CN102107146A - 一种用于乙烯三聚合成己烯-1的催化剂及其应用 - Google Patents
一种用于乙烯三聚合成己烯-1的催化剂及其应用 Download PDFInfo
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- CN102107146A CN102107146A CN2009102432333A CN200910243233A CN102107146A CN 102107146 A CN102107146 A CN 102107146A CN 2009102432333 A CN2009102432333 A CN 2009102432333A CN 200910243233 A CN200910243233 A CN 200910243233A CN 102107146 A CN102107146 A CN 102107146A
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- hexene
- ethylene
- chromium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000005977 Ethylene Substances 0.000 title claims abstract description 26
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- -1 ethylene, ethylene Chemical group 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000013638 trimer Substances 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002253 acid Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical group ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001845 chromium compounds Chemical class 0.000 claims description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 3
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical group CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical group CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical group ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004818 1,2-dichlorobenzenes Chemical group 0.000 claims description 2
- 150000004821 1,3-dichlorobenzenes Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000002608 ionic liquid 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
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 2
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- 238000006073 displacement reaction Methods 0.000 description 11
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 9
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- 238000001914 filtration Methods 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
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- RHLYKLPLFQNWFO-UHFFFAOYSA-N C1(CC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(CC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 RHLYKLPLFQNWFO-UHFFFAOYSA-N 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IBUWSVDQGMTMLO-UHFFFAOYSA-N C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C(C)(C)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 IBUWSVDQGMTMLO-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QXSZNDIIPUOQMB-UHFFFAOYSA-N 1,1,2,2-tetrabromoethane Chemical class BrC(Br)C(Br)Br QXSZNDIIPUOQMB-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 229940044174 4-phenylenediamine Drugs 0.000 description 1
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- LSRLLOZBJURIHL-UHFFFAOYSA-N C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound C1(CCCCC1)[P].[N].C1(=CC=CC=C1)[P]C1=CC=CC=C1 LSRLLOZBJURIHL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
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- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
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- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
本发明涉及一种用于乙烯三聚合成己烯-1的催化剂及其应用，所述催化剂由一种含P和N的化合物a、给电子体b、铬化物c、载体d和促进剂e组成，a、b、c、d和e的摩尔比为0.5～100∶0.5～100∶1∶0.5～10∶50～5000；用于催化乙烯三聚合成己烯-1，在惰性溶剂中进行，在乙烯三聚的常规设备中，按权利要求1所述的催化剂各组分配比的有效量，在乙烯压力下进行催化剂原位制备，并不断地通入乙烯，使其与催化剂充分接触，发生乙烯三聚，反应条件：温度30～150℃，压力0.5～10.0MPa，时间0.1～4小时该催化剂用于乙烯三聚制己烯-1，催化剂活性高、己烯-1选择性高、副产物聚乙烯不粘釜。
Description
技术领域
本发明涉及一种用于乙烯三聚合成己烯-1的催化剂及其应用。
背景技术
EP699648中报道了一种铬系催化剂，催化剂由一种铬盐A、一种有机铝化物B、一种吡咯化合物C和一种13(IIIB)氯化物或一种14(VIB)氯化物组成。最好的铬盐有2-乙基己酸铬和环烷酸铬、乙酰丙酮铬。A、B、D影响催化活性；C影响己烯-1选择性。己烯-1选择性80％、纯度98-99％。特点是用己烯-1作为催化剂制备和乙烯三聚的溶剂，省去了己烯-1与溶剂分离的装置和费用
EP 0608447A中报道了一种铬系催化剂组合物，作为乙烯齐聚和/或共聚的催化剂，其中使用一种含铬的化合物作为催化剂组合物的组分之一；使用吡咯化合物作为铬系催化剂组合物的组分之二；采用了一种以路易士酸和/或金属烷基化合物为活化剂作为该催化剂组合物的组分之三；同时还指出，催化剂体系中还可任选一种卤素源作为该催化剂组合物中的组分之四，该卤素源既可为无机卤化物，也可为众多类型的有机卤化物，该催化剂对己烯-1的选择性较高，但其催化活性不高。
JP 0832519中使用了Sn(OSO2F3)2化合物代替EP 0608447A中第四组分的卤素源，形成了一种新的四元铬系催化剂组合物，该四元铬系催化剂的活性和选择性未得到明显的改进。
USP 5,910,619中报道了采用1，2，3，4，5，6-六氯环己烷作为改进剂，组成四元催化剂组合物，该催化剂的活性虽有所提高；中国专利“一种乙烯齐聚制己烯-1的催化剂及其应用”(CN1294109A)使用了新型催化体系，催化活性有了明显提高。但仍不能满足要求，人们希望进一步改进催化剂的性能，以提高催化活性。
WO2004/05647的乙烯齐聚工艺中，辛烯-1的含量最高69.3％，己烯-1含量为10～20％。
发明内容
本发明的目的是开发一种包括一种含P和N的化合物a、给电子体b、铬化物c、载体d和促进剂e的催化剂，该催化剂用于乙烯三聚制己烯-1，使铬化物在配体和促进剂的作用下，形成三个空轨道，这样有利于乙烯分子的配位，并发生β-H消除反应生成己烯-1。而副产物聚乙烯更易在载体SiO2上形成，从而避免了聚乙烯粘釜，有利于反应器的长周期运行。
本发明涉及一种用于乙烯三聚的铬催化剂体系，是含有以下组分的组合物：
(1)一种含P和N的化合物a，通式为
R1、R2、R3、R4为苯基，苯甲基或萘基；R5为异丙基、丁基、环丙基、环戊基、环己基或芴基。
(2)给电子体b，为1，4-二氯苯、1，1，2-三氯乙烷、1，2-二氯乙烷、氯苯、1，2-二氯苯、1，3-二氯苯和/或1，4-二氯苯。
(3)铬化物c为异辛酸铬、四氢呋喃氯化铬和/或乙酰丙酮铬。
(4)载体d为SiO2
(5)促进剂e为三甲基铝，三乙基铝，三丙基铝，三丁基铝和/或三异丁基铝。
a、b、c、d和e的摩尔比为0.5～100∶0.5～100∶1∶0.5～10∶50～5000，优选为1～80∶1～70∶1∶1～8∶100～4000。
可以将a、b、c、d和e五种组分在惰性环境下混合10分钟后，加入反应釜中，通入乙烯进行三聚反应；也可以将a、b、c、d和e五种组分直接加入反应釜中，通入乙烯进行三聚反应。反应温度通常为30～150℃，优选为20～90℃，更优选为30～70℃；反应压力为0.5～10.0MPa，优选为1～10MPa，更优选为2～6MPa；时间为0.1～4小时，优选为0.3～1小时，更优选为0.5～0.7小时。
乙烯三聚反应主要在惰性溶剂中进行。可选择的溶剂包括烷烃、芳烃、卤代烃、烯烃等。典型的溶剂包括，但不限于苯、甲苯、二甲苯、异丙苯、正庚烷、正己烷、甲基环己烷、环己烷、己烯-1、辛烯-1、离子液体等。
具有活性高、己烯-1选择性好、而副产物聚乙烯不粘釜的特点。
具体实施方式
下面的例子是用来说明本发明，而不是用来限制本发明的范围。
实施例1
1、制备(二苯基)磷氮(环丙基)磷(二苯基)配体
(1)制备N，N-二异丙基二氯磷酰胺
在经N2充分置换的带搅拌的250mL反应器中加入经脱水处理的甲苯(100mL)，加入PCl3(21.87mL，0.25mol)，并降温到-20℃。室温下边搅拌边缓慢地加入二异丙胺(70mL，0.5mol)，搅拌3小时后升至室温再继续反应2小时，然后过滤，干燥得产物38.1g(0.19mol，74％)。
(2)制备苯基溴化镁格试剂
在经N2充分置换的带搅拌的250mL反应器中加入经脱水处理的THF(100mL)，镁粉(9.11g，0.375mol)，冰浴降温并缓慢滴加溴苯(11.775g，0.075mol)。2小时后，加热回流继续反应2小时得到格试剂。
(3)制备二苯基氯化磷
在经N2充分置换的带搅拌的250mL反应器中加入经脱水处理的THF(100mL)，降温至0℃，缓慢加入N，N-二异丙基二氯化磷酰胺(6.64mL，36mmol)。升至室温反应12小时。然后反应混合物用环己烷稀释，并用干燥的H333331气体鼓泡1小时，过滤，干燥得到氯化二苯基磷。
(4)制备(二苯基)磷氮(环丙基)磷(二苯基)
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的二氯甲烷(20mL)，三乙胺(3.75mL)，二苯基氯化磷(1.326mL，7.2mmol)，降温至0℃，缓慢加入环丙胺(3.6mmol)。搅拌反应30min后升至室温继续反应12小时。过滤、干燥得到产物(0.87g，56.6％)。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的甲苯(10mL)，(二苯基)磷氮(环丙基)磷(二苯基)(29mg)，三乙基铝(10mL)，异辛酸铬(0.03mmol)，1，1，2，2-四氯乙烷(7mL，0.54mmol)，SiO2(0.03mmol)室温反应10min后备用。
3、乙烯三聚
500mL的高压釜加热到抽真空2小时，经氮气置换数次后充入乙烯，降温到预定温度，加入经脱水处理的甲苯(200mL)及上述催化剂。
在90℃、4.0MPa的压力下进行齐聚反应，反应40min后用冰浴降温、卸压，用质量分数为10％的酸化乙醇终止反应。结果见附表1。
实施例2
1、制备(二苯基)磷氮(环戊基)磷(二苯基)配体
(1)制备N，N-二异丙基二氯磷酰胺
同实施例1。
(2)制备苯基溴化镁格试剂
同实施例1。
(3)制备二苯基氯化磷
同实施例1。
(4)制备(二苯基)磷氮(环戊基)磷(二苯基)
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的二氯甲烷(20mL)，三乙胺(3.75mL)，二苯基氯化磷(1.326mL，7.2mol)，降温至0℃，缓慢加入环戊基胺(0.415mL，3.5mmol)。搅拌反应30min后升至室温继续反应12小时。过滤、干燥得到产物(0.55g，32.68％)。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的环己烷(10mL)，三甲基铝(10mL)，(二苯基)磷氮(环戊基)磷(二苯基)(31mg)，CrCl3·(THF)3(12mg)，SiO2(0.3mmol)，1，1，2，2四溴乙烷(0.02，0.069mmol)室温反应5min后备用。
3、乙烯三聚
500mL的高压釜加热到抽真空2小时，经氮气置换数次后充入乙烯，降温到预定温度，加入经脱水处理的环己烷(200mL)及上述催化剂。在20℃、7.0MPa的压力下进行齐聚反应，反应20min后用冰浴降温、卸压，用质量分数为10％的酸化乙醇终止反应。结果见附表1。
实施例3
1、制备(二苯基)磷氮(芴基)磷(二苯基)配体
(1)制备N，N-二异丙基二氯磷酰胺
同实施例1。
(2)制备苯基溴化镁格试剂
同实施例1。
(3)制备二苯基氯化磷
同实施例1。
(4)制备(二苯基)磷氮(芴基)磷(二苯基)
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的二氯甲烷(20mL)，三乙胺(3.75mL)，二苯基氯化磷(1.326mL，7.2mol)，降温至0℃，缓慢加入芴胺(0.652g，3.6mmol)。搅拌反应30min后升至室温继续反应12小时。过滤、干燥得到产物(0.48g，24.3％)。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的环己烷(10mL)，三丙基铝(10mL)，SiO2(0.1mmol)，(二苯基)磷氮(芴基)磷(二苯基)(35mg)，Cr(acac)3(12mg)，1，2-二甲氧基乙烷(0.4mL，0.031mmol)，室温反应5min后备用。
3、乙烯三聚
500mL的高压釜加热到抽真空2小时，经氮气置换数次后充入乙烯，降温到预定温度，加入经脱水处理的苯(200mL)及上述催化剂。在30℃、3.0MPa的压力下进行齐聚反应，反应20min后用冰浴降温、卸压，用质量分数为10％的酸化乙醇终止反应。结果见附表1。
实施例4
1、制备1，4-双(N(P(苯基)2)2)-苯配体
(1)制备N，N-二异丙基二氯磷酰胺
同实施例1。
(2)制备苯基溴化镁格试剂
同实施例1。
(3)制备二苯基氯化磷
同实施例1。
(4)制备1，4-双(N(P(苯基)2)2)-苯
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的二氯甲烷(20mL)，三乙胺(3.75mL)，二苯基氯化磷(1.326mL，7.2mmol)，降温至0℃，缓慢加入1，4-苯二胺(0.19g，1.8mmol)。搅拌反应30min后升至室温继续反应12小时。过滤、干燥得到产物(0.8g，52.3％)。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的环己烷(10mL)，三丁基铝溶液(7mL)，SiO2(0.3mmol)，1，4-双(N(P(苯基)2)2)-苯(27mg)，2-乙基己酸铬(10mg)，1，2-二氯乙烷(0.13mmol)，室温反应10min后备用。
3、乙烯三聚
500mL的高压釜加热到抽真空2小时，经氮气置换数次后充入乙烯，降温到预定温度，加入经脱水处理的庚烷((200mL)及上述催化剂。在100℃、7.0MPa的压力下进行齐聚反应，反应10min后用冰浴降温、卸压，用质量分数为10％的酸化乙醇终止反应。结果见附表1。
实施例5
1、制备(二苯基)磷氮(异丙基)磷(二苯基)配体
(1)制备N，N-二异丙基二氯磷酰胺
同实施例1。
(2)制备苯基溴化镁格试剂
同实施例1。
(3)制备二苯基氯化磷
同实施例1。
(4)制备(二苯基)磷氮(异丙基)磷(二苯基)
同实施例1。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的二甲苯(10mL)，SiO2(0.09mmol)，三异丁基铝(10mL)，(二苯基)磷氮(环己基)磷(二苯基)(29mg)，CrCl3·(THF)3(12mg)，1，4-二氯苯(0.069mmol)室温反应5min后备用。
3、乙烯齐聚
500mL的高压釜加热到抽真空2小时，经氮气置换数次后充入乙烯，降温到预定温度，加入经脱水处理的二甲苯((200mL)及上述催化剂。在20℃、5.5MPa的压力下进行齐聚反应，反应60min后用冰浴降温、卸压，用质量分数为10％的酸化乙醇终止反应。结果见附表1。
附表1
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
| 催化剂活性(g齐聚物/mol Cr.h)×107 | 5.8 | 4.1 | 6.4 | 5.1 | 1.6 |
| 丁烯-1选择性(wt％) | 0.3 | 0.4 | 0.8 | 0.4 | 0.9 |
| 己烯-1选择性(wt％) | 95.1 | 95.2 | 95.2 | 96.3 | 97.2 |
| 聚合物(wt％) | 0.02 | 0.05 | 0.04 | 0.07 | 0.02 |
Claims (3)
1.一种用于乙烯三聚合成己烯-1的催化剂，其特征在于：由如下成分组成：
(1)一种含P和N的化合物a，通式为
R1、R2、R3、R4为苯基，苯甲基、萘基；R5为异丙基、丁基、环丙基、环戊基、环己基或芴基。
(2)给电子体b，为1，4-二氯苯、1，1，2-三氯乙烷、1，2-二氯乙烷、氯苯、1，2-二氯苯、1，3-二氯苯和/或1，4-二氯苯；
(3)铬化物c为异辛酸铬、四氢呋喃氯化铬和/或乙酰丙酮铬；
(4)载体d为SiO2；
(5)促进剂e为三甲基铝、三乙基铝、三丙基铝、三丁基铝和/或三异丁基铝；
a、b、c、d和e的摩尔比为0.5～100∶0.5～100∶1∶0.5～10∶50～5000。
2.一种权利要求1所述的用于乙烯三聚合成己烯-1的催化剂的应用，其特征在于：用于催化乙烯三聚合成己烯-1，在惰性溶剂中进行，在乙烯三聚的常规设备中，按权利要求1所述的催化剂各组分配比的有效量，在乙烯压力下进行催化剂原位制备，并不断地通入乙烯，使其与0.5～10.0MPa，时间0.1～4小时。
3.按照权利要求2所述的用于乙烯三聚合成己烯-1的催化剂的应用，其特征在于：惰性溶剂为烷烃、芳烃、卤代烃、烯烃或离子液体；烷烃为正庚烷、正己烷、甲基环己烷或环己烷；芳烃是苯、甲苯、二甲苯或异丙苯；烯烃是己烯-1或辛烯-1。
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|---|---|
| JP5635126B2 (ja) | 2014-12-03 |
| EP2520366A4 (en) | 2013-07-03 |
| JP2013515601A (ja) | 2013-05-09 |
| US9421533B2 (en) | 2016-08-23 |
| US20120310025A1 (en) | 2012-12-06 |
| CN102107146B (zh) | 2013-10-16 |
| EP2520366B1 (en) | 2018-12-26 |
| WO2011079493A1 (zh) | 2011-07-07 |
| EP2520366A1 (en) | 2012-11-07 |
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