CN114029091B - 用于乙烯选择性三聚的双配体催化体系及其制备方法和应用 - Google Patents
用于乙烯选择性三聚的双配体催化体系及其制备方法和应用 Download PDFInfo
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- CN114029091B CN114029091B CN202111594091.2A CN202111594091A CN114029091B CN 114029091 B CN114029091 B CN 114029091B CN 202111594091 A CN202111594091 A CN 202111594091A CN 114029091 B CN114029091 B CN 114029091B
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- aluminum
- formula
- chloride
- ethylene
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- 239000003446 ligand Substances 0.000 title claims abstract description 87
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000005977 Ethylene Substances 0.000 title claims abstract description 41
- 238000005829 trimerization reaction Methods 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 230000009977 dual effect Effects 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 20
- 150000002367 halogens Chemical class 0.000 claims abstract description 20
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 14
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 26
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical group CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims description 24
- -1 acetylacetone anion Chemical class 0.000 claims description 17
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 125000000217 alkyl group Chemical group 0.000 abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 18
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229950011008 tetrachloroethylene Drugs 0.000 description 5
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 4
- IGJQUJNPMOYEJY-UHFFFAOYSA-N 2-acetylpyrrole Chemical compound CC(=O)C1=CC=CN1 IGJQUJNPMOYEJY-UHFFFAOYSA-N 0.000 description 4
- GXSYXPDGMUORDR-UHFFFAOYSA-N 2-ethyl-5-methyl-1h-pyrrole Chemical compound CCC1=CC=C(C)N1 GXSYXPDGMUORDR-UHFFFAOYSA-N 0.000 description 4
- NPCUWXDZFXSRLT-UHFFFAOYSA-N chromium;2-ethylhexanoic acid Chemical compound [Cr].CCCCC(CC)C(O)=O NPCUWXDZFXSRLT-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UAWVMPOAIVZWFQ-UHFFFAOYSA-N 1-(chloromethyl)-2-methoxybenzene Chemical compound COC1=CC=CC=C1CCl UAWVMPOAIVZWFQ-UHFFFAOYSA-N 0.000 description 3
- VGISFWWEOGVMED-UHFFFAOYSA-N 1-(chloromethyl)-3-methoxybenzene Chemical compound COC1=CC=CC(CCl)=C1 VGISFWWEOGVMED-UHFFFAOYSA-N 0.000 description 3
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 3
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 3
- VZGLVCFVUREVDP-UHFFFAOYSA-N 3-chlorobut-1-ene Chemical compound CC(Cl)C=C VZGLVCFVUREVDP-UHFFFAOYSA-N 0.000 description 3
- LOQLDQJTSMKBJU-UHFFFAOYSA-N 4-(chloromethyl)benzonitrile Chemical compound ClCC1=CC=C(C#N)C=C1 LOQLDQJTSMKBJU-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 3
- LBOBESSDSGODDD-UHFFFAOYSA-N 1,3-dichloro-2-(chloromethyl)benzene Chemical compound ClCC1=C(Cl)C=CC=C1Cl LBOBESSDSGODDD-UHFFFAOYSA-N 0.000 description 2
- MOBRMRJUKNQBMY-UHFFFAOYSA-N 1-(chloromethyl)-2-fluorobenzene Chemical compound FC1=CC=CC=C1CCl MOBRMRJUKNQBMY-UHFFFAOYSA-N 0.000 description 2
- APGGSERFJKEWFG-UHFFFAOYSA-N 1-(chloromethyl)-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(CCl)=C1 APGGSERFJKEWFG-UHFFFAOYSA-N 0.000 description 2
- VWVZFHRDLPHBEG-UHFFFAOYSA-N 1-(chloromethyl)-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(CCl)C=C1 VWVZFHRDLPHBEG-UHFFFAOYSA-N 0.000 description 2
- MJGOLNNLNQQIHR-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)-3-fluorobenzene Chemical compound FC1=CC=CC(Cl)=C1CCl MJGOLNNLNQQIHR-UHFFFAOYSA-N 0.000 description 2
- NBXDXMFYTJNWCS-UHFFFAOYSA-N 2,3,4,5-tetrachloro-1h-pyrrole Chemical compound ClC=1NC(Cl)=C(Cl)C=1Cl NBXDXMFYTJNWCS-UHFFFAOYSA-N 0.000 description 2
- MJXRENZUAQXZGJ-UHFFFAOYSA-N 2-(chloromethyl)-1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1CCl MJXRENZUAQXZGJ-UHFFFAOYSA-N 0.000 description 2
- PFRKGGQLYAMPST-UHFFFAOYSA-N 3,4-dichloro-1h-pyrrole Chemical compound ClC1=CNC=C1Cl PFRKGGQLYAMPST-UHFFFAOYSA-N 0.000 description 2
- OJFOWGWQOFZNNJ-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC=C1C OJFOWGWQOFZNNJ-UHFFFAOYSA-N 0.000 description 2
- MSXUEMBOMBFOMG-UHFFFAOYSA-N 3-ethyl-2,5-dimethyl-1h-pyrrole Chemical compound CCC=1C=C(C)NC=1C MSXUEMBOMBFOMG-UHFFFAOYSA-N 0.000 description 2
- UDKQGFMDBMYVHI-UHFFFAOYSA-N 4-bromo-1-(chloromethyl)-2-fluorobenzene Chemical compound FC1=CC(Br)=CC=C1CCl UDKQGFMDBMYVHI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- AIPJZPPOFWCJRC-UHFFFAOYSA-N 1,2-dichloro-3-(chloromethyl)benzene Chemical compound ClCC1=CC=CC(Cl)=C1Cl AIPJZPPOFWCJRC-UHFFFAOYSA-N 0.000 description 1
- YZIFVWOCPGPNHB-UHFFFAOYSA-N 1,2-dichloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C(Cl)=C1 YZIFVWOCPGPNHB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- QCZFALDMBXRELM-UHFFFAOYSA-N 1-(1-chloroethyl)-2,3-dimethylbenzene Chemical compound CC(Cl)C1=CC=CC(C)=C1C QCZFALDMBXRELM-UHFFFAOYSA-N 0.000 description 1
- XPGHWBDZNQUUQD-UHFFFAOYSA-N 1-(chloromethyl)-2,4-difluorobenzene Chemical compound FC1=CC=C(CCl)C(F)=C1 XPGHWBDZNQUUQD-UHFFFAOYSA-N 0.000 description 1
- XZNDXQGZPOZITR-UHFFFAOYSA-N 1-(chloromethyl)-2-methyl-3-nitrobenzene Chemical compound CC1=C(CCl)C=CC=C1[N+]([O-])=O XZNDXQGZPOZITR-UHFFFAOYSA-N 0.000 description 1
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- DILUHKVHAUYQLS-UHFFFAOYSA-N 1-(dichloromethyl)-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C(Cl)Cl DILUHKVHAUYQLS-UHFFFAOYSA-N 0.000 description 1
- GOLKHAUFRFNCPA-UHFFFAOYSA-N 1-(dichloromethyl)-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C(Cl)Cl)C=C1 GOLKHAUFRFNCPA-UHFFFAOYSA-N 0.000 description 1
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- 125000005595 acetylacetonate group Chemical group 0.000 description 1
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- 125000000962 organic group Chemical group 0.000 description 1
- KGCNHWXDPDPSBV-UHFFFAOYSA-N p-nitrobenzyl chloride Chemical compound [O-][N+](=O)C1=CC=C(CCl)C=C1 KGCNHWXDPDPSBV-UHFFFAOYSA-N 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
本发明提供了一种用于乙烯选择性三聚的双配体催化体系及其制备方法和应用,属于过渡金属均相催化技术领域。该催化体系包括:配体,由具有如式(I)所示结构的配体A和具有如式(Ⅱ)所示结构的配体B组成;铬化合物;助催化剂,所述助催化剂包括烷基铝、烷基铝的衍生物中至少一种;含卤促进剂; 其中,式(I)中,n=0,1,2,3,4,5,6,R1为芳香基,R2、R3、R4、R5分别独立选自碳数不大于10的直链或带支链的烷基、环烷基或芳香基;式(Ⅱ)中,R11、R12、R13、R14分别独立选自氢、氯、溴、碘、碳数不大于10的直链及带支链的烷基。本发明的催化剂体系用于乙烯催化乙烯三聚反应,具有催化活性高、1‑己烯选择性高、副产物少的特点。
Description
技术领域
本发明属于过渡金属均相催化技术领域,具体涉及用于乙烯选择性三聚的双配体催化体系及其制备方法和应用。
背景技术
以1-己烯为共聚单体生产的线型低密度聚乙烯及高密度聚乙烯在多项性能指标上超过了以1-丁烯为共聚单体的同类产品。随着全球聚乙烯产能的迅速提高,市场竞争日益激烈,对高性能产品的需求不断增长,从而导致对1-己烯需求的增长。通过乙烯非选择性齐聚生产符合数学分布的线性α-烯烃混合物的工艺存在副产物含量高(1-丁烯>10%、聚合物>1.0%),目标产物选择性低的缺点,已不能满足市场对1-己烯的需求。
乙烯三聚高选择性地生产1-己烯具有原子经济性好、反应条件温和、工艺路线简单等优点,是更符合行业发展趋势的工艺路线。而该路线的技术关键是兼具高活性和高选择性的催化剂体系。Phillips Petroleum公司开发的乙烯三聚(US5523507)工艺,其1-己烯的选择性达到93%,成功地实现了乙烯三聚生产1-己烯的工业化。专利文献(日本特开平08-239419)也报道了以铬化合物、含氮化合物、和烷基铝化合物构成的铬系催化剂可以高收率地得到1-己烯。
乙烯三聚催化剂研发的一个重要思路是设计具有特定空间位阻和电子性质的配体以改变催化活性和产物选择性,但由于反应体系的复杂性,在反应过程中会产生一些对催化剂有害的物种,影响催化性能。
发明内容
本发明旨在提供一种高活性、高选择性地催化乙烯三聚反应的双配体催化体系,通过带有活泼氢的PNP类型磷配体抑制导致催化剂活性和选择性降低的物种,从而有效地稳定乙烯三聚催化剂活性中心,提高乙烯三聚催化剂的活性和对目标产物1-己烯的选择性。
本发明提出一种用于乙烯选择性三聚的催化体系,包括:
配体,由具有如式(I)所示结构的配体A和具有如式(Ⅱ)所示结构的配体B组成;
铬化合物;
助催化剂,所述助催化剂包括烷基铝、烷基铝的衍生物中至少一种;
含卤促进剂;
其中,式(I)中,n=0,1,2,3,4,5,6,R1为芳香基,R2、R3、R4、R5分别独立选自碳数不大于10的直链或带支链的烷基、环烷基或芳香基;
式(Ⅱ)中,R11、R12、R13、R14分别独立选自氢、氯、溴、碘、碳数不大于10的直链及带支链的烷基。
进一步地,R11、R12、R13、R14分别独立选自吡咯、2,4-二甲基吡咯、2,5-二甲基吡咯、2-甲基-5-乙基吡咯、2,5-二甲基-3-乙基吡咯、3,4-二甲基吡咯、3,4-二氯吡咯、2,3,4,5-四氯吡咯、2-乙酰基吡咯等;
更优选的,R11、R12、R13、R14分别独立选自吡咯、2,4-二甲基吡咯、2,5-二甲基吡咯、2-甲基-5-乙基吡咯。
进一步地,配体A与配体B的摩尔比在100:1到1:100之间。
进一步地,铬化合物的负离子为NO3 -、HSO4 -、Cl-、Br-、2-乙基己酸根或乙酰丙酮负离子;优选的,Cl-、2-乙基己酸根和乙酰丙酮负离子。
进一步地,所述烷基铝包括三甲基铝、三乙基铝、三异丁基铝和三正己基铝中至少一种;
所述烷基铝的衍生物包括铝氧烷和氯化烷基铝中至少一种;优选的,所述铝氧烷包括甲基铝氧烷、乙基铝氧烷和异丁基铝氧烷中至少一种;所述氯化烷基铝包括乙基倍半氯化铝、一氯二乙基铝、倍半一氯二乙基铝和二氯化乙基铝中至少一种。
进一步地,含卤促进剂包括C1-C10的直链或支链卤代烷烃、卤代烯烃、卤代芳烃中至少一种;其中,含卤促进剂中的卤素原子为氟、氯、溴或碘。
进一步地,催化剂体系中,铬化合物、配体、助催化剂、含卤促进剂的物质的量的比为1:(1~15):(10~1000):(0.1~60)。
本发明还提出一种乙烯选择性三聚的反应方法,包括上述任一所述催化剂体系存在下进行的乙烯三聚反应。
进一步地,反应在惰性溶剂中进行,所述惰性溶剂为碳原子数不大于16的烷烃、环烷烃、芳烃、烯烃或离子液体中至少一种。
进一步地,反应的温度为0℃0200℃;反应的压力为0.1MPa020MPa。
本发明具有以下优势:
本发明提出的催化剂体系采用两种特定配体吡咯类化合物配体和带有活泼氢的PNP类型磷配体相互协同作用,其中,带有活泼氢的PNP类型磷配体可以有效地抑制体系中导致催化剂失活以及选择性降低的物种,从而提高催化活性,提高目标产物1-己烯的选择性,降低副产物(丁烯及聚合物等)的生成。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
本发明一实施例提出一种用于乙烯选择性三聚的催化体系,包括:
配体,由具有如式(I)所示结构的配体A和具有如式(II)所示结构的配体B组成;
铬化合物;
助催化剂,所述助催化剂包括烷基铝、烷基铝的衍生物中至少一种;
含卤促进剂;
其中,式(I)中,n=0,1,2,3,4,5,6,R1为芳香基,R2、R3、R4、R5分别独立选自碳数不大于10的直链或带支链的烷基、环烷基或芳香基;
式(Ⅱ)中,R11、R12、R13、R14分别独立选自氢、氯、溴、碘、碳数不大于10的直链及带支链的烷基。
现有技术中,单一吡咯类化合物配体的催化体系中,配体/Cr的比例大,则影响乙烯的配位,导致催化活性降低;而降低配体/Cr的比例会导致烷基铝对Cr中心的过度还原,生成黑色粉末状沉淀,从而降低了有效的催化中心浓度,并导致副产物的产生。
本发明实施例提出的催化剂体系,添加两种配体共同作用,配体A为带有活泼氢的PNP类型磷配体,配体B为吡咯类化合物。带有活泼氢的PNP结构的配体A可以充分利用磷原子对Cr中心较弱的配位作用,保护Cr中心不被过度还原,提高有效的催化中心的浓度,进而提高催化剂活性并减少副产物的生成,高选择性乙烯三聚生成1-己烯。
本发明一实施例中,式(I)中,优选n=0,1,2,3,4,更优选n=0,2。
本发明一实施例中,式(II)中,R11、R12、R13、R14分别独立选自氢(H)、氯(Cl)、溴(Br)、碘(I)、碳数不大于10的直链及带支链的烷基。优选的,R11、R12、R13、R14分别独立选自吡咯、2,4-二甲基吡咯、2,5-二甲基吡咯、2-甲基-5-乙基吡咯、2,5-二甲基-3-乙基吡咯、3,4-二甲基吡咯、3,4-二氯吡咯、2,3,4,5-四氯吡咯、2-乙酰基吡咯等。更优选的,R11、R12、R13、R14分别独立选自吡咯、2,4-二甲基吡咯、2,5-二甲基吡咯、2-甲基-5-乙基吡咯。
具体而言,所述芳香基具有式(III)、式(IV)或式(V)所示的结构;
其中,式(III)中,R6、R7、R8、R9、R10分别独立选自H、Cl、Br,、I、碳原子数不大于10的直链及带支链的烷基、环烷基、-OCH3。
本发明一实施例中,配体A与配体B的摩尔比在100:1到1:100之间。优选的,配体A与配体B的摩尔比为(106):(0.106)。更优选的,配体A与配体B的摩尔比为(105.7):(0.305)。
本发明一实施例中,铬化合物的负离子为NO3 -、HSO4 -、Cl-、Br-、2-乙基己酸根或乙酰丙酮负离子;优选的,Cl-、2-乙基己酸根和乙酰丙酮负离子。更优选的,铬化合物为碱式2-乙基己酸铬。铬化合物可以用通式CrXnYm表示,为1种或21种以上的化合物组成的混合物。且n+m=3。通式中,X、Y表示任意的一价的负离子,可以是有机负离子或无机负离子。所述有机基团,可以是碳原子数为1-20的烷氧基、羧基、β-二酮基、β-酮基羧基、β-酮基酯基、酰氨基等;其中,优选碳原子数为6-18的羧基、碳原子数为4-10的β-二酮基和β-酮基羧基,其中,最优选2-乙基己酸基和乙酰丙酮基。所述无机基团包括H2PO3 -、HCO3 -、NO3 -、HSO4 -、Cl-、Br-、I-、OH-、其中优选H2PO3 -、Cl-、OH-、Br-,其中,最优选Cl-、OH-。
本发明一实施例中,所述烷基铝包括三甲基铝、三乙基铝、三异丁基铝和三正己基铝中至少一种;
所述烷基铝的衍生物包括铝氧烷和氯化烷基铝中至少一种;优选的,所述铝氧烷包括甲基铝氧烷、乙基铝氧烷和异丁基铝氧烷中至少一种;所述氯化烷基铝包括乙基倍半氯化铝、一氯二乙基铝、倍半一氯二乙基铝和二氯化乙基铝中至少一种。其中,所述甲基铝氧烷包括改性铝氧烷,如MMAO-3A。更优选的,所述助催化剂包括三乙基铝、乙基倍半氯化铝中至少一种。
本发明一实施例中,含卤促进剂为C1-C10的直链或支链卤代烷烃、卤代烯烃、卤代芳烃中至少一种;其中,含卤促进剂中的卤素原子为氟、氯、溴或碘。
具体而言,含卤促进剂可以包括四氯化碳、1,1,2,2-四氯乙烷、四氯乙烯、五氯乙烷、六氯乙烷、烯丙基氯、氯苯、(邻、间、对)二氯代苯、(均、连、偏)三氯苯、(一、二、三)氯苯甲烷、正丁基氯、仲丁基氯、叔丁基氯、邻、间、对-甲基氯化苄、3,4-二甲基氯化苄、2,6-二甲基氯化苄、2,5-二甲基氯化苄、2,4,6-三甲基氯化苄、1-(1-氯乙基)-2,3-二甲苯、4-异丙基氯苄、2-异丙基氯苄、3-氯-2-甲基丙烯、3-氯-1-丁烯、1-氯-2-丁烯、2-氯苄基氯、3-氯苄基氯、4-氯苄基氯、2-溴苄基氯、3-溴苄基氯、4-溴苄基氯、2-氟苄基氯、3-氟苄基氯、4-氟苄基氯、2-硝基苄基氯、3-硝基苄基氯、4-硝基苄基氯、2-氰基苄基氯、3-氰基苄基氯、4-氰基苄基氯、2-甲氧基苄基氯、3-甲氧基苄基氯、4-甲氧基苄基氯、4-(甲硫基)苄基氯、4-(三氟甲氧基)苄基氯、2,3-二氯苄基氯、2,4-二氯苄基氯、2,6-二氯苄基氯、3,4-二氯苄基氯、2,4-二氟苄基氯、2,6-二氟苄基氯、2-氯-4-氟苄基氯、2-氯-6-氟苄基氯、4-溴-2-氟苄基氯、2-甲基-3-硝基苄基氯、4-甲基-3-硝基苄基氯、5-甲基-2-硝基苄基氯、2-甲基-2-苯氧基苄基氯等。其中优选1,1,2,2-四氯乙烷、四氯乙烯、六氯乙烷、仲丁基氯、叔丁基氯、4-异丙基氯苄、2-异丙基氯苄、3-氯-2-甲基丙烯、3-氯-1-丁烯、1-氯-2-丁烯、2-氯苄基氯、2-溴苄基氯、2-氟苄基氯、3-硝基苄基氯、3-氰基苄基氯、2-甲氧基苄基氯、3-甲氧基苄基氯、4-甲氧基苄基氯、4-(甲硫基)苄基氯、2,6-二氯苄基氯、2,6-二氟苄基氯、2-氯-6-氟苄基氯、4-溴-2-氟苄基氯中至少一种。
优选的,含卤促进剂可以包括四氯乙烯、六氯乙烷、仲丁基氯、叔丁基氯、3-氯-1-丁烯、3-氯-2-甲基丙烯、2-甲氧基苄基氯、3-甲氧基苄基氯、4-甲氧基苄基氯中至少一种。
最优选的,含卤促进剂可以包括四氯乙烯、六氯乙烷中至少一种。
本发明一实施例中,催化剂体系中,铬化合物、配体、助催化剂、含卤促进剂的物质的量的比为1:(1~15):(10~1000):(0.1~60)。催化剂体系中,铬化合物:配体:助催化剂:含卤促进剂的物质的量的比为1:(1~15):(10~1000):(0.1~60);其中优选1:(2~8):(30~200):(1~30),最优选1:(3~7):(40~150):(2~20)。
本发明一实施例还提出上述催化剂体系的制备方法方法,包括将催化剂的各组分在使用前可配制成一定浓度的溶液以便于移取。
本发明一实施例还提出一种乙烯选择性齐聚的反应方法,包括上述任一所述催化剂体系存在下进行的乙烯三聚反应。
本发明一实施例中,反应在惰性溶剂中进行,所述惰性溶剂为碳原子数不大于16的烷烃、环烷烃、芳烃、烯烃或离子液体中至少一种。其中,优选碳原子数为5~10的烷烃环烷烃、芳烃、烯烃。最优选,己烷、环己烷、甲基环己烷、正庚烷和甲苯。
本发明一实施例中,乙烯三聚反应的反应的温度为0℃0200℃;反应的压力为0.1MPa020MPa。其中,优选反应的温度为50℃0150℃。
本发明一实施例中,反应的压力为0.1MPa020MPa。反应的压力为1.0MPa010Mpa;最优选反应的温度为100℃0130℃;反应的压力为3MPa06Mpa。下面对本发明催化剂体系的构建和在乙烯三聚反应中的应用进行说明。
实施例1催化剂1在催化乙烯三聚反应中的应用
催化剂1,由包括如下原料制备而得:
配体1A:具有式1A所示结构,带有活泼氢的PNP型磷配体,可按照参考文献(郑德金,新型PNP配体的合成及应用探索,东北石油大学硕士论文,2014)中所述方法合成;
配体1B:2,5-二甲基吡咯,具有式1B所示结构,为市售商品,纯度≥98%,无需纯化,直接使用;
铬化合物:2-乙基己酸铬;
助催化剂:三乙基铝;
含卤促进剂:六氯乙烷;
溶剂:甲基环己烷溶液。
将80℃连续抽真空干燥2小时以上的500mL不锈钢高压反应釜用高纯氮气置换3次,再抽真空并用乙烯置换3次。在保持釜内微正压的条件下向釜内注入130mL甲基环己烷,开启搅拌,然后依次加入溶解有1.51mg配体1A的甲基环己烷溶液、溶解有1.14mg配体1B的甲基环己烷溶液、溶解10.6mg的六氯乙烷的甲基环己烷溶液、溶解1.44mg的2-乙基己酸铬的甲基环己烷溶液和溶解有25.6mg三乙基铝的甲基环己烷溶液,然后再补充加入甲基环己烷至溶液总体积的计算值至150mL。继续搅拌10分钟后升温至120℃,充入乙烯使釜内压力达到并维持在5.0MPa,保持800rpm的速度进行搅拌,用质量流量计计量乙烯流量。反应25min后切断乙烯进料,高压釜降温至0℃后泄压至常压,过滤去除催化剂与聚合物。滤液称重并取样用气相色谱对其组份进行定量分析。实验结果见表1。
实施例2催化剂2在催化乙烯三聚反应中的应用
同实施例1,不同之处在于,催化剂2中,配体1A和配体1B的比例有所不同(详见表1)。
对比例1-1单配体催化剂在催化乙烯三聚反应中的应用
同实施例1,不同之处在于,仅采用单一配体1B(2,5-二甲基吡咯)(详见表1)制成的单配体催化剂。
对比例1-2单配体催化剂在催化乙烯三聚反应中的应用
同对比例1-1,不同之处在于,仅采用单一配体1A(详见表1)制成的单配体催化剂。
实施例3催化剂3在催化乙烯三聚反应中的应用
同实施例1,不同之处在于,催化剂3中,所用的两种配体分别为配体2A(具有式2A所示结构)、配体1B(2,5-二甲基吡咯),所用的含卤促进剂为四氯乙烯。反应温度为115℃,反应压力为5.5MPa(详见表1)。
实施例4催化剂4在催化乙烯三聚反应中的应用
同实施例3,不同之处在于,催化剂4中,配体2A和配体1B的比例有所不同(详见表1)。
对比例2-1单配体催化剂在催化乙烯三聚反应中的应用
同实施例3,不同之处在于,仅采用单一配体1B(2,5-二甲基吡咯)制成的单配体催化剂(详见表1)。
对比例2-2单配体催化剂在催化乙烯三聚反应中的应用
同对比例2-1,不同之处在于,仅采用单一配体2A制成的单配体催化剂(详见表1)。
实施例5催化剂5在催化乙烯三聚反应中的应用
同实施例1,不同之处在于,配体1A和配体1B的比例有所不同,所用的Cr盐为碱式2-乙基己酸铬(C16H31CrO5),所用的助催化剂为三乙基铝和乙基倍半氯化铝的混合物,所用的含卤促进剂为六氯乙烷。反应温度为130摄氏度(详见表1)。
实施例6催化剂6在催化乙烯三聚反应中的应用
同实施例5,不同之处在于,配体1A和配体1B的比例有所不同(详见表1)。
对比例3-1单配体催化剂在催化三聚反应中的应用
同实施例5,不同之处在于,仅采用单一配体配体1B(2,5-二甲基吡咯)制成的单配体催化剂(详见表1)。
对比例3-2单配体催化剂在催化三聚反应中的应用
同比例3-1,不同之处在于,仅采用单一配体的配体1A制成的单配体催化剂(详见表1)。
从以上实施例和对比例可以看出,采用单一的带有活泼氢的配体A组成的催化体系,对目标产物1-己烯的选择性比较低。采用单一配体B的催化剂体系的活性较低。而同时采用A、B两种配体的催化剂体系在催化活性及对目标产物的选择性方面均较采用单一配体的催化体系有所提高。
Claims (7)
1.一种用于乙烯选择性三聚的双配体催化体系,其特征在于,包括:
配体,由具有如式(I)所示结构的配体A和配体B组成;其中,配体A与配体B的摩尔比为( 1~5.7):(0.3~5);
铬化合物;铬化合物用通式CrXnYm表示,且n+m=3,其中,X、Y表示任意的一价的负离子,负离子为Cl-、2-乙基己酸根或乙酰丙酮负离子;
助催化剂,所述助催化剂包括烷基铝、烷基铝的衍生物中至少一种;
含卤促进剂;
式(I);配体B为2,5-二甲基吡咯;
其中,式(I)中,n=0,1,2,3,4,5,6,R1为芳香基,R2、R3、R4、R5分别独立选自芳香基;
催化剂体系中,铬化合物、配体、助催化剂、含卤促进剂的物质的量的比为1:(3~7):(40~150):(2~20)。
2.按照权利要求1所述的双配体催化剂体系,其特征在于:
所述烷基铝包括三甲基铝、三乙基铝、三异丁基铝和三正己基铝中至少一种;
所述烷基铝的衍生物包括铝氧烷和氯化烷基铝中至少一种。
3.按照权利要求2所述的双配体催化剂体系,其特征在于:
所述铝氧烷包括甲基铝氧烷、乙基铝氧烷和异丁基铝氧烷中至少一种;所述氯化烷基铝包括乙基倍半氯化铝、一氯二乙基铝、倍半一氯二乙基铝和二氯化乙基铝中至少一种。
4.按照权利要求1所述的双配体催化剂体系,其特征在于:
含卤促进剂包括C1-C10的直链或支链卤代烷烃、卤代烯烃、卤代芳烃中至少一种;其中,含卤促进剂中的卤素原子为氟、氯、溴或碘。
5.一种乙烯选择性三聚的反应方法,其特征在于:
包括权利要求1-4任一项所述催化剂体系存在下进行的乙烯三聚反应。
6.按照权利要求5所述的反应方法,其特征在于:
反应在惰性溶剂中进行,所述惰性溶剂为碳原子数不大于16的烷烃、环烷烃、芳烃、烯烃或离子液体中至少一种。
7.按照权利要求5所述的反应方法,其特征在于:
反应的温度为0℃~200℃;
反应的压力为0.1MPa~20Mpa。
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