CN1276931C - 高反应性聚异丁烯的生产方法 - Google Patents
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- 229920002367 Polyisobutene Polymers 0.000 title abstract description 34
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
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- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
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- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical class CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- 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
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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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
Abstract
本发明涉及通过异丁烯或者异丁烯和可与异丁烯共聚的单体在具有弱配位阴离子的溶剂稳定化过渡金属配合物的存在下的阳离子聚合来生产端部乙烯叉基含量高于80mol%和平均分子量为500-10,000道尔顿的高反应性聚异丁烯的方法。
Description
技术领域
本发明涉及通过异丁烯在液相中在具有弱配位阴离子的单体溶剂稳定化过渡金属配合物的存在下的阳离子聚合来生产端部乙烯叉基(vinylidene)含量高于80mol％和平均分子量为500-10,000道尔顿的高反应性聚异丁烯的方法。
背景技术
很早就知道分子量高达几十万道尔顿的高分子量聚异丁烯，例如在H.Güterbock：Polyisobutylene und Mischpolymerisate，77-104页，Springer，Berlin 1959中描述了它们的生产方法。
具有500-5,000道尔顿的分子量的聚异丁烯借助路易酸催化剂，如氯化铝、烷基氯化铝或三氟化硼来生产，它们通常具有10mol％以下的端部双键(乙烯叉基)及在2和5之间的分子量分布(分散度)。
在这些普通聚异丁烯和“高反应性”聚异丁烯之间存在差别，后者具有高于60mol％的高端部乙烯叉基含量。高反应性聚异丁烯具有可观的市场份额，如在DE-A 2702604中所述，它们例如作为生产润滑剂和燃料的添加剂的中间产物使用。这些添加剂通过聚异丁烯的大多数端部双键与马来酸酐的反应来最先制备聚异丁烯/马来酸酐加合物，尤其聚异丁烯基丁二酸酐，然后与某些胺类反应以获得成品添加剂来生产。因为在加合物形成过程中与马来酸酐反应的主要是端部乙烯叉基，因而，取决于它们的位置，此外位于大分子内的双键在不添加卤素的情况下没有获得任何转化或具有明显更低的转化率。端部乙烯叉基在分子中的比例是这类聚异丁烯的重要质量标准。
对于所述预定应用的聚异丁烯的其它质量标准是在聚异丁烯中含有的高分子的平均分子量和分子量分布(也称为分散度)。一般，平均分子量(Mn)500-5,000道尔顿的聚异丁烯用作生产所述润滑剂和燃料添加剂的中间产物。
当将异丁烯聚合时，获得了聚异丁烯产物。它的聚异丁烯组分，即聚异丁烯高分子具有或大或小宽度的无规分子量分布。这些聚异丁烯的分子量分布越宽，具有相对低或相对高分子量的聚异丁烯高分子的含量越高，这将不适合于所述预定应用。
因此，有利的是，生产出具有尽可能最窄分子量分布的中等分子量的高反应性异丁烯，以便减少不想要的、相对低或高分子量聚异丁烯在所得产物中的比例和因此改进它们的质量。
根据DE-A 27 02 604的教导，包括至多88wt％的端部双键的反应性聚异丁烯能够通过异丁烯在-50℃到+30℃温度和低于10分钟的停留时间下的三氟化硼催化的聚合来获得。发现以这种方式生产的聚异丁烯的分散度具有不低于1.8的值。
如果使用部分钝化的催化剂，例如由三氟化硼、醇类和/或醚类制备的配合物，可以获得具有类似高比例的端部双键，但具有较窄分子量分布的聚异丁烯。这类方法例如描述在EP-A 145 235，U.S.专利No.5,408,418和WO 99/64482中。
虽然在以上引用的参考文献及实施例中公开了在0℃以上的反应温度，不过若使用明显在0℃以下的温度，也能获得高于80％的端部双键的高含量。
使用U.S.专利No.3,166,546的气相方法和U.S.专利No.3,024,226的方法，显然有可能生产出具有高达95mol％端部双键的含量的聚异丁烯，在该方法中，使用三氟化硼/二氧化硫气体混合物作为催化剂。这些聚异丁烯根据红外光谱法的结果来表征。然而，根据所述方法生产的聚异丁烯用13C核磁共振波谱(13C NMR波谱)的研究揭示，端部双键的含量为至多40mol％。
U.S.专利No.4,227,027公开了三氟化硼催化的烷基转移反应，其中该催化剂是三氟化硼和二醇或多元醇在40-120℃的温度下的加合物。当将该方法应用于使用三氟化硼/1，2-丁二醇加合物作为催化剂的异丁烯的聚合时，所获得的唯一产物是二异丁烯。没有形成聚异丁烯。
高反应性聚异丁烯的另一种生产方法包括异丁烯的活性阳离子聚合和后续脱氯化氢作用，如在例如U.S.专利No.5,340,881中所述那样。该方法获得了至多100％的端部双键，但要求低温和复合溶剂混合物，这不必要地使未反应的起始原料的再循环复杂化。
因此，如果使用0℃以下的温度，仅获得了平均分子量为500-5,000道尔顿和端部乙烯叉基含量高于80mol％的高反应性聚异丁烯。这种冷却与可观的成本相关，降低了该方法的经济活力。
本发明的目的是开发在0℃以上的温度下操作，并获得了所述高反应性聚异丁烯的经济方法。
现在已发现，如果使用具有弱配位阴离子的单体溶剂稳定化过渡金属配合物作为催化剂，可以实现这种方法。
发明内容
本发明提供了生产具有高于80mol％的端部乙烯叉基含量和500-10,000道尔顿的平均分子量的高反应性异丁烯均聚物和共聚物的方法，其中异丁烯或异丁烯与可共聚的单体在通式[M(R1-CN)4-6](A)2的过渡金属催化剂的存在下聚合，其中
M是来自元素周期系的第3-12周期的金属，
R1是C1-C8烷基和
A是弱配位阴离子。
具体实施方案
可以在本发明的方法中使用的可共聚的单体例如包括异戊二烯和/或苯乙烯。本发明的方法优选用于生产以异丁烯和异戊二烯为基础的共聚物，它们具有约2,000-7,000道尔顿的分子量和具有至多60％的异戊二烯引入量(通过核磁共振波谱法测定)。
根据本发明的方法生产的高反应性聚异丁烯优选具有95-100mol％的端部乙烯叉基含量和2,000-7,000道尔顿的平均分子量。
本发明的聚异丁烯可溶于许多有机溶剂，如氯仿、二氯甲烷、己烷、庚烷、环己烷、甲苯或苯或它们的混合物中。
本发明的方法优选在惰性有机溶剂中进行，其中使用卤化和无卤素烃类(任选可被硝基取代)，或它们的混合物。二氯甲烷、氯仿、二氯乙烷、四氯乙烷、己烷或戊烷，和环烷烃，如环己烷，以及芳族烃类，如甲苯和苯例如是优选的。溶剂的量可以通过常规实验来决定。引入单体在所用溶剂中的浓度优选是在0.01-10mol/l，更优选0.1-2mol/l的范围内。
优选，上述通式的过渡金属催化剂是其中M是Mn、Ni、Cr或Zn和A含有式BF4 -、SbX6 -、PX6 -和/或B(Ar)4 -的阴离子以及由环基桥连的B(Ar)4 -阴离子的那些，其中Ar表示苯基，具有1-5个取代基，如F、Cl或CF3。环状桥基(可以优选考虑用于B(Ar)4 -阴离子)包括咪唑基桥基。
在以上通式中，R1优选表示C1-C4烷基残基，如甲基、乙基、丙基、丁基、异丙基、异丁基或叔丁基。
更优选的过渡金属催化剂包括下式的那些：
[Mn(NCCH3)6][B(C6H3(CF3)2)4]2
[Mn(NCCH3)6][B(C6F5)4]2
[Mn(NCCH3)6][C3H3N2(B(C6F5)3)2]2
[Ni(NCCH3)4][B(C6F5)4]2
这些过渡金属催化剂在本发明的方法中与单体的引入量以1∶15,000,000到1∶10，优选1∶500,000到1∶10,000的摩尔比使用。所引入的催化剂在反应混合物中的浓度是在0.01到10mmol/l，优选0.1到2mmol/l的范围内。
聚合根据本发明在约0-100℃，优选20-60℃的温度下进行。
根据本发明使用的过渡金属催化剂本身是已知的，并且可以使用已知方法，如在例如Wayne E.Buschmann，Joel S.Miller，Chem.Eur.J.1998，4(9)，1731-1737，和Bruce H.Lipshutz，wayne Vaccaro，Bret，Huft，Tetrahedron Letters 1986，27(35)，4095-4098和LaPointe，Robert E.；Roof，Gordon R.；Abboud，KhalilA.；Klosin，Jerzy.New Family of Weakly Coordinating Anions.Journal of theAmerican Chemical Society(200)，122(39)，9560-9561中所述的方法来生产。
通过以下实施例来进一步说明本发明，但本发明不受这些实施例的限制，其中所有份和百分数按重量计，除非另有规定。
实施例
分子量Mn通过凝胶渗透色谱法在氯仿中测定。柱子：WatersUltrastyragel，孔径10,000和100,000，以及Waters Styragel，孔径500，检测：示差折射计(Wagters R 401)，校准：聚苯乙烯标准。
在室温下为气体的单体有利地通过使用装有五氧化二磷和粉碎的钾/氧化铝的柱子来干燥，而液体单体通过装有氧化铝的柱子和在钠/氧化铝上的蒸馏来干燥。
卤化溶剂(例如二氯甲烷)用氢化钙干燥，并在惰性气体下蒸馏。
脂族溶剂(例如己烷)用钠干燥，再蒸馏。
聚合物通过添加2，2’-亚甲基-双(4-甲基-6-叔丁基苯酚)(VulkanoxBKF，Bayer AG，Leverkusen)来稳定。
实施例1
在作为保护气体的氩气气氛下，将12.80mg的引发剂[Mn(NCCH3)6][B(C6H3(CF3)2)4]2(5.0×10-6mol)称量到38ml高压釜中，再在-40℃的冷却浴中，添加20ml干燥二氯甲烷。将3ml(1.988g＝0.0355mol)的新冷凝的异丁烯加入到该引发剂溶液中。异丁烯预先用分子筛和钾/活性炭干燥。密封高压釜，聚合在30℃下进行9小时。溶液在整个聚合过程中保持无色。在9小时后，通过添加甲醇来终止聚合，聚合物沉淀下来。获得了无色高粘度聚合物，再在真空(50℃/0.1毫巴)下干燥至恒重。获得了0.25g的具有9.0×103道尔顿的分子量(Mn)(PDI＝1.6)的聚合物(收率16.9％)。该聚合物能够在空气中储存，并保持完全可溶。
实施例2
在作为保护气体的氩气气氛下，将12.43mg的引发剂[Mn(NCCH3)6][C3H3N2(B(C6F5)3)2]2(5.0×10-6mol)称量到38ml高压釜中，再在-40℃的冷却浴中，添加20ml干燥二氯甲烷。将3ml(1.988g＝0.0355mol)的新冷凝的异丁烯加入到该引发剂溶液中。异丁烯预先用分子筛和钾/活性炭干燥。密封高压釜，聚合在30℃下进行16小时，该溶液在整个聚合过程中也保持无色。在所述时间后，通过添加甲醇来终止聚合，聚合物沉淀下来。获得了无色高粘度聚合物，再在真空(50℃/0.1毫巴)下干燥至恒重。获得了0.59g的具有6.4×103道尔顿的分子量(Mn)(PDI＝1.7)的聚合物(收率39％)。该聚合物能够在空气中储存，并保持完全可溶。
根据1H-NMR，端部乙烯叉基端基的含量是100mol％。
实施例3
在作为保护气体的氩气气氛下，将24.86mg的引发剂[Mn(NCCH3)6][C3H3N2(B(C6F5)3)2]2(1.0×10-5mol)称量到38ml高压釜中，再在-40℃的冷却浴中，添加20ml干燥二氯甲烷。将3ml(1.988g＝0.0355mol)的新冷凝的异丁烯加入到该引发剂溶液中。异丁烯预先用分子筛和钾/活性炭干燥。密封高压釜，聚合在30℃下进行16小时，该溶液在整个聚合过程中也保持无色。在所述时间后，通过添加甲醇来终止聚合，聚合物沉淀下来。获得了无色高粘度聚合物，再在真空(50℃/0.1毫巴)下干燥至恒重。获得了0.69g的具有5.5×103道尔顿的分子量(Mn)(PDI＝1.8)的聚合物(收率45％)。该聚合物能够在空气中储存，并保持完全可溶。
根据1H-NMR，端部乙烯叉基端基的含量是100mol％。
实施例4
异丁烯的等温聚合在40℃下在聚合高压釜中进行。将聚合高压釜进行热处理，再在反应之前用氩气注满。然后引入93mL的二氯甲烷，再调节到40℃的温度。一旦温度达到所需值，在等温条件下添加异丁烯(p(IB)＝2巴)，直到溶液完全饱和为止。饱和在400转/分钟的搅拌速度下进行，而聚合在1,000转/分钟的搅拌器速度下进行。反应通过添加5mL的[Mn(NCCH3)6][B(C6H2(CF3)3)4]2(n(I)＝10μmol)在二氯甲烷中的2mM溶液来开始。用超压力将该引发剂溶液注入到单体溶液中，注射系统再用2mL二氯甲烷(V(CH2Cl2)总共＝100mL)后冲洗。借助外和内冷却(手动控制)，温度在反应过程中保持恒定。连续补充消耗的单体。在16小时的反应时间之后，没有发生进一步的聚合。在缓慢搅拌混合物的同时。排空在高压釜中的超压力，然后聚合物在过量甲醇中沉淀。
一旦溶剂蒸发，将聚合物在高真空下干燥至恒重。证明有可能获得67.0g的具有2,100道尔顿(PDI＝1.2)的摩尔质量(Mn)(用凝胶渗透色谱法测定)的聚合物。
根据1H-NMR，端部乙烯叉基端基的含量是100mol％。
实施例5
在作为保护气体的氩气气氛下，将每份12.43mg的引发剂[Mn(NCCH3)6][C3H3N2(B(C6F5)3)2]2(5.0×10-6mol)称量到十二个38ml高压釜中，再在-40℃的冷却浴中，向各高压釜添加20ml干燥二氯甲烷。改变异戊二烯和异丁烯的称出量。密封高压釜，聚合在30℃下在水浴中进行16小时。一旦聚合物用甲醇沉淀和用BKF(0.02g/样品)稳定，将该聚合物在高真空(0.1毫巴/25℃)下干燥至恒重。转化率用重量分析法测定，而摩尔质量用凝胶渗透色谱法来测定。引入的异戊二烯量用核磁共振波谱法来测定。结果在表1中给出。
表1：异丁烯/异戊二烯用Mn配合物的共聚
| IB∶IP/mol％ | 转化率/％ | Mn.10-3/道尔顿 | Mol％ IB/IP聚合物 |
| 100∶0 | 32.9 | 6.4 | 0.0 |
| 98∶2 | 6.6 | 5.6 | 1.5 |
| 96∶4 | 14.9 | 5.9 | 2.3 |
| 94∶6 | 6.2 | 4.8 | 2.3 |
| 92∶8 | 19.9 | 4.5 | 3.6 |
| 90∶10 | 6.2 | 2.8 | 7.7 |
| 80∶20 | 2.3 | 3.3 | 6.0 |
| 70∶30 | 1.8 | 2.8 | 不能测出 |
| 50∶50 | 3.0 | 2.9 | 不能测出 |
| 30∶70 | 6.1 | 2.9 | 不能测出 |
| 0∶100 | 0.7 | 2.6 | 不能测出 |
所有聚合物完全可溶于甲苯中，是无色高粘度液体。
虽然在前面为了说明的目的而详细描述了本发明，但应该理解的是，这些细节单纯用于该目的，以及除了受权利要求书的限制之外，在不偏离本发明的精神和范围的情况下，本领域的那些技术人员能够在其中做出修改。
Claims (7)
1.生产具有高于80mol％的端部乙烯叉基含量和500-10,000道尔顿的平均分子量的高反应性异丁烯均聚物和共聚物的方法，包括使异丁烯单体或异丁烯与选自异戊二烯、苯乙烯或它们的混合物的可共聚的单体在通式[M(R1-CN)4-6](A)2的过渡金属催化剂的存在下聚合，所述聚合在0-100℃的温度下进行，且催化剂相对于单体的总量以1∶15,000,000-1∶10的摩尔比引入，其中
M是来自元素周期系的第3-12周期的金属，
R1是C1-C8烷基，和
A是式BF4 -或B(Ar)4 -的阴离子以及由环基桥连的B(Ar)4 -阴离子，其中Ar表示具有1-5个取代基的苯基。
2.根据权利要求1的方法，其中聚合在20-60℃的温度下进行。
3.根据权利要求1的方法，其中聚合在惰性有机溶剂中进行。
4.根据权利要求1的方法，其中M是Mn、Ni、Cr或Zn。
5.根据权利要求1的方法，其中取代基是F、Cl或CF3。
6.根据权利要求1的方法，其中R1是C1-C4烷基残基。
7.根据权利要求1的方法，其中R1是甲基、乙基、丙基、丁基、异丁基或叔丁基。
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| WO2021112617A1 (ko) * | 2019-12-06 | 2021-06-10 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리이소부텐의 제조방법 |
| FR3110914B1 (fr) | 2020-05-29 | 2023-12-29 | Total Marketing Services | Utilisation d’une composition de carburant pour nettoyer les parties internes des moteurs essence |
| FR3110913B1 (fr) | 2020-05-29 | 2023-12-22 | Total Marketing Services | Composition d’additifs pour carburant moteur |
| KR20220037612A (ko) * | 2020-09-18 | 2022-03-25 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 이소부텐-이소프렌 공중합체의 제조방법 |
| GB202118107D0 (en) | 2021-12-14 | 2022-01-26 | Innospec Ltd | Fuel compositions |
| GB202118100D0 (en) | 2021-12-14 | 2022-01-26 | Innospec Ltd | Methods and uses relating to fuel compositions |
| GB202118103D0 (en) | 2021-12-14 | 2022-01-26 | Innospec Ltd | Fuel compositions |
| GB202118104D0 (en) | 2021-12-14 | 2022-01-26 | Innospec Ltd | Methods and uses relating to fuel compositions |
| WO2023183460A1 (en) | 2022-03-23 | 2023-09-28 | Innospec Fuel Specialities Llc | Compositions, methods and uses |
| GB202204084D0 (en) | 2022-03-23 | 2022-05-04 | Innospec Ltd | Compositions, methods and uses |
| GB202206069D0 (en) | 2022-04-26 | 2022-06-08 | Innospec Ltd | Use and method |
| GB2618099A (en) | 2022-04-26 | 2023-11-01 | Innospec Ltd | Use and method |
| GB2618101A (en) | 2022-04-26 | 2023-11-01 | Innospec Ltd | Use and method |
| EP4279566A1 (en) | 2022-05-20 | 2023-11-22 | TotalEnergies OneTech | Compounds and compositions useful for scavenging hydrogen sulphide and sulfhydryl-containing compounds |
| WO2024023490A1 (en) | 2022-07-26 | 2024-02-01 | Innospec Fuel Specialties Llc | Improvements in fuels |
| GB202317463D0 (en) | 2022-11-15 | 2023-12-27 | Innospec Fuel Specialties Llc | Compositions, methods and uses |
| WO2024105387A1 (en) | 2022-11-15 | 2024-05-23 | Innospec Fuel Specialties Llc | Compositions, methods and uses |
| WO2024126998A1 (en) | 2022-12-12 | 2024-06-20 | Innospec Limited | Composition, method and use |
| FR3143625A1 (fr) | 2022-12-19 | 2024-06-21 | Totalenergies Onetech | Composition de carburant comprenant une base renouvelable, un ester d’acide gras et un additif polysiloxane |
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| US3024226A (en) * | 1959-11-23 | 1962-03-06 | Texaco Inc | Polymerization process |
| US3166546A (en) * | 1961-06-09 | 1965-01-19 | Texaco Inc | Vapor phase process for the polymerization of isobutylene |
| DE2702604C2 (de) * | 1977-01-22 | 1984-08-30 | Basf Ag, 6700 Ludwigshafen | Polyisobutene |
| US4227027A (en) * | 1979-11-23 | 1980-10-07 | Allied Chemical Corporation | Recyclable boron trifluoride catalyst and method of using same |
| GB8329082D0 (en) * | 1983-11-01 | 1983-12-07 | Bp Chem Int Ltd | Low molecular weight polymers of 1-olefins |
| US4668838A (en) * | 1986-03-14 | 1987-05-26 | Union Carbide Corporation | Process for trimerization |
| US5340881A (en) * | 1992-11-16 | 1994-08-23 | The University Of Akron | Aldehyde-telechelic polyisobutylenes, catalytic method for preparing the same with high conversion and selectivity, and block copolymers made thereform |
| US5880241A (en) * | 1995-01-24 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Olefin polymers |
| DE19528942A1 (de) * | 1995-08-07 | 1997-02-13 | Basf Ag | Verfahren zur Herstellung von halogenfreiem, reaktivem Polyisobuten |
| DE19704482A1 (de) * | 1997-02-06 | 1998-08-13 | Basf Ag | Verfahren zur Herstellung von halogenfreiem, reaktivem Polyisobuten |
| US6407186B1 (en) * | 1997-12-12 | 2002-06-18 | Basf Aktiengesellschaft | Method for producing low-molecular, highly reactive polyisobutylene |
| JPH11322821A (ja) * | 1998-05-18 | 1999-11-26 | Tosoh Corp | オレフィン類重合用触媒成分及びそれを用いたオレフィン類の重合方法 |
| JP4320799B2 (ja) * | 1998-05-18 | 2009-08-26 | 東ソー株式会社 | オレフィン類重合用触媒成分及びそれを用いたオレフィン類の重合方法 |
| DE19825334A1 (de) | 1998-06-05 | 1999-12-09 | Basf Ag | Verfahren zur Herstellung hochreaktiver Polyisobutene |
| US6479425B1 (en) * | 2000-08-18 | 2002-11-12 | Exxonmobile Research And Engineering Company | Late transition metal complexes, their use as catalysts and polymers therefrom |
-
2002
- 2002-03-15 DE DE10211418A patent/DE10211418A1/de not_active Withdrawn
-
2003
- 2003-03-03 DE DE50304702T patent/DE50304702D1/de not_active Expired - Lifetime
- 2003-03-03 EP EP03004368A patent/EP1344785B1/de not_active Expired - Lifetime
- 2003-03-11 US US10/385,556 patent/US20030176606A1/en not_active Abandoned
- 2003-03-12 CA CA002421688A patent/CA2421688A1/en not_active Abandoned
- 2003-03-14 RU RU2003106980/04A patent/RU2308462C2/ru not_active IP Right Cessation
- 2003-03-14 CN CNB031199682A patent/CN1276931C/zh not_active Expired - Fee Related
- 2003-03-14 JP JP2003070662A patent/JP4541652B2/ja not_active Expired - Fee Related
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2004
- 2004-03-25 HK HK04102232A patent/HK1059445A1/xx not_active IP Right Cessation
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2006
- 2006-04-04 US US11/397,104 patent/US7291758B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1445249A (zh) | 2003-10-01 |
| JP4541652B2 (ja) | 2010-09-08 |
| US20060173227A1 (en) | 2006-08-03 |
| HK1059445A1 (en) | 2004-07-02 |
| DE50304702D1 (de) | 2006-10-05 |
| CA2421688A1 (en) | 2003-09-15 |
| JP2003277428A (ja) | 2003-10-02 |
| DE10211418A1 (de) | 2003-09-25 |
| US7291758B2 (en) | 2007-11-06 |
| EP1344785B1 (de) | 2006-08-23 |
| US20030176606A1 (en) | 2003-09-18 |
| EP1344785A1 (de) | 2003-09-17 |
| RU2308462C2 (ru) | 2007-10-20 |
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