CN100369941C - Hydrogenated styrene analog thermoplastic elastomer and its preparation method - Google Patents
Hydrogenated styrene analog thermoplastic elastomer and its preparation method Download PDFInfo
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- CN100369941C CN100369941C CNB2005100695957A CN200510069595A CN100369941C CN 100369941 C CN100369941 C CN 100369941C CN B2005100695957 A CNB2005100695957 A CN B2005100695957A CN 200510069595 A CN200510069595 A CN 200510069595A CN 100369941 C CN100369941 C CN 100369941C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims abstract description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 20
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000004793 Polystyrene Substances 0.000 claims abstract description 13
- 229920002223 polystyrene Polymers 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 239000003292 glue Substances 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 150000003440 styrenes Chemical class 0.000 claims description 12
- 238000010550 living polymerization reaction Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000004904 shortening Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001979 organolithium group Chemical group 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 229920000428 triblock copolymer Polymers 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 230000005311 nuclear magnetism Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- KKDBZWZRJNRBGA-UHFFFAOYSA-L Cl[Ti]Cl.[CH]1C=CC=C1 Chemical compound Cl[Ti]Cl.[CH]1C=CC=C1 KKDBZWZRJNRBGA-UHFFFAOYSA-L 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004811 liquid chromatography Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000007704 transition Effects 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention designs and synthesizes a saturated thermoplastic styrene elastomer whose structure can be expressed as S-R-S, wherein the S is a polystyrene section; the R is a styrene / ethene /1-butylene random copolymerization section or an ethene /1-butylene random copolymerization section with the styrene / ethene /1-butylene random copolymerization section. The preparation method comprises the following steps: negative ions are actively polymerized to initiate styrene/butadiene to synthesize hydrogenated base adhesive; then, double bonds on a polymer are saturated via hydrogenation. Compared with the hydrogenated product SEBS of the traditional styrene / butadiene triblock copolymer SBS, the polymer with the structure has the advantages of good processing performance.
Description
Technical field:
The present invention relates to a kind of hydrogenated styrene analog thermoplastic elastomer and preparation method thereof.
Background technology:
Traditional polystyrene-poly divinyl-polystyrene (SBS) is by obtaining SEBS to polyhutadiene section hydrogenation, wherein EB represented for containing 30-45%1, structure behind the polyhutadiene of 2-structure (PB) hydrogenation is the structure of ethene and 1-butylene random copolymerization, shown in following structural formula:
A: be the structure of SBS
B: be the structure of SEBS
SEBS has been the broad-spectrum novel elastomer material of generally acknowledging in the world since industrial production always.Compare with SBS, because main chain does not contain or contain a small amount of two keys, SEBS also has more advantages of excellent stability and thermotolerance than SBS except that having thermoplastic processibility and caoutchouc elasticity, use temperature can reach 120 ℃ (SBS only is 65 ℃), the outdoor weatherability energy that especially anti-ozone, UV resistant etc. are excellent.But because the difference of the solubility parameter between polystyrene (S) and ethene and the butylene copolymer (EB) is bigger, even melt temperature is higher than on the polystyrene fusing point, the microcell that is separated is still survivable, causes processing characteristics bad.
For the performance of better performance SEBS, many researchists have carried out big quantity research, and traditional SEBS is improved, and develop the SEBS that the multiple trade mark is suitable for the different purposes of multiple industry.
Nineteen ninety-five synthetic rubber company (JSR) is not good enough at oil-proofness and the flowability of SBS, developed unique segmented copolymer of DynaronSEBC (end is a polyethylene kind crystallization microcell block for the PS the other end), this product is better than traditional styrene analog thermoplastic elastomer on mobile and oil-proofness, because PS and polyolefine intermiscibility are good, are preferable modifiers.Thereafter, also having developed two latter ends is the DynaronCEBC of polyethylene kind crystallization microcell block (C is actually 1, the PE section that forms behind the 4-PB hydrogenation, EB is 1,2/1, the random copolymerization section of ethene that forms behind the 4PB hydrogenation and 1-butylene), having good flowability and oil-proofness, is polyolefinic properties-correcting agent such as PE, PP.
Japanese Kurray companies in 1993 have developed PS-ethenoid resin-polyisoprene three block hydrogenation polymkeric substance (Hybar) [bamboo village, プ ラ ス チ ッ Network ス, 1995,46 (5), 77 of anti-seismic performance excellence; ボ リ マ one ダ イ ジ コ ス ト, 1996,48 (12), 118].
U.S. Shell oil company develops the product that is exclusively used in binding agent and sealing agent aspect on the basis of KratonG (ProductName, i.e. SEBS), name to be KratonGPR-6919[AdhesiveAge, 1997,40 (2), 48].It is that SEBS is carried out unique combining with the polyisoprene rubber block, because this combination is arranged, the intensity that can obtain fusion, heat and ozone stable and be provided by the KratonG polymer network is to increase the viscosity and the separability of isoamyl glue.Because the nonsaturation of isoamyl glue is arranged, GPR-6919 can also close reaction with other polymer blending again, and the KratonG polymer features is infiltrated wherein by the blend means, and product can be used as weathering resistance and thermotolerance sealing agent.
Have benefited from the advantage that anionic polymerization can carry out molecular designing,, can prepare and have multiple performance characteristics, meet the styrenic hydrogenation type thermoplastic elastomer of different purposes by the structure design of hydrogenation prepolymer molecule.Though above-mentioned several polymeric design improves at this series products and aspects such as polyolefinic consistency, cohesiveness, after such modification the solubility parameter of polymkeric substance is further reduced, and is unfavorable for the polymer-compatible bigger with polarity.
Summary of the invention:
For solving above-mentioned the problems of the prior art, the invention provides a kind of hydrogenated styrene analog thermoplastic elastomer and preparation method thereof, on the basis of SEBS, employing increases the styrene monomer unit and improves solubility parameter between EB and PS (polystyrene) in interlude EB component, thereby improves Drawing abillity.
Hydrogenated styrene analog thermoplastic elastomer of the present invention, polymericular weight is 5-25 ten thousand, be preferably 8-15 ten thousand, have S-R-S three block structures, wherein S is the polystyrene section, and R is styrene/ethylene/1-butylene random copolymerization structural sections or the ethene/1-butylene random copolymerization structural sections that has styrene/ethylene/1-butylene random copolymerization structural sections.
S accounts for the 15-50% of polymer quality in the above-mentioned thermoplastic elastomer, and R accounts for the 50-85% of polymer quality; Styrol structural unit content accounts for the 5-35% of R quality among the R, and 1-butylene structural unit content accounts for the 10-35% of R quality, and the ethene structural unit accounts for the 50-70% of R quality.
The present invention also provides a kind of preparation method of hydrogenated styrene analog thermoplastic elastomer, adopts negative ion living polymerization synthesizing styrene/butadienecopolymer as hydrogenation basis glue, the method for shortening then, and concrete steps are:
A: the preparation of hydrogenation basis glue:
Adopting organolithium is the anionic polymerization method of initiator, polymerization temperature is 50-90 ℃, polymerization reaction time is 1-3 hour, polymerization single polymerization monomer is vinylbenzene, divinyl, the consumption of styrene monomer is the 20-50% of total monomer quality, be preferably 30-45%, monomeric mass percentage concentration is 6-20% in the polymeric solution, be preferably 14-16%, used organic lithium initiator is the two lithiums of lithium alkylide, phenyl lithium, benzyl lithium, allyl group lithium or isoprene short chain (preparation method of the two lithiums of isoprene short chain is a prior art, referring to ZL01136233.2);
The initiator add-on is the per 100 gram monomers of 0.2-2mmol.
B: shortening: the hydrogenation basis glue that steps A is obtained is in the presence of metallocene-titanium catalyst, feed hydrogen and carry out hydrotreatment, the metallocene-titanium catalyst consumption is per 100 gram hydrogenation basis glue 0.1-2mmol, hydrogenation temperature is controlled between 70-100 ℃, hydrogen pressure is at 1.0-2.5Mpa, reaction times is 1-9 hour, is preferably 1-3 hour, obtains hydrogenated styrene analog thermoplastic elastomer after removal solvent, the drying.
Among the above-mentioned preparation method, when steps A prepares hydrogenation basis glue, can also add structure regulator in right amount, the mol ratio of structure regulator and initiator is 0.1-50, and said structure regulator is any or their miscellany in the following material group: tetrahydrofuran (THF), HMPA, tetramethyl-ethylene base diamines, diglyme, triglyme, glycol dimethyl ether, dioxane, PMDETA.
Prepare the anionic polymerization ordinary method that the method for hydrogenation basis glue is familiar with for those skilled in the art, wherein preparing the used solvent of monomer solution is anionic polymerization alkane, naphthenic hydrocarbon, toluene, benzene or their mixture commonly used in the prior art, and alkane mainly is hexanaphthene, hexane etc.
In order to guarantee enough contacts area and Surface Renewal speed, catalyst efficiency is improved at the stable catalytic activity center, also can add an amount of LiH as promotor in the shortening process.
In order to make polymkeric substance have better properties, in the industrial general requirement polymkeric substance more than 98% two keys be hydrogenated saturatedly, promptly degree of hydrogenation (on the polymkeric substance two keys be hydrogenated saturated degree be called degree of hydrogenation) should be greater than 98%.
The difference that the present invention has overcome the solubility parameter between the polystyrene and ethene and butylene copolymer among the SEBS is bigger, the microcell that is separated is survivable, cause problems such as processing characteristics is bad, the hydrogenated styrene analog thermoplastic elastomer of novel texture provided by the invention has good processing characteristics.
The present invention will be further described below in conjunction with embodiment.
Embodiment
Embodiment 1
Get two 250ml three-necked bottles, 1000ml absorption bottle pours nitrogen through vacuum bakeout, two three-necked bottles pipette the 100ml hexanaphthene with transfer pipet respectively, respectively add 16g vinylbenzene with syringe then, get one of them three-necked bottle and add the 40mmol tetrahydrofuran (THF), 60 ℃ of n-butyl lithium initiator 1.6ml (approximately 1.18mmol) that add 0.73mol/L concentration carry out polymerization, and the time is 0.5h.Transfer pipet pipettes the 700ml hexanaphthene and adds absorption bottle, draws the 54g divinyl, and adds behind the 4g vinylbenzene and the spike solution of above-mentioned polystyrene adds the 2L still together.Start stirring, be warming up to 70 ℃, polymerization 1.0h.Again vinylbenzene in another three-necked bottle is added 2L still, polymerization 1.0h.Removing solvent after the polymkeric substance that takes a morsel stops characterizes polymkeric substance with gel liquid chromatography (GPC), nuclear-magnetism means of testing such as (NMR).
Lead to H upward in Zhi Bei the living polymerization composition glue liquid
2Bubbling is till glue is fully by orange becoming colorless.70 ℃ add down 1.0mmol cyclopentadienyl titanium dichloride catalyzer, feed hydrogen and make the still internal pressure bring up to 1.5MPa, start to stir and carry out hydrogenation, after 2 hours hydrogen are discharged, and splash into then in 90 ℃ the water and remove solvent, are dried to constant weight.Sample carries out tests such as nuclear-magnetism (NMR), mechanical property.The melting index test condition is 200 ℃, the heavy counterweight of 5kg.
The polymericular weight that obtains is 80,000, is distributed as 1.1 to 1.5.Degree of hydrogenation is 98.7%, and S content is 38%wt, and R content is 62%wt; Styrol structural unit content is the 7%wt of R among the R, and 1-butylene structural unit content is 32%wt, and ethene structural unit content is 61%wt.The tensile strength 28.5Mpa of polymkeric substance, 300% 4.4Mpa that stretches surely, elongation at break 523%, tension set 19%, melting index 0.825g/10min.
Embodiment 2
Get two 250ml three-necked bottles, 1000ml absorption bottle pours nitrogen through vacuum bakeout, two three-necked bottles pipette the 100ml hexanaphthene with transfer pipet respectively, respectively add 13.5g vinylbenzene with syringe then, get one of them and add the 0.5mmol diglyme, 60 ℃ of butyllithium initiator 2.4ml (about 1.77mmol) that add 0.73mol/L concentration carry out polymerization, and the time is 0.5h.Transfer pipet pipettes the 700ml hexanaphthene, draws the 81g divinyl, and adds behind the 27g vinylbenzene and the spike solution of above-mentioned polystyrene adds the 2L still together.Start stirring, be warming up to 70 ℃, polymerization 1.0h.2L still, polymerization 1.0h will be added behind the vinylbenzene in another three-necked bottle.Removing solvent after the polymkeric substance that takes a morsel stops characterizes polymkeric substance with gel liquid chromatography (GPC), nuclear-magnetism means of testing such as (NMR).Synthesized new polymers S (SB) BS with SB random copolymerization transition section.
Lead to H upward in Zhi Bei the living polymerization composition glue liquid
2Bubbling is till glue is fully by orange becoming colorless.70 ℃ add down 1.8mmol cyclopentadienyl titanium dichloride catalyzer, feed hydrogen and make the still internal pressure bring up to 1.5MPa, start to stir and carry out hydrogenation, after 2 hours hydrogen are discharged, and splash into then in 90 ℃ the water and remove solvent, are dried to constant weight.Sample carries out tests such as nuclear-magnetism (NMR), mechanical property.The melting index test condition is 200 ℃, the heavy counterweight of 5kg.
The polymericular weight that obtains is 80,000, is distributed as 1.1 to 1.5, and degree of hydrogenation is 98.5%, and S content is 20%wt, and R content is 80%wt; Styrol structural unit content is the 25%wt of R among the R, and 1-butylene structural unit content is 20%wt, and ethene structural unit content is 55%wt.The tensile strength 15.5Mpa of polymkeric substance, 300% 3.1Mpa that stretches surely, elongation at break 510%, tension set 13%, melting index 1.515g/10min.
Embodiment 3
Get two 250ml three-necked bottles, 1000ml absorption bottle pours nitrogen through vacuum bakeout, two three-necked bottles pipette the 100ml hexanaphthene with transfer pipet respectively, respectively add 9g vinylbenzene with syringe then, get one of them and add 0.8mmol tetramethyl-ethylene base diamines, 60 ℃ of phenyl lithium initiator 1.2ml (0.88mmol) that add 0.73mol/L concentration carry out polymerization, and the time is 0.5h.Transfer pipet pipettes the 700ml hexanaphthene, draws the 40.5g divinyl, and adds behind the 9g vinylbenzene and the spike solution of above-mentioned polystyrene adds the 2L still together.Start stirring, be warming up to 70 ℃, polymerization 1.0h.2L still, polymerization 1.0h will be added behind the vinylbenzene in another three-necked bottle.Removing solvent after the polymkeric substance that takes a morsel stops characterizes polymkeric substance with gel liquid chromatography (GPC), nuclear-magnetism means of testing such as (NMR).Synthesized new polymers S (SB) BS with SB random copolymerization transition section.
Lead to H upward in Zhi Bei the living polymerization composition glue liquid
2Bubbling is till glue is fully by orange becoming colorless.90 ℃ add down 0.4mmol cyclopentadienyl titanium dichloride catalyzer, feed hydrogen and make the still internal pressure bring up to 1.5MPa, start to stir and carry out hydrogenation, after 2 hours hydrogen are discharged, and splash into then in 90 ℃ the water and remove solvent, are dried to constant weight.Sample carries out tests such as nuclear-magnetism (NMR), mechanical property.The melting index test condition is 200 ℃, the heavy counterweight of 5kg.
The polymericular weight that obtains is 80,000, is distributed as 1.1 to 1.5, and degree of hydrogenation is 99.1%, and S content is 27%wt, and R content is 73%wt; Styrol structural unit content is the 18%wt of R among the R, and 1-butylene structural unit content is 36%wt, and ethene structural unit content is 56%wt.The tensile strength 17.7Mpa of polymkeric substance, 300% 4.1Mpa that stretches surely, elongation at break 561%, tension set 13%, melting index 0.895g/10min.
Embodiment 4
The 2L still is washed still through lower concentration spike solution, charge into nitrogen, insert end flask with 1000ml and pipette the 900ml hexanaphthene, draw the 60g divinyl, add 30g vinylbenzene, the isoprene oligomerisation short chain dilithium initiator 2.8ml (about 1.4mmol) of 0.5mol/L concentration with syringe then, mixing solutions is added in the still, start stirring, be warming up to 70 ℃, polymerization 1.5h.The polymkeric substance that takes a morsel characterizes polymkeric substance with gel liquid chromatography (GPC), nuclear-magnetism means of testing such as (NMR) after removing solvent.Synthesized new polymers S (SB) B (SB) S with SB random copolymerization transition section.
Lead to H upward in Zhi Bei the living polymerization composition glue liquid
2Bubbling, 70 ℃ add down 0.6mmol cyclopentadienyl titanium dichloride catalyzer, feed hydrogen and make the still internal pressure bring up to 1.5MPa, start to stir and carry out hydrogenation, after 2 hours hydrogen are discharged, and splash into then in 90 ℃ the water and remove solvent, are dried to constant weight.Sample carries out tests such as nuclear-magnetism (NMR), mechanical property.The melting index test condition is 200 ℃, the heavy counterweight of 5kg.
The polymericular weight that obtains is 130,000, is distributed as 1.1 to 1.5.Degree of hydrogenation is 98.3%, and S content is 16%, and R content is 84%wt; Styrol structural unit content is the 19%wt of R among the R, and 1-butylene structural unit content is 15%wt, and ethene structural unit content is 66%wt.The tensile strength 8.3Mpa of polymkeric substance, 300% 2.1Mpa that stretches surely, elongation at break 710%, tension set 38%.Melting index 1.805g/10min.
Embodiment 5
The 2L still is washed still through lower concentration spike solution, charges into nitrogen, and two 1000ml insert end flask and pour nitrogen through vacuum bakeout, respectively pipette the 450ml hexanaphthene with transfer pipet, and each draws the 27g divinyl, and one adds 36g vinylbenzene with syringe.The isoprene oligomerisation short chain dilithium initiator 3.6ml (about 1.8mmol) that does not add flask adding of cinnamic slotting end 0.5mol/L concentration, solution is added in the still, start stirring, be warming up to 70 ℃, behind the 0.5h solution in another flask of slotting end is added polymerization 1.5h in the still.The polymkeric substance that takes a morsel characterizes polymkeric substance with gel liquid chromatography (GPC), nuclear-magnetism means of testing such as (NMR) after removing solvent.Synthesized new polymers S (SB) B (SB) S with SB random copolymerization transition section.
Lead to H upward in Zhi Bei the living polymerization composition glue liquid
2Bubbling, 80 ℃ add down 0.2mmol cyclopentadienyl titanium dichloride catalyzer, feed hydrogen and make the still internal pressure bring up to 1.8MPa, start to stir and carry out hydrogenation, after 2 hours hydrogen are discharged, and splash into then in 90 ℃ the water and remove solvent, are dried to constant weight.Sample carries out tests such as nuclear-magnetism (NMR), mechanical property.The melting index test condition is 200 ℃, the heavy counterweight of 5kg.
The polymericular weight that obtains is 100,000, is distributed as 1.1 to 1.5.Degree of hydrogenation is 99.6%, and S content is 25%wt, and R content is 75%wt; Styrol structural unit content is the 22%wt of R among the R, and 1-butylene structural unit content is 23%wt, and ethene structural unit content is 55%wt.The tensile strength 19.7Mpa of polymkeric substance, 300% 4.2Mpa that stretches surely, elongation at break 730%, tension set 20%.Melting index 2.081g/10min.
Embodiment 6
The 2L still is washed still through lower concentration spike solution, charge into nitrogen, 1000ml inserts end flask, there-necked flask pours nitrogen through vacuum bakeout, pipette 800ml, 100ml hexanaphthene respectively with transfer pipet, insert end flask and draw the 54g divinyl, 0.5mol/L the isoprene oligomerisation short chain dilithium initiator 3.6ml (about 1.8mmol) of concentration, mixing solutions is added in the still, start stirring, be warming up to 60 ℃, the beginning polymerization, there-necked flask adds 36g vinylbenzene with syringe, behind the 20min solution in the there-necked flask is added in the still polymerization 1.0h.The polymkeric substance that takes a morsel characterizes polymkeric substance with gel liquid chromatography (GPC), nuclear-magnetism means of testing such as (NMR) after removing solvent.Synthesized new polymers S (SB) B (SB) S with SB random copolymerization transition section.
Lead to H upward in Zhi Bei the living polymerization composition glue liquid
2Bubbling, 80 ℃ add down 0.5mmol cyclopentadienyl titanium dichloride catalyzer, feed hydrogen and make the still internal pressure bring up to 1.7MPa, start to stir and carry out hydrogenation, after 2 hours hydrogen are discharged, and splash into then in 90 ℃ the water and remove solvent, are dried to constant weight.Sample carries out tests such as nuclear-magnetism (NMR), mechanical property.The melting index test condition is 200 ℃, the heavy counterweight of 5kg.
The polymericular weight that obtains is 100,000, is distributed as 1.1 to 1.5, and degree of hydrogenation is 98.7%, and S content is 32%wt, and R content is 68%wt; Styrol structural unit content is the 18%wt of R among the R, and 1-butylene structural unit content is 15%wt, and ethene structural unit content is 66%wt.The tensile strength 22.4Mpa of polymkeric substance, 300% 3.7Mpa that stretches surely, elongation at break 640%, tension set 28%.Melting index 0.768g/10min.
Embodiment 7
The 2L still is washed still through lower concentration spike solution, charge into nitrogen, 1000ml inserts end flask, there-necked flask pours nitrogen through vacuum bakeout, pipette 800ml, 100ml hexanaphthene respectively with transfer pipet, insert end flask and draw the 54g divinyl, and adding 24g vinylbenzene, 0.5mol/L the isoprene oligomerisation short chain dilithium initiator 2.8ml (about 1.4mmol) of concentration, mixing solutions is added in the still, start stirring, be warming up to 60 ℃, the beginning polymerization, there-necked flask adds 30g vinylbenzene with syringe, behind the 20min solution in the there-necked flask is added in the still polymerization 1.0h.The polymkeric substance that takes a morsel characterizes polymkeric substance with gel liquid chromatography (GPC), nuclear-magnetism means of testing such as (NMR) after removing solvent.Synthesized new polymers S (SB) B (SB) S with SB random copolymerization transition section.
Logical H in the living polymerization composition glue liquid
2Bubbling, 80 ℃ add down 0.5mmol cyclopentadienyl titanium dichloride catalyzer, feed hydrogen and make the still internal pressure bring up to 1.7MPa, start to stir and carry out hydrogenation, after 2 hours hydrogen are discharged, and splash into then in 90 ℃ the water and remove solvent, are dried to constant weight.Sample carries out tests such as nuclear-magnetism (NMR), mechanical property.The melting index test condition is 200 ℃, the heavy counterweight of 5kg.
The polymericular weight that obtains is 130,000, is distributed as 1.1 to 1.5, and degree of hydrogenation is 98.7%, and S content is 45%wt, and R content is 55%wt; Styrol structural unit content is the 33%wt of R among the R, and 1-butylene structural unit content is 10%wt, and ethene structural unit content is 57%wt.The tensile strength 27.3Mpa of polymkeric substance, 300% 4.4Mpa that stretches surely, elongation at break 750%, tension set 29%.Melting index 0.489g/10min.
Claims (6)
1. hydrogenated styrene analog thermoplastic elastomer, polymericular weight is 5-25 ten thousand, have S-R-S three block structures, wherein S is the polystyrene section, and R is styrene/ethylene/1-butylene random copolymerization structural sections or the ethene/1-butylene random copolymerization structural sections that has styrene/ethylene/1-butylene random copolymerization structural sections.
2. according to the thermoplastic elastomer of claim 1, it is characterized in that S accounts for the 15-50% of polymer quality; R accounts for the 50-85% of polymer quality, and styrol structural unit content accounts for the 5-35% of R quality among the R, and 1-butylene structural unit content accounts for the 10-35% of R quality, and the ethene structural unit accounts for the 50-70% of R quality.
3. thermoplastic elastomer according to claim 1 and 2 is characterized in that: the molecular weight of hydrogenated styrene analog thermoplastic elastomer is 8-15 ten thousand.
4. the preparation method of the described hydrogenated styrene analog thermoplastic elastomer of claim 1 adopts negative ion living polymerization synthesizing styrene/butadienecopolymer as hydrogenation basis glue, the method for shortening then, and concrete steps are:
A: the preparation of hydrogenation basis glue:
Adopting organolithium is the anionic polymerization method of initiator, polymerization temperature is 50-90 ℃, polymerization reaction time is 1-3 hour, polymerization single polymerization monomer is vinylbenzene, divinyl, the consumption of styrene monomer is the 20-60% of total monomer quality, the initiator add-on is a 0.2-2mmol/100 gram monomer, and monomeric mass percentage concentration is 6-20% in the polymeric solution;
B: shortening: the hydrogenation basis glue that steps A is obtained is in the presence of metallocene-titanium catalyst, feed hydrogen and carry out hydrotreatment, the metallocene-titanium catalyst consumption is per 100 gram hydrogenation basis glue 0.1-2mmol, hydrogenation temperature is controlled between 70-100 ℃, hydrogen pressure is at 1.0-2.5Mpa, reaction times is 1-9 hour, after removal solvent, the drying, obtains the described hydrogenated styrene analog thermoplastic elastomer of claim 1.
5. according to the preparation method of claim 4, it is characterized in that: during the glue of preparation hydrogenation basis, add structure regulator, the mol ratio of structure regulator and initiator is 0.1-50, and said structure regulator is any or their miscellany in the following material group: tetrahydrofuran (THF), HMPA, tetramethyl-ethylene base diamines, diglyme, triglyme, glycol dimethyl ether, dioxane, PMDETA.
6. according to the preparation method of claim 4 or 5, it is characterized in that: during the glue of preparation hydrogenation basis, used organic lithium initiator is the two lithiums of lithium alkylide, phenyl lithium, benzyl lithium, allyl group lithium or isoprene short chain, the consumption of styrene monomer is the 30-55% of total monomer quality, and monomeric mass percentage concentration is 6-20% in the polymeric solution; The time of shortening is 1-3 hour.
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