 Means for Solving the Problems As a result of various studies in order to obtain a polymer that can solve the above problems, the present inventors have developed an aromatic polymer in which the terminal end of the polymer is modified with an isocyanate group or a polar group derived from an isocyanate group. The present inventors have discovered that a copolymer of a group vinyl compound and a conjugated diene compound in which the unsaturated double bonds are highly hydrogenated satisfies this purpose, leading to the completion of the present invention.

The present invention is a copolymer of an aromatic vinyl compound and a conjugated diene compound, which has an isocyanate group or a polar group derived from an isocyanate group bonded to at least one end of the polymer. Combine at least 3
A modified hydrogenated conjugated diene polymer containing 0% by weight and in which at least 60% of the unsaturated double bonds based on the conjugated diene component in the entire copolymer is hydrogenated, and the combination of this and other resins. A composition and a method for producing the same are provided.

That is, the present invention provides a block copolymer containing 5 to 90% by weight of an aromatic vinyl component and 95 to 10% by weight of a conjugated diene component, wherein at least 60% of the unsaturated bonds in the conjugated diene portion of the copolymer A modified hydrogenated conjugated diene system containing at least 30% by weight of a block copolymer in which an isocyanate group or a polar group derived from an isocyanate group is bonded to at least one end of the copolymer molecule. Polymer (A): A polymer composition consisting of 1 to 99% by weight of the polymer (A) and 99 to 1% by weight of at least one resin selected from polar resins (B) and nonpolar resins (C). A random copolymer of 5 to 90% by weight of an aromatic vinyl compound and 95 to 10% by weight of a conjugated diene compound, wherein at least 60% of the unsaturated bonds in the conjugated diene portion in the polymer are hydrogenated. , and at least 3 random copolymers in which an isocyanate group or a polar group derived from an isocyanate group is bonded to at least one end of the polymer molecule.
Modified hydrogenated conjugated diene polymer composition containing 0% by weight (
A polymer composition consisting of D) 1 to 99% by weight and a polar resin (B) 99 to 1% by weight; and a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an organolithium compound as an initiator. Both)
After polymerization, at least 30% by weight of the resulting polymer
A modified polymer obtained by modifying at least one of the polymer terminals with a polyfunctional isocyanate compound, or the modified polymer is further treated with water, alcohols, amines, amides, hydrazines, hydrazides, epoxy group-containing compounds, carboxyl. Acids, acid anhydrides, mercaptans, phosphoric acids, phosphorous acids, acetylacetone, hydrogen cyanide and the following formula (■): [X and Y are 10N group or C0OR group (
R represents an alkyl group). ] A modified polymer obtained by reacting with one or more compounds selected from active methylene compounds and compounds reactive with isocyanates such as organolithium compounds shown in the formula is added in an inert solvent to a hydrogenation catalyst, preferably a hydrogenation catalyst. (i) at least one selected from a bis(cyclopentagenyl) titanium compound, a bis(cyclopentagenyl) zirconium compound, and a bis(cyclopentagenyl) hafnium compound, and (ii) an aluminum compound, a zinc compound, A reducing organometallic compound containing at least one selected from magnesium compounds, organolithium compounds, and alkoxylithium compounds at a ratio of component (i)/component (ii) (molar ratio) = 110.5 to 1/20. A modified hydrogenated conjugated diene polymer characterized in that at least 60% of the unsaturated bonds in the conjugated diene moiety in the modified polymer are hydrogenated by contacting with hydrogen in the presence of a mixed catalyst. A manufacturing method is provided.

Furthermore, when an isocyanate group or an active organic lithium group is present in the modified hydrogenated conjugated diene polymer, a polymer or a composition thereof obtained by reacting these with a reactive compound is provided.

First, examples of the (co)polymer of an aromatic vinyl compound and a conjugated diene compound used in the present invention include a conjugated diene polymer or a random copolymer and a block copolymer of a conjugated diene compound and an aromatic vinyl compound. It will be done.

The above-mentioned conjugated diene polymer includes a copolymer obtained by copolymerizing a conjugated diene homopolymer and a conjugated diene with each other, or with at least one conjugated diene and at least one olefin monomer copolymerizable with the conjugated diene. Ru. Conjugated dienes used in the production of such conjugated diene polymers include conjugated dienes having from 4 to about 12 carbon atoms, and specific examples include 1,3-butadiene, isoprene, 2 , 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene,
Examples include 4,5-diethyl-1,3-octadiene, 3-butyl-1°3-octadiene, and chlorobrene.

In order to obtain an elastomer that can be effectively used industrially and has excellent physical properties, 1,3-butadiene and isoprene are particularly preferred, and elastomers such as polybutadiene, polyisoprene, and butadiene/isoprene copolymers are particularly preferred. The microstructure of such a polymer is not particularly limited and any structure can be suitably used, but 1,2-
If there are few vinyl bonds, the solubility of the polymer after hydrogenation will decrease, and in order to perform hydrogenation uniformly, the solvent will be limited.
More preferred are polymers containing about 10% or more of 1,2-vinyl bonds.

Furthermore, the method of the present invention is suitably used for hydrogenating a copolymer obtained by copolymerizing at least one conjugated diene and at least one olefin monomer copolymerizable with the conjugated diene. Suitable conjugated dienes used in the preparation of such copolymers include the conjugated dienes described above, while olefin monomers include all heptamers copolymerizable with the conjugated dienes, but especially vinyl-substituted aromatics. Hydrocarbons are preferred.

Copolymers of conjugated dienes and aromatic vinyls are particularly important for obtaining industrially useful and valuable elastomers and thermoplastic elastomers. Specific examples of aromatic vinyls used in the preparation of such copolymers include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p Examples include -aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, and vinylpyridine, with styrene and α-methylstyrene being particularly preferred. As specific examples of copolymers, putadiene/styrene copolymers, isoprene/styrene copolymers, butadiene/α-methylstyrene copolymers, etc. are most preferred since they provide hydrogenated copolymers of high industrial value.

Such copolymers include random copolymers, tapering block dibolymers, and fully block copolymers in which the monomers are statistically distributed throughout the polymers.

In order to obtain an industrially useful polymer, the content of the aromatic vinyl polymer is preferably 5% to 90% by weight.

Further, it is preferable that the 1,2-vinyl bond of the conjugated diene unit is 10% by weight or more of the entire conjugated diene unit, since 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 in terms of polystyrene is 1.
000 to 500.000, preferably s, o
oo~300.000, more preferably io, ooo
~200,000.

The method for producing the polymer is not limited either, but since it is necessary to introduce a functional group at the terminal end, it is desirable to produce it by using an organic alkali metal compound, preferably an organic lithium compound, as an initiator or by ping anionic polymerization.

As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyllithium,
Examples include n-propyllithium, isopropyllithium, n-butyllithium, 38C-butyllithium, tert-butyllithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, and the like.

The conjugated diene random copolymer of the present invention includes hexane,
A conjugated diene compound and an aromatic vinyl compound are mixed in a hydrocarbon solvent such as heptane or cyclohexane, or an ether solvent such as tetrahydrofuran or ethyl ether.
It can be obtained by carrying out (co)polymerization using the above organic alkali metal compound as an initiator in the range of 70 to 130'C.

On the other hand, the method for producing a block copolymer consisting of a conjugated diene and an aromatic vinyl may be any known method, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-1797.
No. 9, Special Publication No. 45-31951, Special Publication No. 46-324
Examples include the method described in No. 15. In these methods, a conjugated diene and an aromatic vinyl are block copolymerized using a polymerization initiator such as the above-mentioned organic alkali metal compound in a hydrocarbon solvent, and the resulting block copolymer is generally -B+,,A4-B-A),,B+A-
B), [wherein A is a polymer block mainly composed of aromatic vinyl, and B is an elastomeric polymer block containing a 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. [In the formula, A and B are the same as above, X represents an initiator such as a polyfunctional organolithium compound, and m and n are 1
is an integer greater than or equal to ] It is expressed as.

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

A plurality of uniformly distributed portions and/or tapered distributed portions may coexist in each block.

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

Particularly preferred block copolymers in the present invention are block copolymers containing at least two aromatic vinyl-based polymer blocks and at least one conjugated diene-based polymer block.

In the present invention, examples of methods for introducing isocyanate groups or polar groups derived from isocyanate groups into the polymer prior to hydrogenation include the following method.

That is, it is a method of introducing an isocyanate group to the polymer terminal by polymerizing by the above-mentioned method or by reacting the active alkali metal terminal of the pinion anion with a polyfunctional isocyanate compound.

There are no particular restrictions on the polyfunctional isocyanate compound, but examples include 2,4- and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
4.4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 5-chloro-2,4- or 5-chloro-2,6-)lylene diisocyanate, 3.
Aromatic diisocyanates such as 3'-dimethyl-4°4-diphenyl diisocyanate, 1,3- or 1,4-xylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3- or 1,4-cyclohexyl Diisocyanates, 1-methyl-2,4- or 1-methyl-2,6-cyclohexyl diisocyanate, aliphatic diisocyanates such as methylene bis(4-cyclohexyl isocyanate), 4,4',4''-triphenylmethane triisocyanate , polyisocyanates such as polymethylene polyphenylisocyanate,
and mixtures thereof are used.

The amount of the isocyanate compound added is 0.2 to 1.5, preferably 0.7 to 1.3 mol per atom of alkali metal. The number of isocyanate groups introduced into the polymer is arbitrary, but preferably 0.5 to 10, more preferably 0.6 to 5 per polymer chain.

In the modified hydrogenated conjugated diene polymer of the present invention, the polymer molecules having an isocyanate group bonded to at least one end of the polymer molecules account for at least 30% by weight, preferably 40% or more of the total polymer molecules. is necessary.

If it is less than 30% by weight, a sufficient improvement effect cannot be obtained. 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. Alternatively, the isocyanate may be hydrogenated while being modified, and then reacted with at least one of the following compound groups to form an incyanate derivative. Groups of compounds that should react with isocyanate groups include water, alcohols, amines, amides, hydrazines, hydrazides, epoxy group-containing compounds, carboxylic acids, acid anhydrides, mercaptans, phosphoric acids, and phosphorous acids. , acetylacetone, hydrogen cyanide and the following formula (■): [X and Y represent a -CN group or a COOR group (R is an alkyl group). ] The active methylene compound shown by these is mentioned.

Specific examples of the alcohols to be reacted with the isocyanate groups used in the present invention include the following compounds.

Allyl alcohol, isoamyl alcohol, octatool, isopropyl alcohol, ethyl alcohol, 2-
Ethylhexanol, 3-chloropropanol, butanol, heptyl alcohol, methanol, methylisobutylcarbinol, 3-methyl-3-methoxybutanol, methoxybutanol, p-ethylphenol, p-
Octylphenol, xylenol, guaiacol, p
-cumylphenol, cresol, chlorophenol,
Cyclohexanol, 2,4-dichlorophenol, 2
．． 4-dinitrophenol, 2.5-di-butylhydroquinone, 2,4.6-)dichlorophenol, 2゜4.6-1-(dimethylaminomethyl)phenol, naphthol, p-ditrophenol, bis( 4-hydroxyphenyl) sulfone, bisphenol-A1 hydroxybenzamide, phenylphenol, phenol, p
-phenol sulfonic acid, pt-butylphenol,
Methylcyclohexanol, metol, ethylene glycol, diethylene glycol, triethylene glycol, octanediol, tridodecyl alcohol, trimethylolpropane, neopentyl glycol, nonyl alcohol, 4-hydroxy-2-butanone, butanediol, 2-7' Chylhydroquinone, propylene glycol, 1°6-hexanediol, hexylene glycol, pentaerythritol, 1.5-bentanediol, polyethylene glycol, polybrobylene glycol, 3-methylpentane-1,3,5-triol, catechol, Hydroquinone, resorcinol, etc.

Specific examples of amines, amides, hydrazines and hydrazides include isopropylamine, ethylamine, 2-ethylhexylamine, isobutylamine, 3-
Ethoxypropylamine, dibutylaminopropylamine, di-2-ethylhexylamine, t-butylamine, 5ec-butylamine, propylamine, methoxypropylamine, methyliminobispropylamine, isopropanolamine, ethanolamine, ethyleneimine, 3- lauryloxypropylamine, butylamine, methylamine, aniline, anisidine, 2-amino-
Thiophenol, p-aminobenzaldehyde, ethylaniline, p-cresidine, chloroaniline, cyclohexylamine, dichloroaniline, 2,6-dichloro-
4-nitroaniline, dicyclohexylamine, cyclohexylamine, dichloroaniline, 2,6-dichloro-4-nitroaniline, diphenylamine, dibenzylamine, tolidine base, toluidine, α-naphthylamine, nitroaniline, p-phenetidine, phenethylamine, phthalimide , methanic acid, methylamine, aminopyridine, 1-aminoethylpiperazine, N-aminopropylmorpholine, imidazole, 4-methylimidazole, 2-methylimidazole, 2-ethyl-4-
Methylimidazole, piperazine, piperidine, pyrrolidine, hexamethyleneimine, melamine, morpholine,
Ethylenediamine, diethylenetriamine, diaminopropane, 1,4-diaminobutane, hexamethylenediamine, polyethyleneimine, m-xylylenediamine,
Dianisidine, 4,4'-diamino-3゜3'-diethyldiphenylmethane, 3,3'-dichlorobenzidine, 3,3'-dimethyl-4,4'diaminodiphenylmethane, sulfanilic acid, m-toluidinediamine, N −
t-octylacrylamide, N,N-dimethylacrylamide, N,N-dimethylacetamide, diaseptone acrylamide, ethylene bissteramide, oleic acid amide, stearic acid amide, methylene bisstearamide, methylolstearamide, thioacetamide , formamide, methacrylamide, N,N-dimethylbis(acrylamide), N-methylolacrylamide, ε-caprolactam, α-amino ε-caprolactam, guanylthiourea, and the like.

Specific examples of the epoxy group-containing compound include propylene oxide, cyclohexane oxide, dibromocresyl glycidyl ether, trimethylpropane polyglycidyl ether, neopenbyl glycol diglycidyl ether, glycerol polyglycidyl ether, polypropylene diglycidyl ether, and the like.

Specific examples of carboxylic acids and acid anhydrides include isobutyric acid, octylic acid, formic acid, glyoxylic acid, crotonic acid, β-chloropropionic acid, β-mercaptopropionic acid, oxalic acid, acetic acid, tartaric acid, sebacic acid, thio Glycolic acid, thioacetic acid, pyruvic acid, propionic acid, malonic acid, β-bromopropionic acid, adipic acid, p-aminobenzoic acid, benzoic acid, chlorobenzoic acid, 4-chloro-3
-nitrobenzoic acid, cyclohexanecarboxylic acid, 2.4
-dichlorobenzoic acid, naphthenic acid, phenylacetic acid, protocatechuic acid, 0-benzoylbenzoic acid, levulinic acid,
Itaconic acid, anthranilic acid, isophthalic acid, oxynaphthoic acid, gamma acid, salicylic acid, terephthalic acid, p
-Hydroxyphenylacetic acid, chloroglycitur, citradinic acid, isobutyric anhydride, itaconic anhydride, acetic anhydride,
Examples include propionic anhydride, maleic anhydride, butyric anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride, and the like.

Specific examples of mercaptans include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, L-dodecyl mercaptan, hexadecyl mercaptan, n-octadecyl mercaptan, thioglycol, and 2-mercaptan. Examples include ethanol, thiobenzoic acid, thiophenol, and thiosalicylic acid.

Specific examples of phosphoric acids and phosphorous acids include phosphonic acid, triethyl phosphate, trimethyl phosphate, tributyl phosphate, phenylphosphonic acid, dimethyldithiophosphoric acid, diethyldithiophosphoric acid, diisopropyldithiophosphoric acid, trimethylphosphite, and the like.

Specific examples of the active methylene compound represented by (I) include cyanoacetic acid, dicyanomethylene, methyl cyanoacetate, ethyl cyanoacetate, propyl cyanoacetate, butyl cyanoacetate, dimethyl malonate, dipropyl malonate, dibutyl malonate, etc. can be mentioned.

The amount of these compounds to be added is preferably equimolar to the isocyanate group since it causes an equimolar reaction with the isocyanate group.

The conjugated diene copolymer of the present invention can be prepared as follows in an inert solvent, for example, a hydrocarbon solvent such as hexane, heptane, cyclohexane, benzene, toluene, or ethylbenzene, or a polar solvent such as methyl ethyl ketone, ethyl acetate, ethyl ether, or tetrahydrofuran. Hydrogenation is carried out using a hydrogenation catalyst or hydrogenation compound such as.

The hydrogenated conjugated diene copolymer of the present invention can be obtained by removing the solvent by a desolvation coagulation treatment using a direct release roll or by steam stripping, or by coagulating with alcohol, and then drying.

Various methods can be used to hydrogenate a polymer, but hydrogenation of a (co)polymer modified with an isocyanate group or a (co)polymer modified with a polar group derived from an isocyanate group is possible. In this regard, it is preferable to use the following hydrogenation catalysts because they can perform hydrogenation at a high rate. That is, as a hydrogenation catalyst, (i) at least one selected from a bis(cyclopentagenyl) titanium compound, a bis(cyclopentagenyl) zirconium compound, and a bis(cyclopentagenyl) hafnium compound; and (ii) aluminum. Preferably, a reducing organometallic compound containing at least one of a zinc compound, a magnesium compound, an organolithium compound, and an alkoxylithium compound is used, preferably component (i)/component (ii) (molar ratio) = 110.5 to 1. Catalysts mixed at a ratio of /20 can be used.

The above-mentioned modified (co)polymer can be suitably hydrogenated by contacting it with hydrogen in the presence of a catalyst consisting of the above-mentioned components (i) and (ii) in an inert solvent.

The hydrogenation ratio (hydrogenation rate) is 60% or more, preferably 70% or more, more preferably 80% or more, particularly preferably 90% of the unsaturated bonds based on the conjugated diene in the polymer.
That's all. 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.

Note that the following method can also be used to obtain the modified hydrogenated conjugated diene polymer of the present invention.

That is, after (co)polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an organolithium compound as an initiator, at least 30% of the terminal end of the polymer is
A polymer modified in weight percent with a polyfunctional isocyanate compound was mixed with (i) a bis(cyclopentadienyl) titanium compound, a bis(cyclopentadienyl)zirconium compound, and a bis(cyclopentadienyl) titanium compound in an inert solvent. (ii) at least one hafnium compound (pentagenyl);
) A reducing organometallic compound containing at least one of an aluminum compound, a zinc compound, a magnesium compound, an organolithium compound, and an alkoxylithium compound, (i) component/(ii) component (molar ratio) = 110.5 to
After hydrogenating at least 60% of the unsaturated bonds in the conjugated diene portion of the polymer by contacting it with hydrogen in the presence of a catalyst mixed in a ratio of 1/20, the isocyanate-modified hydrogenated polymer is treated with water, Alcohols, amines, amides, hydrazines 1. Hydrazides, carboxylic acids, acid anhydrides, mercaptans, phosphoric acids, phosphorous acids, acetylacetone, hydrogen cyanide and the following formula (■): [X and Y represent -CN group or COOR group (R is an alkyl group) . ] A hydrogenated diene polymer whose terminal end is modified with isocyanate or an isocyanate derivative can be obtained by reacting with one or more compounds selected from the active methylene compounds shown below.

Here, each component of the hydrogenation catalyst will be described.

The bis(cyclopentadienyl) titanium compound has the following formula (■): [wherein R1 and Rg are a halogen atom, a hydrocarbon group,
It represents an allyloxy group, an alkoxy group or a carbonyl group, and R1 and RZ may be the same or different. ] It is a compound shown by.

Specific examples of such compounds include bis(cyclopentagenyl)titanium dimethyl, bis(cyclopentagenyl)titanium diethyl, bis(cyclopentagenyl)titanium di-n-butyl, bis(cyclopentagenyl)titanium. Di-5ec-butyl, bis(cyclopentagenyl) titanium diethyl, bis(cyclopentagenyl) titanium dioctyl, bis(cyclopentagenyl) titanium jetoxide, bis(cyclopentagenyl) titanium jetoxide, bis(cyclo pentagenyl) titanium jetoxide, bis(cyclopentagenyl) titanium diphenyl, bis(cyclopentagenyl) titanium di-m-1lyl, bis(cyclopentagenyl) titanium di-p-tolyl,
Bis(cyclopentagenyl) titanium di m+P-
Xylyl, bis(cyclopentagenyl) titanium di-4-ethylphenyl, bis(cyclopentagenyl)
Titanium di-4-butylphenyl, bis(cyclopentagenyl) titanium di-4-hexylphenyl, bis(cyclopentagenyl) titanium diphenoxide, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) Titanium dichloride, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium dioctyl, bis(cyclopentagenyl) titanium dicarbonyl, bis(cyclopentagenyl) titanium chloride methyl, bis(cyclopentagenyl) titanium dichloride (2) titanium chloride ethoxide, bis(cyclopentagenyl) titanium chloride phenoxide, bis(cyclopentagenyl) titanium dibenzyl, etc., and these may be used alone or in combination with each other.

Among these bis(cyclopentagenyl) titanium compounds, it has high hydrogenation activity toward olefinically unsaturated double bonds in polymers and can selectively hydrogenate unsaturated double bonds under mild conditions. Preferred examples include bis(cyclopentagenyl)titanium dimethyl, bis(cyclopentagenyl)titanium di-n-butyl,
Bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium diphenyl, bis(cyclopentagenyl) titanium di-p-tolyl, bis(cyclopentagenyl) titanium dicarbonyl, bis(cyclopentagenyl) titanium dicarbonyl ) titanium dibenzyl, and particularly preferred is bis(cyclopentagenyl) titanium dichloride.

In addition, the bis(cyclopentadienyl)zirconium compound has the following formula (■): [In the formula, R3 and R4 are a halogen atom, a hydrocarbon group,
It represents an allyloxy group, an alkoxy group, or a carbonyl group, and R3 and R4 may be the same or different. ] It is a compound shown by.

Specific examples of such compounds include bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium diethyl, bis(cyclopentagenyl)-zirconium-n-butyl, bis(cyclopentagenyl) Zirconium di5ec-7'chill,
bis(cyclopentadienyl)zirconium diethyl,
Bis(cyclopentagenyl)zirconium dioctyl, bis(cyclopentagenyl)zirconium jetoxide, bis(cyclopentagenyl)zirconium jetoxide, bis(cyclopentagenyl)zirconium jetoxide, bis(cyclopentagenyl) Zirconium diphenyl, bis(cyclopentajenyl)zirconium di-m-tolyl, bis(cyclopentadienyl)zirconium di-p-tolyl, bis(cyclopentagenyl)zirconium-m,p-xylyl, bis(cyclopentadienyl)zirconium-m,p-xylyl, pentagenyl) zirconium di-4-ethylphenyl, bis(cyclopentagenyl) zirconium diphenoxide, bis(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) Zirconium dibromide, bis(cyclopentagenyl)
Examples include zirconium dioctyl, bis(cyclopentagenyl)zirconium dicarbonyl, bis(cyclopentagenyl)zirconium chloride methyl, etc.
These can be used alone or in combination with each other. Among these bis(cyclopentagenyl) zirconium compounds, they have high hydrogenation activity toward olefinically unsaturated double bonds in polymers (and can hydrogenate unsaturated double bonds well and selectively under mild conditions). Preferred examples include bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium di-n-butyl, bis(cyclopentagenyl)zirconium dichloride, and bis(cyclopentagenyl)zirconium dibromide. , bis(cyclopentagenyl)
Examples include zirconium diphenyl, bis(cyclopentadienyl)zirconium di-m-tolyl, and bis(cyclopentagenyl)zirconium dicarbonyl.

More preferable compounds that can be handled more stably and exhibit the greatest activity when combined with the reducing metal compound (ii) are bis(cyclopentagenyl)zirconium dichloride and bis(cyclopentagenyl)zirconium dibromide. , bis(cyclopentagenyl)zirconium diphenyl, bis(cyclopentagenyl)zirconium di-P-)lyl, and bis(cyclopentagenyl)zirconium di-P-)lyl is the most preferred because it has excellent solubility.

The bis(cyclopentadienyl) hafnium compound has the following formula (V): [wherein R5 and R6 are a halogen atom, a hydrocarbon group,
It represents an allyloxy group, an alkoxy group, or a carbonyl group, and R5 and R6 may be the same or different. ] It is a compound shown by.

A specific example is bis(cyclopentagenyl)
Hafnium dimethyl, bis(cyclopentagenyl) hafnium diethyl, bis(cyclopentagenyl) hafnium di-n-butyl, bis(cyclopentagenyl)
hafnium di-sec -butyl, bis(cyclopentagenyl) dihexyl, bis(cyclopentagenyl)
hafnium jetoxide, bis(cyclopentagenyl) hafnium jetoxide, bis(cyclopentagenyl) hafnium jetoxide, bis(cyclopentagenyl) hafnium diphenyl, bis(cyclopentagenyl) hafnium di-m-)lyl, bis(cyclopentagenyl) hafnium di-p-tolyl, bis(cyclopentagenyl) hafnium di-m, p-xylyl, bis(cyclopentagenyl) hafnium diphenoxide,
Bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dicarbonyl , bis(cyclopentagenyl) hafnium chloride methyl, etc., and these can be used alone or in combination with each other. Among these bis(cyclopentagenyl) hafnium compounds, it has high hydrogenation activity toward olefinically unsaturated double bonds in polymers and can selectively hydrogenate unsaturated double bonds under mild conditions. Preferred are bis(cyclopentagenyl)hafnium dimethyl, bis(cyclopentagenyl)hafnium di-n-butyl, bis(cyclopentagenyl)hafnium dichloride, bis(cyclopentagenyl)hafnium dibromide, bis(cyclopentagenyl)hafnium dibromide, (
cyclopentagenyl) hafnium diphenyl, bis(
Examples thereof include cyclopentagenyl) hafnium di-p-tolyl and bis(cyclopentagenyl) hafnium dicarbonyl.

More preferred compounds that can be handled more stably and exhibit the greatest activity when combined with the reducing metal compound (ii) are bis(cyclopentagenyl) hafnium dichloride and bis(cyclopentagenyl) hafnium dibromide. , bis(cyclopentagenyl) hafnium diphenyl, bis(cyclopentagenyl) hafnium di-p-tolyl, bis(cyclopentagenyl)
Hafnium di-P-)lyl is the most preferred because it has excellent solubility.

Specific examples of the reducing organometallic compound (ii) include, as aluminum compounds, trimethylaluminum, triethylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, Diethylaluminum hydride, diisobutylaluminum hydride, triphenylaluminum, tri-
(2-ethylhexyl)aluminum, etc.
Examples of zinc compounds include diethylzinc, bis(cyclopentadienyl)zinc, diphenylzinc, etc., and further examples of magnesium compounds include dimethylmagnesium,
Examples include diethylmagnesium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, dimethylmagnesium, and t-butylmagnesium chloride. In addition to these, compounds containing two or more types of reducing metals such as lithium aluminum hydride are also included.

Considering industrial availability, ease of handling, etc., triethylaluminum, triisobutylaluminum, diethylaluminium chloride, and ethylaluminum dichloride are preferred. Examples of organic lithium compounds include methyllithium, ethyllithium, n-propyllithium, n-butyllithium, 5ec-butyllithium, isobutyllithium, n-hexyllithium, phenyllithium, p-)lyllithium, xylyllithium,
Examples include polymerization active terminal lithium.

Specific examples of alkoxylithium compounds include methoxylithium, ethoxylithium, n-propoxylithium, i-propoxylithium, n-butoxylithium, 5ec-butoxylithium, t-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxylithium, octyloxylithium,
Phenoxylithium, 4-methylphenoxylithium,
Examples include 2.6-di-t-butyl-4-methylphenoxylithium, benzyloxylithium, and reaction products of alkyllithium compounds and alcoholic compounds or phenolic hydroxyl compounds.

2,6-di-t-butyl-4- is more preferable because it is most likely to exhibit activity when combined with catalyst (i) component.
Methyl-phenoxylithium.

Furthermore, the modified hydrogenated conjugated diene polymer of the present invention can also be obtained using the following method.

That is, after (co)polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an organolithium compound as an initiator, at least 30% by weight of the resulting polymer is treated with an isocyanate compound at least one of the polymer terminals. After reacting the modified polymer with an organic lithium compound in an amount equal to or more than the mole of active isocyanate groups, a hydrogenation catalyst, preferably the above-mentioned (i) bis(cyclopentagenyl) titanium, is added in an inert solvent. (ii) at least one selected from aluminum compounds, zinc compounds, magnesium compounds, organolithium compounds and alkoxylithium compounds; and a reducing organometallic compound containing at least one of the above components, in the presence of a catalyst mixed in a ratio of component (i)/component (ii) (molar ratio) = 110.5 to 1/20, and contact with hydrogen. By hydrogenating at least 60% of the unsaturated bonds in the conjugated diene moieties in the modified polymer, the organolithium-added isocyanate-modified hydrogenated polymer is converted into a tin compound, an amino group-containing compound, an amide group-containing compound, Phosphate group-containing compounds, halogen group-containing compounds, carbonyl group-containing compounds, nitroso group-containing compounds, olefinic double and triple bond-containing compounds, nitrile group-containing compounds, isocyanate compounds,
A hydrogenated diene polymer whose terminal end is modified with an isocyanate derivative can be obtained by reacting it with one or more compounds reactive with organolithium selected from active hydrogen-containing compounds.

Examples of organic lithium compounds to be reacted with the active isocyanate group before the hydrogenation reaction include ethyllithium, n-
Examples thereof include propyllithium, isopro-rulithium, n-butyllithium, 5ec-butyllithium, and tert-butyllithium.

Specific examples of compounds that can react with organolithium-added isocyanate groups include halogen compounds such as chlorotrimethyltin, chlorotributyltin, chlorotrioctyltin, dichlorodimethyltin, dichlorodibutyltin, dichlorodioctyltin, and triphenylmonochlortin as tin compounds; Alkenyltin compounds and alkyltin carboxylates such as tetravinyltin, tetraaryltin, divinyldibutyltin, dibutyltin distearate, dibutyltin dioleate-1, dioctyltin distearate, dibutyltin maleate, and dioctyltin maleate are also used. It will be done.

As the amino group-containing compound and the amide group-containing compound, compounds equivalent to the amines and amides reacted with the above-mentioned isocyanate groups are used.

As the phosphate group-containing compound, trial-alkali phosphates, trialkylphenyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trinonylphenyl phosphate, tributylphenyl phosphate, triphenyl phosphate, etc. are used.

Examples of halogen group-containing compounds include chlorobenzene, allyl chloride, cyanuric chloride, P-bromoaniline,
p-Brombenzoic acid, benzoyl chloride, chloroprene rubber, chlorosulfonated polyethylene, etc. are used.

Examples of carbonyl group-containing compounds include acetylacetone,
Acetone, benzophenone, maleic anhydride, methyl methacrylate, and the like are used.

As compounds containing olefinic double bonds and triple bonds,
1-butene, cyclohexene, methacrylic acid ethyl ester, etc. are used.

Acrylonitrile, acetonitrile, etc. are used as the nitrile group-containing compound.

Isocyanate compounds include polyfunctional isocyanate compounds equivalent to those used to introduce isocyanate groups into the terminals of the above polymers, phenyl isocyanate,
Monofunctional isocyanates such as methyl isocyanate are used.

As the active hydrogen compound, water, methyl alcohol, acetic acid, hydrochloric acid, etc. are used.

The modified hydrogenated conjugated diene polymer (8) of the present invention can be used alone, but the polar resin (B) or the non-polar resin (8) can be used alone.
C), or it can be used by blending it with a rubbery polymer.

The ratio of the resin blended with the modified hydrogenated conjugated diene polymer is 1 to 99% by weight, and the optimum mixing ratio varies depending on the purpose of use.

However, the modification effect of the modified hydrogenated conjugated diene polymer of the present invention cannot be achieved when less than 1% by weight is added.

Polar resins used in the present invention include thermoplastics such as ABS resin, acrylic resin, polyacrylamide, polyacrylic acid, polyacrylic ester, polyalkyl acrylate, polymethyl acrylate, polyacrylonitrile, polyacrylonitrile styrene, Polymethacrylamide, polymethacrylic acid, polymethacrylic acid ester, polyalkyl methacrylate, polymethyl methacrylate, polymethacloronitrile, acetal resin, polyacecool, polyoxymethylene, ionomer, chlorinated polyether, coumaron/indene resin, recycled Cellulose, petroleum resin, cellulose derivative, alkali cellulose, cellulose ester, cellulose acetate, cellulose acetate butyrate, cellulose xanthate, cellulose nitrate, cellulose ether, carboxymethyl cellulose, cellulose ether ester,
Fluororesin, FEP, polychlorotrifluoroethylene, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyamide, aliphatic polyamide,
Nylon 11, Nylon 12, Nylon 6, Nylon 6
．． 10, nylon 6.12, nylon 6.6, aromatic polyamide, polyphenylene isophthalamide, polyphenylene terephthalamide, nylon 4,6, polyimide, polyphenylene sulfide, polyether ether ketone, metaxylylene diamine adipamide, polyamide imide, Polyarylate, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, chlorinated polyethylene, chlorosulfonated polyethylene, polycarbonate, CR-39, polysulfone, polyether sulfone, polysulfonamide, polyvinyl alcohol, polyvinyl ester, polyvinyl cinnamate , polyvinyl acetate, polyvinyl ether, polyisobutyl vinyl ether, polymethyl vinyl ether, polyphenylene oxide, polybutylene terephthalate, thermosetting plastics such as amino resin, aniline resin, urea resin, polysulfonamide, melamine resin, allyl resin, CR-39
, diallyl phthalate resin, alkyd resin, epoxy resin, silicone resin, vinyl ester resin, phenol resin, novolac, resorcinol resin, unsaturated polyester, low shrinkage unsaturated polyester, furan resin and the like.

Preferred polar resins are polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polysulfone, polyphenylene oxide, epoxy resin, and phenolic resin.

The blend ratio of the modified hydrogenated conjugated diene polymer (A) and polar resin (B) of the present invention is 1 to 99% by weight/99 to 1% by weight, but by adding (A), (B) In order to fully exhibit the modifying effect of (A), the blending ratio of component (A) is 3 to 50% by weight, more preferably 5 to 30% by weight. If the blending ratio of component (A) is low, a sufficient modifying effect cannot be obtained (but if the blending ratio of component (A) is too high, the original performance of component (B) is likely to be impaired.

The non-polar resin used in the present invention includes polyethylene,
High molecular weight polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, LLDPE (linear low density polyethylene), polyethylene, high molecular weight polyethylene, polybutene, polyisobutylene, polypropylene, polystyrene, IIIPS (high impact polystyrene), polymethyl Examples include styrene and polymethylene.

Preferred non-polar resins are polypropylene, polyethylene and polystyrene.

The blend ratio of the modified hydrogenated conjugated diene polymer (A) and the nonpolar resin (C) of the present invention is 1 to 99% by weight/99 to 1% by weight, but by adding component (A) ( C)
In order to fully exhibit the modifying effect of the component, the blending ratio of the component (8) should be 3 to 50% by weight, more preferably 5 to 3% by weight.
It is 0% by weight. If the blend ratio of component (A) is low, it is difficult to obtain a sufficient modifying effect, and if the blend ratio of component (A) is too high, the original performance of component (C) is likely to be impaired.

A typical example of a rubbery polymer that can be blended with the modified hydrogenated conjugated diene polymer (^) of the present invention is natural rubber (
NR), polyisoprene rubber (IR), styrene butadiene rubber (SBR), polybutadiene rubber (BR),
Diene-based synthetic rubbers such as acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), and ethylene-propylene rubber (EPR), ethylene-propylene-nonconjugated diene rubber (EPDM), and acrylic rubber (ACM).

ANM), fluororubber, urethane rubber, (polyester urethane, polyether urethane), chlorosulfonated polyethylene, butyl rubber, halogenated butyl rubber,
Examples include non-diene synthetic rubbers such as silicone rubber and polyether rubber such as epichlorohydrin rubber. These rubbery polymers may be blended with the hydrogenated polymer (8) of the present invention in any ratio depending on the purpose.

The modified hydrogenated conjugated diene polymer (D) of the present invention is blended with the polar resin (B) at a ratio of 1 to 99% by weight/99 to 1% by weight.

The modified hydrogenated conjugated diene polymer of the present invention and its soft composition can be crosslinked, non-crosslinked, foamed, or non-foamed, and can be formed by extrusion molding, film molding, blow molding, vacuum forming, or press molding. It is also possible to use rubber products such as tires, anti-vibration rubber, and roofing sponges.
Everyday parts, audio parts, industrial goods such as belts, packing materials, cushioning materials, and sea light, transportation parts, automobile parts such as boots, moldings, hoses, sealing materials, bumpers, weather strips, automobile interior and exterior parts, electric wire footwear, etc. It can be used in a wide range of applications, including packaging materials such as materials, cushioning materials, films, and sheets, and has extremely high industrial value.

In addition, the resin composition in which the modified hydrogenated conjugated diene polymer of the present invention is mixed with a resin has excellent impact resistance, heat resistance, and moldability compared to ordinary thermoplastic resins, so it is suitable for use in LEDs.
lamps, relay cases, switches, connectors, coil bobbins, resistors, computer parts, telephone exchange parts,
For telecommunication parts such as condenser cases, tuners, terminal blocks, and timer cases; hair dryers, irons, shavers, egg boilers, coffee makers, and VTRs.
For household electrical parts such as parts, microwave oven parts, TV parts, audio parts, compact discs, refrigerator parts, air conditioner parts, word processors, light covers, etc.: camera bodies, camera parts, watch parts, strobe parts, binoculars,
For precision mechanical parts such as microscope parts and movie projector parts: power tools, vending machine parts, hand labelers, elevator parts, escalator parts, motor cases, oil filter cases, pump parts, bolts, nuts, gears, cams, fiber bobbins For machine-related parts such as counter frames, office computer parts, register parts, calculator parts, typewriter parts, drafting equipment parts, facsimile parts, copying machine parts, etc.For automobiles and vehicles, car heater fans, bumpers, interior parts, etc. Instrument panel, instrument i, motorcycle windshield, headlamp, taillamp,
For automobile and vehicle-related parts such as air conditioning plates, rail insulation parts, vehicle armrests, curtain covers, wiper covers, molded grips, meter needles, and wheel covers, as well as leisure-related parts such as surf riders and golf equipment.
It is particularly useful for applications such as housings, various covers, surface treatment agents, and coatings.

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

In the examples, the hydrogenation rate is 100 MHz, measured using carbon tetrachloride as solvent at a concentration of 15% by weight.
It was calculated from the decrease in the spectrum of the unsaturated bond of H-NMH. To determine the content of isocyanate groups, add 10 d of IN n-butylamine solution to 100 d of hexane solution in which 2 g of polymer is dissolved, mix well, add 100 ml of distilled water, separate the mixed water layer, and use methyl red as an indicator. ,0. It was calculated by titrating unreacted n-butylamine with IN sulfuric acid.

Example 1 Cyclohexane 5 degassed and dehydrated in a 102 autoclave
kg and 150 g of styrene were charged, 5 g of tetrahydrofuran and 0.8 g of n-butyllithium were added, and adiabatic polymerization was carried out 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. Here, 4゜4'-diphenylmethane diisocyanate 2.6
g 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% of the polymer was terminally modified with isocyanate. The reaction solution was heated to 40°.
C, 0.8 g of n-butyllithium and 2,6-di-t
A mixture of 1.5 g of -butyl-p-cresol was added, and further 0.5 g of bis(cyclopentagenyl) titanium dichloride and 2 g of diethylaluminum chloride were added, followed by hydrogenation for 1 hour at a hydrogen pressure of 10 kg/c+a. The hydrogenation rate of the olefinic double bond in the butadiene polymerization part is 98
% and a number average molecular weight of 150.000 was obtained. The amount of bound styrene in the block copolymer before the hydrogenation reaction was 30%, and 40% of the butadiene moieties were 1.2 bonds. The amount of -NGO groups was determined by titration analysis, and the average number of incyanate 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. The polymer solution was dried to remove the solution using a direct release roll to obtain a solid polymer.

Example 2 Cyclohexane 5 degassed and dehydrated in a 102 autoclave
kg, 200 g of styrene and 80 g of 1,3-butadiene
After charging 0g, add 5g of tetrahydrofuran and n
-Add 0.7g of butyllithium to bring the polymerization temperature to 30'
Polymerization was carried out at a temperature of 70°C. Conversion rate is approximately 10
After reaching 0%, 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% of the polymer was terminally modified with an isocyanate group. The reaction solution was heated to 70°C, and 1 g of n-butyllithium and 1 g of 2,6-di-butyl-p-cresol were added, followed by 0.5 g of bis(cyclopentagenyl) titanium dichloride and 2 g of diethylaluminum chloride.
g was added thereto, and hydrogenation was carried out for 1 hour at a hydrogen pressure of 10 g/c4.

A polymer with a hydrogen conversion rate of 95% and a number average molecular weight of 200,000 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 0.8.

Example 3 Cyclohexane 5 degassed and dehydrated in a 101 autoclave
kg and 200 g of styrene were charged, 5 g of tetrahydrofuran and 0.8 g of n-butyllithium were added, and adiabatic polymerization was carried out from 30°C. After 15 minutes, 600 g of butadiene was charged and polymerization was carried out for 30 minutes, and then 200 g of styrene was added and polymerization was carried out for an additional 15 minutes. Then, 5.0 g of 4゜4',4''-triphenylmethane triisocyanate was added to modify the polymer terminals with incyanate. At this time, some coupling occurred, and about 30% by weight became a coupled polymer. The remainder The terminals of 70% of the polymer were modified with isocyanate.The reaction solution was heated to 40°C, 0.5 g of bis(cyclopentadienyl)titanium dichloride and 2 g of diethylaluminium chloride were added, and the mixture was heated with water at a hydrogen pressure of 10 kg/c+d for 2 hours. Attached.

Hydrogenation rate is 100% and number average molecular weight is 150,000
A hydrogenated polymer 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 1.4.

Example 4 Before the isocyanate group-terminated hydrogenated polymer obtained in Example 1 was subjected to desolvation and drying treatment, n-butyl alcohol 1
g and triethylenediamine (hereinafter D) as a reaction catalyst component.
Add 0.3 g of N, F and 3 g at room temperature.
The reaction was carried out for 0 minutes.

Titration analysis of the product showed the absence of isocyanate groups, and infrared spectroscopy (IR) analysis demonstrated that the isocyanate groups and alcohol had reacted to convert the terminal polar groups into urethane.

Examples 5 to 12 In the same manner as in Example 7, the isocyanate group-terminated hydrogenated polymers obtained in Examples 1 to 6 were reacted with various compounds in equimolar amounts to the isocyanate group to produce isocyanate derivatives as shown in Table 1. A terminally hydrogenated polymer was obtained.

Example 13 After charging 5 kg of degassed and dehydrated cyclohexane, 100 g of styrene, and 900 g of 1,3-butadiene into a 10/2 autoclave, 200 g of tetrahydrofuran was charged.
, 0.7 g of n-butyllithium was added, and adiabatic polymerization was carried out at a polymerization temperature of 5°C. Conversion rate is almost 100
%, 2.4-tolylene diisocyanate 2
g was added to modify the polymer terminals with isocyanate. At this time, about 20% by weight of the polymer was coupled,
The remaining 80% of the polymer was terminally modified with isocyanate groups. The number average molecular weight of the polymer is 200,000, the amount of bound styrene is 10%, and 80% of the butadiene moiety is 1,
There were 2 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 0.8. Di-n-butylamine was added in an amount equal to the isocyanate group to this polymer solution, and 3
After stirring for 0 minutes, the reaction mixture was heated to 90°C, and 1 g of n-butyllithium and 1 g of 2,6-di-t-butyl p-cresol were added, followed by 0.5 g of bis(cyclopentagenyl)titanium dichloride and diethylaluminum. 2 g of chloride was added and hydrogenated at a hydrogen pressure of 10 g/cffl for 30 minutes. 9 of the olefinic double bond in the butadiene polymerization part
An 8% hydrogenated polymer was obtained.

This hydrogenated polymer was identified to contain urea groups by infrared spectroscopy.

Example 14 IO! Cyclohexane 5 degassed and dehydrated in an autoclave
kg and 150 g of styrene were charged, 5 g of tetrahydrofuran and 0.7 g of n-butyllithium were added, and adiabatic polymerization was carried out from 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. Here, 4゜4'-diphenylmethane diisocyanate 2.6
g 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% of the polymer was terminally modified with isocyanate. The obtained polymer had a number average molecular weight of 150,000 and a bound styrene content of 30.
% of the block polymer 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. Subsequently, octyl alcohol in an amount equal to the isocyanate group was added to this polymer solution, and the mixture was stirred at 70°C for 15 minutes. The reaction solution was heated to 40°C, and 0.8 g of n-butyllithium and 1.5 g of 2,6-di-t-butyl-p-cresol were added, followed by 0.5 g of bis(cyclopentagenyl) titanium dichloride and diethylaluminium. Add 2g of chloride and increase the hydrogen pressure to 10
kg/ci for 2 hours.

Example 15 Cyclohexane 5 degassed and dehydrated in a 102 autoclave
kg and 150 g of styrene were charged, 5 g of tetrahydrofuran and 0.8 g of n-butyllithium were added, and adiabatic polymerization was carried out at 30"C. After 15 minutes, 700 g of butadiene was charged and polymerization was carried out for 30 minutes, and then 150 g of styrene was added. 4°4'-diphenylmethane diisocyanate 2.
6 g was added to modify the polymer terminals with isocyanate. At this time, some clumping occurred, and about 10% by weight became a coupling polymer. The remaining 90% of the polymer was terminally modified with isocyanate. 40% of the reaction solution
°C, add 0.93 g of n-butyllithium, and further add 0.5 g of bis(cyclopentadienyl)titanium dichloride and 2 g of diethylaluminum chloride.
Hydrogenation was carried out for 1 hour at a hydrogen pressure of 10 kg/cI11.

Hydrogenation rate is 98%, number average molecular weight is 150.000
A hydrogenated polymer was obtained. The amount of bound styrene in the block copolymer before the hydrogenation reaction is 30%, and the amount of bound styrene in the butadiene part is 40%.
% were 1,2 bonds. By titration analysis -NC0,1
The average number of isocyanate groups introduced per molecule was determined to be about 0.9 by dividing by the average number of molecules determined from the number average molecular weight. The polymer solution after the hydrogenation reaction was steam stripped and then dried with hot air to obtain a solid polymer.

The obtained polymer was identified by infrared spectrum as an amide group-containing polymer.

Examples 16 to 23 The n-butyllithium-added isocyanate-terminated hydrogenated polymer obtained in Example 15 after the hydrogenation reaction was reacted with two times the mole of various compounds (Table 2) to change the polar group terminals. A hydrogenated polymer was obtained.

Table 2 Example 24 Cyclohexane 5 degassed and dehydrated in a 101 autoclave
After charging 1 kg of 1.3-butadiene and 1 kg of 1.3-butadiene, 5 g of tetrahydrofuran and 2
g was added to carry out temperature-rising polymerization at a polymerization temperature of 30°C to 70°C. After the conversion rate reached almost 100%, 2
15 g of 4-tolylene diisocyanate was added to modify both ends of the polymer with isocyanate. At this time, about 10% by weight of the polymer was coupled, but both ends of the remaining 90% of the polymer were modified with isocyanate groups. The reaction solution was heated to 50°C, and 4g of n-butyllithium and 2°6-
Add a mixture of 1 g of butyl-p-cresol,
Furthermore, 1 g of bis(cyclopentagenyl) titanium dichloride and 4 g of diethylaluminium chloride were added,
Hydrogenation was carried out at a hydrogen pressure of log/cd for 3 hours.

A polymer with a hydrogen conversion rate of 100% and a number average molecular weight of 5,000 was obtained. By titration analysis of the polymer before hydrogenation -
The average number of isothiaphor l-groups introduced per molecule was determined by quantifying the NGO groups and dividing by the average number of molecules determined from the number average molecular weight, which was about 1.7.

Examples 25 to 26 The low molecular weight hydrogenated polymer containing isocyanate-1 groups at both terminals obtained in Example 24 was reacted with other difunctional compounds to obtain high molecular weight polymers as shown in Table 3. Ta.

The amount of the difunctional compound added was set to be 1.02 times the mole of the isocyanate group.

Comparative Example 1.2 After carrying out the same polymerization reaction as in Example 1.2, 4°4'
- The hydrogenation reaction was carried out without adding diphenylmethane diisocyanate. Hydrogenation rate is 98% and number average molecular weight is 1
50,000 hydrogenated polymers were obtained.

The amount of bound styrene in the block copolymer before hydrogenation reaction is 30
%, 40% of the butadiene moieties were 1.2 bonds.

Comparative Examples 3 to 5 The same polymerization reactions as in Examples 3 to 5 were carried out in the same manner as in Comparative Example 1, and then the hydrogenated polymers as shown in Table 4 were produced by carrying out the hydrogenation reaction without adding an isocyanate compound. Obtained.

The polymer obtained in Example 2.5.7.13.15.21 and Comparative Example 1.2.3.5 and the thermoplastic resin shown in Table 5 were mixed and melt-mixed using a twin-screw extruder. Thereafter, pelletized thermoplastic resin compositions as shown in Table 5 were obtained. After sufficiently drying, test pieces for evaluation were obtained using an injection molding machine, and evaluated according to the following evaluation criteria.

Evaluation method: (1) Measurement was made using ASTM D256 standard K Mi'A'' with a notch at 23°C.

A plate-shaped molded product was obtained and visually evaluated according to the following evaluation criteria.

O: Good appearance. ×: Poor appearance phenomena such as pearl luster, flow marks, and rough surface are observed.

Example 4.13.15.16 and Comparative Example 1.4 above
25 parts by weight of the polymer obtained above and 75 parts by weight of polypropylene were melt-mixed in a Pan Bali mixer.

After kneading, pelletize with a pelletizer, then 6.5
A test piece was produced using an ounce injection molding machine (manufactured by Nippon Steel Corporation, 6.5 ounce in-line screw type). The injection molding conditions are shown below.

In addition, the results of the physical property test are shown in Table-6.

Recorded injection pressure knee pyrotechnic 500kg/cffl secondary pressure 400
kg/d Injection time: 15 seconds at knee pyrotechnic pressure 12 seconds Molding temperature: 240°C Cooling time: 40°C The polypropylene used was Noblen BC- manufactured by Mitsubishi Yuka ■.
It is 2.

Each physical property was measured according to the following method.

(1) Melt flow rate (CMPR): Measured in accordance with JIS 7210 at a temperature of 230° C. and a load of 2.16 kg.

(2) Izot impact strength: According to JIS 7110.

(3) Flexural modulus (FM): JIS K 7
Measured according to 203.

(4) Surface gloss (GL): JIS 710
Measured according to 5.

(5) Adhesive strength of coating film A sheet with a thickness of 2 ITlffl obtained by injection molding was degreased with ethanol, then surface treated with trichloroethane vapor, and a primer (RB29111 manufactured by Nippon B Chemical ■) was first applied to this sheet. Next, a polyurethane paint (R263, manufactured by Nippon B Chemical ■) was applied in a dry thick film to a thickness of about 50 μm.

After drying and curing, the coating film was peeled off at 180° at a tensile rate of 30 cm/min, and the adhesive strength was measured.

The results are shown in Table-6.

As is clear from the results shown in the above Examples and Comparative Examples, the hydrogenated polymer containing terminal isocyanates or isocyanate derivatives of the present invention has the effect of increasing the impact strength of polar resins and improving the molded appearance, and is effective in improving the molded appearance of non-polar resins. It has the effect of improving paint adhesion.

f0 Effects of the invention The modified hydrogenated conjugated diene polymer composition of the invention alone has
It is also used for modifying various resins, and can be widely applied to various fields such as the automatic field, electrical and electronic fields, and has extremely high industrial value.

Patent applicant: Japan Synthetic Rubber Co., Ltd. (2 others)

Claims (8)

[Claims] (1) A block copolymer containing 5 to 90% by weight of an aromatic vinyl component and 95 to 10% by weight of a conjugated diene component and having a polystyrene equivalent number average molecular weight of 1,000 to 500,000, A block copolymer in which at least 60% of the unsaturated bonds in the conjugated diene portion of the copolymer are hydrogenated, and an isocyanate group or a polar group derived from an isocyanate group is bonded to at least one end of the copolymer molecule. A modified hydrogenated conjugated diene polymer composition containing at least 30% by weight of (2) The modified hydrogenated conjugated diene polymer (A
) 1 to 99% by weight, and 99 to 1% by weight of at least one resin selected from polar resins (B) and nonpolar resins (C). (3) A random copolymer of 5 to 90% by weight of an aromatic vinyl compound and 95 to 10% by weight of a conjugated diene compound, wherein at least 60% of the unsaturated bonds in the conjugated diene part in the polymer are hydrogenated. A modified hydrogenated conjugated diene polymer (D ) 1 to 99% by weight, and polar resin (B) 9
A polymer composition comprising 9 to 1% by weight. (4) After (co)polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an organolithium compound as an initiator, at least 30% of the obtained polymer
A modified polymer obtained by modifying at least one of the polymer terminals of % by weight with a polyfunctional isocyanate compound, or a modified polymer obtained by further reacting the modified polymer with a compound reactive with isocyanate, is dissolved in an inert solvent. (i) at least one selected from a bis(cyclopentadienyl) titanium compound, a bis(cyclopentadienyl) zirconium compound, and a bis(cyclopentadienyl) hafnium compound; and (ii) an aluminum compound and zinc. (i) component/(ii) component (molar ratio) = 1/0.5.
A modified water characterized in that at least 60% of the unsaturated bonds in the conjugated diene moiety in the modified polymer are hydrogenated by contacting with hydrogen in the presence of a catalyst mixed in a ratio of ~1/20. A method for producing a conjugated diene polymer. (5) After (co)polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an organolithium compound as an initiator, at least 30% of the obtained polymer
A modified polymer obtained by modifying at least one of the polymer terminals in weight percent with an isocyanate compound is mixed with (i) a bis(cyclopentadienyl) titanium compound, a bis(cyclopentadienyl) zirconium compound, and a bis(cyclopentadienyl) zirconium compound in an inert solvent. A reducing organometallic compound containing at least one selected from bis(cyclopentadienyl) hafnium compounds and (ii) at least one selected from aluminum compounds, zinc compounds, magnesium compounds, organolithium compounds, and alkoxylithium compounds. , (i) component/(ii) component (molar ratio) = 1/0.5
A modified hydrogenated conjugated diene polymer in which at least 60% of the unsaturated bonds in the conjugated diene moiety in the modified polymer is hydrogenated by contacting with hydrogen in the presence of a catalyst mixed at a ratio of ~1/20. A method for producing a modified hydrogenated conjugated diene polymer, which comprises reacting the polymer with a compound reactive with isocyanate. (6) After (co)polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using an organolithium compound as an initiator, at least 30% of the obtained polymer
A modified polymer obtained by modifying at least one of the polymer terminals with an isocyanate compound in weight percent is reacted with an organic lithium compound in an amount equal to or more than the same mole as the active isocyanate group, and then (i) bis(cyclo pentadienyl) titanium compounds, bis(cyclopentadienyl) zirconium compounds and bis(cyclopentadienyl)
(i) component/a reducing organometallic compound containing at least one selected from hafnium compounds; (ii) Component (molar ratio) = 1/0.5
A modified water characterized in that at least 60% of the unsaturated bonds in the conjugated diene moiety in the modified polymer are hydrogenated by contacting with hydrogen in the presence of a catalyst mixed in a ratio of ~1/20. A method for producing a conjugated diene polymer. (7) The following general formula (I) obtained by reacting the modified hydrogenated conjugated diene polymer produced by the method described in claim (6) with a compound capable of reacting with organolithium: ▲Mathematical formula, chemical formula, table etc. ▼・・・・・・・・・(
I) [In the formula, R_1 represents an organic group of an organolithium compound, R_2 represents an adduct of an organolithium and a reactive compound or hydrogen, R_3 represents an organic group having 1 to 30 carbon atoms, and n is 0 to It is 10. ] A hydrogenated conjugated diene polymer composition containing 30% by weight or more of a portion less than the polymer represented by: (8) 1 to 99% by weight of the modified hydrogenated conjugated diene polymer (A) according to claim (7) and 99 to 99% of at least one resin selected from polar resins (B) and nonpolar resins (C). 1
A polymer composition consisting of % by weight.