CN109810209A - A kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers - Google Patents
A kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers Download PDFInfo
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- CN109810209A CN109810209A CN201811591353.8A CN201811591353A CN109810209A CN 109810209 A CN109810209 A CN 109810209A CN 201811591353 A CN201811591353 A CN 201811591353A CN 109810209 A CN109810209 A CN 109810209A
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- butadiene
- styrene
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- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003292 glue Substances 0.000 claims abstract description 19
- 150000003283 rhodium Chemical class 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000010276 construction Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 125000001979 organolithium group Chemical group 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 ether compound Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- 239000010948 rhodium Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 150000003284 rhodium compounds Chemical group 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003426 co-catalyst Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical group [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 claims description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 2
- 229910001630 radium chloride Inorganic materials 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002815 homogeneous catalyst Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001993 dienes Chemical group 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011952 anionic catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000040710 Chela Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WGWACCCAJWZIML-UHFFFAOYSA-N benzene;buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N.C1=CC=CC=C1 WGWACCCAJWZIML-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N n-butyl-benzene Natural products CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MKDJIADBNUOBJH-UHFFFAOYSA-N octanoic acid;rhodium Chemical compound [Rh].[Rh].CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O.CCCCCCCC(O)=O MKDJIADBNUOBJH-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Abstract
The present invention relates to Polymer Synthesizing fields, particularly disclose a kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers.The preparation method of the hydrogenated styrene-butadiene-styrene block copolymers; it is characterized by: under inert gas shielding; using organolithium as catalyst; styrene is placed in progress one-step polymerization reaction in cyclohexane solvent; composite construction regulator is added simultaneously; then addition butadiene carries out two sections of polymerization reactions, and styrene is added after the completion of polymerization and carries out three sections of copolyreaction, obtains adding the basic glue SBS of hydrogen；Using homogeneous rhodium series catalysts to adding hydrogen to carry out hydrogenation with basis glue SBS, product is obtained.Rationally, hydrogenation catalyst dosage is less for present invention process design, and catalyst activity and selectivity is high, and reaction condition is mild, product purity and high income, is suitable for wide popularization and application.
Description
(1) technical field
The present invention relates to Polymer Synthesizing field, in particular to a kind of hydrogenated styrene-butadiene-styrene block copolymers
Preparation method.
(2) background technique
Styrene-Butadiene-Styrene Block Copolymer (SBS) belongs to basic material, is widely used in rubber product, plastics
The big field of modifying agent, adhesive and asphalt modifier etc. four, due to containing double bond on its strand, weatherability and thermal stability are not
Foot, limits its application.Hydrogenated styrene-butadiene-styrene block copolymers (SEBS) are by the soft segment in SBS ---
Polybutadiene adds hydrogen to be saturated to form polyethylene-poly-1-butylene block, is a kind of widely used novel block copolymer, is more
The effective ways for the defects of mending SBS weatherability and insufficient thermal stability.Compared with SBS, SEBS has a series of excellent performances,
Such as heat-resisting oxygen, ozone resistance, uvioresistant, creep-resistant property, can be widely applied to modifying plastics, high polymer alloy, height
The fields such as performance sealant, adhesive and auto industry.
Block copolymer SBS mainly uses anionic solution polymerization method to synthesize, and passes through addition in polymerization process
Structure regulator adjusts its each block concentration, its is made to meet hydrogenation needs.After corresponding catalyst is added in active SBS,
It is passed through hydrogen and carries out selective hydrogenation, control the degree of hydrogenation on phenyl ring less than 5%, and butadiene segment degree of hydrogenation is greater than 98%, i.e.,
The SEBS that can be required.The research emphasis of hydrogen addition technology is the optimization of hydrogenation catalyst.
SBS, which adds hydrogen to study more catalyst, to be had: (1) traditional catalyst, traditional hydrogenation catalyst have heterogeneous and equal
Point of phase catalyst.1. heterogeneous catalysis be by VIII race's Metal Supported over celite, heterogeneous catalysis activity low and item
Part is harsh, need to carry out at high temperature under high pressure, causes polymer to decompose and is gelled with reaction system, causes energy consumption excessively high, simultaneous reactions
The influence of system viscosity and polymer steric hindrance also adversely affects catalyst activity, thus increase catalyst amount, and
And catalyst is also to be improved to conjugated diene unit hydrogenation selectivity.2. homogeneous catalyst, homogeneous catalyst system has transition
Metal carboxylate or alkoxide compound, such as the chela of complex compound and iron, cobalt and nickel that cobaltous dichloride and amide or urea are formed
The product that conjunction object etc., i.e. organo-metallic compound are reacted in a solvent with reducing agent, homogeneous catalyst activity is higher,
A small amount of catalyst can be obtained satisfied plus hydrogen effect under low-temp low-pressure, if the condition that selection is suitable, also can be improved catalyst
Selectivity, even if the unsaturated double-bond of conjugated diene unit preferentially adds hydrogen.But homogeneous catalyst also has a negative side, i.e.,
Homogeneous catalyst needs to mix and could sufficiently show under the premise of constantly pipetting product its activity immediately in its each ingredient, reappears
Property is poor.In addition homogeneous catalyst stability is poor, needs the extemporaneous preparation before adding hydrogen every time.(2) metallocene catalyst, metallocene
Hydrogenation catalyst is a kind of novel hydrogenation catalyst, is the hot spot studied at present, is the revolution of SBS hydrogen addition technology, it
The shortcomings that overcoming traditional hydrogenation technique, with the height that catalyst activity is high, concentration is low, dosage is few, reaction condition is mild, stable
Hydrogenation rate and fabulous degree of hydrogenation, hydrogenation reaction high repeatability and other advantages, make its residue in final polymeric articles
Content is extremely low, can save purification removing process, and simplification of flowsheet is reduced investment outlay.Recent domestic SEBS industry metaplasia
Production. art mostly uses metallocene hydrogenation catalyst, such as Ba Ling petrochemical industry, U.S. Shell, Japanese Asahi Chemical Industry etc..(3) noble metal
Complex compound catalyst, the noble metal homogeneous catalysis agent such as ruthenium (Ru), rhodium (Rh) because its high activity, highly selective and hydrogenation products without
Gelatin phenomenon is concerned, and the application in high polymer selective hydration receives more and more attention, and in recent years, noble metal is urged
Agent is mainly that ruthenium catalyst system is also used for SBS and adds hydrogen, it is shown that hydrogenation activity is high, reaction condition is mild, selectivity is good etc.
Advantage.
Recently as the exploitation and development of new catalyst, hydrogenation technique technology also has corresponding development.It is reported that China
In the research that SBS hydrogenation reaction forms SEBS, mainly using nickel system, cobalt system metal or luxuriant titanium as hydrogenation catalyst.
CN104226365A discloses a kind of preparation method of novel hydrogenation catalyst for synthesizing SEBS, which belongs to luxuriant titanium and urge
Change system.CN101423569A discloses the method for a kind of selection of styrene/conjugated diene polymers plus hydrogen, with bicyclic penta 2
Alkene titanium chloride is major catalyst, and hydrogenation reaction 1 hour, degree of hydrogenation was greater than 98%.CN1834113B discloses a kind of rhodium system catalysis
Agent is catalyzed the method for hydrotreating of conjugated diene in the presence of organic solvent-free.CN1865294A discloses a kind of hydrogenated styrene analog
The preparation method of block copolymer, the patent, to adding hydrogen-based plinth relatively to carry out catalytic hydrogenation, are processed using metallocene-titanium catalyst
The better SEBS of performance.Chlorination (triphenylphosphine) rhodium complex is used for acrylonitrile-butadiene-benzene second by British patent 2070023A
Carbon carbon selectivity is carried out in the unsaturated organic polymer of alkene copolymer etc. and adds hydrogen, and this method carries out in aqueous emulsion.
From the point of view of patent literature report and commercial practice, nickel system, cobalt system catalyst system catalysis SBS hydrogenation plus hydrogen
Time is longer, and degree of hydrogenation is lower, and luxuriant titanium catalyst system is not easy to store as hydrogenation catalyst, easy in inactivation, wants to reaction condition
Ask harsher.In recent years, noble metal catalyst be also applied to butylbenzene copolymer plus hydrogen, the noble metal catalysts such as Rh, Ru, Pd
Because of its high activity, the features such as highly selective and reaction condition is mild, especially contains in high polymer and easily polymerize with being reduced group
Object (such as nitrile rubber) in selective hydrogenation application it is more and more extensive.SBS is carried out plus hydrogen prepares SEBS block copolymer,
Seek the catalyst system that a kind of activity is high, hydrogenation degree is high, selectivity is good, not only there is important theory significance, but also there is reality
Industrial application background, studying at present more is catalyzed by ruthenium complexes system, and adds hydrogen for SBS to Rhodium Complexes Catalyzed system
Research have not been reported.
(3) summary of the invention
That in order to compensate for the shortcomings of the prior art, the present invention provides a kind of catalyst amounts is few, activity and selectivity is high, reaction item
The preparation method of the mild hydrogenated styrene-butadiene-styrene block copolymers of part.
The present invention is achieved through the following technical solutions:
A kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers, includes the following steps:
(1) under inert gas shielding, using organolithium as catalyst, it is anti-that styrene is placed in progress one-step polymerization in cyclohexane solvent
It answers, while composite construction regulator is added, butadiene is then added and carries out two sections of polymerization reactions, benzene second is added after the completion of polymerization
Alkene carries out three sections of copolyreaction, obtains adding the basic glue SBS of hydrogen；
(2) product is obtained to adding hydrogen to carry out hydrogenation with basis glue SBS using homogeneous rhodium series catalysts.
The present invention is added composite construction regulator to prepare and adds hydrogen-based plinth glue, use in the presence of organic lithium initiator
Homogeneous rhodium series catalysts are to adding the selection of hydrogen-based plinth glue plus hydrogen；Composite construction regulator can carry out spirit to the structure for adding hydrogen-based plinth glue
Quick adjusting, composite construction regulator does not influence hydrogenation reaction almost without residual after reaction.
In step (1), inert gas is nitrogen, and organolithium is n-BuLi, and butadiene is polymer grade butadiene, composite junction
Structure regulator is the structure regulator that ether compound and aminated compounds compound.
Wherein, the ether compound is glycol ether or propylene glycol, and aminated compounds is tetramethyl-ethylene base diamines
Or pentamethyldivinyltriamine；The compounding molar ratio of ether compound and aminated compounds is 0.1-5.0.
The molar ratio of composite construction regulator and organolithium is 0.1-1.0, adds the hydrogen to be with the molecular weight of basis glue SBS
65000-150000, wherein the mass ratio of butadiene and styrene is 30:70-40:60, and the mass fraction of vinyl is 30-
70%。
In step (2), the homogeneous rhodium series catalysts are made of the major catalyst that molar ratio is 1-15 and co-catalyst,
In, major catalyst is rhodium compound, and co-catalyst is phosphine compound.
The preparation method of the homogeneous rhodium series catalysts is to be placed in a reaction flask phosphine compound, is dissolved with ethyl alcohol, nitrogen
Heating Water after displacement three times is stirred at reflux to being completely dissolved；After rhodium compound is dissolved with ethyl alcohol, importing fills phosphine compound
Reaction flask in, constant temperature water bath reaction after, reaction product is filtered, washed in nitrogen atmosphere to get product.
Wherein, it is trimethyl that rhodium compound, which is four carbonyl of dichloro, two rhodium, radium chloride, rhodium caprylate or rhodium nitrate, phosphine compound,
Phosphine, triphenylphosphine, tri isopropyl phosphine or tributylphosphine.
Add hydrogen basis glue SBS in the presence of homogeneous rhodium series catalysts, is passed through pressurized with hydrogen, is heated to hydrogen temperature under stirring
Degree carries out hydrogenation reaction, and homogeneous rhodium series catalysts dosage is the 0.01-0.3%, hydrogenation temperature 40-180 of basic glue SBS mass
DEG C and the love time be 20-300min, hydrogenation pressure 0.5-3.5MPa.
The present invention, as hydrogenation catalyst, controls hydrogenation temperature, hydrogenation time, hydrogenation pressure using homogeneous rhodium series catalysts
With the reaction conditions such as speed of agitator, the SEBS that degree of hydrogenation is greater than 99% can be prepared.
Process provided by the invention, has the advantages that
(1) plus the microstructure of hydrogen-based plinth glue SBS has decisive influence to hydrogenation reaction, is prepared by SEBS to its structure control
Key link in journey, structure regulator dosage used in this method is lower, adjusts high sensitivity to structure；
(2) this method reaction condition is mild, and less than 70 DEG C, hydrogenation pressure controls within 1MPa hydrogenation temperature；
(3) the catalyst amount base of this method, reaction time are no more than 1 hour, degree of hydrogenation >=99%.
Rationally, hydrogenation catalyst dosage is less for present invention process design, and catalyst activity and selectivity is high, reaction condition temperature
With product purity and high income, suitable for wide popularization and application.
(4) specific embodiment
The present invention will be further detailed in the following examples, but the range being not intended to limit the present invention.
Embodiment 1:
(common N under inert gas protection2Make protection gas), it is original with the existing polymer grade butadiene of company, self-produced styrene
Material selects glycol ether/tetramethyl-ethylene base diamines compounding structure regulator using n-BuLi as anionic catalyst,
In the item that monomer ratio (St/Bd) is 30/70,5 hours reaction time, 60 DEG C of reaction temperature, structure regulator/catalyst are 0.1
The basic glue SBS for being suitble to add hydrogen is synthesized under part, calculating 1,2 structural contents in SBS product through infra-red sepectrometry is 28.7%.
Embodiment 2:
Experimentation is with embodiment 1, and structure regulator selects propylene glycol/pentamethyldivinyltriamine, knot in experimentation
Structure regulator/Li is 1.0, and calculating 1,2 structural contents in SBS product through infra-red sepectrometry is 65.7%.
Embodiment 3:
Experimentation is with embodiment 1, and structure regulator selects propylene glycol/pentamethyldivinyltriamine, knot in experimentation
Structure regulator/Li is 0.5, and calculating 1,2 structural contents in SBS product through infra-red sepectrometry is 45.2%.
Embodiment 4:
(common N under inert gas protection2Make protection gas), it is original with the existing polymer grade butadiene of company, self-produced styrene
Material selects glycol ether/tetramethyl-ethylene base diamines compounding structure regulator using n-BuLi as anionic catalyst,
Under conditions of monomer ratio (St/Bd) is 30/70, reaction 5 hours, 60 DEG C of reaction temperature, structure regulator/catalyst are 0.5
Synthesis is suitble to plus the basic glue SBS of hydrogen.
It takes a certain amount of ligand tri isopropyl phosphine that reaction flask is added, is dissolved with ethyl alcohol, take a certain amount of rhodium compound chlorination
Rhodium is poured into after being dissolved with ethyl alcohol in the reaction flask for filling phosphine compound, isothermal reaction certain time, by reaction product in nitrogen gas
It is filtered, washed in atmosphere, can be obtained and add hydrogen final catalyst.
It will add hydrogen-based plinth glue SBS in the presence of above-mentioned catalyst, and be passed through pressurized with hydrogen, be heated to hydrogenation temperature under stiring
Hydrogenation reaction is carried out, hydrogenation catalyst dosage is 0.02g/100gSBS, and 50 DEG C of hydrogenation temperature, hydrogenation time 50min adds hydrogen pressure
Power 1.0MPa is 98.9% using nuclear magnetic resonance spectroscopy test degree of hydrogenation.
Embodiment 5:
Ligand is become triphenylphosphine in catalyst preparation process with embodiment 4 by experimentation, and rhodium based compound becomes octanoic acid
Rhodium, other conditions are constant, are 99.8% using nuclear magnetic resonance spectroscopy test degree of hydrogenation.
Embodiment 6:
Ligand is become tributylphosphine in catalyst preparation process, rhodium based compound becomes nitric acid with embodiment 4 by experimentation
Rhodium, other conditions are constant, are 97.6% using nuclear magnetic resonance spectroscopy test degree of hydrogenation.
Embodiment 7:
Experimentation is with embodiment 5, and it is 0.3g/100gSBS that experimentation, which changes catalyst amount, and other conditions are constant, utilizes
It is 99.9% that nuclear magnetic resonance spectroscopy, which tests degree of hydrogenation,.
Embodiment 8:
Experimentation changes 180 DEG C of hydrogenation temperature with embodiment 5, experimentation, and other conditions are constant, utilize nuclear magnetic resonance spectroscopy
Testing degree of hydrogenation is 96.9%.
Embodiment 9:
Experimentation is with embodiment 5, and it is 300min that experimentation, which changes hydrogenation time, and other conditions are constant, utilize nuclear magnetic resonance
Hydrogen spectrum test degree of hydrogenation is 99.9%.
Embodiment 10:
Experimentation is with embodiment 5, and it is 3.5MPa that experimentation, which changes hydrogenation pressure, and other conditions are constant, utilize nuclear magnetic resonance
Hydrogen spectrum test degree of hydrogenation is 99.5%.
Claims (8)
1. a kind of preparation method of hydrogenated styrene-butadiene-styrene block copolymers, it is characterized in that, include the following steps:
(1) under inert gas shielding, using organolithium as catalyst, styrene is placed in progress one-step polymerization reaction in cyclohexane solvent,
Composite construction regulator is added simultaneously, butadiene is then added and carries out two sections of polymerization reactions, styrene is added after the completion of polymerization
Three sections of copolyreaction are carried out, obtain adding the basic glue SBS of hydrogen；(2) using homogeneous rhodium series catalysts to add hydrogen basis glue SBS into
Row hydrogenation, obtains product.
2. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
Be: in step (1), inert gas is nitrogen, and organolithium is n-BuLi, and butadiene is polymer grade butadiene, composite construction
Regulator is the structure regulator that ether compound and aminated compounds compound.
3. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
Be: in step (1), the molar ratio of composite construction regulator and organolithium is 0.1-1.0, adds the molecule of the basic glue SBS of hydrogen
Amount is 65000-150000, wherein the mass ratio of butadiene and styrene is 30:70-40:60, and the mass fraction of vinyl is
30-70%。
4. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
Be: in step (2), the homogeneous rhodium series catalysts are made of the major catalyst that molar ratio is 1-15 and co-catalyst, wherein
Major catalyst is rhodium compound, and co-catalyst is phosphine compound.
5. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 1, feature
It is: in step (2), adds hydrogen basis glue SBS in the presence of homogeneous rhodium series catalysts, be passed through pressurized with hydrogen, stirs lower heating
Hydrogenation reaction is carried out to hydrogenation temperature, homogeneous rhodium series catalysts dosage is the 0.01-0.3% of basic glue SBS mass, hydrogenation temperature
It is 20-300min, hydrogenation pressure 0.5-3.5MPa for 40-180 DEG C and love time.
6. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 2, feature
Be: the ether compound is glycol ether or propylene glycol, and aminated compounds is tetramethyl-ethylene base diamines or pentamethyl
Diethylene triamine；The compounding molar ratio of ether compound and aminated compounds is 0.1-5.0.
7. the preparation method of hydrogenated styrene-butadiene-styrene block copolymers according to claim 4, feature
Be: the preparation method of the homogeneous rhodium series catalysts is to be placed in a reaction flask phosphine compound, is dissolved with ethyl alcohol, nitrogen is set
Heating Water after changing three times is stirred at reflux to being completely dissolved；After rhodium compound is dissolved with ethyl alcohol, importing fills phosphine compound
In reaction flask, after constant temperature water bath reaction, reaction product is filtered, washed in nitrogen atmosphere to get product.
8. the preparation method of the hydrogenated styrene-butadiene-styrene block copolymers according to claim 4 or 7, special
Sign is: the rhodium compound be four carbonyl of dichloro, two rhodium, radium chloride, rhodium caprylate or rhodium nitrate, phosphine compound be trimethyl-phosphine,
Triphenylphosphine, tri isopropyl phosphine or tributylphosphine.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157565A (en) * | 2020-01-20 | 2020-05-15 | 极晨智道信息技术(北京)有限公司 | Method for analyzing hydrogenation degree of styrene butadiene rubber SEBS (styrene-butadiene-styrene block copolymer) by utilizing nuclear magnetic resonance technology |
| CN111205416A (en) * | 2020-03-18 | 2020-05-29 | 山东润科化工股份有限公司 | Preparation method of styrene-butadiene-styrene block copolymer |
| CN113278119A (en) * | 2021-07-08 | 2021-08-20 | 广东众和高新科技有限公司 | Hydrogenated styrene-butadiene block copolymer and preparation method and application thereof |
| CN115895094A (en) * | 2022-10-27 | 2023-04-04 | 泉州匹克鞋业有限公司 | Composition for ultralight elastic sole and preparation method thereof |
| CN115947880A (en) * | 2023-03-10 | 2023-04-11 | 南京聚隆科技股份有限公司 | Preparation method of SEBS (styrene-ethylene-butadiene-styrene) by catalytic hydrogenation of ionic liquid-ruthenium/rhodium phosphine |
| CN116162215A (en) * | 2022-12-27 | 2023-05-26 | 沈阳化工研究院有限公司 | Polyolefin triblock copolymer and preparation method and application thereof |
| CN117003652A (en) * | 2022-04-28 | 2023-11-07 | 中国石油化工股份有限公司 | A kind of N,N-dimethylaminoglycol ether and its preparation and application as polymerization structure regulator |
| CN119176919A (en) * | 2023-06-21 | 2024-12-24 | 中国石油化工股份有限公司 | SEBS synthesis method with side chains uniformly distributed |
| CN119724383A (en) * | 2023-09-27 | 2025-03-28 | 中国石油化工股份有限公司 | SEBS hydrogenation degree prediction and precise control method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2061961A (en) * | 1979-10-26 | 1981-05-20 | Asahi Chemical Ind | Catalytic hydrogenation of diene copolymers |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | A kind of method for the hydrogenation of unsaturated copolymer and its used bimetallic catalyst system |
| CN1491236A (en) * | 2000-12-21 | 2004-04-21 | 阿托菲纳公司 | Hydrogenation method of unsaturated block copolymer and hydrogenated block copolymer |
| CN101280034A (en) * | 2008-05-23 | 2008-10-08 | 北京化工大学 | Method for controlling the vinyl content of polybutadiene in elastomers |
-
2018
- 2018-12-25 CN CN201811591353.8A patent/CN109810209A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2061961A (en) * | 1979-10-26 | 1981-05-20 | Asahi Chemical Ind | Catalytic hydrogenation of diene copolymers |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | A kind of method for the hydrogenation of unsaturated copolymer and its used bimetallic catalyst system |
| CN1491236A (en) * | 2000-12-21 | 2004-04-21 | 阿托菲纳公司 | Hydrogenation method of unsaturated block copolymer and hydrogenated block copolymer |
| CN101280034A (en) * | 2008-05-23 | 2008-10-08 | 北京化工大学 | Method for controlling the vinyl content of polybutadiene in elastomers |
Non-Patent Citations (2)
| Title |
|---|
| 杨京伟等: "苯乙烯-丁二烯-苯乙烯三嵌段共聚物新型加氢催化剂的研究", 《高分子学报》 * |
| 胡桢等: "《新型高分子合成与制备工艺》", 31 May 2014, 哈尔滨工业大学出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111205416A (en) * | 2020-03-18 | 2020-05-29 | 山东润科化工股份有限公司 | Preparation method of styrene-butadiene-styrene block copolymer |
| CN113278119A (en) * | 2021-07-08 | 2021-08-20 | 广东众和高新科技有限公司 | Hydrogenated styrene-butadiene block copolymer and preparation method and application thereof |
| CN117003652A (en) * | 2022-04-28 | 2023-11-07 | 中国石油化工股份有限公司 | A kind of N,N-dimethylaminoglycol ether and its preparation and application as polymerization structure regulator |
| CN115895094A (en) * | 2022-10-27 | 2023-04-04 | 泉州匹克鞋业有限公司 | Composition for ultralight elastic sole and preparation method thereof |
| CN116162215A (en) * | 2022-12-27 | 2023-05-26 | 沈阳化工研究院有限公司 | Polyolefin triblock copolymer and preparation method and application thereof |
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