CN100591699C - Hydrogenated block copolymer and composition thereof - Google Patents
Hydrogenated block copolymer and composition thereof Download PDFInfo
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- CN100591699C CN100591699C CN 200680005602 CN200680005602A CN100591699C CN 100591699 C CN100591699 C CN 100591699C CN 200680005602 CN200680005602 CN 200680005602 CN 200680005602 A CN200680005602 A CN 200680005602A CN 100591699 C CN100591699 C CN 100591699C
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Abstract
Disclosed is a hydrogenated block copolymer having excellent flexibility, heat resistance, abrasion resistance and surface touch (e.g., free from adhesion or oil bleeding) and good processing properties or a composition comprising the copolymer. A hydrogenated block copolymer which comprises one or more polymer blocks A each consisting of a vinyl aromatic compound, one or more hydrogenated polymerblocks B each consisting of a random copolymer of a conjugated diene and a vinyl aromatic compound, and one or more hydrogenated polymer blocks C each consisting of a conjugated diene polymer havinga vinyl bond content of 30% or more, and which has a vinyl aromatic compound content of more than 50 wt% and less than 95 wt%. A composition comprising the hydrogenated block copolymer.
Description
Technical field
The present invention relates to have the hydrogenated block copolymer of ad hoc structure and make up this hydrogenated block copolymer and the hydrogenated block copolymer compositions of softener of rubber, other thermoplastic resins and rubbery polymer.Composition of the present invention is provided at flexibility, thermotolerance, wear resistant and surface touch (not having adhesion sense and oil impregnate etc.) the various moulding product that the aspect is outstanding and processibility is good, and described moulding product are used to wrapping material, toy, trolley part and the medical apparatus etc. of household electrical appliances-industrial part etc.
Background technology
In the segmented copolymer that constitutes by conjugated diolefine and vinyl aromatic hydrocarbon, under the less situation of vinyl aromatic hydrocarbon, even uncured then, also have at normal temperatures and vulcanized natural rubber and the same elasticity of synthetic rubber, and at high temperature have the processibility same, so be widely used in fields such as footwear, modifying plastics, asphalt modification, adhesive bond material with thermoplastic resin.In addition, under the many situation of vinyl aromatic hydrocarbon content, this segmented copolymer can obtain thermoplastic resin transparent and that shock-resistance is outstanding, therefore is used in the wrapping material, toy of food container, household product, household electrical appliances-industrial part etc. etc.And weathering resistance, the thermotolerance of the hydride of these multipolymers are outstanding, and therefore, except above-mentioned purposes field, this hydride has also obtained practicability widely at aspects such as trolley part and medical apparatus.
Yet though the less segmented copolymer flexibility of vinyl aromatic hydrocarbon is good, there is the shortcoming of wear resistant difference in it, and this is playing restrictive function aspect its purposes further enlarging.On the other hand, the flexibility of the segmented copolymer that vinyl aromatic hydrocarbon content in the past is more is poor, uncomfortable cooperation soft material.
As material with flexibility, the composition (for example referring to patent documentation 1) of a kind of hydrogenated diene analog copolymer and acrylic resin is disclosed, wherein, described hydrogenated diene analog copolymer is that the vinyl aromatic hydrocarbon content is the random copolymers of 3 weight %～50 weight %, is that molecular weight distribution (Mw/Mn) is below 10 and the vinyl binding capacity of the diene in multipolymer part is that 10%～90% multipolymer obtains through hydrogenation.The composition (for example referring to patent documentation 2) of another kind of hydrogenated diene analog copolymer and acrylic resin is also disclosed in addition, wherein, described hydrogenated diene analog copolymer is that the vinyl aromatic hydrocarbon content is the random copolymers of 5 weight %～60 weight %, and the vinyl binding capacity that is the diene part in the multipolymer is that the multipolymer more than 60% obtains through hydrogenation.
About above-mentioned such hydrogenated diene analog copolymer, carried out using it for the trial of the purposes that the flexible vinyl chloride resin used in the past.Produce the problem of halogen, the environmental problem of environmental hormone that softening agent causes etc. when there is burning in the flexible vinyl chloride resin, in this case, the task of top priority is its equivalent material of exploitation., when above-mentioned such hydrogenated diene analog copolymer was used for purposes that the flexible vinyl chloride resin used in the past, characteristics such as its flexibility and wear resistant were insufficient.
In recent years, for the more segmented copolymer of vinyl aromatic hydrocarbon content, carried out obtaining having the trial of the material of flexibility, and disclose the formed material based on the hydrogenated block copolymer that contains following multipolymer: described multipolymer contains the block of vinylbenzene main body and contains block (for example referring to patent documentation 3) based on Butadiene.Yet hydrogenated copolymer disclosed herein lacks flexibility, is unsuitable for using the purposes of flexible vinyl chloride resin.
As mentioned above, although the task of top priority is that the equivalent material of the flexible vinyl chloride resin that has the problem on the various environment is developed, present situation remains the material that does not obtain having the characteristic (flexibility and wear resistant etc.) that is equal to mutually with the flexible vinyl chloride resin.
We carry out the exploitation of the equivalent material of flexible vinyl chloride resin, formerly develop to have the hydrogenated copolymer (for example, referring to patent documentation 4) that is equal to mutually with the flexibility and the wear resistant of this resin.Yet, compare with this multipolymer, wish to occur the more excellent material of a kind of thermotolerance.
Patent documentation 1 spy opens flat 2-158643 communique
Patent documentation 2 spies open flat 6-287365 communique
Patent documentation 3WO98/12240
Patent documentation 4WO03/35705
Summary of the invention
Problem of the present invention provides outstanding and hydrogenated block copolymer or its composition that processibility is good aspect flexibility, thermotolerance, wear resistant and surface touch (not having adhesion sense and oil impregnate etc.).
In order to solve above-mentioned problem, the present inventor has carried out further investigation repeatedly, found that, has the aromatic vinyl compound polymer block A more than 1 respectively, the hydropolymer B block of the random copolymers of conjugated diolefine and vinyl aromatic compounds and vinyl binding capacity are that the content of the hydropolymer block C of the conjugated diolefin polymer more than 30% and vinyl aromatic compounds can effectively solve above-mentioned problem greater than 50 weight % less than the hydrogenated block copolymer of 95 weight %, and the particular composition that contains described hydrogenated block copolymer can play same effect, thereby has finished the present invention.
Promptly, the present invention relates to a kind of hydrogenated block copolymer and the composition that contains this hydrogenated block copolymer, described hydrogenated block copolymer is the hydride of the multipolymer that formed by conjugated diolefine and vinyl aromatic compounds, it is characterized in that having the characteristic of following (1)～(6).
(1) have the polymer blocks of at least one following a, b and c:
A. aromatic vinyl compound polymer block A,
B. the hydropolymer B block of the random copolymers of conjugated diolefine and vinyl aromatic compounds,
C. the vinyl binding capacity is the hydropolymer block C of the conjugated diolefin polymer more than 30%;
(2) content of described vinyl aromatic compounds is greater than 50 weight % and less than 95 weight %;
(3) weight-average molecular weight is 50,000～1,000,000;
(4) the vinyl binding capacity of the conjugated diene monomeric unit of the hydrogenation prepolymer of the described hydropolymer B block of formation is more than 10% and less than 20%;
(5) hydrogenation ratio of two keys of described conjugated diene monomeric unit is more than 75%;
(6) content of described aromatic vinyl compound polymer block A is that the content of 20 weight %～50 weight %, hydrogenated copolymer B block is that the content of 30 weight %～80 weight %, hydropolymer block C is 10 weight %～35 weight %.
Hydrogenated block copolymer of the present invention or the composition that contains this hydrogenated block copolymer are outstanding and processibility is good aspect flexibility, thermotolerance, wear resistant and surface touch, as the equivalent material of flexible vinyl chloride resin, can be suitable for the purposes such as wrapping material, toy, trolley part and medical apparatus of household electrical appliances-industrial part etc.
Embodiment
Describe the preferred form of implementation of the present invention below in detail.
Hydrogenated block copolymer of the present invention is the hydride that contains the multipolymer of conjugated diolefine and vinyl aromatic compounds.
Have in the hydrogenated block copolymer of the present invention at least one, preferred 2 above aromatic vinyl compound polymer block A (following sometimes also claim " polymer blocks A "), and the hydrogenated copolymer B block and the vinyl binding capacity that have the random copolymers of at least 1 conjugated diolefine and vinyl aromatic compounds respectively are the hydropolymer block C of the conjugated diolefin polymer more than 30%.
In the hydrogenated block copolymer of the present invention, polymer blocks A is important for the aspect of thermotolerance and surface touch (not having the adhesion sense).From the aspect of thermotolerance and surface touch, the content of polymer blocks A is preferably more than the 20 weight %, and from the aspect of flexibility, the content of polymer blocks A is preferably below the 50 weight %.Will obtain especially under the situation of the good hydrogenated block copolymer of thermotolerance etc., the content of suggestion polymer blocks A is 25 weight %～50 weight %, is preferably 30 weight %～50 weight %.In addition, obtain especially under the situation of the good hydrogenated block copolymer of flexibility etc., the content of suggestion polymer blocks A is 20 weight %～45 weight %, is preferably 20 weight %～40 weight %.
Among the present invention, the content of polymer blocks A can utilize with the perosmic anhydride method (I.M.KOLTHOFF, et al., J.Polym.Sci.1, the methods of 429 (1946) records that to be catalyzer come the multipolymer before the oxygenolysis hydrogenation by tertbutyl peroxide.Be called the perosmic anhydride acid system later on) measure.In addition, content for polymer blocks A, can also be with the multipolymer before the hydrogenation and the multipolymer behind the hydrogenation as the inspection product, adopt nuclear magnetic resonance device (NMR) that it is measured (Y.Tanaka, et al., the method of RUBBER CHEMISTRY and TECHNOLOGY 54,685 (1981) records.Be called the NMR method later on).Moreover, in this case, use the content (note is made Ns) of content (note is made Os) and polymer blocks A by the copolymer assay after the NMR method use hydrogenation of the polymer blocks A of the copolymer assay before the hydrogenation to have the relation shown in the following formula (F) by the perosmic anhydride acid system.
(Os)=-0.012 (Ns)
2+ 1.8 (Ns)-13.0 ... formula (F)
Therefore, obtain under the situation of content of polymer blocks A of the segmented copolymer after the hydrogenation with the NMR method among the present invention, with (Os) value of obtaining by following formula (F) content as the polymer blocks A of the present invention's regulation.
Hydrogenated block copolymer of the present invention has the hydrogenated copolymer B block of the random copolymers of at least 1 conjugated diolefine and vinyl aromatic compounds.And there is not the peak crystallization that is caused by the hydrogenated copolymer B block in fact in preferred hydride in-20 ℃～80 ℃ scope in differential scanning calorimetry (DSC) chart.Herein, " in-20 ℃～80 ℃ scope, there is not the peak crystallization that causes by the hydrogenated copolymer B block in fact " and is meant the peak that in this temperature range, does not have appearance to cause by hydrogenated copolymer B block crystallization partly, even the peak that causes by crystallization perhaps occurred, the heat of the peak crystallization that causes by this crystallization less than 3J/g, preferably less than 2J/g, be more preferably less than 1J/g, preferred especially peak crystallization does not have heat.
In-20 ℃～80 ℃ scope, do not exist the flexibility of hydrogenated block copolymer of the peak crystallization that causes by the hydrogenated copolymer B block good, be fit on the purposes of the soft vinyl chloride resin of present use, expand.In order to obtain the hydrogenated block copolymer that in-20 ℃～80 ℃ scope, does not have the peak crystallization that causes by the hydrogenated copolymer B block in fact as described above, can use non-hydrogenation multipolymer to carry out hydrogenation reaction and obtain this hydrogenated block copolymer, described non-hydrogenation multipolymer is to use adjustment vinyl binding capacity as described later or adjusts conjugated diene compound and the adjustment agent of the random copolymerization of vinyl aromatic compounds, carries out under the such condition of aftermentioned that polyreaction obtains.
From the angle of wear resistant, the content of hydrogenated copolymer B block is preferably 30 weight %～80 weight %.More preferably 35 weight %～70 weight % are preferably 40 weight %～60 weight % especially.Among the present invention, suggestion constitutes conjugated diolefine in the random copolymers of hydrogenated copolymer B block and the part by weight of vinyl aromatic compounds is 50/50 to 10/90, is preferably 40/60 to 15/85, and more preferably 35/65 to 20/80.
Among the present invention, the microtexture of the conjugated diolefine part in the polymer blocks before the hydrogenation of hydrogenated copolymer B block (ratio of cis, trans, vinyl) can change arbitrarily according to the use of polar compound described later etc., usually, conjugated diolefine is 1, during the 3-divinyl, from the angle of wear resistant, 1,2-vinyl binding capacity is 10%～20%.
From the angle of flexibility and surface touch (no oil impregnate etc.), in hydrogenated block copolymer of the present invention, the vinyl binding capacity of the conjugated diolefine before the hydrogenation of hydropolymer block C is more than 30%.Be preferably 35%～80%, more preferably 39%～75%, be preferably 43%～70% especially.Moreover among the present invention, the back is with 1,2-vinyl binding capacity and 3, (when using 1,3-butadiene as conjugated diolefine is 1 to the total amount of 4-vinyl binding capacity, 2-vinyl binding capacity is 3 when using isoprene as conjugated diolefine, 4-vinyl binding capacity) be called the vinyl binding capacity.The vinyl binding capacity can be grasped by utilizing infrared spectrophotometer to use multipolymer before the hydrogenation to measure (for example Hampton method (hampton method)) as the inspection product.
In addition, from the angle of flexibility, wear resistant and surface touch (no oil impregnate etc.), the content of the hydropolymer block C in the hydrogenated block copolymer of the present invention is preferably 10 weight %～35 weight %.13 weight %～30 weight % more preferably.
Among the present invention, from flexibility, thermotolerance, wear resistant equal angles, the content of vinyl aromatic compounds is greater than 50 weight % and less than 95 weight % in the hydrogenated block copolymer.Be preferably 55 weight %～less thaies, 90 weight %, more preferably 58 weight %～85 weight %.In addition, among the present invention, segmented copolymer before the content of vinyl aromatic compounds can use ultraviolet spectrophotometer with hydrogenation in the hydrogenated block copolymer or the segmented copolymer behind the hydrogenation serve as that the inspection product are known.
From the equilibrated angle of thermotolerance, physical strength, wear resistant etc. and forming process, the weight-average molecular weight of hydrogenated block copolymer of the present invention is 50,000～1,000,000.Suggestion is preferably 100,000～700,000, and more preferably 150,000～500,000.
Among the present invention, molecular weight distribution is below 10, is generally 1～8, is preferably 1.01～5.The molecular weight of hydrogenated block copolymer uses gel permeation chromatography (GPC) to measure, and is to use by the typical curve (using the peak molecular weight of polystyrene standard to make) that the mensuration of commercially available polystyrene standard is obtained and calculates the weight-average molecular weight that the molecular weight of the peak value of chromatographic column is tried to achieve.The molecular weight distribution of hydrogenated block copolymer also can similarly be obtained by the mensuration of GPC, and this molecular weight distribution is the ratio of weight-average molecular weight and number-average molecular weight.
Hydrogenated block copolymer of the present invention is the hydride that contains the segmented copolymer of conjugated diolefine and vinyl aromatic compounds, from the angle of thermotolerance, wear resistant, surface touch, more than 75% of two keys of the conjugated diene compound in the multipolymer, preferred more than 80%, more preferably more than 85%, preferably especially be hydrogenated more than 90%.Moreover, be not particularly limited for the hydrogenation ratio of the two keys of the aromatic series of the vinyl aromatic hydrocarbon in the hydrogenated block copolymer, but preferred hydrogenation ratio is below 50%, is preferably below 30%, more preferably below 20%.The hydrogenation ratio of hydrogenated copolymer can adopt nuclear magnetic resonance device (NMR) etc. to know.
Among the present invention, the structure of hydrogenated block copolymer is not particularly limited, can uses the hydrogenated block copolymer of any structure.As the hydrogenated copolymer that contains at least 1, preferred 2 polymer blocks A, at least 1 hydrogenated copolymer B block and at least 1 hydropolymer block C, can enumerate and have for example hydrogenated copolymer of the structure of following general formula.
C-(B-A)
n、C-(A-B)
n、C-(A-B-A)
l、
C-(B-A-B)
n、A-C-(B-A)
l、A-C-(A-B)
l、
A-C-(B-A)
l-B、[(A-B-C)
l]
m-X、[A-(B-C)
l]
m-X、
[(A-B)
l-C]
m-X、[(A-B-A)
l-C]
m-X、
[(B-A-B)
l-C]
m-X、[(C-B-A)
l]
m-X、
[C-(B-A)
l]
m-X、[C-(A-B-A)
l]
m-X、
[C-(B-A-B)
l]
m-X
(in the following formula, A is that polymer blocks, the B based on vinyl aromatic compounds is that hydrogenated copolymer block, the C of the random copolymers of conjugated diolefine and vinyl aromatic compounds is the hydropolymer block based on the polymkeric substance of conjugated diolefine.The border of distinguishing each block is not necessarily obvious.Vinyl aromatic hydrocarbon in the hydrogenated copolymer B block of random copolymers can also can distribute by taper in the homogeneous distribution.In addition, in the B block, the part that part that vinyl aromatic hydrocarbon homogeneous distributes and/or taper distribute can coexist more than two separately.In addition, in the B block, the different segment of vinyl aromatic hydrocarbon content can coexist more than two.Simultaneously, 1 is the integer more than 1, is preferably 1～5 integer, and n is the integer more than 2, is preferably 2～5 integer.M is the integer more than 2, is preferably 2～11 integer.X represents the residue of coupler or the residue of multifunctional initiator.In multipolymer, block A, B block or block C exist respectively in the plural situation, and structures such as their molecular weight and composition can be the same or different.Simultaneously, the structure that is incorporated into the polymer chain of X can be the same or different.)
Wherein, from the angle of thermotolerance and physical strength, preferred two ends have the multipolymer of the structure of block A, preferred especially A-C-B-A structure.
Hydrogenated block copolymer of the present invention can also be any mixture with material of the structure that above-mentioned general formula represents.In addition, hydrogenated block copolymer can also mixed ethylene base aromatic compound polymer or multipolymer with A-B structure, B-A-B structure.
Among the present invention, conjugated diolefine is the diolefine with 1 pair of conjugated double bond, for example 1,3-divinyl, 2-methyl isophthalic acid, 3-divinyl (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadienes etc. are particularly as common conjugated diolefine, can enumerate 1,3-butadiene, isoprene.These conjugated diolefines can be used a kind of, also can use two or more.Simultaneously, as vinyl aromatic compounds, can enumerate for example vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, 1,1-diphenylethlene, N, the N-dimethyl is to aminoethyl vinylbenzene, N, the N-diethyl is to aminoethyl vinylbenzene etc., and it is a kind of that these vinyl aromatic compounds can use, and also can use two or more.
Among the present invention, can for example in hydrocarbon solvent, use the multipolymer before initiator such as organic alkali metal compound obtains hydrogenation by active anionic polymerization reaction.As hydrocarbon solvent, for example can enumerate aliphatic hydrocarbons such as normal butane, Trimethylmethane, Skellysolve A, normal hexane, normal heptane, octane; Ester ring type hydro carbons such as hexanaphthene, suberane, methyl suberane; Or aromatic hydrocarbonss such as benzene,toluene,xylene, ethylbenzene.
In addition, as initiator, can enumerate usually knownly has the active aliphatic hydrocarbon alkali metal compound of anionoid polymerization, aromatic hydrocarbons alkali metal compound, organic amino alkali metal compound etc. to conjugated diene compound and vinyl aromatic compounds, as basic metal, can enumerate lithium, sodium, potassium etc.Preferred organic alkali metal compound is that carbonatoms is 1～20 aliphatics and aromatic hydrocarbons lithium compound, and it is included in the compound that contains 1 lithium in 1 molecule; Two lithium compounds, three lithium compounds, four lithium compounds that in 1 molecule, contain two above lithiums.Specifically can enumerate the resultant of reaction of n-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, n-pentyl lithium, hexyllithium, phenmethyl lithium, phenyl lithium, tolyl lithium, di isopropenylbenzene and s-butyl lithium and the resultant of reaction of Vinylstyrene, s-butyl lithium and a spot of 1,3-butadiene etc.
In addition, can also use No. 092 specification sheets, the 2nd, 241, No. 239 specification sheetss of English Patent, the 5th, 527, No. 753 disclosed organic alkali metal compounds such as specification sheets of United States Patent (USP) by United States Patent (USP) the 5th, 708.
Among the present invention, use organic alkali metal compound as under the situation of polymerization starter with conjugated diene compound and vinyl aromatic compounds copolymerization, incorporate the vinyl of polymkeric substance in conjunction with (1 in order to adjust based on conjugated diene compound, 2-or 3, the 4-combination) the random copolymerization functionality of amount, adjustment conjugated diene compound and vinyl aromatic compounds can add tertiary amine compound or ether compound as adjusting agent.Tertiary amine compound is a general formula R
1R
2R
3N (wherein, R
1, R
2, R
3Be that carbonatoms is 1～20 alkyl or the alkyl with uncle's amino) shown in compound.For example can enumerate Trimethylamine 99, triethylamine, Tributylamine, N, accelerine, N-ethylpiperidine, N-crassitude, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetraethylethylenediamine, 1,2-two piperidines ethane, trimethylammonium aminoethylpiperazine, N, N, N '; N ", N "-pentamethyl-second triamine, N, N '-dioctyl-p-phenylenediamine etc.
As ether compound, select from straight chain shape ether compound and cyclic ether compound, as straight chain shape ether compound, can enumerate the dialkyl ether compounds class of ethylene glycol such as dme, diethyl ether, phenyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; The dialkyl ether compounds class of Diethylene Glycols such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether.In addition,, can enumerate tetrahydrofuran (THF), diox, 2,5-dimethyl butylene oxide ring, 2,2,5,5-tetramethyl-epoxy butane, 2, the alkyl oxide of two (the 2-butylene oxide ring base) propane of 2-, furfuryl alcohol etc. as the cyclic ether compound.
Among the present invention, using organic alkali metal compound can be batchwise polymerization as polymerization starter with the method for conjugated diene compound and vinyl aromatic compounds copolymerization, also can be successive polymerization, or their combination.In the time of will obtaining the outstanding multipolymer of thermotolerance especially, the method for batchwise polymerization is adopted in suggestion.Polymerization temperature is generally 0 ℃～180 ℃, is preferably 30 ℃～150 ℃.Required time of polymerization is different and different according to condition, but is generally in 48 hours, is preferably 0.1 hour especially～10 hours.In addition, the atmosphere of polymerization system preferably adopts indifferent gas atmosphere such as nitrogen.Be not particularly limited for polymerization pressure, can be enough to keep monomer and solvent in above-mentioned polymerization temperature scope is that the pressure range of liquid phase gets final product.And, should be noted that and not sneak into impurity for example water, oxygen, the carbonic acid gas etc. that make catalyzer and reactive polymer inactivation in the polymerization system.
Among the present invention, can when above-mentioned polymerization finishes, add necessary amount 2 officials can more than coupler carry out coupled reaction.As 2 officials energy coupler, can use known arbitrary substance, be not particularly limited.For example can enumerate dihalide compounds such as dimethyldichlorosilane(DMCS), dimethyl two bromo-silicanes; Esters of gallic acid such as methyl benzoate, ethyl benzoate, phenol benzoate, phthalic acid ester class etc.In addition, can use known arbitrary substance by above multifunctional coupler, be not particularly limited as 3 officials.For example can enumerate polynary epoxy compounds, for example METHYL TRICHLORO SILANE, tertiary butyl trichlorosilane, silicon tetrachloride and these bromides etc. such as polyalcohols more than 3 yuan, epoxidized soybean oil, diglycidyl dihydroxyphenyl propane with general formula R
4-nSiX
nPolydentate compounds such as the halogenated silicon compound (wherein R is that carbonatoms is 1～20 alkyl, and X is a halogen, and n is 3～4 integer) of expression, for example methyl tin trichloride, tertiary butyl tin trichloride, tin tetrachloride etc. are with general formula R
4-nSnX
nThe tin halides compound (wherein, R represents that carbonatoms is 1～20 alkyl, and X is a halogen, and n is 3～4 integer) of expression.Can also use methylcarbonate and diethyl carbonate etc.
The present invention also is included in the modified hydrogenated copolymer that is combined with the atomic group with functional group on the above-mentioned hydrogenated copolymer.As the atomic group that contains functional group, can enumerate to contain and be selected from for example hydroxyl, carbonyl, thiocarbonyl, acid halide group, anhydride group, carboxyl, the thiocarboxylic acid base, aldehyde radical, thioformyl, carboxylic acid ester groups, amide group, sulfonic group, sulfonate group, phosphate, phosphate-based, amino, imino-, itrile group, pyridyl, quinolyl, epoxy group(ing), the sulfo-epoxy group(ing), thioether group, isocyanate group, isothiocyanate group, silyl halide, silanol group, alcoxyl is silica-based, the halogenation tinbase, the alcoxyl tinbase, the atomic group of at least a kind of functional group in the functional groups such as phenyl tinbase.In addition, preferred combination has the modified hydride block copolymer of the atomic group of at least one functional group that is selected from hydroxyl, epoxy group(ing), amino, silanol group, alcoxyl silylation.
Example as properties-correcting agent with functional group, can enumerate the four glycidyl group m-xylene diamine, four glycidyl group-1, the two amino methyl hexanaphthenes of 3-, 6-caprolactone, δ-Wu Neizhi, 4-methoxyl group benzophenone, γ-glycidoxy ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-dimethyl phenoxy group silane, two (γ-glycidoxy propyl group) methyl-prop TMOS, 1,3-dimethyl-2-imidazolone, 1,3-diethyl-2-imidazolone, N, N '-dimethylpropylene urea, N-Methyl pyrrolidone etc.
Modified hydride block copolymer of the present invention can followingly obtain: the properties-correcting agent that can generate the atomic group that contains functional group in the reactive terminal addition of the segmented copolymer that uses organolithium compound to obtain with above-mentioned method as polymerizing catalyst, obtain segmented copolymer thus, obtain modified hydride block copolymer of the present invention by hydrogenation on this segmented copolymer.
Among the present invention, temperature of reaction is preferably 0 ℃～150 ℃, more preferably 20 ℃～120 ℃.Required time of modified-reaction is different because of the difference of other conditions, but is preferably in 24 hours, is preferably 0.1 hour especially～10 hours.
By above-mentioned segmented copolymer that obtains or modified block copolymer are carried out hydrogenation, can access hydrogenated block copolymer of the present invention etc.Hydrogenation catalyst is not particularly limited, and the loaded heterogeneous system hydrogenation catalyst, (2) that can use known in the past (1) to support metals such as Ni, Pt, Pd, Ru with carbon, silicon-dioxide, aluminum oxide, diatomite etc. uses the homogenous system hydrogenation catalysts such as so-called organometallic complex of the organometallic compound of the so-called Ziegler-type hydrogenation catalyst, (3) Ti, Ru, Rh, Zr of reductive agents such as transition metal salt such as the organic acid salt of Ni, Co, Fe, Cr etc. or acetylacetonate and organoaluminum etc. etc.As concrete hydrogenation catalyst, can use the hydrogenation catalyst of putting down in writing in special public clear 42-8704 communique, special public clear 43-6636 communique, special public clear 63-4841 communique, special fair 1-37970 communique, special fair 1-53851 communique, the special fair 2-9041 communique.As preferred hydrogenation catalyst, can enumerate the mixture of luxuriant titanium (titanocene) compound and/or reductibility organometallic compound.
As cyclopentadiene titanium compound, can use the spy to open the compound of putting down in writing in the flat 8-109219 communique, as its object lesson, can enumerate the compound that dicyclopentadiene titanium dichloride, single pentamethyl-cyclopentadiene titanous chloride etc. have the dentate that has (replacement) cyclopentadienyl skeleton, indenes skeleton or fluorene skeleton more than at least.In addition, as the reductibility organometallic compound, can enumerate organic alkali metal compound, organo-magnesium compound, organo-aluminium compound, organoboron compound or organic zinc compounds etc. such as organolithium.
Among the present invention, hydrogenation generally 0 ℃～200 ℃, more preferably in 30 ℃～150 ℃ temperature range, implement.The pressure that is proposed to be used in the hydrogen of hydrogenation is 0.1MPa～15MPa, is preferably 0.2MPa～10MPa, more preferably 0.3MPa～5MPa.In addition, the hydrogenation time is generally 3 minutes～and 10 hours, be preferably 10 minutes～5 hours.Hydrogenation can adopt any one mode in batch mode, continuous mode or their combination.
For the solution of the above-mentioned hydrogenated block copolymer that obtains like that, remove catalyst residue as required after, can from solution, separate hydrogenated block copolymer.As the separation method of solvent, for example can enumerate that to add acetone or alcohol etc. in the reaction solution after hydrogenation be the polar solvent of poor solvent to hydrogenated block copolymer, make the method that reclaims behind the polymer precipitation; Stir down reaction solution is put in the hot water, remove and reclaim the method for solvent by steam stripped; Or direct heating polymers soln distillation removes the method for desolvating etc.In addition, can also add stablizers such as various phenol stabilizers, Phosphorus stablizer, sulphur class stablizer, amine stablizer in the hydrogenated block copolymer of the present invention.
Hydrogenated copolymer of the present invention can pass through α, beta-unsaturated carboxylic acid or for example derivatives such as its acid anhydrides, carboxylate, amidate, imidization thing carry out graft modification, it is combined with the atomic group with functional group.As α, the object lesson of beta-unsaturated carboxylic acid or derivatives thereof can be enumerated maleic anhydride, maleic anhydride imines, vinylformic acid or its ester, methacrylic acid or its ester, end-cis-dicyclo [2,2,1]-5-heptene-2,3-dicarboxylic acid or its acid anhydrides etc.With respect to per 100 weight part hydropolymers, α, the addition of beta-unsaturated carboxylic acid or derivatives thereof are generally 0.01 weight part～20 weight parts, are preferably 0.1 weight part～10 weight parts.
Among the present invention, the temperature of reaction when carrying out graft modification is preferably 100 ℃～300 ℃, more preferably 120 ℃～280 ℃.About the details of the method for carrying out graft modification, can open clear 62-79211 communique referring to for example spy.
Above-mentioned hydrogenated block copolymer of the present invention (below be also referred to as composition (1)) can obtain being applicable to the hydrogenated block copolymer compositions of various formed materials with softener of rubber (below be also referred to as composition (2)) combination.
The softener of rubber that the present invention uses makes the gentle remollescent of composition also give its processibility simultaneously.As softener of rubber, can enumerate mineral oil, aqueous or low-molecular-weight synthetic tenderizer, the processing oil or the extending oil (extender oil) of preferred especially naphthalene class and/or paraffin class.The mineral oils softener of rubber is the mixture of aromatic ring, naphthalene nucleus and paraffin chain, wherein the carbonatoms of the paraffin chain tenderizer more than 50% that accounts for whole carbon atoms is called paraffin class, the carbonatoms of naphthalene nucleus is that 30%～45% tenderizer is called the naphthalene class, and the aromatic series carbonatoms surpasses 30% tenderizer and is called the fragrant same clan.Can use synthetic tenderizer in the composition, polybutene, low molecular weight polybutadiene, whiteruss etc. all can use, still, and preferred above-mentioned mineral oils softener of rubber.With respect to the hydrogenated block copolymer of 100 weight parts, the use level of the softener of rubber in the composition is 5 weight parts～100 weight parts, is preferably 10 weight parts～80 weight parts, more preferably 20～60 weight parts.When the amount of softener of rubber surpasses 100 weight parts, be easy to generate and ooze out, the surface touch variation.
For the hydrogenated block copolymer compositions that contains hydrogenated block copolymer and softener of rubber of the present invention, suggestion is in the determination of viscoelasticity chart that it obtains, and there is 1 in the peak of tan δ (loss tangent) at least in 0 ℃～40 ℃, preferred 5 ℃～35 ℃, more preferably 10 ℃～30 ℃.The peak of this tan δ is based on the hydropolymer B block of random copolymers of conjugated diolefine in the polymer chain of hydrogenated block copolymer and vinyl aromatic compounds and the peak of softener of rubber.Consider that from the wear resistant of hydrogenated copolymer composition and the equilibrated aspect of flexibility this peak needs to exist 1 at least in 0 ℃～40 ℃ scope.In addition, among the present invention, location based on the peak of the tan δ of the aromatic vinyl compound polymer block A in the polymer chain that is combined in hydrogenated copolymer etc. is not particularly limited, surpasses 80 ℃ and smaller or equal in 150 ℃ the temperature range but be present in usually.
Except softener of rubber (composition (2)), hydrogenated block copolymer of the present invention (composition (1)) can further make up the hydrogenated block copolymer compositions that obtains being applicable to various formed materials with at least a kind of composition (the following composition (3) that also these is called) that is selected from the group of being made up of thermoplastic resin and rubbery polymer.With respect to the composition (1) of 100 weight parts, the use level of composition (3) is 5 weight parts～100 weight parts, is preferably 10 weight parts～80 weight parts, more preferably 20 weight parts～60 weight parts.When the amount of composition (3) increased, flexibility descended, transparent variation.
After the thermoplastic resin mixing with hydrogenated block copolymer compositions of the present invention and polypropylene etc., can obtain outstanding compositions such as mechanical characteristics and thermotolerance.
As thermoplastic resin, can enumerate the block copolymerized resin and the hydride (but different) thereof of conjugated diene compound and vinyl aromatic compounds with above-mentioned hydrogenated block copolymer of the present invention; The polymkeric substance of above-mentioned vinyl aromatic compounds; Above-mentioned vinyl aromatic compounds and for example other the copolymer resins of vinyl monomer such as methacrylic esters such as acrylate such as ethene, propylene, butylene, vinylchlorid, vinylidene chloride, vinyl-acetic ester, vinylformic acid and methyl acrylate, methacrylic acid and methyl methacrylate, vinyl cyanide, methacrylonitrile; Rubber-modified styrene resin (HIPS), acrylonitrile-butadiene-styrene (ABS) copolymer resins (ABS); Methacrylic ester-butadiene-styrene copolymer resin (MBS) etc.
In addition, can enumerate polyethylene; The ethene that contains the above ethylidene of 50 weight % with can with other monomeric multipolymers of its copolymerization, for example polythylene resins such as ethylene-propylene copolymer, ethylene-butene copolymer, ethene-hexene copolymer, ethylene-octene copolymer, vinyl-vinyl acetate copolymer and hydrolyzate thereof, ethylene-acrylic acid ionomer and chlorinatedpolyethylene; Polypropylene; The propylene that contains the above propylidene of 50 weight % with can with other monomeric multipolymers of its copolymerization, for example polypropylene-based resins such as propylene-ethylene copolymers, propylene-ethyl acrylate copolymer and Chlorinated Polypropylene III; Cyclic olefin resinoids such as ethylene-norbornene resin; The polybutene resinoid; Polyvinyl chloride resin; Polyvinyl acetate esters resin and hydrolyzate thereof etc.
In addition, also can enumerate the polymkeric substance of vinylformic acid and ester thereof, its acid amides; The polyacrylic ester resinoid; The polymkeric substance of vinyl cyanide and/or methacrylonitrile; The multipolymer of aforesaid propylene nitrile monomer and other copolymerisable monomers, i.e. nitrile resin, it contains the above vinyl cyanide monomer of 50 weight %; Polyamide-based resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, PA-12, nylon-6 PA-12 multipolymer; Polyester resin; The thermoplastic polyurethanes resin; Gather-4,4 '-dihydroxyl phenylbenzene-2, polycarbonate polymers such as 2 '-propane carbonic ether; Thermoplasticity polysulfones such as polyethersulfone and polyene propyl group sulfone; The polyoxyethylene resinoid; Polyphenylene oxide resinoids such as poly-(2,6-dimethyl-1,4-phenylene) ether; Polyphenylene sulfide, poly-4, polyphenylene sulfide resinoids such as 4 '-diphenyl sulfide; The polyacrylic ester resinoid; Polyetherketone polymkeric substance or multipolymer; Polyketone resinoid, fluorine-type resin, poly-(2-hydroxybenzoyl) base polymer; Polyimide based resin; 1, polyhutadiene resinoids such as 2-polyhutadiene, trans polybutadiene etc.
In these thermoplastic resins (composition (3)), particularly preferably be styrene resins such as polystyrene, rubber-modified styrene resin; Polyethylene based polymers such as polyethylene, ethylene-propylene copolymer, ethylene-propylene-butylene copolymer, ethylene-butene copolymer, ethene-hexene copolymer, ethylene-octene copolymer, ethane-acetic acid ethyenyl ester analog copolymer, ethylene-acrylic acid lipin polymer, ethylene-methyl acrylate analog copolymer; Polypropylene-based resin such as polypropylene, propylene-ethylene copolymers; Polyamide-based resin; Polyester resin; The polycarbonate resinoid.The number-average molecular weight of these thermoplastic resins is generally more than 1000, is preferably 5000～5,000,000, and more preferably 10,000～1,000,000.
In addition, hydrogenated block copolymer of the present invention and rubbery polymer can obtain outstanding compositions such as elongation characteristics after mixing.
As rubbery polymer, can enumerate divinyl rubber and hydride thereof; Styrene butadiene rubbers and hydride thereof (but different) with hydrogenated copolymer of the present invention; Synthetic polyisoprene; Acrylonitrile-butadiene rubber and hydride thereof; 1, olefin type elastomers such as 2-polyhutadiene, neoprene, ethylene-propylene rubber, ethylene-propylene-elastoprene (EPDM), ethene-butylene-elastoprene, ethene-butene rubber, ethene-hexene rubber, ethylene-octene rubber; Isoprene-isobutylene rubber; Acrylic rubber; Viton; Silicon rubber; Chlorinated polyethylene rubber etc.
In addition, can also enumerate epichloro hydrin rubber, α, alpha, beta-unsaturated nitriles-acrylate-conjugated diolefine copolymer rubber, urethanes, many sulphur rubbers, styrene-butadiene block copolymer and styrenic elastomerics, natural rubbers etc. such as hydride, styrene-isoprene block copolymer and hydride thereof.
In these rubbery polymers (composition (3)), styrenic elastomericss such as styrene-butadiene block copolymer and hydride thereof, styrene-isoprene block copolymer and hydride thereof preferably; 1,2-polyhutadiene, ethene-butene rubber, ethylene-octene rubber, ethylene-propylene-elastoprene olefin type elastomers such as (EPDM); Isoprene-isobutylene rubber.These rubbery polymers can be the modified rubbers that has functional group.The number-average molecular weight of these rubbery polymers is preferably more than 10,000, and more preferably 20,000～1,000,000, more preferably 30,000～800,000.
In addition, these thermoplastic resins and rubbery polymer can share more than 2 kinds as required.When share, being not particularly limited, can be to share between the thermoplastic resin composition, also can be to share between the rubbery polymer composition, or thermoplastic resin and rubbery polymer share.
In addition, the present invention also provides the hydrogenated block copolymer compositions that contains the above-mentioned hydrogenated block copolymer that the present invention relates to.This hydrogenated block copolymer compositions contains the above-mentioned hydrogenated block copolymer that the present invention relates to (the following composition (a) that also claims), is different from the hydrogenated block copolymer (the following composition (b) that also claims) of composition (a), thermoplastic resin (the following composition (c) that also claims), softener of rubber (the following composition (d) that also claims).
Herein, composition (b) is a hydrogenated block copolymer, it carries out hydrogenation based on the polymer blocks D of vinyl aromatic compounds and at least 1 segmented copolymer based on the polymer blocks E of conjugated diolefine and obtains comprising at least 2, and it has the characteristic of following (7)～(9).
(7) content of the whole vinyl aromatic compounds in the hydrogenated block copolymer is 10 weight %～40 weight %, and all the ratio based on the polymer blocks D of vinyl aromatic compounds is more than the 80 weight % in the vinyl aromatic compounds.
(8) weight-average molecular weight of hydrogenated block copolymer is 200,000～600,000.
(9) two keys of the conjugated diene monomeric unit in the hydrogenated block copolymer is hydrogenated more than 75%.
As composition (b), for example preferably has hydrogenated block copolymer with the structure of following general formula.
D-(E-D)
n、E-(D-E)
n、(D-E)
m、(D-E)
m-X
In the following formula, D is the polymer blocks based on vinyl aromatic compounds, and E is the polymer blocks based on conjugated diene compound.In addition, n represents 2～10 integer, and m represents 2～8 integer, and X represents the residue of coupler or the residue of multifunctional initiator, and composition (b) can be the material with single structure, also can be the mixture of the different material of the different material of structure, hydrogenation ratio.
In the hydrogenated block copolymer of composition (b), " for main body " this phraseology is meant that corresponding monomer accounts for more than 50% at least, preferably accounts for more than 70%.
In the hydrogenated block copolymer of composition (b), all the content of vinyl aromatic compounds is 10 weight %～40 weight %, is preferably 24 weight %～36 weight %.The material of the content that uses whole vinyl aromatic compounds in the scope of the present invention's regulation for obtain flexibility, the good material of thermotolerance is necessary.
In addition, from obtaining the angle of the good material of physical strength, in the hydrogenated block copolymer of composition (b), all the ratio based on the polymer blocks D of vinyl aromatic compounds is more than the 80 weight % in the vinyl aromatic compounds, be preferably more than the 85 weight %, more preferably more than the 90 weight %.
In the hydrogenated block copolymer of composition (b), based on the polymer blocks D of vinyl aromatic compounds with based on the distribution of the conjugated diene compound in the molecular chain of polymer blocks E in polymer blocks separately of conjugated diene compound or its hydride or its hydride and vinyl aromatic compounds can be random distribution, also can be scattered in taper (monomer component increases or reduces along molecular chain), part block-wise or these combination arbitrarily, have separately under the situation more than 2 based on the polymer blocks D of this vinyl aromatic compounds with based on the polymer blocks E of conjugated diene compound or its hydride, each polymer blocks can be respectively identical structure, also can be different structures.
As the vinyl aromatic compounds of the hydrogenated block copolymer of constituent (b), can be from vinylbenzene for example, alpha-methyl styrene, Vinyl toluene, select more than a kind to the t-butyl styrene etc., optimization styrene wherein.In addition, as conjugated diene compound, can be from for example divinyl, isoprene, 1,3-pentadiene, 2, select more than a kind wherein preferred divinyl, isoprene and their combination in 3-dimethyl-1,3 divinyl etc.And, can at random select microstructure in its block based on the polymer blocks B of conjugated diene compound or its hydride, for example, under the situation of the polybutadiene block before hydrogenation, aspect from flexibility and tenderizer confining force, 1,2-vinyl binding capacity is 25 weight %～55 weight %, is preferably 30 weight %～50 weight %.
From the angle of thermotolerance, physical strength, oil absorbency, the polystyrene conversion value of the weight-average molecular weight of the hydrogenated block copolymer of composition (b) is 200,000～600,000, is preferably 220,000～500,000.Molecular weight distribution is below 5, is generally 1～4, is preferably 1～3.
When the hydrogenated block copolymer of composition (b) has said structure, its manufacture view is not particularly limited, for example can be according to the method for the public clear 40-23798 communique record of spy, with lithium catalyst synthesis of vinyl aromatics-conjugated diene compound segmented copolymer in inert solvent.In addition, manufacture method as the conjugated diene compound segmented copolymer of the vinyl aromatic compounds-hydrogenation of the better performance of performance, can adopt the method for for example special public clear 42-8704 communique, special public clear 43-6636 communique record, but, for the weathering resistance of special requirement height and the purposes of heat-resistant aging, the titanium type hydrogenation catalyst is used in suggestion, and can enumerate for example special method that clear 59-133203 communique, spy are opened clear 60-79005 communique of opening.Derive from this moment in the aliphatic double bonds of conjugated diene compound more than 75%, preferred more than 80%, more preferably more than 90% by hydrogenation, and the big polymorphic up conversion of conjugated diene compound is the alkene compound.For example, the butadiene polymer block is to the polymer blocks conversion based on ethene-butylene.
In addition, in the hydrogenated block copolymer of composition (b), to being not particularly limited based on the polymer blocks D of vinyl aromatic compounds with based on the hydrogenation ratio of the two keys of aromatic series of the vinyl aromatic compounds on the polymer blocks E of conjugated diene compound or its hydride from copolymerization as required, but this hydrogenation ratio is preferably below 20%.
Secondly, the thermoplastic resin of composition (c) is not particularly limited,, can enumerates following resin as the example.
As the thermoplastic resin of composition (c), the example comprises the block copolymerized resin and the hydride (but different with above-mentioned composition (a) that the present invention relates to and hydrogenated block copolymer (b)) thereof of conjugated diene compound and vinyl aromatic compounds; The polymkeric substance of above-mentioned vinyl aromatic compounds; Above-mentioned vinyl aromatic compounds and for example copolymer resins of other vinyl monomers such as methacrylic esters such as acrylate such as ethene, propylene, butylene, vinylchlorid, vinylidene chloride, vinyl-acetic ester, vinylformic acid and methyl acrylate, methacrylic acid and methyl methacrylate, vinyl cyanide, methacrylonitrile; Rubber-modified styrene resin (HIPS); Acrylonitrile-butadiene-styrene (ABS) copolymer resins (ABS); Methacrylic ester-butadiene-styrene copolymer resin (MBS); Polyethylene; The ethene that contains the above ethylidene of 50 weight % with can with other monomeric multipolymers of its copolymerization, for example polythylene resins such as ethylene-propylene copolymer, ethylene-butene copolymer, ethene-hexene copolymer, ethylene-octene copolymer, vinyl-vinyl acetate copolymer and hydrolyzate thereof, ethylene-acrylic acid ionomer and chlorinatedpolyethylene; Polypropylene; The propylene that contains the above propylidene of 50 weight % with can with other monomeric multipolymers of its copolymerization, for example polypropylene-based resins such as propylene-ethylene copolymers, propylene-ethyl acrylate copolymer and Chlorinated Polypropylene III; Cyclic olefin resinoids such as ethylene-norbornene resin; The polybutene resinoid; Polyvinyl chloride resin; Polyvinyl acetate esters resin and hydrolyzate thereof; The polymkeric substance of vinylformic acid and ester thereof and acid amides; The polyacrylic ester resinoid; The polymkeric substance of vinyl cyanide and/or methacrylonitrile; But the monomeric multipolymer of aforesaid propylene nitrile monomer and other copolymerization, i.e. nitrile resin, it contains the above vinyl cyanide monomer of 50 weight; Polyamide-based resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, PA-12, nylon-6 PA-12 multipolymer; Polyester resin; The thermoplastic polyurethanes resin; Poly--4,4 ' dihydroxyl phenylbenzene-2, polycarbonate polymers such as 2 '-propane carbonic ether; Thermoplasticity polysulfones such as polyethersulfone or polyene propyl group sulfone; The polyoxyethylene resinoid; Polyphenylene oxide resinoids such as poly-(2,6-dimethyl-1,4-phenylene) ether; Polyphenylene sulfide, poly-4, polyphenylene sulfide resinoids such as 4 '-diphenyl sulfide; The polyacrylic ester resinoid; Polyetherketone polymkeric substance or multipolymer; The polyketone resinoid; Fluorine-type resin; Poly-(2-hydroxybenzoyl) base polymer; Polyimide based resin; 1, polyhutadiene resinoids such as 2-polyhutadiene, trans polybutadiene etc.
The number-average molecular weight of these thermoplastic resins is generally more than 1000, is preferably 5000～5,000,000, and more preferably 10,000～1,000,000.Thermoplastic resin as composition (c), the olefine kind resin (polyolefin resin) of styrene resin, vinyl and propylene class preferably, angle from thermotolerance, physical strength, flowability (forming process), versatility, more preferably olefine kind resin particularly preferably is propylene resin.
About use level as the thermoplastic resin of composition (c), with respect to the hydrogenated block copolymer of the mentioned component (a) that adds up to 100 weight parts and the hydrogenated block copolymer of mentioned component (b), (c) composition is 20 weight parts～200 weight parts, be preferably 25 weight parts～150 weight parts, more preferably 30 weight parts～100 weight parts.Though also relevant with the rigidity and the hardness of purpose composition, when the use level of composition (c) was less than 20 weight parts, the thermotolerance of the composition that obtains and flowability (forming process) descended, and be therefore not preferred.On the other hand, the use level of composition (c) is during greater than 200 weight parts, and the flexibility of the composition that obtains and wear resistant descend, and be therefore not preferred.In addition, these compositions (c) thermoplastic resin also can share two or more as required.
Moreover mentioned component (a) and composition (b) proportioning in adding up to 100 weight parts is for example following: composition (a) is 10 weight %～90 weight %, and composition (b) is 90 weight %～10 weight %.
The softener of rubber of composition (d) makes the composition softish that obtains give composition mobile property (forming process) simultaneously.As the softener of rubber of composition (d), can enumerate mineral oil and aqueous or low-molecular-weight synthetic tenderizer, the processing oil or the extending oil of especially preferred naphthalene class and/or paraffin class.The mineral oils softener of rubber is the mixture of aromatic ring, naphthalene nucleus and paraffin chain, what the carbonatoms of paraffin chain accounted for whole carbon atoms is called paraffin class more than 50%, the carbonatoms of naphthalene nucleus account for 30%～45% be called the naphthalene class, the aromatic series carbonatoms surpasses 30% the fragrant same clan that is called.Composition of the present invention can use synthetic tenderizer, also can use polybutene, low molecular weight polybutadiene, whiteruss etc., and preferred above-mentioned mineral oils softener of rubber.In the thermotolerance of special requirement height, the situation of mechanical properties, the kinematic viscosity of mineral oils softener of rubber under 40 ℃ is preferably more than the 60cst, more than 120cst.
With respect to the mentioned component (a) and the mentioned component (b) that add up to 100 weight parts, the use level of the softener of rubber of composition (d) is 20 weight parts～250 weight parts, is preferably 30 weight parts～230 weight parts, more preferably 40 weight parts～200 weight parts.Though also relevant with flowability (forming process) with the hardness of purpose composition, when the use level of composition (d) was less than 20 weight parts, the flowability of the composition that obtains (formability) descended, and is therefore not preferred.Conversely, when the use level of composition (d) during greater than 250 weight parts, the composition that obtains descends aspect wear resistant and the adhesion sense appears in the surface touch aspect, and is therefore not preferred.And these softener of rubber can share two or more as required.
Further in composition of the present invention, add organopolysiloxane, can obtain the higher composition of wear resistant.Organopolysiloxane is outstanding to the surfaction effect of the composition that obtains, is used as wear resistant and improves auxiliary agent.The form of organopolysiloxane comprises low viscous liquid state, full-bodied liquid state, solid-state, but its form is not particularly limited, and from the viewpoint to the dispersiveness of composition, preferred liquid object is so-called silicone oil.In addition, from the angle by the surface touch of oozing out generation of polysiloxane self, preferred movement viscosity is more than the 90cst, and more preferably kinematic viscosity is more than the 1000cst.Kind as organopolysiloxane, comprise general silicone oil such as dimethyl polysiloxane (polydimethylsiloxane), methyl phenyl silicone and alkyl-modified, polyether-modified, fluorine modification, pure modification, various modified silicon oils such as amino modified, epoxide modified, and be not particularly limited, but, from improve the angle of the effect of auxiliary agent as wear resistant, wherein particularly preferably be dimethyl polysiloxane.With respect to the mentioned component (a) and (b) that add up to 100 weight parts, (c) and (d), the addition of organopolysiloxane is in the scope of 0.1 weight part～10 weight parts, particularly from upgrading effect and the angle of oozing out, the addition of organopolysiloxane is 0.2 weight part～7 weight parts preferably.In addition, these organopolysiloxanes can share two or more as required.
Angle from shaping processability, containing mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d) melt flow rate (MFR) (MFR) under 230 ℃, 2.16kg is preferably 0.1g/10 minute～100g/10 minute, more preferably 0.1g/10 minute～75g/10 minute, be preferably 0.1g/10 minute especially～30g/10 minute.
In addition, hydrogenated block copolymer compositions of the present invention is below 40%, to be preferably below 35% 23 ℃ rebound resilience.
The composition of hydrogenated block copolymer of the present invention, this hydrogenated block copolymer or contain mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d) and can cooperate additive arbitrarily as required.Kind to additive is not particularly limited, and gets final product so long as be generally used for the additive of thermoplastic resin and rubbery polymer.
For example, can enumerate the pigment and the tinting material of carbon black, titanium oxide etc.; Lubricants such as stearic acid, mountain Yu acid, Zinic stearas, calcium stearate, Magnesium Stearate, ethylenebisstearamide; Release agent; Fatty acid esters such as phthalic acid ester class and adipic acid ester compound, azelate compound; Mineral wet goods softening agent; Antioxidant such as hindered phenolic antioxidants, Phosphorus thermo-stabilizer; Steric hindrance amine photostabilizer; The benzotriazole category UV light absorber; Antistatic agent; Stiffenerss such as organic fibre, glass fibre, carbon fiber, whisker crystalline substance; Other additives or their mixture etc.
Can in hydrogenated block copolymer compositions of the present invention, cooperate weighting agent and fire retardant arbitrarily as required.Weighting agent and fire retardant are not particularly limited, get final product so long as be generally used for the material of thermoplastic resin and rubbery polymer.
As weighting agent, can enumerate for example inorganic fillers such as silica, lime carbonate, magnesiumcarbonate, magnesium hydroxide, aluminium hydroxide, calcium sulfate, barium sulfate, carbon black, glass fibre, granulated glass sphere, glass hollow ball, glass flake, graphite, titanium oxide, potassium titanate palpus crystalline substance, carbon fiber, aluminum oxide, kaolin, silicic acid, Calucium Silicate powder, quartz, mica, talcum, clay, zirconium white, potassium titanate, aluminum oxide, metallics; Organic fillers such as wood chip, wood powder, paper pulp.Shape is not particularly limited, and can be flakey, spherical, granular, powder, indefinite shape.These weighting agents may be used singly or in combination of two or more use.
Secondly, as fire retardant, can enumerate halogen based on bromine compounds, based on aromatics Phosphorus, based on the fire retardant of the mineral-type of metal hydroxides etc., but because environmental problem in recent years etc., inorganic combustion inhibitor becomes main flow, so preferred inorganic combustion inhibitor.As inorganic combustion inhibitor, can enumerate for example metal hydroxidess such as magnesium hydroxide, aluminium hydroxide, calcium hydroxide; Metal oxide such as zinc borate, barium borate; Other lime carbonate, clay, alkaline magnesium carbonate, hydrotalcite etc.; Main hydrogenous metallic compound etc.Among the present invention, from improving the angle of flame retardant resistance, metal hydroxides such as preferred magnesium hydroxide in the above-mentioned fire retardant.In addition, in the above-mentioned fire retardant, also can contain so-called flame retardant, himself flame retardant effect is low, when share with other fire retardants, and the effect that collaborative performance is more excellent.
Weighting agent, fire retardant can also use weighting agent, the fire retardant that has carried out the surface-treated type through surface treatment agents such as silane coupling agents in advance.
In addition, these weighting agents, fire retardant can share two or more as required.Being not particularly limited when share, can be to share between the weighting agent composition, also share between the fire retardant, and also weighting agent and fire retardant share.
The composition of hydrogenated block copolymer of the present invention, this hydrogenated block copolymer or contain in mentioned component (a) and (b), (c) and the hydrogenated block copolymer compositions (d) also can add other additive or their mixture etc. of record in " rubber plastic compounding chemicals " (ラ バ one ダ イ ジ エ ス ト society volume) etc. as required.
As required, the composition of hydrogenated block copolymer of the present invention, this hydrogenated block copolymer or contain mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d) and can take place crosslinked.Crosslinked method can be enumerated the chemical process by the co-crosslinker that adds linking agent such as superoxide, sulphur and use as required etc.; Radiation crosslinking etc.As crosslinking process, can enumerate static method, dynamic vulcanization process etc.
As linking agent, can enumerate organo-peroxide, sulphur, phenols, isocyanates, thiurams, morpholine disulphide etc., these can share with crosslinking coagents such as stearic acid, oleic acid, Zinic stearas, zinc oxide, co-crosslinker, sulphurized catalyst etc.As the organo-peroxide linking agent, can enumerate hydrogen peroxide, dialkyl peroxide, diallyl superoxide, diacyl peroxide, peroxy esters, ketone peroxide etc.Can also adopt the physical crosslinking method of utilizing electron beam, radiation etc.
The composition of this hydrogenated block copolymer of the present invention or the manufacture method that contains mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d) are not particularly limited, can adopt known method.Can adopt and use Banbury mixing tank for example, single screw extrusion machine, twin screw extruder, common mixing machine such as kneader (co-kneader), multiple screw extruder dissolves compounding process altogether; After each composition dissolving or dispersing and mixing, add the method for heat extraction solvent etc.Among the present invention,, preferably utilize the hybrid system that dissolves of forcing machine from productivity, the good angle of mixing property.Shape to the hydrogenated copolymer composition that obtains is not particularly limited, and can enumerate particulate state, sheet, strand form, shred etc.In addition, can also directly make the moulding product after mixing dissolving.
Obtain the composition of hydrogenated block copolymer of the present invention, this hydrogenated block copolymer or contain under the situation of expanded moldings of mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d), can be used for method of the present invention and comprise chemical process, physical method etc., separately by adding chemical foaming agents such as mineral-type whipping agent, organic class whipping agent; Whipping agents such as pneumatogen make material internal distribution bubble.By making foam material, can seek lightweight, improve flexibility, improve appearance design etc.As the mineral-type whipping agent, can enumerate sodium bicarbonate, volatile salt, bicarbonate of ammonia, ammonium nitrite, acidic cpd, sodium borohydride, metal powder etc.
As organic class whipping agent, can enumerate Cellmic C 121, azobisformamide ABFA, azobis isobutyronitrile, barium azodicarboxylate, N, N '-dinitrosopentamethylene tetramine, N, N '-dinitroso-N, N '-dimethyl terephthalamide, benzol sulfohydrazide, p-toluene sulfonyl hydrazide, p, the two benzol sulfohydrazides of p '-hydroxyl, p-toluene sulfonylsemicarbazide etc.
As pneumatogen, can enumerate hydrocarbon such as pentane, butane, hexane; Halohydrocarbon such as chloromethane, methylene dichloride; Gas such as nitrogen, air; Fluorinated hydrocarbons such as trichlorofluoromethane, Refrigerant 12, Refrigerant R 113, chlorine C2H4F2 C2H4F2, hydrogen fluorohydrocarbon etc.
The composition of hydrogenated block copolymer of the present invention, this hydrogenated block copolymer or the formed body that contains mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d) can print, cover with paint, lacquer, colour wash, etc., squeeze wrinkle etc. as required to be decorated etc. on the formed body surface, to improve aesthetic appearance, weathering resistance, scratch resistance etc.When carrying out surface treatment for improving printing, covering with paint property etc., the surface-treated method is not particularly limited, physical method, chemical process etc. be can use, Corona discharge Treatment, ozonize, Cement Composite Treated by Plasma, flame treating, acid-alkali processing etc. for example can be enumerated.Wherein, from difficulty, the cost implemented, can handle equal angles continuously, preferred Corona discharge Treatment.
The composition of hydrogenated block copolymer of the present invention, this hydrogenated block copolymer or contain mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d) and can after adding various additives as required, be used for various purposes.Concrete form about hydrogenated copolymer of the present invention and hydrogenated copolymer composition can be suitable for i) add solidity filling agent title complex, (ii) cross-linking agent, (iii) foam, (iv) moulding such as multilayer film and multilayer tablet product, (v) material of construction, (vi) damping-soundproof material, (vii) wire coating material, (the viii) molten viscous composition of high frequency, (ix) slush moulding (slush moulding) material, (x) tackiness composition, (xi) bituminous composition, (xii) medical instruments material, (xiii) automotive material etc.
As mentioned above, the composition of hydrogenated block copolymer of the present invention, this hydrogenated block copolymer or contain mentioned component (a) and (b), (c) and hydrogenated block copolymer compositions (d) and can be used for various purposes, when making the use of moulding product, as forming method, can enumerate extrusion moulding, injection molding, slush molding, the empty moulding of pressure, vacuum forming, foaming, resettable layer extrusion moulding, resettable layer injection molding, molten type, slush moulding and the calendering formation etc. of sticking into of high frequency.As the example of moulding product, can enumerate sheet, film, pipe, non-woven fabrics and fibrous moulding product; Synthetic leather etc.The moulding product that formed by hydrogenated copolymer of the present invention and hydrogenated copolymer composition can be used for packaging material for food; The medical instruments material; Household appliances and parts thereof; Electronics and parts thereof; Trolley part; Industrial part; Raw material such as houseware, toy; The footwear raw material; Fibrous material; Adhesion-tackiness agent raw material; Asphalt modifier agent etc.As the object lesson of trolley part, that can enumerate side filler rod (side mall), oil seal ring (grommet), knob, panel strip, window frame and sealing member thereof, handrail, door knob, steering wheel, little thing box, headrest, dashboard, snubber, spoiler, airbag unit takes in lid etc.As the object lesson of medical instruments, can enumerate blood bag, blood platelet storage bag, transfusion (soup) bag, hemodialysis's usefulness bag, medical pipe, conduit etc.Can be used for other industrial or food with flexible pipe, dust collector hose, electric cold filling, electric wire and other various covering materials, handle with covering material, soft image etc., tacky adhesion adhesive tape-sheet-film base material, surface protection film base material and this film with tacky adhesion, blanket with tacky adhesion, packaging stretched film, heat-shrinkable film, lining steel pipe with covering material, sealing agent etc.
Embodiment
Specifically describe the present invention according to following examples, but the present invention is not subjected to the qualification of these examples.
In addition, in the following examples, the characteristic of polymkeric substance and the mensuration of rerum natura are following carrying out.
I. the preparation of hydrogenated block copolymer and characteristic
I-1) styrene content of hydrogenated block copolymer
(Shimadzu Seisakusho Ltd. produces, and UV-2450) multipolymer before the hydrogenation is measured with ultraviolet spectrophotometer.
I-2) the polystyrene block A content of hydrogenated block copolymer
With I.M.Kolthoff, et al., J.Polym.Sci.1, the multipolymer of the perosmic anhydride acid systems of record before to hydrogenation measured in 429 (1946).0.1g/125ml osmic acid t-butanol solution is used in the decomposition of multipolymer.
I-3) the vinyl binding capacity of hydrogenated block copolymer
(Japanese beam split company produces, and FT/IR-230) multipolymer before the hydrogenation is measured with infrared spectrophotometer.The vinyl binding capacity of multipolymer is calculated according to the Hampton method.
I-4) molecular weight of hydrogenated block copolymer and molecular weight distribution
Produce by Waters with the GPC[device] measure.Solvent uses tetrahydrofuran (THF), is that 35 ℃ condition determination is measured in temperature.The typical curve that utilizes the known commercially available polystyrene standard of weight-average molecular weight and number-average molecular weight to make adopts this typical curve to calculate weight-average molecular weight.In addition, molecular weight distribution is the ratio of weight-average molecular weight (Mw/Mn) and number-average molecular weight (Mn).
I-5) hydrogenation ratio of two keys of the conjugated diene monomeric unit of hydrogenated block copolymer (hydrogenation rate)
Use nuclear magnetic resonance device (BRUKER society produces for device name: DPX-400, Germany) that the hydrogenated copolymer after the hydrogenation is measured.
I-6) crystallization peak and crystallization peak heat
Produce DSC3200S with DSC[MAC Science society] measure.Be warmed up to 150 ℃ from room temperature with 30 ℃/minute heat-up rate, after this, cool to-100 ℃, measure the crystallization curve, confirm to have or not the crystallization peak with 10 ℃/minute cooling rates.In addition, when having the crystallization peak, be the crystallization peak temperature with the temperature that peak value occurs, measure crystallization peak heat.
I-7) peak temperature of tan δ (loss tangent)
Measure the visco-elasticity spectrum with determination of viscoelasticity analytical equipment ((strain) Rheology company produces, model DVE-V4), obtain the peak temperature of tan δ (loss tangent).Measuring frequency is 10Hz.
II. the characteristic of hydrogenated block copolymer compositions
II-1) flexibility
Measure tensile properties according to JIS K6251.The index of flexibility is 100% stress (below be called 100%Mo) when stretching.100%Mo is more little, and then flexibility is good more.When measuring, draw speed is 500mm/min, and measuring temperature is 23 ℃.
II-2) thermotolerance
Carry out permanent compression test according to JIS K6262.Condition determination is 70 ℃ of temperature, 22 hours.
II-3) wear resistant
Use and learn (the テ ス タ one Industry Co., Ltd production of vibration shape friction tester, the AB-301 type), under the condition of load 500g, matrix band surface (rhicnosis machined surface) rubbed,, pass judgment on following standard according to the volume reduction after the friction with No. 3 cottons of friction cloth カ Na キ Application.
◎: rub after 10000 times, the volume reduction is below the 0.01ml
Zero: rub after 10000 times, the volume reduction is greater than 0.01ml, but below 0.1ml
△: rub after 10000 times, the volume reduction is greater than 0.1ml, but below 0.2ml
*: rub after 10000 times, the volume reduction is greater than 0.2ml
II-4) processibility＜melt flow rate (MFR) (MFR) 〉
According to JIS K6758, measure 230 ℃, the melt flow rate (MFR) of load under the 2.16kg.
II-5) surface touch
Make the thick stamping of 2mm, estimate with following method.
Adhesion sense:, confirm to have or not to be clamminess with the finger contactor segment.
Oil impregnate: between sheet, sandwich paper, after 24 hours, confirm to have or not the transfer of oil to paper.
III. the rerum natura that contains the composition of composition (a) and (b), (c), (d)
III-1) flowability＜melt flow rate (MFR) (MFR) 〉
According to JIS K6758, measure 230 ℃, the MFR of load under the 2.16kg.
III-2) hardness
According to JIS K6253, with the fixed value after 10 seconds of A type hardness tester instrumentation.
III-3) extensibility when tensile stress, tensile strength, fracture
According to JIS K6251, measure with No. 3 dumbbells, 500mm/ minute conditions of pinblock speed.
III-4) Deng Luopu (Dunlop) rebound resilience
According to BS903, measure at 23 ℃.
III-5) wear resistant 1 (mensuration of the remaining rate of the wrinkle degree of depth)
Use and learn (the テ ス タ one Industry Co., Ltd production of vibration shape friction tester, the AB-301 type), after with friction cloth カ Na キ Application No. 3 cottons matrix band surface (rhicnosis machined surface/wrinkle is about 90 μ m deeply) being rubbed under the condition of load 500g, measure the wrinkle degree of depth, according to the remaining rate of the wrinkle degree of depth (calculating), pass judgment on following standard by following formula 1.The wrinkle degree of depth is measured with the surface roughness meter E-35A that the accurate society in Tokyo produces.
Remaining rate=(the wrinkle degree of depth after the friction) of the wrinkle degree of depth/(the wrinkle degree of depth before the friction) * 100 (formulas 1)
◎: rub after 20000 times, the remaining rate of the wrinkle degree of depth is more than 75%
Zero: rub after 20000 times, the remaining rate of the wrinkle degree of depth is less than 75%, but more than 50%
△: rub after 20000 times, the remaining rate of the wrinkle degree of depth is less than 50%, but more than 25%
*: rub after 20000 times, the remaining rate of the wrinkle degree of depth is less than 25%
III-6) wear resistant 2 (friction rear surface state)
With the above-mentioned III-5 of finger contact) the test of vibration consumption after the sheet surface, confirm to have or not adhesion sense (being clamminess), and pass judgment on by following standard.
Zero: friction finishes the back nothing and is clamminess
*: have after friction finishes and be clamminess
III-7) surface touch
Make the thick stamping of 2mm,, confirm to have or not adhesion sense (being clamminess), and pass judgment on following standard with finger contactor segment surface.
Zero: sheet surface nothing is clamminess
*: the sheet surface has is clamminess
III-8) oil absorbency
Make the thick stamping of 2mm, with sheet in paraffin oil (productions of emerging products of PW-90/ bright dipping society) in 70 ℃ of immersions 30 days, mensuration is passed judgment on following standard with respect to the weight of the oil that sheet absorbed of 100 weight parts.
Zero: the oil of absorption is more than 100 weight parts
*: the oil of absorption is less than 100 weight parts
In addition, each composition of cooperation is as follows.
The preparation of＜hydrogenation catalyst 〉
In following embodiment and the comparative example, the hydrogenation catalyst that uses in the hydrogenation of multipolymer is prepared with following method.
In nitrogen metathetical reaction vessel, add 1 liter of drying, purified hexanaphthene, and add two (the η 5-cyclopentadienyl) titanium dichloride of 100 mmoles, fully stir down, add the hexane solution that contains 200 mmole trimethyl aluminiums, it was reacted about 3 days.
[preparation of hydrogenated block copolymer]
＜polymkeric substance 1 〉
Use band whipping appts and the telescopic groove type reactor of internal volume 10L to carry out batchwise polymerization.At first, drop into the cyclohexane solution (concentration 20 weight %) that contains 15 parts by weight of styrene.Then, add the n-Butyl Lithium of 0.06 weight part, and add 0.7 mole of N with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts, N, N ', N '-Tetramethyl Ethylene Diamine (to call TMEDA in the following text) was 70 ℃ of polymerizations 1 hour.Add the cyclohexane solution (concentration be 20 weight %s) that contain 20 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 50%.Then, add the cyclohexane solution (concentration is 20 weight %) that contains 14 weight parts of butadiene and 42 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.Measure the vinyl binding capacity of the polymkeric substance of sampling this moment, this value is 36%.At last, drop into the cyclohexane solution that contains 9 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 66 weight %, and polystyrene block content is 30 weight %, and the vinyl binding capacity of polybutadiene block part is 50 weight %, and molecular weight is 18.8 ten thousand, and molecular weight distribution is 1.1.
Then, in the polymkeric substance that obtains,, add the above-mentioned hydrogenation catalyst of 100ppm, under the condition of 65 ℃ of hydrogen pressure 0.7MPa, temperature, carry out hydrogenation in titanium with respect to per 100 parts by weight polymer., add methyl alcohol,, add 0.3 mass parts octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester as stablizer then with respect to 100 mass parts polymkeric substance thereafter.
The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 1) is 98%.The characteristic of the hydrogenated copolymer that obtains sees Table-1.
In addition, measure the DSC of the hydrogenated copolymer that obtains, find not exist the crystallization peak.
＜polymkeric substance 2 〉
Similarly make polymkeric substance with polymkeric substance 1.After input contains the cyclohexane solution of 17 parts by weight of styrene, add 0.05 weight part n-Butyl Lithium, and add 0.65 mole of TMEDA, 70 ℃ of polymerizations 1 hour with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts.Add the cyclohexane solution that contain 20 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 39%.Then, add the cyclohexane solution that contains 12 weight parts of butadiene and 40 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.At last, drop into the cyclohexane solution that contains 11 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 68 weight %, and polystyrene block content is 34 weight %, and the vinyl binding capacity of polybutadiene block part is 39 weight %, and molecular weight is 22.2 ten thousand, and molecular weight distribution is 1.1.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 2).
The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 2) is 98%.
＜polymkeric substance 3 〉
Similarly make polymkeric substance with polymkeric substance 1.After input contains the cyclohexane solution of 20 parts by weight of styrene, add 0.06 weight part n-Butyl Lithium, and add 0.7 mole of TMEDA, 70 ℃ of polymerizations 1 hour with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts.Add the cyclohexane solution that contain 15 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 53%.Then, add the cyclohexane solution that contains 15 weight parts of butadiene and 35 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.At last, drop into the cyclohexane solution that contains 15 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 70 weight %, and polystyrene block content is 40 weight %, and the vinyl binding capacity of polybutadiene block part is 53 weight %, and molecular weight is 19.2 ten thousand, and molecular weight distribution is 1.1.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 3).The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 3) is 99%.
＜polymkeric substance 4 〉
Similarly make polymkeric substance with polymkeric substance 1.After input contains the cyclohexane solution of 17 parts by weight of styrene, add 0.05 weight part n-Butyl Lithium, and add 0.7 mole of TMEDA, 70 ℃ of polymerizations 1 hour with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts.Add the cyclohexane solution that contain 30 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 48%.Then, add the cyclohexane solution that contains 12 weight parts of butadiene and 28 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.Measure the vinyl binding capacity of the polymkeric substance of sampling this moment, this value is 39%.At last, drop into the cyclohexane solution that contains 13 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 58 weight %, and polystyrene block content is 34 weight %, and the vinyl binding capacity of polybutadiene block part is 48 weight %, and molecular weight is 22.4 ten thousand, and molecular weight distribution is 1.1.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 4).The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 4) is 99%.
＜polymkeric substance 5 〉
Use band whipping appts and the telescopic groove type reactor of internal volume 10L to carry out batchwise polymerization.At first, drop into the cyclohexane solution (concentration is 20 weight %) that contains 15 parts by weight of styrene.Then, add the n-Butyl Lithium of 0.04 weight part, and add 0.7 mole of TMEDA, 70 ℃ of polymerizations 1 hour with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts.Add the cyclohexane solution (concentration be 20 weight %s) that contain 20 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 50%.Then, add the cyclohexane solution (concentration is 20 weight %) that contains 15 weight parts of butadiene and 41 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.Measure the vinyl binding capacity of the polymkeric substance of sampling this moment, this value is 36%.At last, drop into the cyclohexane solution that contains 9 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.
In the polymkeric substance that obtains, styrene content is 65 weight %, and polystyrene block content is 26 weight %, and the vinyl binding capacity of polybutadiene block part is 49 weight %, and weight-average molecular weight is 25.0 ten thousand, and molecular weight distribution is 1.2.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated block copolymer (polymkeric substance 5).The hydrogenation ratio of the hydrogenated block copolymer that obtains is 99%.In addition, measure the DSC of the hydrogenated block copolymer that obtains, and do not find to exist the crystallization peak value.
＜polymkeric substance 6 〉
Use band whipping appts and the telescopic groove type reactor of 2 internal volume 10L to carry out successive polymerization.Supplying with butadiene concentration from the bottom of first reactor with 4.51L/ hour feeding speed is the cyclohexane solution of 24 weight %, supplying with concentration of styrene with 5.97L/ hour feeding speed is the cyclohexane solution of 24 weight %, and supply with n-Butyl Lithium concentration is adjusted into 0.077g with respect to the 100g monomer cyclohexane solution with 2.0L/ hour feeding speed, and the speed of further supplying with the cyclohexane solution of 0.44 mole of TMEDA with relative 1 mole of n-Butyl Lithium supplies with the cyclohexane solution of TMEDA, carries out successive polymerization at 90 ℃.Temperature of reaction is regulated with bushing temperature, and near the temperature the bottom of reactor is about 88 ℃, and near the temperature the reactor top is about 90 ℃.Average retention time in polymerization reactor is about 45 minutes, and the transformation efficiency of divinyl is approximately 100%, and cinnamic transformation efficiency is 99%.
From the polymers soln that the bottom supply of second reactor is come out from first reactor, simultaneously, supplying with concentration of styrene with 2.38L/ hour feeding speed to the bottom of second reactor is the cyclohexane solution of 24 weight %, carries out successive polymerization at 90 ℃.In the exit of second reactor, cinnamic transformation efficiency is 98%.
The polymkeric substance that obtains with successive polymerization is analyzed, and wherein, styrene content is 67 weight %, polystyrene block content is 20 weight %, the vinyl binding capacity of the divinyl part of random block part is 14 weight %, and weight-average molecular weight is 200,000, and molecular weight distribution is 1.9.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 6).The hydrogenation ratio of the hydrogenated copolymer that obtains is 99%.
＜polymkeric substance 7 〉
Use band whipping appts and the telescopic groove type reactor of internal volume 10L to carry out batchwise polymerization.At first, drop into the cyclohexane solution (concentration is 20 weight %) that contains 16 parts by weight of styrene.Then, add the n-Butyl Lithium of 0.058 weight part, and add 0.7 mole of N with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts, N, N ', N '-Tetramethyl Ethylene Diamine (to call TMEDA in the following text) was 70 ℃ of polymerizations 1 hour.Add the cyclohexane solution (concentration be 20 weight %s) that contain 20 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 50%.Then, add the cyclohexane solution (concentration is 20 weight %) that contains 14 weight parts of butadiene and 42 parts by weight of styrene, 30 ℃ of polymerizations 1 hour.At last, drop into the cyclohexane solution that contains 10 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 68 weight %, and polystyrene block content is 30 weight %, and the vinyl binding capacity of polybutadiene block part is 45 weight %, and molecular weight is 21.5 ten thousand, and molecular weight distribution is 1.1.Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated block copolymer (polymkeric substance 7).The hydrogenation ratio of the hydrogenated block copolymer that obtains is 98%.
＜polymkeric substance 8 〉
Similarly make polymkeric substance with polymkeric substance 1.At first, drop into contain the cyclohexane solution of 15 parts by weight of styrene after, add 0.06 weight part n-Butyl Lithium with respect to whole monomers of 100 weight parts, and add 0.07 mole of TMEDA, 70 ℃ of polymerizations 1 hour with respect to 1 mole of n-Butyl Lithium.Add the cyclohexane solution that contain 6 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Then, add the cyclohexane solution that contains 27 weight parts of butadiene and 43 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.At last, drop into the cyclohexane solution that contains 9 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 67 weight %, and polystyrene block content is 30 weight %, and the vinyl binding capacity of polybutadiene block part is 49 weight %, and molecular weight is 19.2 ten thousand, and molecular weight distribution is 1.1.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 8).
The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 8) is 99%.
＜polymkeric substance 9 〉
Similarly make polymkeric substance with polymkeric substance 1.After input contains the cyclohexane solution of 14 parts by weight of styrene, add 0.065 weight part n-Butyl Lithium, and add 0.65 mole of TMEDA, 70 ℃ of polymerizations 1 hour with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts.Add the cyclohexane solution that contain 40 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 39%.Then, add the cyclohexane solution that contains 9 weight parts of butadiene and 29 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.At last, drop into the cyclohexane solution that contains 9 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 52 weight %, and polystyrene block content is 26 weight %, and the vinyl binding capacity of polybutadiene block part is 46 weight %, and molecular weight is 17.6 ten thousand, and molecular weight distribution is 1.1.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 9).
The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 9) is 98%.
＜polymkeric substance 10 〉
Use band whipping appts and the telescopic groove type reactor of internal volume 10L to carry out batchwise polymerization.At first, drop into the cyclohexane solution (concentration is 20 weight %) that contains 30 parts by weight of styrene.Then, add the n-Butyl Lithium of 0.06 weight part, and add 0.7 mole of N with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts, N, N ', N '-Tetramethyl Ethylene Diamine (to call TMEDA in the following text) was 70 ℃ of polymerizations 1.2 hours.Add the cyclohexane solution (concentration be 20 weight %s) that contain 20 weight parts of butadiene, 70 ℃ polymerizations 1 hour thereafter.Measure the polyhutadiene vinyl binding capacity partly of the polymkeric substance of sampling this moment, this value is 50%.Then, add the cyclohexane solution (concentration is 20 weight %) that contains 13 weight parts of butadiene and 37 parts by weight of styrene, 70 ℃ of polymerizations 1 hour.In the polymkeric substance that obtains, styrene content is 67 weight %, and polystyrene block content is 30 weight %, and the vinyl binding capacity of polybutadiene block part is 47 weight %, and molecular weight is 19.4 ten thousand, and molecular weight distribution is 1.1.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 10).
The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 10) is 98%.
＜polymkeric substance 11 〉
Use band whipping appts and the telescopic groove type reactor of internal volume 10L to carry out batchwise polymerization.At first, drop into the cyclohexane solution (concentration is 20 weight %) that contains 20 parts by weight of styrene.Then, add the n-Butyl Lithium of 0.09 weight part, and add 0.7 mole of TMEDA, 70 ℃ of polyase 13s 0 minute with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts.Add the cyclohexane solution (concentration be 20 weight %s) that contain 33 weight parts of butadiene and 47 parts by weight of styrene, 70 ℃ polymerizations 1 hour thereafter.Then, reactive polymer that makes the multipolymer that obtains and ethyl benzoate reaction as coupling agent are with respect to 0.5 mole of the n-Butyl Lithium reaction of using in the polymerization.In the polymkeric substance that obtains, styrene content is 67 weight %, and polystyrene block content is 20 weight %, and weight-average molecular weight is 19.0 ten thousand, and molecular weight distribution is 1.4.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated block copolymer (polymkeric substance 11).The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 11) is 99%.
＜polymkeric substance 12 〉
Use SEBS: commercially available hydrogenation segmented copolymer (production of Kraton G1651:Kraton Polymers society).
＜polymkeric substance 13 〉
Use band whipping appts and the telescopic groove type reactor of internal volume 10L to carry out batchwise polymerization.At first, drop into the cyclohexane solution (concentration is 12 weight %) that contains 15 parts by weight of styrene.Then, add the n-Butyl Lithium of 0.055 weight part, and add 0.3 mole of TMEDA with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts., add the cyclohexane solution (concentration be 12 weight %s) that contain 71 weight parts of butadiene carry out polymerization thereafter, last, drop into the cyclohexane solution (concentration is 12 weight %) that contains 14 parts by weight of styrene and carry out polymerization.Polymerization temperature is controlled between 40 ℃～80 ℃.In the polymkeric substance that obtains, styrene content is 29 weight %, and weight-average molecular weight is 20.2 ten thousand, and molecular weight distribution is 1.1.
Then, use with the same method of polymkeric substance 1 polymkeric substance that obtains is carried out hydrogenation, obtain hydrogenated copolymer (polymkeric substance 13).The hydrogenation ratio of the hydrogenated copolymer that obtains (polymkeric substance 13) is 99%.
＜composition (b) 〉
Use band whipping appts and the telescopic groove type reactor of internal volume 10L to carry out batchwise polymerization.At first, drop into the cyclohexane solution (concentration is 12 weight %) that contains 16 parts by weight of styrene.Then, add the n-Butyl Lithium of 0.04 weight part, and add 0.3 mole of TMEDA with respect to 1 mole of n-Butyl Lithium with respect to whole monomers of 100 weight parts.Add the cyclohexane solution (concentration be 12 weight %s) that contain 68 weight parts of butadiene and carry out polymerization thereafter.At last, drop into the cyclohexane solution (concentration is 12 weight %) that contains 16 parts by weight of styrene and carry out polymerization.Polymerization temperature is controlled between 40 ℃～80 ℃.In the polymkeric substance that obtains, styrene content is 32 weight %, and the vinyl binding capacity of divinyl part is 37 weight %, and weight-average molecular weight is 280,000, and molecular weight distribution is 1.05, and polystyrene block content is 97 weight %.
Then, use with the same method of composition (a)-1 polymkeric substance that obtains carried out hydrogenation, hydrogenated block copolymer.The hydrogenation ratio of the hydrogenated block copolymer that obtains is 99%.
＜composition (c) 〉
Thermoplastic resin: acrylic resin, PC630A (SunAllomer production), MFR (230 ℃, 2.16kg): 7.5g/10 minute.
＜composition (d) 〉
Softener of rubber: paraffin oil oil-1), PW-90 (production of the emerging product of bright dipping society)
Oil-2) paraffin oil, PW-380 (production of the emerging product of bright dipping society)
＜composition (e) 〉
Silicone oil: SH2005000cs (production of DOW CORNING Dong Li society)
[embodiment 1～5]
The hydrogenated copolymer (polymkeric substance 1～4) that obtains is made after the powder shaped, made it oil suction 24 hours with the composition of table-2.Thereafter, it is mixing to utilize twin screw extruder (PCM30) to carry out, and carries out granulating, obtains copolymer compositions thus.Extrusion condition is, barrel zone temperature is 220 ℃, and the screw rod revolution is 300rpm.The composition that obtains 200 ℃ of compressed mouldings, is made the thick sheet of 2mm, obtain the physical property measurement sheet.
Measure the rerum natura of each test film, the results are shown in Table-2.
[comparative example 1]
200 ℃ with polymkeric substance 5 compressed mouldings, make the thick matrix band of 2mm, measure rerum natura.
[comparative example 2]
Use polymkeric substance 5, similarly obtain composition, be made into matrix, measure rerum natura with embodiment.
[comparative example 3～6,8]
Use polymkeric substance 7～10,13, similarly obtain composition, be made into matrix, measure rerum natura with embodiment.
[comparative example 7]
Use polymkeric substance 12, similarly obtain composition with embodiment, but fail to make matrix band.
[embodiment 6～8]
As hydrogenated block copolymer, polymkeric substance 1 is made after the powder shaped, use the Henschel mixing tank will show each composition mixing shown in-3, utilize the twin screw extruder of 30mm diameter to carry out melting mixing then 230 ℃ condition, obtain the particle of composition.Further the said composition particle is carried out roll-in with 3.5 inches roller at 200 ℃, utilize the oil pressure punching press thereafter, at 200 ℃, 100kg/cm
2Condition under carry out extrusion forming, make the thick matrix band of 2mm.Its rerum natura sees Table-3.
[embodiment 9]
As hydrogenated block copolymer, polymkeric substance 5 is made after the powder shaped, use the method same with embodiment 1～3, each composition shown in the table-3 is made the thick matrix band of 2mm.Its rerum natura sees Table-3.
[comparative example 9～18]
As hydrogenated block copolymer, polymkeric substance 1, polymkeric substance 6, polymkeric substance 11, composition (b) are made after the powder shaped, use the Henschel mixing tank will show each composition mixing shown in-3, twin screw extruder with the 30mm diameter carries out melting mixing 230 ℃ condition then, obtains the particle of composition.With the method same, said composition is made the thick matrix band of 2mm with embodiment 1～3.Its rerum natura sees Table-3.
[embodiment 10,11]
As hydrogenated block copolymer, polymkeric substance 1, polymkeric substance 5 are made after the powder shaped, carry out roll-in with 3.5 inches rollers at 200 ℃, then, utilize the oil pressure punching press, at 220 ℃, 100kg/cm
2Condition under carry out extrusion forming, make the thick matrix band of 2mm.Its oil absorbency sees Table-4.
Table 4
[comparative example 19,20]
As hydrogenated block copolymer, polymkeric substance 6, polymkeric substance 11 are made after the powder shaped, carry out roll-in with 3.5 inches rollers at 200 ℃, then, utilize the oil pressure punching press, at 210 ℃, 100kg/cm
2Condition under carry out extrusion forming, make the thick matrix band of 2mm.Its oil absorbency sees Table-4.
Utilize possibility on the industry
Hydrogenated copolymer of the present invention and composition thereof are at flexibility, heat resistance, abrasion performance and table The aspect is outstanding, and processability is good for face sense of touch (not having adhesion sense and oil impregnate). And its characteristic makes it can Substitution material as the flexible vinyl chloride resin.
Utilize these features, can be processed into various shapes by injection moulding, extrusion molding etc. Products formed can be used for automobile component (automotive interior trim material, automobile exterior trim material), doctor Treat various containers, electrical home appliances, industrial part, the toys etc. such as apparatus material, food container.
Claims (13)
1, a kind of hydrogenated block copolymer, it is the hydride of the multipolymer that formed by conjugated diolefine and vinyl aromatic compounds, it has the characteristic of following (1)～(6):
(1) have the polymer blocks of at least one following a, b and c:
A. aromatic vinyl compound polymer block A,
B. the hydropolymer B block of the random copolymers of conjugated diolefine and vinyl aromatic compounds,
C. the vinyl binding capacity is the hydropolymer block C of the conjugated diolefin polymer more than 30%;
(2) content of described vinyl aromatic compounds is greater than 50 weight % and less than 95 weight %;
(3) weight-average molecular weight is 50,000～1,000,000;
(4) the vinyl binding capacity of the conjugated diene monomeric unit of the hydrogenation prepolymer of the described hydropolymer B block of formation is more than 10% and less than 20%;
(5) hydrogenation ratio of two keys of described conjugated diene monomeric unit is more than 75%;
(6) content of described aromatic vinyl compound polymer block A is that the content of 20 weight %～50 weight %, hydrogenated copolymer B block is that the content of 30 weight %～70 weight %, hydropolymer block C is 10 weight %～35 weight %.
2, hydrogenated block copolymer as claimed in claim 1, wherein, the content of described hydropolymer block C is 10 weight %～30 weight %.
3, hydrogenated block copolymer as claimed in claim 1 or 2, wherein, described hydrogenated block copolymer has at least 2 described aromatic vinyl compound polymer block A.
4, hydrogenated block copolymer as claimed in claim 3, wherein, described hydrogenated block copolymer has described aromatic vinyl compound polymer block A at two ends.
5, hydrogenated block copolymer as claimed in claim 1 or 2, wherein, described hydrogenated block copolymer also is combined with the atomic group with functional group.
6, a kind of hydrogenated block copolymer compositions, said composition contain each described hydrogenated block copolymer of 100 weight parts (1) claim 1～5 and 5 weight parts～100 weight parts (2) softener of rubber.
7, hydrogenated block copolymer compositions as claimed in claim 6, wherein, described hydrogenated block copolymer compositions is in the determination of viscoelasticity chart that obtains, and there is 1 in the peak value of loss tangent tan δ at least at 0 ℃～40 ℃.
8, a kind of hydrogenated block copolymer compositions, said composition contain each described hydrogenated block copolymer of 100 weight parts (1) claim 1～5,5 weight parts～100 weight parts (2) softener of rubber, 5 weight parts～100 weight parts (3) thermoplastic resin and/or rubbery polymer.
9, a kind of hydrogenated block copolymer compositions, it contains following compositions (a)～(d):
(a) each described hydrogenated block copolymer of claim 1～5;
(b) hydrogenated block copolymer, it carries out hydrogenation based on the polymer blocks D of vinyl aromatic compounds and at least 1 segmented copolymer based on the polymer blocks E of conjugated diolefine and obtains comprising at least 2, and it has the characteristic of following (7)～(9):
(7) content of the whole vinyl aromatic compounds in the hydrogenated block copolymer is 10 weight %～40 weight %, and all the ratio based on the polymer blocks D of vinyl aromatic compounds in the vinyl aromatic compounds is more than the 80 weight %,
(8) weight-average molecular weight of hydrogenated block copolymer is 200,000～600,000,
(9) two keys of the conjugated diene monomeric unit in the hydrogenated block copolymer is hydrogenated more than 75%;
(c) thermoplastic resin;
(d) softener of rubber;
In the formation of described hydrogenated block copolymer compositions, with respect to above-mentioned (a) that add up to 100 weight parts and (b) composition, (c) composition is 20 weight parts～200 weight parts, and softener of rubber is 20 weight parts～250 weight parts.
10, hydrogenated block copolymer compositions as claimed in claim 9, wherein, described thermoplastic resin contains at least a kind of polyolefin resin.
11,, wherein, in the described hydrogenated block copolymer compositions,, also contain the organopolysiloxane of 0.1 weight part～10 weight parts with respect to this hydrogenated block copolymer compositions of 100 weight parts as claim 9 or 10 described hydrogenated block copolymer compositions.
12, hydrogenated block copolymer compositions as claimed in claim 11, wherein, described organopolysiloxane is liquid polydimethylsiloxane, and is more than the 90cst 25 ℃ kinematic viscosity.
13, as claim 9 or 10 described hydrogenated block copolymer compositions, wherein, the MFR of described hydrogenated block copolymer compositions under 230 ℃, 2.16kg is below 40% in the scope of 0.1g/10 minute～100g/10 minute 23 ℃ rebound resiliences.
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| CN110325593A (en) * | 2017-02-20 | 2019-10-11 | 电化株式会社 | Resin combination and biological model |
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| CN102119190B (en) * | 2008-08-12 | 2012-11-07 | 旭化成化学株式会社 | Hydrogenated block copolymer composition and molded body using the same |
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| JP2012217551A (en) * | 2011-04-06 | 2012-11-12 | Olympus Corp | Member for medical device |
| CN103102584B (en) * | 2011-11-11 | 2015-07-01 | 中国石油化工股份有限公司 | Hydrogenated block polymer elastomer-polypropylene blend |
| CN102617970B (en) * | 2012-04-26 | 2014-03-05 | 湖南汇中新材料有限公司 | Composition of hydrogenated segmented copolymer elastomer-nylon 6 |
| US20160002826A1 (en) * | 2013-02-22 | 2016-01-07 | Kuraray Co., Ltd. | Fiber, fabric, and nonwoven fabric |
| MY176208A (en) * | 2014-01-23 | 2020-07-24 | Asahi Chemical Ind | Block copolymer and adhesive composition |
| WO2017130681A1 (en) * | 2016-01-29 | 2017-08-03 | 日本ゼオン株式会社 | Resin composition and use thereof |
| BR112019026934A2 (en) * | 2017-06-30 | 2020-07-07 | Dow Global Technologies Llc | filling composition and damping tube |
| WO2019045833A1 (en) * | 2017-08-30 | 2019-03-07 | Dow Global Technologies Llc | Thermoplastic polyolefin for non-carpeted flooring |
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| WO2021153183A1 (en) * | 2020-01-30 | 2021-08-05 | Ｍｃｐｐイノベーション合同会社 | Thermoplastic elastomer composition and molded body formed therefrom |
| WO2023145369A1 (en) * | 2022-01-25 | 2023-08-03 | 旭化成株式会社 | Hydrogenated block copolymer, hydrogenated block copolymer composition, and molded article |
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| CN110325593A (en) * | 2017-02-20 | 2019-10-11 | 电化株式会社 | Resin combination and biological model |
| CN110325593B (en) * | 2017-02-20 | 2021-09-21 | 电化株式会社 | Resin composition and biological model |
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