CN100338104C - 聚异丁烯的制备 - Google Patents
聚异丁烯的制备 Download PDFInfo
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- CN100338104C CN100338104C CNB2004800027013A CN200480002701A CN100338104C CN 100338104 C CN100338104 C CN 100338104C CN B2004800027013 A CNB2004800027013 A CN B2004800027013A CN 200480002701 A CN200480002701 A CN 200480002701A CN 100338104 C CN100338104 C CN 100338104C
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- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006471 dimerization reaction Methods 0.000 claims description 3
- 229920001083 polybutene Polymers 0.000 claims description 3
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004435 Oxo alcohol Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 150000001299 aldehydes Chemical class 0.000 abstract description 4
- 150000002576 ketones Chemical class 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- -1 boron trifluoride ether complexes Chemical class 0.000 description 4
- 230000003750 conditioning effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000005068 transpiration Effects 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007616 round robin method Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
- C08F110/10—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
- C08F4/14—Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本文描述了一种制备亚乙烯端基占至少75mol%的聚异丁烯的方法，其中，在以下组成的三氟化硼络合物催化剂的存在下，使异丁烯或异丁烯类烃混合物在液相中聚合，(BF3)a·L1 b·L2 c·L3 d，其中L1是水、伯C1-C5-链烷醇和/或仲C3-C5-链烷醇，L2是至少一种醛和/或一种酮，L3是有至少5个碳原子的醚，有至少6个碳原子的仲链烷醇，有至少6个碳原子的伯链烷醇和/或叔链烷醇，比值b∶a在0.9到3.0的范围内，比值c∶a在0.01到0.5的范围内，比值d∶a在0到1.0的范围内。
Description
本发明涉及亚乙烯基端基占至少75mol％的聚异丁烯的制备
对本申请而言，亚乙烯基端基或双键端基指在聚异丁烯大分子中的位置为以下通式所示的双键。
其中R是聚异丁烯。在聚丁烯中的双键的类型和比例可用1H或13C NMR谱来测定。
这种高反应活性的聚异丁烯用作制造燃料助剂和润滑剂的中间体，例如DE-A27026Q4所述。具有2-甲基取代的亚乙烯基端基表现出最高的反应活性，而新戊基取代或位置更靠近大分子中心的双键，在常规的官能化反应中，取决于它们的位置，即使有也只有很小的反应活性。因此，在大分子中的亚乙烯基端基的比例便成了这类聚异丁烯的最重要的质量评价标准。
US5,286,823描述了通过在三氟化硼和有3到20个碳原子的仲醇和/或有2到20个碳原子的醚的存在下的异丁烯阳离子聚合制备高反应活性聚异丁烯的方法。
WO93/10063公开了的三氟化硼醚络合物，其中醚有至少一个键合到醚的氧原子上的叔碳原子。该络合物用于烯的聚合，特别是异丁烯的聚合，得到亚乙烯基含量高的聚合物。
EP-A1026175描述了至少80mol％的分子带有亚乙烯终端结构的异丁烯聚合物的制备，其采用的复合催化剂为三氟化硼，醚和醇和/或一定量的水。
在其它因素中，聚异丁烯可达到的分子量强烈地取决于三氟化硼络合物催化剂基于所使用的烯单体的相对量。较大量的催化剂产生较低的分子量，反之亦然。制备低分子量的聚异丁烯时，所需的三氟化硼的量在成本中占相当份额。萃取入水相中的催化剂的去活产物的处理也会产生相当大的废水负担。US6,407,186和WO02/40553推荐了除去催化剂和使其循环的方法。
本发明的目的是提供制备其终端亚乙烯双键含量高的聚异丁烯的方法，其中在给定三氟化硼催化剂相对量的情况下可以得到较低的分子量或者可以为了得到指定的分子量降低催化剂的量。
我们已经发现，通过在组成如下的三氟化硼络合物催化剂存在下，使异丁烯或异丁烯类烃混合物在水相中聚合制备末端亚乙烯基双键含量至少75mol％的聚异丁烯的方法可以达到这一目的，
(BF3)a·L1b·L2c·L3d
其中，
-L1是水，伯C1-C5链烷醇和/或仲C3-C5链烷醇，
-L2是至少一种醛和/或酮，
-L3是有至少5个碳原子的醚，有至少6个碳原子的仲烷醇，有至少6个碳原子的伯链烷醇和/或叔链烷醇，
-比值b∶a在0.9到3.0之间，优选1.1到2.5，
-比值c∶a在0.01到0.5之间，优选0.04到0.3，
-比值d∶a在0到1之间，优选0.1到1，特别是0.1到0.6。
可用于本发明的方法的原料(异丁烯原料)是纯异丁烯和异丁烯类烃混合物，如从裂化器来的低丁二烯C4残液或其异丁烯含量大于40重量％的异丁烯脱氢化的C4馏分。还可以使用惰性溶剂如饱和烃(如戊烷，己烷，异辛烷)或卤代烃(如二氯甲烷或三氯甲烷)。
用于本发明的方法的催化剂是三氟化硼络合物，它含有至少一种启动剂(选自水、伯C1-C5链烷醇和仲C3-C5链烷醇)，一种调节剂(选自醛和酮)，还可含有至少一种增溶剂(选自有至少5个碳原子的醚，有至少6个碳原子的仲醇，有至少6个碳原子的伯醇和叔醇)。启动剂和调节剂的特定组合影响三氟化硼的聚合活性，其影响的方式是：首先是使聚合产生低分子量的聚异丁烯，其次使三氟化硼的异构化活性(关于使聚异丁烯分子的双键端基异构化为分子内的没有反应活性或反应活性极低的双键)降低。“启动剂”，“调节剂”和“增溶剂”等名词仅作解释之用。
启动剂L1是具有键合到氧原子上面的、没受到严重的空间位阻影响的氢原子的化合物。之所以称其为“启动剂”是因为其活泼氢原子在聚异丁烯链生长开始时就被结合了。合适的L1的例子是水、甲醇、乙醇、2-丙醇和/或1-丙醇。在这些化合物中，最优选甲醇。
根据本发明，调节剂L2是醛和/或酮，其一般具有1-20个碳原子，优选2-10个碳原子，且除羰基外优选没有其它官能团。适合的L2的例子是甲醛、乙醛、丙醛、正丁醛、异丁醛、丙酮、甲乙酮和二乙酮，最优选丙酮。
增溶剂L3有增溶作用并能增加催化剂络合物在原料中的溶解度。它们是有至少5个碳原子的醚或长链和/或具有空间位阻作用的醇(它们能对异丁烯分子进入提供屏蔽)。优选使用有5到20个碳原子的二烷基醚，有6到20个碳原子的仲链烷醇，6到20个碳原子的伯链烷醇和/或C4-C20链烷叔醇。当使用伯链烷醇时优选有β分支的，即在与羟基直接相连的碳原子相邻的碳原子上具有分支。适合的代表物例如选自甲基叔丁基醚、二正丁基醚、二正己基醚、二辛醚、2-乙基己醇、2-丙基庚醇、以及二聚或三聚丁烯以及二聚、三聚、四聚丙烯的羰基合成醇、直链-1-醇(例如可由Alfol法制得的)，只要它们在反应条件下为液体即可，例如正己醇或正辛醇，和叔丁醇。所有这些化合物中，最优选2-乙基己醇。
三氟化硼络合物催化剂可以在使用之前预活化或者在聚合反应器中原位产生(如EP-A628575所述)。制备三氟化硼络合物催化剂的原料宜采用气体三氟化硼，可以是含少量二氧化硫和SiF4的工业级三氟化硼[纯度：96.5重量％]，虽然优选使用高纯度三氟化硼[纯度：99.5重量％]。特别优选使用不含四氟化硅的三氟化硼制备催化剂。
每mol烯单体优选使用0.1到25mmol，特别是0.5到10mmol的络合物催化剂(以三氟化硼计算)
异丁烯聚合优选采用连续方法。为此，可采用常规反应器如管式反应器、管束反应器或搅拌罐。优选使聚合在环管反应器(即具有恒定反应混合物循环的管状或管束反应器)中进行，进料对循环的比值F/C一般可以在1∶5到1∶500之间变化，优选在1∶10到1∶200v/v之间变化
聚合适宜在0℃以下的温度下进行，优选在0到-40℃下进行，特别是在0到-30℃之间进行，更优选在-10到-30℃下进行。一般而言，聚合在压力0.5到20巴(绝对压力)下完成。压力范围的选择主要由工艺条件决定。例如，在搅拌罐的情况下，推荐使用蒸发冷却，因此，在自生压力下即在低于大气压的压力下进行工作，而循环反应器(环管反应器)则在高于大气压的压力下进行工作更好。同时，压力和湍流加快三氟化硼的计量加入，因此，更优选使用这种类型的反应器。但是，总的来说压力的选择对聚合反应的结果并不重要。
聚合优选在等温下进行。因为该聚合反应是放热的，必须除去聚合热。这一般借助例如以液氨为冷却剂的冷却设备的运行来完成。另一方法是在反应器产物一侧以蒸发冷却的方法除去聚合热。通过异丁烯和/或异丁烯原料的其它挥发性组分的蒸发可以完成这一任务。冷却方法取决于所用反应器的类型。管状反应器优选采用例如外部冷方式使之制冷，而将反应管冷却可采用例如使用沸腾的氨冷却夹套。搅拌罐反应器优选采用内部冷却(例如冷却盘管)调节器温度，或者在产物一侧进行蒸发冷却。
被聚合的异丁烯在反应器中的停留时间在1到120分钟之间，优选5到60分钟之间，这取决于反应条件和所希望得到的聚合物的性质。
为后处理起见，宜将反应排出物导入使聚合催化剂去活的介质中以使聚合终止。为此，可从采用例如水、醇、醚、乙腈、氨、胺、或无机碱水溶液如碱金属或碱土金属的氢氧化物水溶液、这些金属的碳酸盐水溶液等等。优选采用水在20到40℃下，例如通过在压力下洗涤的方式使聚合终止。所用水的温度取决于所希望的混合温度(在此温度发生相分离)。在此后的后处理过程中，聚合混合物可以经一次或多次萃取以除去残留的催化剂，一般要经甲醇或水洗涤。在水洗中，除了催化剂之外，还将除去在聚合过程中生成的氟化氢。此后，未转化的异丁烯、溶剂和挥发性异丁烯低聚物用蒸馏法除去。采用例如薄膜蒸发器、降膜蒸发器、环形缝隙蒸发器或Sambay蒸发器从塔底物中去除残留溶剂和单体，也可以加入蒸汽和氮气。
当采用纯异丁烯作原料时，可以将其如异丁烯低聚物和溶剂一样再循环入聚合中。在使用异丁烯类C4馏分时，未转化的异丁烯和留下的C4烃一般不再循环，而是将其送入其它用途，例如制备低分子量的聚异丁烯或制备甲基叔丁基醚。含氟的挥发性副产物如仲丁基或叔丁基氟化物可以和其它烃一起从聚异丁烯中除去并以蒸馏法或萃取法使其从这些烃中分离出来。
利用本发明的方法能从异丁烯出发或从异丁烯类烃混合物出发制得高活性聚异丁烯。本发明的方法能使数均分子量的范围在500至5000道尔顿之间，优选500到5000道尔顿之间，特别是500至2500道尔顿之间，双键端基含量至少75mol％，优选至少78mol％，特别是至少80mol％。并且，所制得的聚异丁烯具有窄的分子量分布。其优选的分子量分布Mw/Mn在1.3至5之间，特别是1.3至2之间。
以下实施例用以阐述本发明。
实施例
采用具有直径6mm、长7.1m的聚四氟乙烯管的循环反应器，借助于齿轮泵使1000升/小时反应器内容物通过这根管子进行循环。聚四氟乙烯管和泵头安置在温度-25℃的冷却浴内。所用原料是烃流，其组成(重量％)如下，它是从以石脑油运行的蒸汽裂化器的C4馏分的选择丁二烯氢化而得到的。
异丁烷 3
正丁烷 14
异丁烯 28
1-丁烯 23
顺-2-丁烯 11
反-2-丁烯 21
丁二烯 0.050
加料速度是700g/小时，将原料在3分子筛上在5℃下干燥至水含量小于3ppm，预冷到-25℃，输入到循环反应器中。BF3和络合剂按下表中所述的量输入到循环泵的吸入一侧再直接进入循环反应器。反应器流出物在离开循环反应器之后立即在混合泵中用水使之快速终止，除去水相，有机相在3分子筛上干燥，在220℃和2毫巴下除去低沸物和异丁烯低聚物之后，测定所得剩余物的亚乙烯基含量，分子量Mw和Mn。
结果见下表。所有实施例的反应器内部温度都约为-18℃，异丁烯稳态浓度约4.1重量％。
| 实施例 | BF3(mmol/小时) | 甲醇(mmol/小时) | 丙酮(mmol/小时) | 2-乙基己醇(mmol/小时) | 摩尔质量MN | Mw/Mn | 亚乙烯基[％] |
| 组成 | 8.55 | 15.75 | - | 0.43 | 980 | 1.65 | 90 |
| 1 | 6.78 | 14.06 | 0.34 | 1.49 | 930 | 1.61 | 90 |
| 2 | 5.01 | 11.25 | 0.69 | 2.52 | 960 | 1.64 | 88 |
| 3 | 4.42 | 8.44 | 1.03 | 1.22 | 930 | 1.62 | 86 |
上述结果说明，在采用少量的丙酮时，可减少使用BF3而不会损害产生的聚异丁烯的性质。
Claims (3)
1.制备亚乙烯端基占至少75mol％的聚异丁烯的方法，其中，在以下组成的三氟化硼络合物催化剂的存在下，使异丁烯或异丁烯类烃混合物在液相中聚合，
(BF3)a·L1 b·L2 c·L3 d
其中
-L1是甲醇、乙醇、2-丙醇和/或1-丙醇，
-L2是丙酮、甲乙酮和/或二乙酮，
-L3是具有至少6个碳原子并具有β-分支的伯醇，
-比值b∶a在0.9到3.0的范围内，
-比值c∶a在0.01到0.5的范围内，
-比值d∶a在0.1到1.0的范围内。
2.权利要求1的方法，其中L3选自2-乙基己醇、2-丙基庚醇、二和三聚丁烯以及二聚、三聚和四聚丙烯的羰基合成醇。
3.权利要求1或2的方法，用于制备其数均分子量Mn为500到2500道尔顿的聚异丁烯。
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| EP2768871B1 (de) * | 2011-10-21 | 2015-09-30 | Basf Se | Verfahren zur herstellung von isobutenhomo- oder -copolymeren |
| KR101929082B1 (ko) | 2011-10-26 | 2018-12-13 | 티피씨 그룹 엘엘씨 | 낮은 희석제 함량 반응 매질로 제조된 폴리아이소부틸렌 |
| WO2013062758A1 (en) | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Polyisobutylene prepared at high velocity and circulation rate |
| EP2771375B1 (en) | 2011-10-26 | 2021-03-10 | TPC Group LLC | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
| US9034998B2 (en) | 2011-12-16 | 2015-05-19 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
| US8853336B2 (en) | 2012-02-17 | 2014-10-07 | Basf Se | Boron trifluoride-catalyst complex and process for preparing high-reactivity isobutene homopolymers |
| SG10201606559UA (en) | 2012-02-17 | 2016-09-29 | Basf Se | Boron trifluoride catalyst complex and method for producing highly reactive isobutene homopolymers |
| RU2485139C1 (ru) * | 2012-04-05 | 2013-06-20 | Открытое акционерное общество "ЭКТОС-Волга" | Способ получения высокореактивного низкомолекулярного полиизобутилена |
| US9156924B2 (en) | 2013-03-12 | 2015-10-13 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
| US9631038B2 (en) | 2013-10-11 | 2017-04-25 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
| KR101628897B1 (ko) * | 2014-06-18 | 2016-06-09 | 대림산업 주식회사 | 노르말 프로판올을 포함한 촉매를 이용한 폴리부텐의 제조방법 |
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| JP6605939B2 (ja) * | 2015-12-17 | 2019-11-13 | Ｊｘｔｇエネルギー株式会社 | ブテンポリマーの製造方法 |
| US10047174B1 (en) | 2017-06-28 | 2018-08-14 | Infineum International Limited | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
| US10167352B1 (en) | 2017-06-28 | 2019-01-01 | University Of Massachusetts | Polymerization initiating system and method to produce highly reactive olefin functional polymers |
| US10174138B1 (en) | 2018-01-25 | 2019-01-08 | University Of Massachusetts | Method for forming highly reactive olefin functional polymers |
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| CN1277617A (zh) * | 1998-08-25 | 2000-12-20 | 日本石油化学株式会社 | 丁烯聚合物的制造方法 |
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