CN101168588B - Crystallization-amorphism-crystallization stereo triblock polybutadiene and preparation method thereof - Google Patents
Crystallization-amorphism-crystallization stereo triblock polybutadiene and preparation method thereof Download PDFInfo
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- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 29
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 28
- 238000002425 crystallisation Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000005064 Low cis polybutadiene Substances 0.000 claims abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 56
- -1 alkyl lithium Chemical compound 0.000 claims description 34
- 229910052744 lithium Inorganic materials 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 230000001588 bifunctional effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 159000000009 barium salts Chemical class 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- HDCBNJSFYPZDSJ-UHFFFAOYSA-N barium;5-methyl-2-propan-2-ylphenol Chemical compound [Ba].CC(C)C1=CC=C(C)C=C1O HDCBNJSFYPZDSJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 230000003712 anti-aging effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002790 naphthalenes Chemical class 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- PXXRRQOFRCDQHK-UHFFFAOYSA-N CC1=CC=CC2=CC=CC=C12.[Li] Chemical compound CC1=CC=CC2=CC=CC=C12.[Li] PXXRRQOFRCDQHK-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QKURYSZZHGXIFQ-UHFFFAOYSA-N [Ba].CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC Chemical compound [Ba].CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC QKURYSZZHGXIFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- FUGIIBWTNARRSF-UHFFFAOYSA-N decane-5,6-diol Chemical compound CCCCC(O)C(O)CCCC FUGIIBWTNARRSF-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical group CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229920003194 trans-1,4-polybutadiene polymer Polymers 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 230000007704 transition Effects 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000005066 High trans polybutadiene Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 238000011925 1,2-addition Methods 0.000 description 1
- ZEYRJQQZSRXHIF-UHFFFAOYSA-N 1-butylbenzo[a]anthracene Chemical compound C1=CC=CC2=CC3=C4C(CCCC)=CC=CC4=CC=C3C=C21 ZEYRJQQZSRXHIF-UHFFFAOYSA-N 0.000 description 1
- SFGSCWQCLSTTPQ-UHFFFAOYSA-N 5-phenylhexan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)CCC(C)C1=CC=CC=C1 SFGSCWQCLSTTPQ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention relates to crystalline-noncrystalline-crystalline stereotriblock polybutadiene, which belongs to the technical field of the high molecular material synthesis and the preparation. The invention is characterized in that the polymer has the following symmetric structure: HTBR-LCBR-HTBR, wherein, HTBR is high trans-1,4-polybutadiene block, LCBR is low cis-polybutadiene block, the numberaverage molecular weight of stereoblock polymer is 5*10 <4> to 55*10 <4>, the block ratio of HTBR/LCBR is 10/90 to 60/40 (weight ratio), the general range of 1, 2-structural content in the LCBR block is 5 percent to 55 percent (weight percentage), and the general range of trans-1, 4-structural content in the HTBR block is 50 percent to 95 percent (weight percentage). The invention has the advantages that the preparation method for the crystalline-noncrystalline-crystalline stereotriblock polybutadiene is provided, and important promotion effect to the characterization research work of the crystalline and noncrystalline polymer is realized.
Description
Technical field
The invention belongs to the synthetic and preparing technical field of macromolecular material; Relate to crystallization-amorphism-crystallization stereo triblock polybutadiene and preparation method thereof; This block polymer has following symplex structure: HTBR-LCBR-HTBR; Wherein: HTBR is a high trans 1 block, and LCBR is the low-cis-polybutadiene block.The prepared upright structure triblock polymer over-all properties of the present invention is better, and wet-sliding resistant performance, anti-cold flow properties, wear resisting property can reach balance preferably.
Background technology
Polyhutadiene has cis 1 usually, 4-, trans 1,4-, 1, three kinds of structures of 2-addition.When adopting lithium alkylide to be initiator, divinyl is polymerization in non-polar solvent, and prepared polyhutadiene is low-cis-polybutadiene (LCBR); Its microtexture is: 1, and 2-addition number of structures is about 8%, cis 1; 4-addition structure is about 42%, and is trans 1, and 4-addition structure is about 50%.When in above-mentioned system, adding a certain amount of polar additive, the microtexture of gained polyhutadiene, its 1,2-addition number of structures increases along with the increase of polar additive consumption.
High trans 1; The 4-polyhutadiene has advantages such as stress at definite elongation is big, hardness is high, wear resisting property is good, good resistance to fatigue and anti-breach generation and extendability, lower compression heat generation are low, higher draw tensile strength, is the ideal material of development high-performance radial.The catalystsystem of trans-polybutadiene rubber mainly contains titanium system, nickel system, group of the lanthanides, chromium system, vanadium system, lithium system etc.Lithium system adopts lithium alkylide to be initiator, to synthesize high trans-polybutadiene based on the living anion polymerization method; Other catalystsystem all is difficult to realize living polymerization and the preparation that can't be used for block polymer; Therefore; Lithium is that polymerization method is the most effectively means of preparation high trans 1 block polymer.Adopt second main group pure salt-aluminum alkyls-first main group metal catalystsystem to synthesize high trans 1; 4-structure/high by 1; 2-structure diblock polyhutadiene appear in the newspapers (USP 4669518, Tire tread having high trans butadiene based elastomeric blockcopolymers and blends, 1987); But adopting the bifunctional alkyl lithium initiator to prepare three block high trans 1 does not appear in the newspapers as yet.With diblock high trans 1; 4-polyhutadiene " crystallization-noncrystalline " (hard-soft) structure is compared, and three block high trans 1 have " crystallization-noncrystalline-crystallization " (hard-soft-hard) structure; Characteristic with thermoplastic elastomer, its over-all properties has remarkable advantages.
Be used for the synthetic high trans 1 of living anion polymerization method; The initiator system of 4-polyhutadiene comprises: (a) organolithium compound (lithium alkylide); (b) organo-aluminium compound (aluminum alkyls), (c) the second main group metal organic salt (organic barium salt), (d) alcohol or alkoxyl group lithium; (e) polar additive, wherein (d) and (e) be for optional in the system in catalysis.Initiator system used in the present invention select oneself the technology disclosed any initiator system that the lithium alkylide initiator system prepares trans polybutadiene that can be used for, generally be selected from lithium alkylide, organic barium salt, aluminum alkyls ternary system.
Summary of the invention
The objective of the invention is to prepare the upright structure triblock polybutadiene of one type of crystallization, one a noncrystalline crystallization; Through control stereoblock structure; The stereoblock ratio of concrete control HTBR and LCBR, control in the HTBR stereoblock trans 1; In 4-structural content, the control LCBR stereoblock 1; The molecular weight of 2-structural content, controlling polymers not only can prepare rubber with special performance but also can be made by a kind of monomer and is similar to the thermoplastic elastomer that SBS (divinyl, styrene triblock copolymer), SIS (isoprene, styrene triblock copolymer) have the micron-scale phase separation structure.
The prepared crystallization-amorphism-crystallization stereo triblock polybutadiene of the present invention has following symplex structure: HTBR-LCBR-HTBR, wherein: HTBR, LCBR connotation as stated, the number-average molecular weight general range of stereo-block polymer is 5 * 10
4～55 * 10
4, optimum range is 10 * 10
4～35 * 10
4The HTBR/LCBR block is 10/90～60/40 (weight ratio, below identical) than general range, and optimum range is 20/80-40/60; In the LCBR block 1,2-structural content general range is 5%～55% (weight percent, below identical), and optimum range is 10%～35%; Trans 1 in the HTBR block, 4-structural content general range is 50%～95% (weight percent, below identical); Optimum range is 65%～95%.
The preparation method of crystallization-amorphism-crystallization stereo triblock polybutadiene involved in the present invention is following:
In the non-polar hydrocarbon kind solvent, once join divinylic monomer in the reactor drum; Monomer concentration is 10%～20% (weight percent); Simultaneously optional polar additive is joined in the reactor drum, the requirement of looking LCBR block microtexture determines whether to use polar additive, and the kind of polar additive and consumption are looked the value of 1.2-structural content in the LCBR block and decided; Open stirring; After reaching kick off temperature, the initiation reaction temperature is 30 ℃～80 ℃, adds the bifunctional alkyl lithium initiator; The consumption of bifunctional alkyl lithium initiator is decided according to the size of required polymkeric substance number-average molecular weight, and the number-average molecular weight scope of block polymer is generally 5 * 10
4～55 * 10
4The bifunctional alkyl lithium initiator is selected from the mixture of a kind of bifunctional alkyl lithium initiator or several kinds of bifunctional alkyl lithium initiators; Generally be selected from two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof, the two lithiums of naphthalene class, the two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof; At first cause polymerizing butadiene and prepare the LCBR block, when LCBR block length reaches preset value, add structure regulator aluminum alkyls and organic barium salt simultaneously; Begin to prepare the HTBR block; To look its kind, HTBR block trans 1 because of its regulating power different for the consumption of aluminum alkyls and organic barium salt, the height of 4-structural content and deciding, and the joining day of aluminum alkyls and organic barium salt decides according to the block ratio of HTBR/LCBR.In the HTBR block trans 1; 4-structural content general range is 50%～95% (weight percent), and the general range of HTBR/LCBR block ratio is 10/90～60/40 (weight ratio), after the divinyl total overall reaction finishes; Add anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4); Adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the upright structure triblock polymer of HTBR-LCBR-HTBR.
Initiator used in the present invention is the bifunctional alkyl lithium initiator, is selected from the mixture of one or more bifunctional alkyl lithium initiators, and the bifunctional alkyl lithium initiator generally is selected from: two lithiums of (1) two haloalkane hydro carbons and the two lithiums of oligopolymer thereof; Its structural formula is LiRLi, Li (DO) nR (DO) nLi, and wherein: R is that carbonatoms is 4～10 alkyl, and DO is that carbonatoms is 4～8 a kind of conjugated diene or the mixture of several kinds of conjugated dienes; With 1,3-butadiene, isoprene is good, and n is the oligomerisation degree; N is generally 2～8, is good with 3～6, and two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof generally are selected from: 1; 4-two lithium butane, 1,2-two lithiums-1,2-diphenylethane, 1; 4-two lithiums-1,1,4; 4-tetraphenyl butane, 1,4-dimethyl--1,4-diphenyl butane two lithiums, polyhutadiene two lithium oligopolymers, TR 301 two lithium oligopolymers; (2) the two lithiums of naphthalene class generally are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium; (3) two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof generally are selected from: 1,1 '-(1; The 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1, the two lithiums, 1 of 1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer; The two lithiums, 1 of 1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, 1 '-(1; The 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1, the two lithiums, 1 of 1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer; The two lithiums of 1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer.
Organic barium salt used in the present invention select oneself the technology disclosed any organic barium salt that the lithium alkylide initiator system prepares trans polybutadiene that can be used for; Generally be selected from: the mixture of one or more the organic barium salts in the phenates of the alcohol ether salt of alkoxyl group barium salt, cycloalkyloxy barium salt, barium, the pure ammonium salt of barium, barium; More preferably certainly: the terepthaloyl moietie ammonium salt of glycol ether salt, barium, preferably certainly: thymol barium, diethylene glycol monoethyl ether base barium, dinonyl phenol barium.
Aluminum alkyls used in the present invention select oneself the technology disclosed any aluminum alkyls that the lithium alkylide initiator system prepares trans polybutadiene that can be used for; Generally be selected from: the mixture of one or more aluminum alkylss in trimethylaluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three tertiary butyl aluminium and the tri-butyl aluminum, preferably certainly: triethyl aluminum, triisobutyl aluminium.
Polar additive used in the present invention is selected from the mixture that contains oxygen, nitrogenous, sulfur-bearing, contains one or more polar compounds in the Phosphorus polar compound, as: (1) oxygenatedchemicals generally is selected from: ether, THF, R
1OCH
2CH
2OR
2(wherein: R
1, R
2Be that carbonatoms is 1～6 alkyl, R
1, R
2Can be identical also can be different, with R
1, R
2Be not all good, like glycol dimethyl ether, ethylene glycol diethyl ether), R
1OCH
2CH
2OCH
2CH
2OR
2(wherein: R
1, R
2Be that carbonatoms is 1～6 alkyl, R
1, R
2Can be identical also can be different, with R
1, R
2Be not all good, like diethylene glycol dimethyl ether, dibutyl ethylene glycol ether), crown ether; (2) nitrogenous compound generally is selected from: triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane (DPE), preferred TMEDA; (3) P contained compound is generally selected HMPA (HMPA) for use.
Non-polar organic solvent used in the present invention is selected from the mixture of one or more varsols in nonpolar aromatic hydrocarbons and the nonpolar fatty hydrocarbon; Generally be selected from: benzene, toluene, ethylbenzene, YLENE, pentane, hexane, heptane, octane, hexanaphthene, BTX aromatics (as: Mixed XYLENE), mixing-in fat hydrocarbon (as: raffinating oil) etc., preferably from: hexane, hexanaphthene, raffinate oil.
The used terminator of the present invention is the disclosed any terminator that can be used for anionic polymerisation of prior art, as: water, methyl alcohol, ethanol or Virahol etc.
Effect of the present invention and benefit have provided the preparation method of the upright structure triblock polybutadiene of crystallization-noncrystalline-crystallization, and the characterization research work of crystallization and non-crystalline polymer is had important promoter action.
Description of drawings
Accompanying drawing is poor formula scanning calorimetric (DSC) curve of crystallization-amorphism-crystallization stereo triblock polybutadiene.
Embodiment
Further specify the present invention below in conjunction with embodiment, Comparative Examples, but and the scope of unrestricted claim protection of the present invention.
Embodiment 1
In 5 liters of stainless steel cauldrons that have a stirring; Add 3.5 liters of hexanaphthenes, 350 gram divinyl, be warmed up to 60 ℃, add bifunctional alkyl lithium initiator 1; 1 '-(1; The 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums begin to prepare the LCBR block, and the lithium alkylide consumption is 8 * 10 by the polymkeric substance number-average molecular weight
4Metering when the butadiene polymerization transformation efficiency reaches 50%, adds thymol barium (BAT) and triisobutyl aluminium; Begin to prepare the HTBR block, thymol barium (BAT) consumption is 0.5mmolBa/100gBd (divinyl), and the triisobutyl aluminium consumption is pressed Ba/Al/Li than being (mol ratio) 1.0/4.0/4.0 metering; Continue reaction up to the whole polymerizations of divinyl, after butadiene polymerization is all over, adds anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) 3.5 and restrain; Adopt traditional method to carry out the glue aftertreatment, obtain the upright structure triblock polybutadiene of HTBR-LCBR-HTBR after the drying, the block ratio is 25/50/25; It adopts classical way specimen structure and performance, and the DSC curve of the upright structure triblock polybutadiene of HTBR-LCBR-HTBR is as shown in Figure 1, and the result is following: in the upright structure triblock polybutadiene trans 1; 4-structure total content is 60.8%; Trans 1 in the HTBR block, the 4-structural content is 77.0%, and molecular weight distributing index is 1.56; Second-order transition temperature is-92.5 ℃, and Tc (the pairing temperature value of peak crystallization vertex) is-64.4 ℃.
Embodiment 2
When the butadiene polymerization transformation efficiency reaches 70%, add thymol barium (BAT) and triisobutyl aluminium, other preparation condition and embodiment 1 are identical; The upright structure triblock polybutadiene block ratio of prepared HTBR-LCBR-HTBR is 15/70/15; Its structure and results of performance analysis are following: trans 1 in the upright structure triblock polybutadiene, 4-structure total content is 57.5%, in the HTBR block trans 1; The 4-structural content is 77.0%; Molecular weight distributing index is 1.30, and second-order transition temperature is-92.1 ℃, and Tc is-65.8 ℃.
Embodiment 3
When the butadiene polymerization transformation efficiency reaches 30%, add thymol barium (BAT) and triisobutyl aluminium, other preparation condition and embodiment 1 are identical; The upright structure triblock polybutadiene block ratio of prepared HTBR-LCBR-HTBR is 35/30/35; Its structure and results of performance analysis are following: trans 1 in the upright structure triblock polybutadiene, 4-structure total content is 67.5%, in the HTBR block trans 1; The 4-structural content is 77.0%; Molecular weight distributing index is 1.38, and second-order transition temperature is-91.4 ℃, and Tc is-64.1 ℃.
Embodiment 4
Barium salt adopts diethylene glycol monoethyl ether base barium (BaDEGEE), and other preparation condition and embodiment 1 are identical, and the upright structure triblock polybutadiene block ratio of prepared HTBR-LCBR-HTBR is 25/50/25; Its structure and results of performance analysis are following: trans 1 in the upright structure triblock polybutadiene, 4-structure total content is 62.2%, in the HTBR block trans 1; The 4-structural content is 75.2%; Molecular weight distributing index is 1.32, and second-order transition temperature is-92.5 ℃, and Tc is-64.9 ℃.
Comparative Examples 1
In 5 liters of stainless steel cauldrons that have a stirring, add 3.5 liters of hexanaphthenes, 350 gram divinyl, be warmed up to 60 ℃; Add thymol barium (BAT) and triisobutyl aluminium; Begin to prepare the HTBR block, thymol barium (BAT) consumption is 0.5mmolBa/100g Bd (divinyl), and the triisobutyl aluminium consumption is pressed Ba/Al/Li than being (mol ratio) 1.0/4.0/4.0 metering; Add n-butyl lithium initiator, the n-Butyl Lithium consumption is 8 * 10 by the polymkeric substance number-average molecular weight
4Metering after butadiene polymerization is all over, adds anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) 3.5 and restrains; Adopt traditional method to carry out the glue aftertreatment, obtain high trans-polybutadiene HTBR after the drying, adopt classical way specimen structure and performance; The result is following: trans 1 in the polyhutadiene, the 4-structural content is 78.1%, and molecular weight distributing index is 1.33; Second-order transition temperature is-90.8 ℃, and no peak crystallization occurs.
Comparative Examples 2
In 5 liters of stainless steel cauldrons that have a stirring, add 3.5 liters of hexanaphthenes, 350 gram divinyl, be warmed up to 60 ℃, add n-butyl lithium initiator, begin to prepare the LCBR block, the n-Butyl Lithium consumption is 8 * 10 by the polymkeric substance number-average molecular weight
4Metering when the butadiene polymerization transformation efficiency reaches 50%, adds thymol barium (BAT) and triisobutyl aluminium; Begin to prepare the HTBR block, thymol barium (BAT) consumption is 0.5mmolBa/100g Bd (divinyl), and the triisobutyl aluminium consumption is pressed Ba/Al/Li than being (mol ratio) 1.0/4.0/4.0 metering; Continue reaction up to the whole polymerizations of divinyl, after butadiene polymerization is all over, adds anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) 3.5 and restrain; Adopt traditional method to carry out the glue aftertreatment, obtain the upright structure diblock polyhutadiene of LCBR-HTBR after the drying, the block ratio is 50/50; It adopts classical way specimen structure and performance, and the result is following: trans 1 in the upright structure diblock polyhutadiene, 4-structure total content is 61.8%; Trans 1 in the HTBR block, the 4-structural content is 77.0%, and molecular weight distributing index is 1.46; Have two second-order transition temperatures: one of which is-93.5 ℃, and it two is-52.3 ℃.
Claims (21)
1. the crystallization-amorphism-crystallization stereo triblock polybutadiene is characterized in that this block polymer has following symplex structure: HTBR-LCBR-HTBR, and wherein: HTBR is a high trans 1 block; LCBR is the low-cis-polybutadiene block; The number-average molecular weight of stereo-block polymer is 5 * 10
4～55 * 10
4Block is 10/90～60/40 (weight ratio) than HTBR/LCBR, and in the LCBR block 1, the 2-structural content is 5%～55% (weight ratio), and trans 1 in the HTBR block, the 4-structural content is 50%～95% (weight ratio).
2. crystallization-amorphism-crystallization stereo triblock polybutadiene according to claim 1 is characterized in that wherein the number-average molecular weight of block polymer is 10 * 10
4～35 * 10
4
3. crystallization-amorphism-crystallization stereo triblock polybutadiene according to claim 1 is characterized in that block is 20/80～40/60 (weight ratio) than HTBR/LCBR.
4. crystallization-amorphism-crystallization stereo triblock polybutadiene according to claim 1 is characterized in that in the LCBR block 1, and the 2-structural content is 10%～35% (weight ratio).
5. crystallization-amorphism-crystallization stereo triblock polybutadiene according to claim 1 is characterized in that in the HTBR block transly 1, and the 4-structural content is 65%～90% (weight ratio).
6. the method for preparing the described crystallization-amorphism-crystallization stereo triblock polybutadiene of claim 1; It is characterized in that: in the non-polar hydrocarbon kind solvent, divinylic monomer is once joined in the reactor drum, monomer concentration is 10%～20% (weight ratio), simultaneously optional polar additive is joined in the reactor drum; The requirement of looking LCBR block microtexture determines whether to use polar additive; And the kind of polar additive and consumption are looked the value of 1.2-structural content in the LCBR block and are decided, and open stirring, reach kick off temperature after; The initiation reaction temperature is 30 ℃～80 ℃; Add the bifunctional alkyl lithium initiator, the consumption of bifunctional alkyl lithium initiator is decided according to the size of required polymkeric substance number-average molecular weight, and the number-average molecular weight of block polymer is 5 * 10
4～55 * 10
4, the bifunctional alkyl lithium initiator is selected from the mixture of a kind of bifunctional alkyl lithium initiator or several kinds of bifunctional alkyl lithium initiators, at first causes polymerizing butadiene and prepares the LCBR block; When LCBR block length reaches preset value, add structure regulator aluminum alkyls and organic barium salt simultaneously, begin to prepare the HTBR block; The consumption of aluminum alkyls and organic barium salt is because of different its kind, the HTBR blocks trans 1 looked of its regulating power; The height of 4-structural content and deciding, the joining day of aluminum alkyls and organic barium salt decides according to the block ratio of HTBR/LCBR, after the divinyl total overall reaction finishes; Adding 1010 and 2.6.4 are with weight ratio 1:1 blended anti-aging agent; Adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain the upright structure triblock polymer of HTBR-LCBR-HTBR; Wherein polar additive is selected from the mixture that contains oxygen, nitrogenous, sulfur-bearing, one or more polar compounds in phosphorous.
7. method according to claim 6; Wherein the bifunctional alkyl lithium initiator is selected from: (1) LiRLi, Li (DO) nR (DO) nLi; R is that carbonatoms is 4～10 alkyl; DO is that carbonatoms is 4～8 a kind of conjugated diene or the mixture of several kinds of conjugated dienes, and n is the oligomerisation degree, and n is 2～8; (2) the two lithiums of naphthalene class; (3) two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof.
8. method according to claim 7, wherein conjugated diene is selected from divinyl, isoprene, and oligomerisation degree n is 3～6.
9. method according to claim 7, wherein two lithiums of diene hydro carbons and oligopolymer dilithium initiator thereof are selected from: 1,1 '-(1; The 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1, the two lithiums, 1 of 1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer; 1 '-(1; The 3-penylene)-two two lithiums, 1 of [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, 1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1; 1 '-(1; The 4-penylene)-two two lithiums, 1 of [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, the two lithiums of 1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer.
10. method according to claim 7, wherein the two lithiums of naphthalene class are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium.
11. method according to claim 6, wherein organic barium salt is selected from: the alcohol ether salt of alkoxyl group barium salt, cycloalkyloxy barium salt, barium, the pure ammonium salt of barium, the phenates of barium.
12. method according to claim 11, wherein organic barium salt is selected from: thymol barium, diethylene glycol monoethyl ether base barium, dinonyl phenol barium.
13. method according to claim 6, wherein aluminum alkyls is selected from: trimethylaluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, three tertiary butyl aluminium, tri-butyl aluminum.
14. method according to claim 13, wherein aluminum alkyls is selected from: triethyl aluminum, triisobutyl aluminium.
15. method according to claim 6, wherein the non-polar hydrocarbon kind solvent is selected from: benzene, toluene, ethylbenzene, YLENE, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil.
16. method according to claim 15, wherein the non-polar hydrocarbon kind solvent is selected from: hexane, hexanaphthene, raffinate oil.
17. method according to claim 6 wherein contains the oxygen polar additive and is selected from: ether, THF, R
1OCH
2CH
2OR
2, R
1OCH
2CH
2OCH
2CH
2OR
2, wherein: R
1, R
2Be that carbonatoms is 1～6 alkyl, R
1, R
2Identical or different.
18. method according to claim 17 wherein contains the oxygen polar additive and is selected from: glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether.
19. method according to claim 6, wherein nitrogenous polar additive is selected from: triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
20. method according to claim 19, wherein nitrogenous polar additive is selected from: Tetramethyl Ethylene Diamine.
21. method according to claim 6, wherein phosphorous polar additive is selected HMPA for use.
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