CN106188153A - 一种乙烯齐聚用后过渡金属催化剂及其制备方法 - Google Patents
一种乙烯齐聚用后过渡金属催化剂及其制备方法 Download PDFInfo
- Publication number
- CN106188153A CN106188153A CN201610522611.1A CN201610522611A CN106188153A CN 106188153 A CN106188153 A CN 106188153A CN 201610522611 A CN201610522611 A CN 201610522611A CN 106188153 A CN106188153 A CN 106188153A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- late transition
- metal catalyst
- ethylene oligomerization
- catalyst
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000005977 Ethylene Substances 0.000 title claims abstract description 80
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 67
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 67
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002262 Schiff base Substances 0.000 claims abstract description 8
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 8
- 125000003368 amide group Chemical group 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 2
- 240000000203 Salix gracilistyla Species 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000003446 ligand Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 10
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 10
- 0 CC(C)C1C=CC=C(C(C)C)[C@]1C=C(C)C1N(C(P)Cl)C(*)=CC=C1 Chemical compound CC(C)C1C=CC=C(C(C)C)[C@]1C=C(C)C1N(C(P)Cl)C(*)=CC=C1 0.000 description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 8
- 150000002466 imines Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 238000011085 pressure filtration Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000555268 Dendroides Species 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- ZVBAIEDGQVLUOD-UXBLZVDNSA-N C/N=C/C12C=CC=CC1C2O Chemical compound C/N=C/C12C=CC=CC1C2O ZVBAIEDGQVLUOD-UXBLZVDNSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000158723 Melia Species 0.000 description 1
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical compound P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001190 organyl group Chemical group 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- 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
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
本发明提供了一种乙烯齐聚用后过渡金属催化剂及其制备方法。以低代端基为胺基的超支化分子、水杨醛或水杨醛衍生物为原料,配合无水硫酸钠和乙醇,氮气条件下回流反应,过滤,得到水杨醛席夫碱混合物;然后在氮气条件下,将带结晶水的后过渡金属卤化物的乙醇溶液缓慢滴入到水杨醛席夫碱混合物中反应,过滤洗涤后,得到乙烯齐聚用后过渡金属催化剂。本发明采用“一锅法”制备乙烯齐聚用后过渡金属催化剂的制备方法简单、避免了常规乙烯齐聚用后过渡金属催化剂对其配体进行提纯这一复杂过程,催化剂的收率为80%‑90%;且该催化剂具有较高的催化乙烯齐聚活性,易于工业化生产。
Description
技术领域
本发明属于催化剂技术领域,涉及一种乙烯齐聚用后过渡金属催化剂及其制备方法。
背景技术
后过渡金属催化剂是20世纪90年代出现的对烯烃聚合具有高活性的新一代烯烃聚合催化剂。该催化剂可以实现极性单体催化聚合及极性单体与非极性单体的共聚,还可以得到高分子量的聚乙烯、聚α-烯烃以及α-烯烃。与茂金属催化剂相比,后过渡金属催化剂的催化活性比茂金属催化剂的高,聚合产物的分子量和支化度可以调节和控制,催化剂价格便宜、性能稳定、易于制备,可以合成工艺简产率较高,成本较低,易于工业化生产。后过渡金属催化剂为通用树脂和α-烯烃的合成开辟了一个新的领域。
后过渡金属催化剂催化乙烯齐聚制备的α-烯烃具有线性化程度高、碳数分布窄、产物由偶数碳原子组成、分离费用低等优点,成为生产α-烯烃的主要方法,也是获得线性α-烯烃最先进的技术路线,而乙烯齐聚制备高碳α-烯烃的核心技术是催化剂的开发。
孙文华等人(Ma Z,Sun W H,Li Z L.Ethylene polymerization by ironcomplexes with symmetrical and unsymmetrical ligands[J].PolymerInternational,2002,51:994-997.)合成了一种铁系后过渡金属催化剂,其结构如式(a)所示,该催化剂催化乙烯齐聚的活性为6.6×105g/(mol·Fe·h),聚合产物主要为C4-C10,其中α-烯烃选择性达99.4%。
Bianchini等人(Bianchin C,Mantovani G,Melia,Migiliacci F.Selictiveoligomerization of ethylene to linear-olefins by tetrahedral cobalt(II)complexes with 6-(organyl)-2-(imino)pyridyl ligands:influence of theheteroatom in the organyl group on the catalytic activity[J].Organometallics,2003,22(13):2545)合成了一种苯取代亚胺型氯化钴后过渡金属催化剂,其结构如式(b)所示,该催化剂在MAO活化下,催化乙烯齐聚的活性为3.6×107g/(mol·Co·h),聚合产物主要是C4烯烃。
镍系催化剂与其他过渡金属催化剂相比,具有催化活性高、选择性好、产品分布可调、反应条件温和等优点,因此成为乙烯齐聚制备α-烯烃用过渡金属催化剂研究的热点。
Shell公司开发的SHOP型膦氧双齿镍催化剂,其结构如式(c)所示,该催化剂催化乙烯齐聚可生成高碳α-烯烃,C12-C20的选择性高达63.3%。该催化剂的合成路线较长,且存在歧化、异构化反应。
Malgas等人(Malgas R,Mapolie S,Smith G,et al.The application of noveldendritic nickel catalysts in the oligomerization of ethylene[J].CatalysisCommunications,2008,9(7):1612-1617)采用1.0代树枝状聚丙烯亚胺为配体骨架合成了树枝状水杨醛亚胺Ni催化剂,结构如式(d)所示,在EtAlCl2的活化下,催化乙烯齐聚的活性为1.40×106g/(mol·Ni·h),聚合产物主要为C10和C12的长链烯烃。
王俊等人(Wang J,Zhang P,Chen S,et,al.The preparation of dendriticnickel complex and performance evaluation in the oligomerization of ethylene[J].Journal of Macromolecular Science,Part A:Pure and Applied Chemistry[J].2013,50:163-167.)采用低代树枝状聚酰胺-胺为配体骨架合成了一类树枝状水杨醛亚胺Ni催化剂,其结构式如式(e)所示,该催化剂在MAO活化下,催化乙烯齐聚活性高达4.80×106g/(mol·Ni·h),聚合产物主要为C10-C16烯烃。
上述的这些文献合成后过渡金属催化剂,均可以催化乙烯齐聚,且具有较高的催化活性。然而合成步骤较长,均需要对催化剂配体进行提纯,总收率较低,不易实现工业化生产。
发明内容
基于上述现有技术中存在的问题,本发明的目的在于提供一种乙烯齐聚用后过渡金属催化剂及其制备方法。该方法采用“一锅法”,能够避免常规乙烯齐聚用后过渡金属催化剂对其配体进行提纯这一复杂过程。
本发明的目的通过以下技术方案得以实现:
本发明提供一种乙烯齐聚用后过渡金属催化剂,该乙烯齐聚用后过渡金属催化剂的结构式如式(1)所示:
其中,R为环己烷基或C2-C18偶碳数饱和的直链烷基;R1为H、甲基或叔丁基;M为Ni、Co或Fe。
上述乙烯齐聚用后过渡金属催化剂中,优选地,R为环己烷基、乙烷基、丁烷基、十四烷基或十八烷基。
本发明还提供一种乙烯齐聚用后过渡金属催化剂的制备方法,其包括以下步骤:
步骤一,在氮气氛围下,将无水硫酸钠、低代端基为胺基的超支化分子、水杨醛或水杨醛衍生物混合溶于乙醇中,室温下混合均匀,然后升温并在乙醇回流下进行反应,过滤得到水杨醛席夫碱混合物;其中,低代端基为胺基的超支化分子与水杨醛或水杨醛衍生物的摩尔比为1:5-2:5;
步骤二,在氮气氛围下,将带结晶水的后过渡金属卤化物的乙醇溶液缓慢滴入到步骤一中的水杨醛席夫碱混合物中,室温下进行反应,然后加入乙醚进行沉淀,过滤得到固体产物,将该固体产物采用低温乙醚洗涤,并于真空条件下室温干燥,得到乙烯齐聚用后过渡金属催化剂;其中,带结晶水的后过渡金属氯化物与低代端基为胺基的超支化大分子的摩尔比为1:1-2:1。
上述制备方法中,优选地,所述低代端基为胺基的超支化分子结构式如式(2)所示:
其中,R为环己烷基或C2-C18偶碳数饱和的直链烷基。
上述制备方法中,优选地,R为环己烷基、乙烷基、丁烷基、十四烷基或十八烷基。
上述制备方法中,优选地,所述水杨醛或水杨醛衍生物的分子结构式如式(3)所示:
其中,R1为H、甲基或叔丁基。
上述制备方法中,优选地,所述带结晶水的后过渡金属卤化物为NiCl2·6H2O、CoCl2·6H2O或FeCl2·4H2O。
上述制备方法中,优选地,所述步骤一中得到的水杨醛席夫碱混合物不需要提纯,直接参与步骤二的反应。
上述制备方法中,优选地,所述步骤一中,升温的温度为70-80℃;回流反应时间为12-24h;
上述制备方法中,优选地,在步骤二中,室温下进行反应的反应时间为24-48h;反应过滤得到的固体产物采用低温乙醚洗涤,并于真空条件下室温干燥,其中,低温乙醚的温度为5-15℃,洗涤次数为3-5次;干燥时间为5-10h。
上述制备方法中,无水硫酸钠、乙醇、乙醚的添加量可以根据实际需要、按照常规进行合理的调整。
本发明的有益效果:
本发明采用“一锅法”制备乙烯齐聚用后过渡金属催化剂的制备方法简单、避免了常规乙烯齐聚用后过渡金属催化剂对其配体进行提纯这一复杂过程,催化剂的收率为80%-90%;且该催化剂具有较高的催化乙烯齐聚活性,易于工业化生产。
附图说明
图1为本发明实施例1的乙烯齐聚用后过渡金属催化剂的红外光谱图;
图2为本发明实施例2的乙烯齐聚用后过渡金属催化剂的红外光谱图;
图3为本发明实施例3的乙烯齐聚用后过渡金属催化剂的红外光谱图;
图4为本发明实施例4的乙烯齐聚用后过渡金属催化剂的红外光谱图;
图5为本发明实施例5的乙烯齐聚用后过渡金属催化剂的红外光谱图;
图6为本发明实施例6的乙烯齐聚用后过渡金属催化剂的活性随反应温度变化的关系曲线图;
图7为本发明实施例6的乙烯齐聚用后过渡金属催化剂的活性随反应时间变化的关系曲线图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解,现对本发明的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。
实施例1
本实施例提供一种乙烯齐聚用后过渡金属催化剂,其结构式如式(1-1)所示:
本实施例还提供式(1-1)所述乙烯齐聚用后过渡金属催化剂的制备方法,其包括以下步骤:
步骤一,在氮气氛围下,于三口瓶中加入3g无水硫酸钠、环已胺为核1.0G超支化大分子(3.27g,0.01mol)的乙醇(20mL)的溶液和水杨醛(3.66g,0.03mol)的乙醇(20mL)的溶液,于室温下搅拌30min,然后升温至78℃,在乙醇回流下反应12h后过滤除去无水硫酸钠,得到以环已胺为核的超支化水杨醛亚胺配体混合溶液;
步骤二,在氮气氛围下,将NiCl2·6H2O(2.38g,0.01mol)的乙醇的(20mL)溶液缓慢滴入到步骤一得到的以环已胺为核的超支化水杨醛亚胺配体混合溶液中,室温下恒温反应24h;然后向反应的混合物中缓慢加入无水乙醚(50mL),固体析出,负压过滤得到浅绿色固体,用10℃的无水乙醚(100mL)洗涤固体3次,将所得固体在室温、真空条件下干燥5h,得到以环己胺为核超支化水杨醛亚胺镍催化剂,即为本实施例乙烯齐聚用后过渡金属催化剂,产物收率为85.3%。
上述制备过程化学反应方程式如式(1-2)所示。
对本实施例制备的乙烯齐聚用后过渡金属催化剂进行红外分析。结果如图1所示,图1为本实施例制备的乙烯齐聚用后过渡金属催化剂红外光谱图。
由图1可以看出:在1624cm-1处出现了强的特征吸收峰,归属于ν(C=N)的伸缩振动,1541cm-1处为苯环骨架的振动特征峰,1276cm-1和1260cm-1处为苯环二取代面内弯曲振动特征峰,757cm-1处为苯环邻位二取代面外振动特征峰,661cm-1处出现特征峰,归属于ν(N-Ni)特征峰,表明Ni与配体产生配位作用。
实施例2
本实施例提供一种乙烯齐聚用后过渡金属催化剂,其结构式如式(2-1)所示:
本实施例还提供式(2-1)所述乙烯齐聚用后过渡金属催化剂的制备方法,其包括以下步骤:
步骤一,在氮气氛围下,于三口瓶中加入3g无水硫酸钠、直链十四胺为核1.0G超支化大分子(4.30g,0.01mol)的乙醇(20mL)的溶液和水杨醛(6.11g,0.05mol)的乙醇(20mL)的溶液,于室温下搅拌30min,然后升温至80℃,在乙醇回流下反应24h后过滤除去无水硫酸钠,得到以直链十四胺为核的超支化水杨醛亚胺配体混合溶液;
步骤二,在氮气氛围下,将NiCl2·6H2O(4.76g,0.02mol)的乙醇的(40mL)溶液缓慢滴入到步骤一得到的以直链十四胺为核的超支化水杨醛亚胺配体混合溶液中,室温下恒温反应48h;然后向反应的混合物中缓慢加入无水乙醚(60mL),固体析出,负压过滤得到浅绿色固体,用5℃的无水乙醚(200mL)洗涤固体5次,将所得固体在室温、真空条件下干燥10h,得到以直链十四胺为核超支化水杨醛亚胺镍催化剂,即为本实施例乙烯齐聚用后过渡金属催化剂,产物收率为89.1%。
上述制备过程化学反应方程式如式(2-2)所示:
对本实施例制备的乙烯齐聚用后过渡金属催化剂进行红外分析。结果如图2所示,图2为本实施例制备的乙烯齐聚用后过渡金属催化剂红外光谱图。
由图2可以看出:在1629cm-1处出现了强的特征吸收峰,归属于ν(C=N)的伸缩振动,1585cm-1处为苯环骨架的振动特征峰,1281cm-1和1260cm-1处为苯环二取代面内弯曲振动特征峰,754cm-1处为苯环邻位二取代面外振动特征峰,592cm-1处出现特征峰,归属于ν(N-Ni)特征峰,表明Ni与配体产生配位作用。
实施例3
本实施例提供一种乙烯齐聚用后过渡金属催化剂,其结构式如式(3-1)所示:
本实施例还提供式(3-1)所述乙烯齐聚用后过渡金属催化剂的制备方法,其包括以下步骤:
步骤一,在氮气氛围下,于三口瓶中加入3g无水硫酸钠、直链十八胺为核1.0G超支化大分子(4.86g,0.01mol)的乙醇(20mL)的溶液和水杨醛(3.05g,0.025mol)的乙醇(20mL)的溶液,于室温搅拌30min,然后升温至70℃,在乙醇回流下反应18h后过滤除去无水硫酸钠,得到以直链十八胺为核的超支化水杨醛亚胺配体混合溶液;
步骤二,在氮气氛围下,将CoCl2·6H2O(2.38g,0.01mol)的乙醇的(20mL)溶液缓慢滴入到步骤一得到的以直链十八胺为核的超支化水杨醛亚胺配体混合溶液中,室温下恒温反应36h;然后向反应的混合物中缓慢加入无水乙醚(60mL),固体析出,负压过滤得到浅红色固体,用10℃的无水乙醚(160mL)洗涤固体4次,将所得固体在室温、真空条件下干燥8h,得到以十八胺为核超支化水杨醛亚胺钴催化剂,即为本实施例乙烯齐聚用后过渡金属催化剂,产物收率为88.5%。
上述制备过程化学反应方程式如式(3-2)所示:
对本实施例制备的乙烯齐聚用后过渡金属催化剂进行红外分析。结果如图3所示,图3为本实施例制备的乙烯齐聚用后过渡金属催化剂红外光谱图。
由图3可以看出:在1627cm-1处出现了强的特征吸收峰,归属于ν(C=N)的伸缩振动,1581cm-1处为苯环骨架的振动特征峰,1283cm-1和1265cm-1处为苯环二取代面内弯曲振动特征峰,751cm-1处为苯环邻位二取代面外振动特征峰,629cm-1处出现特征峰,归属于ν(N-Co)特征峰,表明Co与配体产生配位作用。
实施例4
本实施例提供一种乙烯齐聚用后过渡金属催化剂,其结构式如式(4-1)所示:
本实施例还提供式(4-1)所述乙烯齐聚用后过渡金属催化剂的制备方法,其包括以下步骤:
步骤一,在氮气氛围下,于三口瓶中加入3g无水硫酸钠、乙胺为核1.0G超支化大分子(2.73g,0.01mol)的乙醇(20mL)的溶液和3-甲基水杨醛(4.1g,0.03mol)的乙醇(20mL)的溶液,于室温下搅拌30min,然后升温至78℃,在乙醇回流下反应12h后过滤除去无水硫酸钠,得到以乙胺为核的超支化水杨醛亚胺配体混合溶液;
步骤二,在氮气氛围下,将NiCl2·6H2O(3.57g,0.015mol)的乙醇的(20mL)溶液缓慢滴入到步骤一得到的以乙胺为核的超支化水杨醛亚胺配体混合溶液中,室温下恒温反应36h;然后向反应的混合物中缓慢加入无水乙醚(60mL),固体析出,负压过滤得到浅红色固体,用10℃的无水乙醚(120mL)洗涤固体3次,将所得固体在室温、真空条件下干燥8h,得到以乙胺为核超支化水杨醛亚胺镍催化剂,即为本实施例乙烯齐聚用后过渡金属催化剂,产物收率为85.3%。
上述制备过程化学反应方程式如式(4-2)所示。
对本实施例制备的乙烯齐聚用后过渡金属催化剂进行红外分析。结果如图4所示,图4为本实施例制备的乙烯齐聚用后过渡金属催化剂红外光谱图。
由图4可以看出:在1627cm-1处出现了强的特征吸收峰,归属于ν(C=N)的伸缩振动,在1629cm-1处出现了强的特征吸收峰,归属于ν(C=N)的伸缩振动,1582cm-1处为苯环骨架的振动特征峰,1272cm-1和1225cm-1处为苯环1,2,3三取代面内弯曲振动特征峰,775cm-1处为苯环邻位三取代面外振动特征峰,550cm-1处出现特征峰,归属于ν(N-Ni)特征峰,表明Ni与配体产生配位作用。
实施例5
本实施例提供一种乙烯齐聚用后过渡金属催化剂,其结构式如式(5-1)所示:
本实施例还提供式(5-1)所述乙烯齐聚用后过渡金属催化剂的制备方法,其包括以下步骤:
步骤一,在氮气氛围下,于三口瓶中加入3g无水硫酸钠、丁胺为核1.0G超支化大分子(3.01g,0.01mol)的乙醇(20mL)的溶液和3-叔丁基水杨醛(7.13g,0.04mol)的乙醇(20mL)的溶液,于室温下搅拌30min,然后升温至78℃,在乙醇回流下反应12h后过滤除去无水硫酸钠,得到以丁胺为核的超支化水杨醛亚胺配体混合溶液;
步骤二,在氮气氛围下,将FeCl2·4H2O(2.38g,0.01mol)的乙醇的(20mL)溶液缓慢滴入到步骤一得到的以丁胺为核的超支化水杨醛亚胺配体混合溶液中,室温下恒温反应24h;然后向反应的混合物中缓慢加入无水乙醚(60mL),固体析出,负压过滤得到浅红色固体,用10℃的无水乙醚(120mL)洗涤固体3次,将所得固体在室温、真空条件下干燥5h,得到以丁胺为核超支化水杨醛亚胺铁催化剂,即为本实施例乙烯齐聚用后过渡金属催化剂,产物收率为80.1%。
上述制备过程化学反应方程式如式(5-2)所示:
对本实施例制备的乙烯齐聚用后过渡金属催化剂进行红外分析。结果如图5所示,图5为本实施例制备的乙烯齐聚用后过渡金属催化剂红外光谱图。
由图5可以看出:在1621cm-1处出现了强的特征吸收峰,归属于ν(C=N)的伸缩振动,1575cm-1处为苯环骨架的振动特征峰,1276cm-1处为苯环1,2,3三取代面内弯曲振动特征峰,771cm-1处为苯环邻位三取代面外振动特征峰,545cm-1处出现特征峰,归属于ν(N-Fe)特征峰,表明Fe与配体产生配位作用。
实施例6
将250mL反应釜抽真空并用乙烯置换三次后,在乙烯气体保护下加入50mL甲苯溶剂;以Al/Ni比为500加入助催化剂倍半铝;将1mL浓度为5mg/mL实施例2中制备得到的乙烯齐聚用后过渡金属催化剂的甲苯溶液加到反应釜中,通入乙烯至一定压力并维持该压力,恒压反应30min后,放空至常压;分别考察了反应压力和反应温度对该催化剂催化乙烯齐聚活性和C10以上选择性的影响,采用气相色谱对齐聚混合液进行分析,分析结果见图6和图7,研究该类催化剂催化乙烯齐聚的性能。
由图6和图7可以看出:实施例2中制备得到的乙烯齐聚用后过渡金属催化剂具有良好的催化乙烯齐聚活性;随着乙烯压力的增加,乙烯齐聚的活性和C10以上产物含量均先增加后减小;随反应温度的升高,乙烯齐聚的活性下降,C10以上产物含量增加。
综上所述,本发明采用“一锅法”制备乙烯齐聚用后过渡金属催化剂的制备方法简单、避免了常规乙烯齐聚用后过渡金属催化剂对其配体进行提纯这一复杂过程,催化剂的收率为80%-90%;且该催化剂具有较高的催化乙烯齐聚活性,易于工业化生产。
Claims (10)
1.一种乙烯齐聚用后过渡金属催化剂,其特征在于,该乙烯齐聚用后过渡金属催化剂的结构式如式(1)所示:
其中,R为环己烷基或C2-C18偶碳数饱和的直链烷基;R1为H、甲基或叔丁基;M为Ni、Co或Fe。
2.根据权利要求1所述的乙烯齐聚用后过渡金属催化剂,其特征在于,R为环己烷基、乙烷基、丁烷基、十四烷基或十八烷基。
3.制备权利要求1或2所述的乙烯齐聚用后过渡金属催化剂的方法,其包括以下步骤:
步骤一,在氮气氛围下,将无水硫酸钠、低代端基为胺基的超支化分子、水杨醛或水杨醛衍生物混合溶于乙醇中,室温下混合均匀,然后升温并在乙醇回流下进行反应,过滤得到水杨醛席夫碱混合物;其中,低代端基为胺基的超支化分子与水杨醛或水杨醛衍生物的摩尔比为1:5-2:5;
步骤二,在氮气氛围下,将带结晶水的后过渡金属卤化物的乙醇溶液缓慢滴入到步骤一中的水杨醛席夫碱混合物中,室温下进行反应,然后加入乙醚进行沉淀,过滤得到固体产物,将该固体产物采用低温乙醚洗涤,并于真空条件下室温干燥,得到乙烯齐聚用后过渡金属催化剂;其中,带结晶水的后过渡金属氯化物与低代端基为胺基的超支化大分子的摩尔比为1:1-2:1。
4.根据权利要求3所述的方法,其特征在于,所述低代端基为胺基的超支化分子结构式如式(2)所示:
其中,R为环己烷基或C2-C18偶碳数饱和的直链烷基。
5.根据权利要求4所述的方法,其特征在于,R为环己烷基、乙烷基、丁烷基、十四烷基或十八烷基。
6.根据权利要求3所述的方法,其特征在于,所述水杨醛或水杨醛衍生物的分子结构式如式(3)所示:
其中,R1为H、甲基或叔丁基。
7.根据权利要求3所述的方法,其特征在于,所述带结晶水的后过渡金属卤化物为NiCl2·6H2O、CoCl2·6H2O或FeCl2·4H2O。
8.根据权利要求3所述的方法,其特征在于,所述步骤一中得到的水杨醛席夫碱混合物不需要提纯,直接参与步骤二的反应。
9.根据权利要求3所述的方法,其特征在于,
在步骤一中,升温最终达到的温度为70-80℃;回流反应时间为12-24h。
10.根据权利要求3所述的方法,其特征在于,
在步骤二中,室温下进行反应的反应时间为24-48h;反应过滤得到的固体产物采用低温乙醚洗涤,并于真空条件下室温干燥,其中,低温乙醚的温度为5-15℃,洗涤次数为3-5次;干燥时间为5-10h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610522611.1A CN106188153B (zh) | 2016-07-05 | 2016-07-05 | 一种乙烯齐聚用后过渡金属催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610522611.1A CN106188153B (zh) | 2016-07-05 | 2016-07-05 | 一种乙烯齐聚用后过渡金属催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106188153A true CN106188153A (zh) | 2016-12-07 |
CN106188153B CN106188153B (zh) | 2019-02-15 |
Family
ID=57466117
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610522611.1A Active CN106188153B (zh) | 2016-07-05 | 2016-07-05 | 一种乙烯齐聚用后过渡金属催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106188153B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109939736A (zh) * | 2019-03-05 | 2019-06-28 | 东北石油大学 | 碳纳米管负载金属乙烯齐聚催化剂及制备方法和用途 |
CN110013877A (zh) * | 2019-03-01 | 2019-07-16 | 东北石油大学 | 一种席夫碱配体共价接枝碳纳米管负载后过渡金属烯烃聚合催化剂及其制备方法 |
CN114702529A (zh) * | 2022-05-09 | 2022-07-05 | 东北石油大学 | 酞菁镍系配合物及其制备方法和在乙烯齐聚中的应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103418435A (zh) * | 2013-08-22 | 2013-12-04 | 东北石油大学 | 一种超支化镍系烯烃聚合催化剂及其制备方法 |
-
2016
- 2016-07-05 CN CN201610522611.1A patent/CN106188153B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103418435A (zh) * | 2013-08-22 | 2013-12-04 | 东北石油大学 | 一种超支化镍系烯烃聚合催化剂及其制备方法 |
Non-Patent Citations (4)
Title |
---|
JUN WANG等: "Synthesis and Ethylene Oligomerization of Hyperbranched Salicylaldimine Nickel Complexes", 《ADVANCES IN POLYMER TECHNOLOGY》 * |
李翠勤等: "一种树状桥联水杨醛亚胺配体的合成与表征", 《合成化学》 * |
王俊等: "乙烯齐聚合成α-烯烃镍配合物催化剂研究进展", 《化工进展》 * |
王俊等: "树枝状桥联过渡金属催化剂的合成、表征与性能", 《化工进展》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110013877A (zh) * | 2019-03-01 | 2019-07-16 | 东北石油大学 | 一种席夫碱配体共价接枝碳纳米管负载后过渡金属烯烃聚合催化剂及其制备方法 |
CN110013877B (zh) * | 2019-03-01 | 2020-03-10 | 东北石油大学 | 一种席夫碱配体共价接枝碳纳米管负载后过渡金属烯烃聚合催化剂及其制备方法 |
CN109939736A (zh) * | 2019-03-05 | 2019-06-28 | 东北石油大学 | 碳纳米管负载金属乙烯齐聚催化剂及制备方法和用途 |
CN109939736B (zh) * | 2019-03-05 | 2021-05-25 | 东北石油大学 | 碳纳米管负载金属乙烯齐聚催化剂及制备方法和用途 |
CN114702529A (zh) * | 2022-05-09 | 2022-07-05 | 东北石油大学 | 酞菁镍系配合物及其制备方法和在乙烯齐聚中的应用 |
CN114702529B (zh) * | 2022-05-09 | 2023-08-11 | 东北石油大学 | 酞菁镍系配合物及其制备方法和在乙烯齐聚中的应用 |
Also Published As
Publication number | Publication date |
---|---|
CN106188153B (zh) | 2019-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Jie et al. | Bridged bis-pyridinylimino dinickel (II) complexes: Syntheses, characterization, ethylene oligomerization and polymerization | |
Yu et al. | Synthesis, characterisation and ethylene oligomerization behaviour of N-(2-substituted-5, 6, 7-trihydroquinolin-8-ylidene) arylaminonickel dichlorides | |
CN104707660B (zh) | 一种用于烯烃氢甲酰化反应的固体多相催化剂及其制备方法和应用 | |
Sun et al. | Synthesis, characterization and ethylene oligomerization studies of nickel complexes bearing 2-imino-1, 10-phenanthrolines | |
CN106188153B (zh) | 一种乙烯齐聚用后过渡金属催化剂及其制备方法 | |
Shao et al. | Ethylene oligomerization promoted by group 8 metal complexes containing 2-(2-pyridyl) quinoxaline ligands | |
CN103201034A (zh) | 用于聚合物合成的催化剂和方法 | |
CN102698799B (zh) | 一种聚合物负载的季铵盐离子催化剂及其制备方法与应用 | |
CN103087223B (zh) | 邻、对位苯乙基取代的苊α-二亚胺镍(Ⅱ)烯烃聚合催化剂及其制备和应用 | |
CN104245640B (zh) | 乙烯的四聚 | |
CN107641138A (zh) | 用于乙烯和1‑己烯聚合的含有邻位二苯甲基取代的不对称α‑二亚胺镍(Ⅱ)配合物 | |
CN104250270B (zh) | 一种不对称二苯甲基α‑二亚胺镍配合物及其制备与应用 | |
CN107698699A (zh) | 用于催化乙烯和2‑己烯聚合的含有对位二苯甲基取代的α‑二亚胺镍(Ⅱ)配合物 | |
JP6466652B2 (ja) | エチレンオリゴマー化のための触媒組成物及び方法 | |
CN105693896B (zh) | 苊醌‑1,2‑不对称二亚胺镍配合物催化剂及其制备方法与应用 | |
CN103172607A (zh) | 一种二氧化碳与环氧化合物合成环状碳酸酯的方法 | |
CN110013877A (zh) | 一种席夫碱配体共价接枝碳纳米管负载后过渡金属烯烃聚合催化剂及其制备方法 | |
Zhang et al. | Nickel (II) complexes chelated by 2, 6-pyridinedicarboxamide: syntheses, characterization, and ethylene oligomerization | |
US20130018214A1 (en) | Catalyst composition for oligomerization of ethylene and processes of oligomerization | |
CN104415790A (zh) | 一种乙烯四聚催化剂组合物及应用 | |
CN105315309A (zh) | 2,6-二亚胺吡啶并环庚烷铁和钴配合物催化剂及其制备方法与应用 | |
Gao et al. | Synthesis of bimodal polyethylene with unsymmetrical α-diimine nickel complexes: Influence of ligand backbone and unsym-substituted aniline moiety | |
CN102050840B (zh) | 含萘环的α-二亚胺镍(Ⅱ)配合物及其制备和应用 | |
CN103272644A (zh) | 一种用于液相环氧化反应的希夫碱金属催化剂及其制备方法 | |
Hao et al. | Nickel complexes bearing N, N, N-tridentate quinolinyl anilido–imine ligands: Synthesis, characterization and catalysis on norbornene addition polymerization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |