CN1681847A - 生产聚异丁烯的方法 - Google Patents
生产聚异丁烯的方法 Download PDFInfo
- Publication number
- CN1681847A CN1681847A CNA038221934A CN03822193A CN1681847A CN 1681847 A CN1681847 A CN 1681847A CN A038221934 A CNA038221934 A CN A038221934A CN 03822193 A CN03822193 A CN 03822193A CN 1681847 A CN1681847 A CN 1681847A
- Authority
- CN
- China
- Prior art keywords
- iso
- butylene
- polyisobutene
- alcohol
- boron trifluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 25
- 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 45
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 11
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 150000001983 dialkylethers Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 150000003509 tertiary alcohols Chemical class 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000002989 phenols Chemical class 0.000 abstract description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 150000003138 primary alcohols Chemical class 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000005068 transpiration Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 108010037444 diisopropylglutathione ester Proteins 0.000 description 2
- 238000004821 distillation Methods 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
- 239000000178 monomer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 1,1-dimethyl-1-propyl Chemical group 0.000 description 1
- FCBJLBCGHCTPAQ-UHFFFAOYSA-N 1-fluorobutane Chemical group CCCCF FCBJLBCGHCTPAQ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IXHWZHXLJJPXIS-UHFFFAOYSA-N 2-fluorobutane Chemical compound CCC(C)F IXHWZHXLJJPXIS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 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
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003879 lubricant additive 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
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012071 phase 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
- 238000005086 pumping Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
本发明公开了一种生产含有至少75mol％端亚乙烯基的聚异丁烯的方法。根据本发明方法，在三氟化硼配合物催化剂存在下在液相中聚合异丁烯或含异丁烯的烃混合物，所述催化剂具有如下组成：a(BF3):b(Co1):c(Co2)，其中Co1代表至少一种叔醇，Co2代表选自水、伯醇、仲醇、二烷基醚、链烷羧酸和酚的化合物，比例c∶b为0.9－1.8，且比例(b+c)∶a为0.9－3.0。
Description
本发明涉及一种制备含有至少75mol％端亚乙烯基的聚异丁烯的方法。
在本申请的上下文中，端亚乙烯基或端双键应理解为在聚异丁烯大分子中的位置如下式所述的那些双键：
其中R为聚异丁烯基。存在于聚异丁烯中的双键的类型和比例可以借助1H或13C-NMR光谱法确定。
将该类高度反应性的聚异丁烯用作制备润滑剂和燃料用添加剂，例如如DE-A 27 02 604所述。在常规官能化反应中，具有2-甲基取代的端亚乙烯基显示出最高反应性，而新戊基取代或进一步位于大分子内部的双键没有反应性或仅具有低反应性，这取决于它们在大分子中的位置。端亚乙烯基在该分子中的比例因此是这类聚异丁烯的最重要的质量标准。
由重均分子量Mw和数均分子量Mn表征的分子量分布的宽度是聚异丁烯的另一重要质量标准。优选窄分子量分布，即小的Mw/Mn比值。
US 5,286,823描述了一种通过异丁烯在三氟化硼和3-20个碳原子的仲醇和/或2-20个碳原子的醚存在下的阳离子聚合制备高度反应性聚异丁烯的方法。
WO 93/10063公开了三氟化硼-醚配合物，其中该醚具有至少一个键于醚氧原子上的叔碳原子。这些配合物用于聚合烯烃，尤其是异丁烯，以得到具有高亚乙烯基含量的聚合物。
EP-A 1 026 175描述了使用以特定量包含三氟化硼、醚和醇和/或水的配合物催化剂制备包含至少80mol％具有端亚乙烯基结构的分子的异丁烯聚合物。
除了其他因素外，可以达到的聚异丁烯分子量决定性地取决于三氟化硼配合物催化剂相对于所用烯烃单体的量。使用较大量的催化剂获得较低的分子量，反之亦然。三氟化硼的所需量在低分子量聚异丁烯的制备中构成相当的成本因素。
本发明的目的是提供一种制备具有高含量的端亚乙烯基双键的聚异丁烯的方法，其中使用给定相对量的配合物催化剂得到较低分子量或可以降低催化剂的量以获得给定的分子量。此外，所得聚异丁烯应具有窄分子量分布。
我们发现该目的根据本发明通过一种制备含有至少75mol％端亚乙烯基双键的聚异丁烯的方法实现，在该方法中在具有如下组成的三氟化硼配合物催化剂存在下在液相中聚合异丁烯或含异丁烯的烃混合物：
a(BF3)∶b(Co1)∶c(Co2)
其中
-Co1为至少一种叔醇，
-Co2为至少一种选自水、伯醇、仲醇、二烷基醚、链烷羧酸和酚的化合物，
-比例c∶b为0.9-1.8，优选0.8-1.2，和
-比例(b+c)∶a为0.9-3.0，优选1.0-2.5。
用于本发明方法的合适原料(异丁烯原料)既可是纯异丁烯，也可是含异丁烯的烃混合物，例如来自裂化器的不含丁二烯的精制C4馏分或来自异丁烷脱氢的异丁烯含量大于40重量％的C4切取馏分。可以存在惰性溶剂如饱和烃类如戊烷、己烷或异辛烷，或卤代烃类如二氯甲烷或三氯甲烷。
用于本发明方法中的催化剂是具有至少两种配位剂，即具有至少一种叔醇和至少一种选自水、伯醇、仲醇、二烷基醚、链烷羧酸和酚的化合物的三氟化硼配合物。配位剂以如下方式影响三氟化硼的聚合活性：一方面聚合得到低分子量聚异丁烯，另一方面三氟化硼对于端双键异构化成位于聚异丁烯分子内部的非反应性或仅轻微反应性双键的异构化活性降低。
合适的配位剂Co1例如是叔丁醇和1，1-二甲基-1-丙醇，其中最优选叔丁醇。合适的配位剂Co2是水；伯醇，优选C1-C20醇；仲醇，优选C3-C20醇；酚类，如苯酚，其可以带有一个或多个烷基取代基；羧酸，优选C1-C20羧酸；以及二烷基醚，优选C2-C20二烷基醚，其中优选的是至少一个烷基为仲或叔烷基的那些。水，伯醇，优选具有1-10个碳原子，尤其是1-4个碳原子的那些，以及仲醇，优选具有3-10个碳原子，尤其是3或4个碳原子的那些，水和伯或仲醇的混合物以及伯醇和仲醇的混合物是优选的助催化剂Co2。更优选最多具有4个碳原子的伯醇和仲醇。最优选甲醇、乙醇、2-丙醇和2-丁醇作为配位剂Co2。
在使用之前，可以将三氟化硼配合物催化剂预模塑或优选可以在聚合反应器中就地生产，如EP-A 628 575所述。有利地将气态三氟化硼用作制备三氟化硼配合物催化剂的原料，可以使用仍含有少量二氧化硫和SiF4的工业级三氟化硼(纯度：96.5重量％)，但优选使用高纯度三氟化硼(纯度：99.5重量％)。特别优选将不含四氟化硅的三氟化硼用于制备催化剂。
优选每mol烯烃单体使用0.5-10mmol的配合物催化剂，以三氟化硼计算。
异丁烯的聚合优选通过连续方法进行。可以将常规反应器如管式反应器、管束反应器或搅拌釜用于该目的。聚合优选在环管反应器，即具有反应介质的连续循环的管式反应器或管束反应器中进行，通常可以在1∶5-1∶500，优选1∶10-1∶200v/v的范围内改变进料与循环的比例F/C。
聚合有利地在低于0℃，优选0℃至-40℃，尤其是-10℃至-40℃，特别优选-20℃至-40℃下进行。通常在0.5-20巴(绝对)下进行聚合。压力范围的选择主要取决于工艺工程条件。因此，有利的是在搅拌釜情况下使用蒸发冷却并因此使用自生压力，即减压，而循环反应器(环管反应器)更好地在超计大气压下操作。同时三氟化硼的混入通过加压和湍流加速，因而优选该反应器类型。然而，压力的选择对于聚合反应的结果通常并不重要。
聚合优选在等温条件下进行。因为聚合反应是放热的，因此此时必须除去聚合热。这通常借助可以例如用液氨作为冷却剂操作的冷却设备进行。另一种可能性是通过在反应器的产物侧蒸发冷却除去聚合热。这通过蒸发异丁烯和/或异丁烯原料的其他更易挥发性组分而进行。冷却的类型取决于每种情况下使用的反应器类型。优选通过外部冷却来冷却管式反应器，例如借助带有沸腾氨的冷却夹套冷却反应管。搅拌釜反应器优选例如借助冷却旋管通过内部冷却恒温，或通过在产物侧蒸发冷却而恒温。
待聚合异丁烯在反应器中的停留时间为1-120分钟，优选5-60分钟，这取决于反应条件和待制备聚合物的所需性能。
对于处理，有利地将反应排出物通入钝化聚合催化剂并以此方式停止聚合的介质中。例如，可以将水、醇、醚、乙腈、氨、胺或无机碱的水溶液如碱金属和碱土金属氢氧化物溶液、这些金属的碳酸盐溶液等用于该目的。优选用水在20-40℃下例如以在加压下涤气形式停止。所用水的温度取决于进行相分离所需的混合温度。在处理的其他过程中，需要的话将聚合混合物进行一次或多次萃取以除去残留量的催化剂，通常为甲醇，或用水涤气。在用水涤气的情况下，除了除去催化剂外，还除去在聚合过程中形成的氟化氢。然后通过蒸馏分离未转化的异丁烯、溶剂和挥发性异丁烯低聚体。底部产物例如借助环隙蒸发器或通过在挤出机中脱挥发分而除去溶剂和单体的残留物。
还可以例如通过加入具有1-4个或3-4个碳原子的伯或仲醇和/或水和/或通过冷却而从反应器流出液中分离三氟化硼配合物，以降低三氟化硼配合物在反应器流出液中的溶解性。可以从反应器流出液中分离至少一部分配合物并在用三氟化硼富集后再引入反应器中。借此可以节省额外量的三氟化硼。
若将纯异丁烯用作原料，则可以象异丁烯低聚体和溶剂一样将其再循环到聚合中。使用含异丁烯的C4切取馏分时通常不再循环未转化的异丁烯和其他C4烃类，而是将它们投入其他应用，例如用于制备低分子量聚异丁烯或甲基叔丁基醚。易挥发的含氟副产物如仲丁基氟和叔丁基氟可以与其他烃类一起从聚异丁烯中除去并可以通过蒸馏或萃取与这些烃分离。
本发明方法使得可以从纯异丁烯和含异丁烯的烃混合物二者制备高度反应性的聚异丁烯。借助本发明方法可以达到的数均分子量为500-50000，优选500-2500道尔顿，以及端双键含量为至少75mol％，优选至少78mol％，特别优选至少80mol％。此外，所得聚异丁烯的特征在于分子量分布窄。它们优选具有的分散度Mw/Mn为1.3-5，特别是1.2-2。
下列实施例说明本发明。
实施例
微型设备：
所用反应器为由内径为4mm和长度为7.1m的不锈钢管和供给量为50L/h的齿轮泵组成的循环反应器；总反应体积为100mL。将管和泵压头浸入浴温为-15℃的低温恒温器中。进料位于齿轮泵的吸入侧且反应器出口经由内径为2mm和长度为40cm的毛细管和将压力保持为3巴的装置位于加压侧。紧邻压力控制装置之后的是混合泵，借助该泵引入水以使反应停止。在具有液面保持装置的沉降器中在20℃下分离水相并将有机相在吸附塔中在氧化铝上干燥(停留时间为5分钟)，然后以两步脱挥发分。第一步脱挥发分在大气压力和150℃的底部温度下操作，而第二步在10毫巴和210℃的底部温度下操作。冷凝蒸气并在试验开始2小时后将其再循环到聚合体系中，并补充消耗的异丁烯。
试验程序：
首先用纯己烷填充设备。然后引入307g/h异丁烯和317g/h己烷以及所有其他进料，其中配位剂以10％浓度的己烷溶液计量加入。使用水作为助配位剂，将水与异丁烯一起供入反应器中。确保进料点不浸入低温恒温器的冷却液体中，从而不使水冻结。在恒定速率下计量加入BF3并调节配位剂的量以使转化率为90％。通过低温恒温器的浴温将聚合温度调节为-10℃。
下表显示了聚合结果。
| 实施例 | 进料 | 在1小时后的PIB | 在3天后的PIB | |||||
| BF3[mmol/h] | 叔丁醇[mmol/h] | 助配位剂 | 分子量MN | 反应性[％] | 分子量MN | 反应性[％] | ||
| 类型 | [mmol/h] | |||||||
| 1 | 10 | - | 甲醇 | 15 | 1150 | 78 | - | - |
| 2 | 10 | - | 乙醇 | 17 | 1070 | 82 | - | - |
| 3 | 10 | - | 异丙醇 | 18 | 1030 | 85 | - | - |
| 4 | 10 | 12 | - | - | 没有稳定过程 | |||
| 5 | 10 | 9 | 甲醇 | 9 | 790 | 82 | 750 | 85 |
| 5 | 10 | 8 | 甲醇水 | 55 | 800 | 82 | 770 | 85 |
| 6 | 10 | 9 | 异丙醇 | 9 | 780 | 85 | 730 | 83 |
| 7 | 10 | 10 | DIPE | 10 | 800 | 83 | 780 | 83 |
| 8 | 10 | 11 | MTBE | 11 | 820 | 84 | 790 | 85 |
DIPE＝二异丙基醚
MTBE＝甲基叔丁基醚
Claims (5)
1.一种制备含有至少75mol％端亚乙烯基的聚异丁烯的方法，其中在具有如下组成的三氟化硼配合物催化剂存在下在液相中聚合异丁烯或含异丁烯的烃混合物：
a(BF3)∶b(Co1)∶c(Co2)
其中
-Co1为至少一种叔醇，
-Co2为至少一种选自水、伯醇、仲醇、二烷基醚、链烷羧酸和酚的化合物，
-比例c∶b为0.9-1.8，和
-比例(b+c)∶a为0.9-3.0。
2.如权利要求1所要求的方法，其中Co1为叔丁醇。
3.如权利要求1或2所要求的方法，其中Co2为甲醇、乙醇、2-丙醇或2-丁醇。
4.如权利要求1或2所要求的方法，其中Co2为二烷基醚且其中至少一个烷基为仲或叔烷基。
5.如前述权利要求中任一项所要求的方法，用于制备数均分子量Mn为500-50 000道尔顿的聚异丁烯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10243576A DE10243576A1 (de) | 2002-09-19 | 2002-09-19 | Verfahren zur Herstellung von Polyisobuten |
| DE10243576.6 | 2002-09-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1681847A true CN1681847A (zh) | 2005-10-12 |
| CN100334116C CN100334116C (zh) | 2007-08-29 |
Family
ID=31969286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038221934A Expired - Fee Related CN100334116C (zh) | 2002-09-19 | 2003-09-18 | 生产聚异丁烯的方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7485764B2 (zh) |
| EP (1) | EP1546213B1 (zh) |
| JP (1) | JP4204551B2 (zh) |
| KR (1) | KR101007952B1 (zh) |
| CN (1) | CN100334116C (zh) |
| AR (1) | AR041257A1 (zh) |
| AT (1) | ATE328010T1 (zh) |
| AU (1) | AU2003266397A1 (zh) |
| BR (1) | BR0314360A (zh) |
| CA (1) | CA2498830A1 (zh) |
| DE (2) | DE10243576A1 (zh) |
| MX (1) | MXPA05002389A (zh) |
| WO (1) | WO2004029099A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011035545A1 (zh) * | 2009-09-25 | 2011-03-31 | 中国石油化工股份有限公司 | 阳离子聚合引发体系及聚合方法 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005049236A1 (de) * | 2005-10-14 | 2007-04-19 | Basf Ag | Verfahren zur Herstellung von Polyisobuten |
| KR100827273B1 (ko) | 2006-11-02 | 2008-05-07 | 대림산업 주식회사 | 삼불화붕소 착물 촉매의 제조방법 및 이를 이용한 고반응성폴리부텐의 제조방법 |
| KR101088529B1 (ko) * | 2008-12-15 | 2011-12-05 | 대림산업 주식회사 | 삼불화붕소 착화합물 촉매 및 이를 이용한 고반응성 폴리부텐의 제조방법 |
| BR112014009478B1 (pt) | 2011-10-26 | 2021-09-21 | Tpc Group Llc | Método de preparação de um polímero de poli-isobutileno em um reator loop de recirculação |
| MX354421B (es) | 2011-10-26 | 2018-03-02 | Tpc Group Llc | Polimeros de poliisobutileno de alta viscosidad, con contenido de vinilideno de intervalo medio. |
| KR101929082B1 (ko) | 2011-10-26 | 2018-12-13 | 티피씨 그룹 엘엘씨 | 낮은 희석제 함량 반응 매질로 제조된 폴리아이소부틸렌 |
| US11072570B2 (en) | 2012-01-09 | 2021-07-27 | Basf Se | Process for continuously preparing polyisobutylene |
| SG11201403143VA (en) * | 2012-01-09 | 2014-10-30 | Basf Se | Method for the continuous production of polyisobutylene |
| US8853336B2 (en) | 2012-02-17 | 2014-10-07 | Basf Se | Boron trifluoride-catalyst complex and process for preparing high-reactivity isobutene homopolymers |
| EP2814852B1 (de) | 2012-02-17 | 2019-01-23 | Basf Se | Bortrifluorid-katalysatorkomplex und verfahren zur herstellung von hochreaktiven isobutenho-mopolymeren |
| JP2016526091A (ja) * | 2013-06-05 | 2016-09-01 | テリム インダストリアル カンパニー リミテッド | 多様な分子量を有するポリブテンの製造装置および方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2702604C2 (de) | 1977-01-22 | 1984-08-30 | Basf Ag, 6700 Ludwigshafen | Polyisobutene |
| BE1006694A5 (fr) * | 1991-06-22 | 1994-11-22 | Basf Ag | Procede de preparation de polyisobutenes extremement reactifs. |
| DE69127473T2 (de) * | 1991-11-18 | 1998-02-19 | Amoco Corp | Bf3-tertiäre etheratkomplexe zur isobuthylen-polymerisation |
| DE19619267A1 (de) | 1996-05-13 | 1997-11-20 | Basf Ag | Verfahren zur Herstellung von mittelmolekularem, hochreaktivem Polyisobuten |
| DE19825334A1 (de) * | 1998-06-05 | 1999-12-09 | Basf Ag | Verfahren zur Herstellung hochreaktiver Polyisobutene |
| KR20010031186A (ko) * | 1998-08-25 | 2001-04-16 | 사이카와 겐조오 | 부텐중합체의 제조 방법 |
| KR100486044B1 (ko) * | 2000-11-13 | 2005-04-29 | 대림산업 주식회사 | 폴리부텐의 제조방법 |
-
2002
- 2002-09-19 DE DE10243576A patent/DE10243576A1/de not_active Withdrawn
-
2003
- 2003-09-15 AR ARP030103333A patent/AR041257A1/es not_active Application Discontinuation
- 2003-09-18 DE DE50303611T patent/DE50303611D1/de not_active Expired - Lifetime
- 2003-09-18 MX MXPA05002389A patent/MXPA05002389A/es unknown
- 2003-09-18 JP JP2004538952A patent/JP4204551B2/ja not_active Expired - Fee Related
- 2003-09-18 EP EP03798168A patent/EP1546213B1/de not_active Expired - Lifetime
- 2003-09-18 CA CA002498830A patent/CA2498830A1/en not_active Abandoned
- 2003-09-18 BR BR0314360-0A patent/BR0314360A/pt not_active IP Right Cessation
- 2003-09-18 WO PCT/EP2003/010429 patent/WO2004029099A1/de active IP Right Grant
- 2003-09-18 CN CNB038221934A patent/CN100334116C/zh not_active Expired - Fee Related
- 2003-09-18 KR KR1020057004459A patent/KR101007952B1/ko not_active IP Right Cessation
- 2003-09-18 AU AU2003266397A patent/AU2003266397A1/en not_active Abandoned
- 2003-09-18 US US10/526,936 patent/US7485764B2/en not_active Expired - Fee Related
- 2003-09-18 AT AT03798168T patent/ATE328010T1/de not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011035545A1 (zh) * | 2009-09-25 | 2011-03-31 | 中国石油化工股份有限公司 | 阳离子聚合引发体系及聚合方法 |
| US8883943B2 (en) | 2009-09-25 | 2014-11-11 | China Petroleum & Chemical Corporation | Isoolefin polymers and process for preparing the same |
| US8937138B2 (en) | 2009-09-25 | 2015-01-20 | China Petroleum & Chemical Corporation | Initiating system for cationic polymerization and polymerization process |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2498830A1 (en) | 2004-04-08 |
| DE10243576A1 (de) | 2004-04-01 |
| US7485764B2 (en) | 2009-02-03 |
| KR20050057345A (ko) | 2005-06-16 |
| EP1546213A1 (de) | 2005-06-29 |
| ATE328010T1 (de) | 2006-06-15 |
| BR0314360A (pt) | 2005-07-05 |
| DE50303611D1 (de) | 2006-07-06 |
| KR101007952B1 (ko) | 2011-01-14 |
| MXPA05002389A (es) | 2005-05-27 |
| JP4204551B2 (ja) | 2009-01-07 |
| EP1546213B1 (de) | 2006-05-31 |
| AU2003266397A1 (en) | 2004-04-19 |
| WO2004029099A1 (de) | 2004-04-08 |
| CN100334116C (zh) | 2007-08-29 |
| US20060122447A1 (en) | 2006-06-08 |
| JP2005539132A (ja) | 2005-12-22 |
| AR041257A1 (es) | 2005-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU702804B2 (en) | Preparation of low molecular weight, highly reactive polyisobutene | |
| US5910550A (en) | Preparation of medium molecular weight, highly reactive polyisobutene | |
| JP5166663B2 (ja) | ポリイソブテンの連続的製造方法 | |
| CN1139607C (zh) | 高反应活性聚异丁烯的制备 | |
| KR101458404B1 (ko) | 폴리부텐의 제조 방법 | |
| CN100334116C (zh) | 生产聚异丁烯的方法 | |
| CN100338104C (zh) | 聚异丁烯的制备 | |
| US6753389B1 (en) | Method for the production of highly reactive polyisobutenes | |
| US6518373B1 (en) | Method for producing highly reactive polyisobutenes | |
| CN1314638C (zh) | 异丁烯阳离子聚合的液态反应排出物的处理方法 | |
| EP1753793B1 (de) | Polymerisation von isobuten in gegenwart von komplexen von elektronendonoren mit fluor-haltigen säuren | |
| CN111848842B (zh) | 生产高度反应性的聚丁烯的方法 | |
| EP0902798A1 (en) | Process for polymerizing olefins | |
| US7956156B2 (en) | Method for the removal of isobutene oligomers from an isobutene polymer | |
| JP2024104523A (ja) | ポリイソオレフィンの製造方法 | |
| JP2000063436A (ja) | ブテンポリマーの製造方法 | |
| MXPA97008837A (en) | Preparation of polyburgen of molecular weight, highly react | |
| US8853336B2 (en) | Boron trifluoride-catalyst complex and process for preparing high-reactivity isobutene homopolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070829 Termination date: 20160918 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |