CN102617970B - Composition of hydrogenated segmented copolymer elastomer-nylon 6 - Google Patents
Composition of hydrogenated segmented copolymer elastomer-nylon 6 Download PDFInfo
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- CN102617970B CN102617970B CN201210123770.6A CN201210123770A CN102617970B CN 102617970 B CN102617970 B CN 102617970B CN 201210123770 A CN201210123770 A CN 201210123770A CN 102617970 B CN102617970 B CN 102617970B
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Abstract
The invention relates to a composition of hydrogenated segmented copolymer elastomer-nylon 6. The hydrogenated segmented copolymer elastomer is a segmented copolymer formed by performing negative ion copolymerization on a vinyl aromatic hydrocarbon and alkadiene; the segmented copolymer is hydrogenated selectively; the content of the vinyl aromatic hydrocarbon is high (50-70 percent); the structural content of a polybutylene-1 structure is up to 60-70 percent; and a middle segment contains hydrogenated styrene, a butadiene random copolymerized transition segment. The composition of the hydrogenated segmented copolymer-nylon 6 has the advantages of high strength, high impact resistance and superior water absorption resistance.
Description
technical field:
The present invention relates to a kind of composition of hydrogenated block copolymer elastomerics-nylon 6, relate in particular to the hydrogenated block copolymer elastomerics of a kind of vinyl-arene and conjugated diene and the composition of nylon 6, belong to macromolecular material Application Areas.
background technology:
The technology of preparing of the anionic block copolymers of monovinylarene and conjugated diene has a lot of countries to grasp in the world, as China, the U.S., Japan, Korea S, Italy, France, Spain, Germany etc., in U.S.Pat.3149182 patent, described and adopted vinylbenzene and the synthetic line style ABA segmented copolymer of divinyl, patent 200810190932.1 has been described the SBS that adopts vinylbenzene and the synthetic hub-and-spoke configuration of divinyl, the styrene content of its requirement is 55-85%, butadiene content is 45-15%, these polymkeric substance can hydrogenation form more stable segmented copolymer, as patent U.S.Pat.3595942, description in U.S.Re.27145.
Nylon 6(PA6) resin belongs to high crystalline polymkeric substance, one of five large general engineering plastic, because it has that quality is light, good mechanical performance, electrical insulating property that chemical stability is good, good, consume energy little, creep strain is little, and there is resistance to gasoline, resistant to elevated temperatures characteristic, it is the rare material that can meet the harsh requirement of automotive engine component, thereby be widely used in automotive industry, wave-detector shell and wheel cover cap for petroleum prospecting.But the low-temperature impact resistance of PA6 is poor, very easily water suction, for improving the defect of PA6, generally all need PA6 to carry out blending and modifying, properties-correcting agent has ethylene-propylene rubber(EPR), terpolymer EP rubber, paracril, styrene-butadiene rubber(SBR) etc., and thermoplastic elastomer has SBS(styrene-butadiene block copolymer), SEBS(hydrogenation SBS), EVA, EAA(ethene, acrylic copolymer).Karayannidis etc. have studied the toughness reinforcing glass fiber enhanced nylon system of SEBS-g-MAH, and the weight fraction of SEBS-g-MAH is respectively 2.5,7,7.5 and 12.5% and phase and the thermal characteristics of the blend of PA6.Department of chemistry engineering polymer institute of Tsing-Hua University section Jian Hua etc. utilizes SEBS grafted maleic anhydride (MAH) to make the tough PP/PA nylon alloy of superelevation, and its Morphologic Characteristics is studied; The Wang Yong of Changchun Ying Hua institute etc. has studied the polypropylene grafted glytidyl methacrylate of PA46/PP-g-GMA() preparation of alloy and physical and mechanical properties characterize.And thermoplastic elastomer SEBS modified Pa 6 has become the main direction of current research, because PA6 is strong polarity engineering plastics, common SEBS is apolar substance, and the consistency of the two is bad, is difficult to reach the effect of modification.For solving its consistency, need to increase by the 3rd monomer and carry out functionalization and modification.As maleic anhydride (MAH), vinylformic acid and its derivative are all used as, functional group is grafted to PP, SEBS to a lot of polar monomers or SBS is upper, conventionally the functional group of grafting can with PA6 on reacted with functional groups.For example, the MAH group of PP-g-MAH can react with the amino of PA6 and form new amido linkage or imino-and link.In the co-mixing system of thermoplastic elastomer and PA6, it is very important that reaction between two-phase interface seems, the multipolymer that two kinds of different polymkeric substance form on interface effectively reduces interfacial tension as expanding material, increased the connection power between two-phase, interfacial thickness is increased, in form, show as Radius of the particles and significantly reduce, and become evenly, the gap between interface disappears or narrows down.Chinese patent 96100724.9 is introduced a kind of MC nylon modifying copolymer, mainly adds sodium hydroxide, toluene diisocyanate and some properties-correcting agent (anti-wear agent, static inhibitor, fire retardant), makes modified product have the performances such as antistatic, wear-resisting, fire-retardant; Chinese patent 891074724 has been introduced a kind of modified nylon rubber combination, by adding a kind of thioic acid sulfoacid that nylon and rubber are reacted, is mainly in order to improve the modulus of rubber.Chinese patent 200610064507.9 has been announced a kind of high finish surface modified nylon material and preparation method, and main component is nylon 66, nylon 6, roving glass fiber, Calucium Silicate powder, oxidation inhibitor, products obtained therefrom surface-brightening, good mechanical property.
Summary of the invention
The object of the present invention is to provide a kind of composition of hydrogenated block copolymer elastomerics-nylon 6, said composition has high strength, high-impact and excellent water absorption resistance energy.
The invention provides a kind of composition of hydrogenated block copolymer elastomerics-nylon 6, comprise the component of following parts by weight:
A composition for hydrogenated block copolymer-nylon 6, is characterized in that, it comprises the component of following parts by weight
Hydrogenated block copolymer elastomerics 8-20 part
Nylon 6 60-80 parts
Extending oil 10-30 part
Auxiliary agent 0.5-1.0 part.
The segmented copolymer that hydrogenated block copolymer elastomerics of the present invention is formed by vinyl-arene and conjugated diene obtains by selective hydrogenation, the two keys of phenyl ring C=C and the two keys of the more than 95% alkene C=C of conjugated diene block of vinyl-arene block 0-5% after hydrogenation, have been reduced, contain at least one polymer blocks A after by the hydrogenation of vinyl-arene block and at least one polymer blocks B after by conjugated diene block hydrogenation, this hydrogenated block copolymer not hydrogenation pre-structure is A-(C-B)-A type, A accounts for the 30-40% of elastomerics quality, B accounts for the 30-50% of elastomerics quality, C is the transition section that vinyl-arene and conjugated diene form, content is the 40-60% of total vinyl-arene quality and the 10-20% of conjugated diene, 1, the B of 2-structure accounts for the 60%-70% of B total mass, hydrogenated block copolymer is A-(C-B)-A type, A accounts for the 30-40% of elastomerics quality, B accounts for the 30-50% of elastomerics quality, C is the transition section that selective hydrogenation vinyl-arene and conjugated diene form, content is the 40-60% of total vinyl-arene quality and the 10-20% of conjugated diene, and the B of polybutene-1 structure accounts for the 60%-70% of B total mass.Conjugated diene of the present invention also adds polar molecular structure conditioning agent in the process adding; Described polar molecular structure conditioning agent is tetrahydrofuran (THF), triethylamine, Tetramethyl Ethylene Diamine or tetrahydrofurfuryl alcohol ether.
Hydrogenated block copolymer elastomerics of the present invention has the vinyl-arene of high level, and vinyl aromatic content reaches 50-70%.
The elastomeric number-average molecular weight of hydrogenated block copolymer of the present invention is 16-20 ten thousand, and the number-average molecular weight of each A block is 2.4-3.0 ten thousand, and the number-average molecular weight of each B block is 6.4-8.0 ten thousand, and the number-average molecular weight of each transition section C is 6.4-8.0 ten thousand.
Vinyl-arene of the present invention is vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinyl toluene or to butylstyrene, optimization styrene; Conjugated diene is isoprene or divinyl, is preferably divinyl.
Extending oil of the present invention be the white oil compatible with hydrogenated block copolymer elastomeric block or cycloalkanes by, preferred aromatic hydrocarbons content is not more than 5% paraffinic base white oil, such oil comprises paraffinic oils or naphthenic oil, and extending oil should have low volatility, and particularly preferably kinematic viscosity (40 ℃) is 26-60mm
2the paraffinic oils of/s or naphthenic oil.
Auxiliary agent of the present invention is the material of lower molecular weight, and it comprises Zinic stearas, stearic acid, ethylenebisstearamide EBS, polyoxyethylene glycol or erucicamide etc., preferably EBS.
The key ingredient of the present composition is hydrogenated block copolymer elastomerics, this elastomerics has two outstanding features, the one, this elastomerics have higher polybutene-1 structural content (be before hydrogenation, have 1,2-structural content), the 2nd, middle elastomeric block exists styrene butadiene random copolymerization divinyl section by the transition section of hydrogenation; Higher polybutene-1 structural content makes this hydrogenated block copolymer elastomerics have good processing characteristics, polyhutadiene, by the existence of the styrene butadiene random copolymerization transition section of hydrogenation, makes it in the situation that not needing grafting the 3rd monomer, can have good consistency with nylon 6.When synthetic this hydrogenated block copolymer elastomerics, adding of conjugated diene monomer and polar molecular structure conditioning agent, make before hydrogenation that vinyl-arene of the present invention and conjugated diene form in elastomer block copolymer 1 of conjugated diene, 2-structural content (1, the conjugated diene of 2-structure accounts for the content of conjugated diene total mass) reach 60%-70%, far away higher than 1 of conjugated diene in common vinyl-arene-conjugated diene block copolymer, 2-structural content (1, 2-structural content scope is 35%-45%), hydrogenated block copolymer elastomerics processing fluidity of the present invention is good, under certain shearing rate, there is good consistency with nylon 6, this composition has high strength, high-impact and excellent water absorption resistance energy.
The blend of hydrogenated block copolymer elastomerics-nylon of the present invention, preferred technical scheme is:
12 parts of hydrogenated styrene-butadiene block copolymers;
6 77.5 parts of nylon
16 parts of extending oils
0.5 part of EBS.
The preparation method of hydrogenated block copolymer elastomerics-nylon 6 composition of the present invention is, 10-30 part extending oil and 8-20 part hydrogenated block copolymer elastomerics are mixed, after multipolymer fully absorbs extending oil, add 60-80 part nylon 6 and 0.5-1.0 part auxiliary agent, through twin screw extruder granulation, obtain elastomerics hydrogenated block copolymer-nylon 6 composition, in the process that described hydrogenated block copolymer elastomerics preparation adds at conjugated diene, add polar molecular structure conditioning agent.
Hydrogenated block copolymer elastomerics-nylon 6 composition of the present invention has high strength, high-impact and excellent water absorption resistance energy, can be widely used in automotive industry, wave-detector shell and wheel cover cap for petroleum prospecting.
Accompanying drawing explanation
Fig. 1 is the carbon-13 nmr spectra figure of the synthetic hydrogenated styrene-butadiene block copolymer of embodiment 1
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 2, for special construction SEBS modification of nylon 6 sample impact fracture surface figure, less at 6 kinds of SEBS dispersed phase particles of nylon, and evenly, the interface of disperse phase and external phase is fuzzy
Fig. 3 is the scanning electron microscope (SEM) photograph of comparative example 1, for YH-502 modification of nylon 6 impact fracture surface figure, by figure, can be seen, SEBSYH-502 is not of uniform size at nylon 6 dispersed phase particles, and dispersed particle smooth surface has obvious interface between disperse phase and external phase.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but be not limitation of the invention further.
embodiment 1
Hydrogenated styrene-butadiene block copolymer is synthetic
In the 5L stainless steel polymeric kettle through nitrogen purge, add 3 liters of nonpolar mixed solutions, 90% hexanaphthene wherein, 10% hexane (to account for the mass percent of mixed solution), 2mmol tetrahydrofuran (THF), polymerization kettle temperature raising is to 45-50 ℃, add initiator n-Butyl Lithium 12ml(n-Butyl Lithium concentration 0.4mol/l), stir 2-3 minute, add 45 grams of vinylbenzene to carry out polymerization, react after 30 minutes, by 2ml tetrahydrofurfuryl alcohol ether and 90 grams of vinylbenzene, the mixture of 24 grams of divinyl joins together polymeric kettle and carries out polyreaction, reacting after 20 minutes adds 96 grams of divinyl to carry out polyreaction again, temperature is controlled at 50 ℃-55 ℃, react and after 90-100 minute, add 45 grams of vinylbenzene, react and carry out hydrogenation reaction after 30 minutes, first add 72 grams of promotor dimethyl phthalates to carry out passivation reaction about 30 minutes, add again the luxuriant titanium of 0.3mmol Primary Catalysts two, pass into hydrogen (purity >=99%), reaction pressure remains on 1.0MPa-1.5 Mpa, temperature of reaction is 80-100 ℃, reaction times is 80-90 minute, the irgasfos 168 that adds antioxidant 1076 and 0.3 (wt) % based on multipolymer weighing scale 0.2 (wt) % after having reacted, stir 5 minutes, finally product is added in the mixture of water vapor and water, solvent is evaporated, multipolymer emanates out with solid state.By carbon-13 nmr spectra, test and obtain 1 of multipolymer, 2-structural content is 67.0%, GPC tests molecular weight of copolymer, number-average molecular weight is 18.4 ten thousand, Fig. 1 is the carbon-13 nmr spectra figure of unhydrided styrene-butadiene block copolymer, and displacement is that 4.9ppm place is 1,2-structural content peak, displacement is that 5.4ppm place is Isosorbide-5-Nitrae-structural content peak.
By extending oil, (kinematic viscosity (40 ℃) is 32mm
2/ s) and hydrogenated styrene-butadiene block copolymer SEBS mix, after extending oil fully being absorbed until hydrogenated styrene-butadiene block copolymer SEBS completely, adding nylon 6(melt flow rate (MFR) is 1.2 g/10min) and auxiliary agent EBS, at high-speed stirring pot, mix, through twin screw granulation, pellet is made test sample and is carried out scanning electron microscope (being SEM, as Fig. 2) test SEBS in deployment conditions, water-intake rate and the physical and mechanical properties of nylon 6, and the parts by weight of each component are as follows:
12 parts of hydrogenated styrene-butadiene block copolymers;
6 77.5 parts of nylon
16 parts of extending oils
0.5 part of EBS.
Table 1 sample test results of property
| Tensile strength, MPa | Flexural strength, MPa | Breach resistance to impact shock, KJ/m 2 | Water-intake rate, % |
| 52.1 | 70 | 88.8 | 0.42 |
comparative example 1
Choose domestic general SEBSYH-502 and do simultaneous test with reference to above-mentioned formula, processing condition, working method are completely consistent with embodiment 2, and its results of property is as table 2, and SEM schemes as shown in Figure 3.
Table 2 sample test results of property
| Tensile strength, MPa | Flexural strength, MPa | Breach resistance to impact shock, KJ/m 2 | Water-intake rate, % |
| 42.1 | 58 | 44.7 | 1.74 |
From the test result of table 1 and table 2, the SEBS of general structure is poor to the modified effect of nylon 6, and the effect of the SEBS modification of nylon 6 of this special construction is fine, and particularly resistance to water-intake rate performance is fine.
Wherein sample Mechanics Performance Testing employing standard is ISO/R527-1996E, and breach shock resistance test employing standard is GB/T1843-1996, and scanning electron microscope model is JXA840, and during test, sample surfaces spraying plating gold is avoided accumulation.
The test process of water-intake rate is as follows:
(1) sample (W that weighs after dry 24h in the vacuum drying oven of 90-95 ℃
1)
(2) sample is immersed to 24h in 20 ℃ of distilled water
(3) take out sample, with the moisture that filter paper the blots sample surfaces (W that weighs again
2)
(4) sample is put into the vacuum drying oven (W that weighs after continuing dry 24h at 90-95 ℃
3)
(5) water-intake rate calculation formula is:
Water-intake rate=(W
2-W
3) * 100%/W
1
Embodiment of the present invention is only the description that the preferred embodiment of the present invention is carried out; not design of the present invention and scope are limited; do not departing under the prerequisite of design philosophy of the present invention; various modification and improvement that in this area, engineering technical personnel make technical scheme of the present invention; all should fall into protection scope of the present invention; the technology contents that the present invention asks for protection, is all documented in claims.
Claims (10)
1. a composition for hydrogenated block copolymer-nylon 6, is characterized in that, it comprises the component of following parts by weight
Hydrogenated block copolymer elastomerics 8-20 part
Nylon 6 60-80 parts
Extending oil 10-30 part
Auxiliary agent 0.5-1.0 part
The segmented copolymer that described hydrogenated block copolymer elastomerics is formed by vinyl-arene and conjugated diene obtains by hydrogenation, the two keys of phenyl ring C=C and the two keys of the more than 95% alkene C=C of conjugated diene block of vinyl-arene block 0-5% after hydrogenation, have been reduced, contain at least one polymer blocks A after by the hydrogenation of vinyl-arene block and at least one polymer blocks B after by conjugated diene block hydrogenation, this hydrogenated block copolymer is A-(C-B)-A type, A accounts for the 30-40% of elastomerics quality, B accounts for the 30-50% of elastomerics quality, C is the transition section that selective hydrogenation vinyl-arene and conjugated diene form, content is the 40-60% of total vinyl-arene quality and the 10-20% of conjugated diene, the B of polybutene-1 structure accounts for the 60%-70% of B total mass.
2. composition according to claim 1, is characterized in that, the component that comprises following parts by weight:
12 parts of hydrogenated styrene-butadiene block copolymers;
6 77.5 parts of nylon
16 parts of extending oils
0.5 part of EBS.
3. according to the composition described in claim 1,2, it is characterized in that, hydrogenated block copolymer elastomerics has the vinyl-arene of high level, and vinyl aromatic content is 50-70%.
4. composition according to claim 3, it is characterized in that the described elastomeric number-average molecular weight of hydrogenated block copolymer is 16-20 ten thousand, the number-average molecular weight of each A block is 2.4-3.0 ten thousand, the number-average molecular weight of each B block is 6.4-8.0 ten thousand, and the number-average molecular weight of each transition section C is 6.4-8.0 ten thousand.
5. according to the composition described in claim 3,4, it is characterized in that described vinyl-arene is vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinyl toluene or to butylstyrene; Conjugated diene is isoprene or divinyl.
6. according to the composition described in claim 3 to 5, it is characterized in that described vinyl-arene is vinylbenzene; Conjugated diene is divinyl.
7. composition according to claim 1, is characterized in that described extending oil is naphthenic oil or paraffinic oils, and kinematic viscosity is 26-60mm
2/ s, the melt flow rate (MFR) of nylon 6 is 1.0-3.0g/10min, auxiliary agent is Zinic stearas, stearic acid, ethylenebisstearamide EBS, polyoxyethylene glycol or erucicamide.
8. the preparation method of the arbitrary described hydrogenated block copolymer elastomerics-nylon 6 composition of claim 1 to 7, it is characterized in that, 10-30 part extending oil and 8-20 part hydrogenated block copolymer elastomerics are mixed, after multipolymer fully absorbs extending oil, add 60-80 part nylon 6 and 0.5-1.0 part auxiliary agent, through twin screw extruder granulation, obtain hydrogenated block copolymer elastomerics-nylon composite, in the process that described hydrogenated block copolymer elastomerics preparation adds at conjugated diene, add polar molecular structure conditioning agent.
9. preparation method of composition according to claim 8, is characterized in that, described polar molecular structure conditioning agent is tetrahydrofuran (THF), triethylamine, Tetramethyl Ethylene Diamine or tetrahydrofurfuryl alcohol ether.
10. preparation method of composition according to claim 8, it is characterized in that, when synthesizing hydrogenated segmented copolymer, the vinyl-arene of 40-60% joins mid-block, and be mixed together and add with mid-block 10-20% conjugated diene, when the transformation efficiency of the mixture of vinyl-arene and conjugated diene reaches 90% left and right, add remaining conjugated diene.
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| CN104725838A (en) * | 2014-10-26 | 2015-06-24 | 深圳市欧龙优新材料科技有限公司 | Novel nylon 6 elastomer material with excellent flexibility |
| CN108239225B (en) * | 2016-12-23 | 2020-04-10 | 中国石油天然气股份有限公司 | Styrene butadiene rubber and preparation method thereof |
| CN114478930B (en) * | 2022-01-20 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method of polybutadiene latex and prepared ABS resin |
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| EP1916267A1 (en) * | 2005-07-29 | 2008-04-30 | Zeon Corporation | Block copolymer and method for producing same, composition for resin modification, and modified resin composition and method for producing same |
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| US20090312449A1 (en) * | 2006-02-13 | 2009-12-17 | Shigeru Sasaki | Hydrogenated block copolymer, resin composition comprising the hydrogenated block copolymer, and crosslinked product and crosslinked foamed product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896114A (en) * | 2001-02-01 | 2007-01-17 | 可乐丽股份有限公司 | Block copolymer and thermoplastic resin composition |
| CN1643015A (en) * | 2002-02-07 | 2005-07-20 | 克拉通聚合物研究有限公司 | Articles prepared from hydrogenated controlled distribution block copolymers |
| CN1823105A (en) * | 2003-06-04 | 2006-08-23 | 克拉通聚合物研究有限公司 | Articles prepared from hydrogenated block copolymers |
| CN1997681A (en) * | 2004-03-03 | 2007-07-11 | 克拉通聚合物研究有限公司 | Block copolymers having high flow and high elasticity |
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