CN103435647B - Bridge type non-metallocene, preparation and application thereof - Google Patents
Bridge type non-metallocene, preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 38
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 175
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 136
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 66
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002262 Schiff base Substances 0.000 claims description 25
- 150000004753 Schiff bases Chemical class 0.000 claims description 25
- 239000012968 metallocene catalyst Substances 0.000 claims description 14
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- PFLOQESOFSAPAG-UHFFFAOYSA-N ethenyl-methyl-(trifluoromethyl)silane Chemical compound C(=C)[SiH](C(F)(F)F)C PFLOQESOFSAPAG-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000003780 insertion Methods 0.000 abstract description 4
- 230000037431 insertion Effects 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 238000006772 olefination reaction Methods 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 64
- 238000010792 warming Methods 0.000 description 64
- 238000005406 washing Methods 0.000 description 52
- 239000003446 ligand Substances 0.000 description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 44
- 239000007787 solid Substances 0.000 description 44
- 238000003756 stirring Methods 0.000 description 44
- 239000012299 nitrogen atmosphere Substances 0.000 description 40
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 20
- 239000005977 Ethylene Substances 0.000 description 18
- 229960000935 dehydrated alcohol Drugs 0.000 description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 239000000843 powder Substances 0.000 description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 8
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- AGWDRNRLEPQWAB-UHFFFAOYSA-N [Na].C1(=CC=CC=C1)O.OCC1=C(C(=O)C2=CC=CC=C2)C=CC=C1 Chemical group [Na].C1(=CC=CC=C1)O.OCC1=C(C(=O)C2=CC=CC=C2)C=CC=C1 AGWDRNRLEPQWAB-UHFFFAOYSA-N 0.000 description 5
- 125000005574 norbornylene group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 150000001941 cyclopentenes Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HCPJEHJGFKWRFM-UHFFFAOYSA-N 2-amino-5-methylphenol Chemical compound CC1=CC=C(N)C(O)=C1 HCPJEHJGFKWRFM-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- MMANAUVSMFIKKY-UHFFFAOYSA-N PS(=O)(=O)N.[Ni+2] Chemical class PS(=O)(=O)N.[Ni+2] MMANAUVSMFIKKY-UHFFFAOYSA-N 0.000 description 1
- 241000355635 Rachita Species 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- LQMCLODQWWUWLH-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]-phenylmethanone Chemical group OCC1=CC=CC=C1C(=O)C1=CC=CC=C1 LQMCLODQWWUWLH-UHFFFAOYSA-N 0.000 description 1
- GMVCNRHTKVQYNA-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=CC(=N1)C=1NC2=C(N=1)C=CC=C2[Ti+2]C1=CC=CC=2N=C(NC=21)C1=NC(=CC=C1)C Chemical compound [Cl-].[Cl-].CC1=CC=CC(=N1)C=1NC2=C(N=1)C=CC=C2[Ti+2]C1=CC=CC=2N=C(NC=21)C1=NC(=CC=C1)C GMVCNRHTKVQYNA-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical class [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a bridge type non-metallocene, and a preparation method and an application thereof; the structure of the bridge-type non-metallocene is shown in a general formula (1), wherein M in the general formula 1 is Ti, Zr, Ni, Nd, Y, Rh, Hf, Sc, La or Sm; x is Cl or Br; r is H, C1～C10Aliphatic hydrocarbon group of 6～C20An aromatic hydrocarbon group; r'1，R’2，R’3，R’4，R1，R2，R3，R4Is H or C1～C10An aliphatic hydrocarbon group in which any two substituents may be the same or different; it is used for catalyzing polymerization or copolymerization of non-polar olefin, or copolymerization of non-polar olefin and polar olefin; the catalyst has high catalytic activity, good stability, less cocatalyst consumption, high molecular weight of the obtained copolymer and high monomer insertion rate.
Description
Technical field
The invention belongs to olefinic polymerization non-metallocene catalyst and field of olefin polymerisation, be specifically related to the preparation of bridge type non-metallocene catalyst for vinyl polymerization or alpha-olefinic copolymerization and the preparation of olefin polymer.
Background technology
The development of polyolefin industry depends on the research and development of catalyzer, make a general survey of the development course of catalyzer, developed into the catalyzer of non-luxuriant system of today by initial Ziegler-Natta catalyst, polyolefin industry have also been obtained swift and violent development and wide application prospect.The discovery of metallocene catalyst has led a much progress of alkene catalyst, but because metallocene catalyst also exists a series of limiting factor, such as less stable, cost is higher, structural modification difficulty, impelled the research direction of alkene catalyst to turn to can to change the non cyclopentadienyl catalyst of ligand structure (1. west is beautiful for dawn. the progress [J] of non-metallocene catalyst. petrochemical technology and application, 2002,20,327-333.2. Liu Wei spoils, Huang Qigu, justice is for army building. the progress [J] of Catalysts for Olefin Polymerization. and polymer is circulated a notice of, 2010,6,1-33.).A lot (the Tshuva E Y. of mild condition required for the preparation process of non cyclopentadienyl catalyst, Goldberg I, Kol M.Isospecific Living Polymerization of1-Hexene by a Readily Available Nonmetallocene C2-Symmetrical Zirconium Catalyst [J] .J.Am.Chem.Soc.2000, 122, 10706-10707.), therefore, based on above advantage, non cyclopentadienyl catalyst becomes rapidly a large focus (Sudhakar P of alkene catalyst research, Sundararajan G.Tuning the Reactivity of N, O, O, O-Non-Metallocene Catalysts for a-Olefin Polymerization:Issues Related to Ligand Symmetry and Derivatization [J] .Macromol.Rapid Commun.2005, 26, 1854 – 1859.).
In order to realize polymer molecule " cutting out ", report about the ligand structure of non-metallocene catalyst has had a lot, comprise [N, N] (Zhang W J, Sun W – H, Wu B, Zhang S, Ma H W, Li Y, Chen J T, Hao P.Synthesis of palladium complexes containing2-methoxy carbonyl-6-iminopyridine ligand and their catalytic behaviors in reaction of ethylene and norbornene [J] .J.of Organometallic Chem.2006, 691:4759-4767.), [N, N, N] (Li Gang, Lamberti M, D ' Amora S, Pellecchia C.C
1-Symmetric Pentacoordinate Anilidopyridylpyrrolide Zirconium (IV) Complexes as Highly Isospecific Olefin Polymerization Catalysts.Macromolecules2010, 43 (21): 8887 – 8891.), [N, O] (Younkin T R, Connor E F, Henderson J I, Friedrich S K, Grubbs R H, Bansleben D A.Neutral, Single-Component Nickel (II) Polyolefin Catalysts That Tolerate Heteroatoms [J] .Science, 2000, 287:460-462.), [N, N, O] (Liu S F, Zuo W W, Zhang S, Hao P, Wang D, Sun W – H, Bis (2-(6-methylpyridin-2-yl)-benzimidazolyl) titanium dichloride and Titanium bis (6-benzimidazolylpyridine-2-carboxylimidate): Synthesis, Characterization, and Their Catalytic Behaviors for Ethylene Polymerization [J] .J of Polym.Sci.Part A:Polym.Chem., 2008, 46:3411-3423). with [O, N, S] (RACHITA M J, HUFF R L, BENNETT J L, BROOKHART M.Oligomerization of Ethylene to Branched Alkenes Using Neutral Phosphinosulfonamide Nickel (II) Complexes [J] .Journal of Polymer Science:Part A:Polymer Chemistry, 2000, 38, 4627 – 4640.) etc. coordinating group.Huang Qigu [Xinli Zhang, Qigu Huang, et al, Journal of Polymer Science:Part A:Polymer Chemistry, 2012,50,2068 – 2074. and Xinli Zhang, Qigu Huang, et al, Polymer International, 2013,62,419-426.] prepare [N, N, O, O] non-metallocene catalyst of part, can efficient catalytic olefinic polymerization after the activation of promotor MAO, obtain ethene/1-hexene and the ethylene/propene lonitrile copolymer of narrow molecular weight distributions.Ishii [Ishii SI, et al, Mol CatA:Chem179:11 – 17 (2002)] has prepared the non-metallocene catalyst with two phenoxy group ammonia parts by substituted salicylic aldehydes, replacement ammonia and TiCl4.Todd [Todd R Y, et al.Science, 2000,287,460-462.] report one [O, N, P] polydentate ligand Ni title complex, can effectively catalyzed ethylene and the norbornylene copolymerization containing hydroxyl or ester group group, the copolymerized ability of norbornylene is fine, and insertion rate is up to 22wt%.Drent [Drent E, et al.Chem Comm, 2002,744-745.] have studied the complex-catalyzed ethene of [P, O] Pd and acrylic ester copolymerization, and the insertion rate of acrylate monomer is up to 10mol%.
The invention discloses with salicylic aldehyde (ketone), diphenyl phosphorus chloride, substituted aniline as main raw material, synthesizing new bridge type Nonmetallocene, in this, as Primary Catalysts, MAO etc. are promotor (also considering not add promotor), the polymerization of catalysis nonpolar olefinic or copolymerization or nonpolar olefinic and polar olefin copolymerization.
Summary of the invention
The object of this invention is to provide a kind of bridge type non-metallocene catalyst for olefinic polymerization and preparation method thereof.
Another object of the present invention is to provide and a kind ofly utilizes that gained novel bridge type non-metallocene catalyst catalyzed alkene is all polymerized, ethylene/alpha-olefin copolymerization, propylene/alpha-olefins copolymerization, ethene/polar olefin copolymerization or propylene/polar olefin copolymerization method.
Olefinic polymerization non-metallocene metal catalyst system provided by the present invention comprises Primary Catalysts and promotor.Wherein the structure of Primary Catalysts meets general formula (1), and promotor adopts methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), and the mol ratio of Primary Catalysts and promotor is 1:(100-5000).
In general formula 1, M is Ti, Zr, Ni, Nd, Y, Rh, Hf, Sc, La or Sm; X is Cl, Br; R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical, preferred H, Me; R '
1, R '
2, R '
3, R '
4, R
1, R
2, R
3, R
4h, C
1~ C
10aliphatic group, wherein any two substituting groups can be the same or different, preferred H, Me, t-Bu.
The part prepared required for Primary Catalysts meets general formula 2.
In general formula 2, R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical, preferred H, Me; R '
1, R '
2, R '
3, R '
4, R
1, R
2, R
3, R
4h, C
1~ C
10aliphatic group, wherein any two substituting groups can be the same or different, preferred H, Me, t-Bu.
The reaction conditions prepared required for part is:
Temperature of reaction is 0 DEG C ~ 90 DEG C, preferably 20 DEG C ~ 60 DEG C;
Reaction times is 0.5h ~ 24h, preferred 2h ~ 8h;
The mol ratio of the compound and diphenyl phosphorus chloride that meet general formula 3 is 1:0.5 – 1:1.5;
In reaction process, solvent for use is toluene, methylene dichloride, dimethylbenzene or its mixed solution.
One of raw material required for synthetic ligands is diphenyl phosphorus chloride.
Two of raw material required for synthetic ligands is the Schiff base intermediate meeting general formula 3.
In general formula 3, R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical, preferred H, Me; R '
1, R '
2, R '
3, R '
4, R
1, R
2, R
3, R
4h, C
1~ C
10aliphatic group, wherein any two substituting groups can be the same or different, preferred H, Me, t-Bu.
The reaction conditions prepared required for Schiff base intermediate is:
Temperature of reaction is 40 DEG C ~ 180 DEG C, preferably 70 DEG C ~ 110 DEG C;
Reaction times is 6h ~ 48h, preferred 8h ~ 24h;
In reaction process, solvent for use is ethanol, methyl alcohol, dimethylbenzene, toluene, methylene dichloride or its mixed solution.
One of synthesis Schiff base intermediate desired raw material is the substituted aniline meeting general formula 4.
R in general formula 4
1, R
2, R
3, R
4h, C
1~ C
10aliphatic group, wherein any two substituting groups can be the same or different, preferred H, Me, t-Bu.
Two of synthesis Schiff base intermediate desired raw material is the compounds meeting general formula 5.
In general formula 5, R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical, preferred H, Me; R '
1, R '
2, R '
3, R '
4h, C
1~ C
10aliphatic group, wherein any two substituting groups can be the same or different, preferred H, Me, t-Bu.
The mol ratio meeting general formula 4 and general formula 5 compound is 1:0.5 – 1:2.
Meet part and the metal halide MX of general formula (2)
nreaction preparation meets general formula (1) non-metallocene catalyst, and wherein M is Ti, Zr, Ni, Nd, Y, Rh, Hf, Sc, La or Sm; X is halogen atom, is selected from Cl, Br; N=3 or 4.
The reaction conditions of synthesis general formula (1) is:
Temperature of reaction is 10 DEG C ~ 80 DEG C;
Reaction times is 2h ~ 12h;
Meet part and the metal halide MX of general formula 2
nmol ratio be 1:0.5 – 1:3;
Solvent in reaction process is tetrahydrofuran (THF), toluene, the solvent that normal hexane and existing document have been reported.
The non-metallocene catalyst catalysis nonpolar olefinic copolymerization of [N, P, O] provided by the present invention part or nonpolar olefinic and polar olefin copolymerization, described nonpolar olefinic is selected from C
2~ C
15alpha-olefin, optimal ethylene, propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, cyclopentenes, vinylbenzene, alpha-methyl styrene, 3-methyl-1-butene, 4-methyl-1-pentene, isoprene, 1,3-butadiene, norbornylene; Described polar olefin is methyl methacrylate, methyl acrylate, butyl acrylate, vinyl trifluoro dimethylsilane etc.
Reaction conditions required for described copolymerization:
Polymerization temperature is 30 DEG C-90 DEG C;
Gaseous tension is 0.2-2Mpa;
Polymerization reaction time is 5min-240min.
Olefin polymerization catalysis provided by the present invention is when catalyzed ethylene and alpha-olefin or the copolymerization of polarity vinyl monomer, and catalytic activity is high, and the molecular weight of the multipolymer obtained is high, and the insertion rate of monomer is high, the good stability of Primary Catalysts, and promotor consumption is few.
Embodiment
Embodiment 1
1) preparation of salicylic aldehyde phenol sodium: under the protection of high pure nitrogen, adds 0.38g(9.5mmol in 300mL reaction flask) sodium hydroxide, 60mL dehydrated alcohol, stirs and makes sodium hydroxide be dissolved in dehydrated alcohol completely.In this solution, dropwise add 1mL salicylic aldehyde, normal-temperature reaction 3h, leave standstill, filter, with absolute ethanol washing 2-3 time, must the salicylic aldehyde phenol sodium of 1.31g pale yellow powder shape after draining, productive rate 91.3%.
2) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 0.72g salicylic aldehyde phenol sodium (5mmol) solid dehydrated alcohol, stirs, adds 0.62g(5mmol) 2-amino-4-methylphenol.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain schiff bases phenol sodium 0.65g red solid powder, productive rate 73.5%.
3) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.55g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.45g ligand L 1, productive rate 33.9%.
4) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 1, be dissolved in 30ml toluene.At 0 DEG C, drip 0.09ml(0.8mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.21g Cat.1.
5) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.9mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 2
1) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 0.72g salicylic aldehyde phenol sodium (5mmol) solid dehydrated alcohol, stirs, adds 0.62g(5mmol) 2-amino-5-methylphenol.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain schiff bases phenol sodium 0.63g red solid powder, productive rate 71.8%.
2) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.55g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.46g ligand L 2, productive rate 33.5%.
3) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 2, be dissolved in 30ml toluene.At 0 DEG C, drip 0.09ml(0.8mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.19g Cat.2.
4) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.9mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 3
1) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 0.72g salicylic aldehyde phenol sodium (5mmol) solid dehydrated alcohol, stirs, adds 0.83g(5mmol) 2-amino-4-TBP.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain 0.91g red solid powder, productive rate 62.1%.
2) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.58g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.27g ligand L 3, productive rate 30.1%.
3) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 3, be dissolved in 30ml toluene.At 0 DEG C, drip 0.45ml(0.4mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.17g Cat.3.
4) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.7mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 4
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 1, be dissolved in 30ml toluene.At 0 DEG C, add 0.19g(0.8mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.28g Cat.4.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 3mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 5
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 2, be dissolved in 30ml toluene.At 0 DEG C, add 0.19g(0.8mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.27g Cat.5.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 3mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 6
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 3, be dissolved in 30ml toluene.At 0 DEG C, add 0.15g(0.4mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.21g Cat.6.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.5mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 7
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 1, be dissolved in 30ml toluene.At 0 DEG C, add 0.17g(0.8mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.26g Cat.7.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 8
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 2, be dissolved in 30ml toluene.At 0 DEG C, add 0.17g(0.8mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.24g Cat.8.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 9
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 3, be dissolved in 30ml toluene.At 0 DEG C, add 0.14g(0.4mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.19g Cat.9.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.1mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 10
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 1, be dissolved in 30ml toluene.At 0 DEG C, add 0.12g(0.8mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.21g Cat.10.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.4mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 11
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.20g(0.8mmol) ligand L 2, be dissolved in 30ml toluene.At 0 DEG C, add 0.12g(0.8mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.22g Cat.11.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.4mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 12
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 3, be dissolved in 30ml toluene.At 0 DEG C, add 0.06g(0.4mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.15g Cat.12.
2) vinyl polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.2mL MAO (10%wt/v), pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 13
1) preparation of substituted salicylic aldehydes phenol sodium: under the protection of high pure nitrogen, adds 0.38g(9.5mmol in 300mL reaction flask) sodium hydroxide, 60mL dehydrated alcohol, stirs and makes sodium hydroxide be dissolved in dehydrated alcohol completely.In this solution, add 1.29g5-cresotinic acid aldehyde, normal-temperature reaction 3h, leave standstill, filter, with absolute ethanol washing 2-3 time, must 1.70g5-cresotinic acid aldehyde phenol sodium after draining, productive rate 90.5%.
2) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 0.79g5-cresotinic acid aldehyde phenol sodium (5mmol) solid dehydrated alcohol, stirs, adds 0.62g(5mmol) 2-amino-4-methylphenol.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain 1.01g red solid powder, productive rate 76.6%.
3) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.53g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.30g ligand L 4, productive rate 35.1%.
4) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.34g(0.8mmol) ligand L 4, be dissolved in 30ml toluene.At 0 DEG C, drip 0.09ml(0.8mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.31g Cat.13.
5) propylene polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 14
1) preparation of substituted salicylic aldehydes phenol sodium: under the protection of high pure nitrogen, adds 0.38g(9.5mmol in 300mL reaction flask) sodium hydroxide, 60mL dehydrated alcohol, stirs and makes sodium hydroxide be dissolved in dehydrated alcohol completely.In this solution, add 1.69g5-tertiary butyl salicylic aldehyde, normal-temperature reaction 3h, leave standstill, filter, with absolute ethanol washing 2-3 time, must 1.75g5-cresotinic acid aldehyde phenol sodium after draining, productive rate 91.8%.
2) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 1.00g5-tertiary butyl salicylic aldehyde phenol sodium (5mmol) solid dehydrated alcohol, stirs, adds 0.62g(5mmol) 2-amino-4-methylphenol.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain 1.18g pressed powder, productive rate 73.2%.
3) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.64g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.32g ligand L 5, productive rate 33.2%.
4) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.38g(0.8mmol) ligand L 5, be dissolved in 30ml toluene.At 0 DEG C, drip 0.09ml(0.8mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.34g Cat.14.
5) propylene polymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.1mL MAO (10%wt/v), add 10mL1-hexene, pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 15
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.34g(0.8mmol) ligand L 4, be dissolved in 30ml toluene.At 0 DEG C, add 0.19g(0.8mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.40g Cat.15.
2) copolymerization of propylene: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.1mL MAO (10%wt/v), add 10mL1-octene, pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 16
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.38g(0.8mmol) ligand L 5, be dissolved in 30ml toluene.At 0 DEG C, add 0.19g(0.8mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.42g Cat.16.
2) copolymerization of propylene: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2mL MAO (10%wt/v), add 10mL cyclopentenes, pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 17
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.34g(0.8mmol) ligand L 4, be dissolved in 30ml toluene.At 0 DEG C, add 0.17g(0.8mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.43g Cat.17.
2) copolymerization of propylene: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.2mL MAO (10%wt/v), add 10mL norbornylene, pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 18
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.38g(0.8mmol) ligand L 5, be dissolved in 30ml toluene.At 0 DEG C, add 0.17g(0.8mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.40g Cat.18.
2) copolymerization of propylene: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2mL MAO (10%wt/v), add 10mL MMA, pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 19
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.34g(0.8mmol) ligand L 4, be dissolved in 30ml toluene.At 0 DEG C, add 0.12g(0.8mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.32g Cat.19.
2) copolymerization of propylene: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), add 10mL MA, pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 20
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.38g(0.8mmol) ligand L 5, be dissolved in 30ml toluene.At 0 DEG C, add 0.12g(0.8mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.39g Cat.20.
2) copolymerization of propylene: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.1mL MAO (10%wt/v), add 3mL1-hexene, pass into propylene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 21
1) preparation of adjacent hydroxymethyl benzophenone phenol sodium: under the protection of high pure nitrogen, add 0.38g(9.5mmol in 300mL reaction flask) sodium hydroxide, 60mL dehydrated alcohol, stirs and makes sodium hydroxide be dissolved in dehydrated alcohol completely.In this solution, add the adjacent hydroxymethyl benzophenone of 1.29g, normal-temperature reaction 3h, leaves standstill, and filters, with absolute ethanol washing 2-3 time, after draining 1.31g neighbour hydroxymethyl benzophenone phenol sodium, productive rate 87.6%.
2) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 0.79g adjacent hydroxymethyl benzophenone phenol sodium (5mmol) solid dehydrated alcohol, stirs, add 0.62g(5mmol) 2-amino-4-methylphenol.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain 0.79g pressed powder, productive rate 60.2%.
3) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.53g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.25g ligand L 6, productive rate 29.6%.
4) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 6, be dissolved in 30ml toluene.At 0 DEG C, drip 0.45ml(0.4mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.14g Cat.21.
5) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), 4mL1-hexene, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 22
1) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 0.79g adjacent hydroxymethyl benzophenone phenol sodium (5mmol) solid dehydrated alcohol, stirs, add 0.62g(5mmol) 2-amino-5-methylphenol.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain 0.81g pressed powder, productive rate 61.4%.
2) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.53g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.26g ligand L 7, productive rate 30.2%.
3) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 7, be dissolved in 30ml toluene.At 0 DEG C, drip 0.45ml(0.4mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.16g Cat.22.
4) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), 4mL1-octene, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 23
1) preparation of schiff bases phenol sodium: in the 300mL reaction flask being full of high pure nitrogen atmosphere, disperses 0.79g adjacent hydroxymethyl benzophenone phenol sodium (5mmol) solid dehydrated alcohol, stirs, add 0.83g(5mmol) 2-amino-4-TBP.At 80 DEG C, backflow 8h.Cooling, leaves standstill, and filters, and washing, drains, obtain 0.90g pressed powder, productive rate 59.1%.
2) preparation of part: anhydrous and oxygen-free and high pure nitrogen protection under, get 0.61g schiff bases phenol sodium, be dispersed in 30ml toluene; at 0 DEG C; drip 0.36ml(2mmol wherein) diphenyl phosphorus chloride, reaction 2h, leaves standstill; filter; washing, recrystallization, vacuum is drained; obtain 0.27g ligand L 8, productive rate 28.8%.
3) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 8, be dissolved in 30ml toluene.At 0 DEG C, drip 0.45ml(0.4mmol) titanium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.17g Cat.23.
4) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.2mL MAO (10%wt/v), 4mL1-certain herbaceous plants with big flowers alkene, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 24
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 6, be dissolved in 30ml toluene.At 0 DEG C, add 0.045g(0.4mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.13g Cat.24.
2) copolymerization of propylene: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.1mL MAO (10%wt/v), 4mL1-hexene, passes into propylene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 25
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 7, be dissolved in 30ml toluene.At 0 DEG C, add 0.045g(0.4mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.14g Cat.25.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.1mL MAO (10%wt/v), 4mL1-octene, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 26
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 8, be dissolved in 30ml toluene.At 0 DEG C, add 0.045g(0.4mmol) zirconium tetrachloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.12g Cat.26.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2mL MAO (10%wt/v), 5mL methyl methacrylate, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 27
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 6, be dissolved in 30ml toluene.At 0 DEG C, add 0.14g(0.4mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.21g Cat.27.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.2mL MAO (10%wt/v), 5mL methyl acrylate, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 28
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 7, be dissolved in 30ml toluene.At 0 DEG C, add 0.14g(0.4mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.23g Cat.28.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.2mL MAO (10%wt/v), 5mL alpha-methyl styrene, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 29
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 8, be dissolved in 30ml toluene.At 0 DEG C, add 0.14g(0.4mmol) neodymium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.17g Cat.28.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2mL MAO (10%wt/v), 5mL3-methyl isophthalic acid-butylene, pass into ethene, keeps pressure 2atm, be warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 30
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 6, be dissolved in 30ml toluene.At 0 DEG C, add 0.06g(0.4mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.11g Cat.30.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), 5mL1,3-divinyl, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 31
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.17g(0.4mmol) ligand L 7, be dissolved in 30ml toluene.At 0 DEG C, add 0.06g(0.4mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.12g Cat.31.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.3mL MAO (10%wt/v), 5mL norbornylene, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Embodiment 32
1) preparation of olefinic polymerization Nonmetallocene Primary Catalysts: under the protection of nitrogen atmosphere, get 0.18g(0.4mmol) ligand L 8, be dissolved in 30ml toluene.At 0 DEG C, add 0.06g(0.4mmol) yttrium trichloride, be warming up to 40 DEG C gradually after 30min, stirring reaction 4h.Leave standstill, filter, with n-hexane, vacuum is drained, and obtains 0.14g Cat.28.
2) ethylene copolymerization: add 80mL solvent successively in the reaction flask of anhydrous and oxygen-free, 20mg catalyzer and 2.1mL MAO (10%wt/v), 5mL cyclopentenes, passes into ethene, keeps pressure 2atm, is warming up to 40 DEG C, reaction 60min.By the ethanolic soln termination reaction containing 10% hydrochloric acid (volume ratio), obtain white solid, washing, dry, weigh.
Table 1
Claims (4)
1. a bridge type Nonmetallocene, is characterized in that: this bridge type Nonmetallocene structure is as general formula (1)
In general formula 1, M is Ti, Zr, Ni, Nd, Y, Rh, Hf, Sc, La or Sm; X is Cl or Br; R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical; R '
1, R '
2, R '
3, R '
4, R
1, R
2, R
3, R
4h or C
1~ C
10aliphatic group, wherein any two substituting groups can be the same or different.
2. a preparation method for bridge type Nonmetallocene according to claim 1, is characterized in that:
(1) preparation of Schiff base intermediate:
The Schiff base intermediate prepared and meet general formula 3 is reacted by general formula 4 and general formula 5
The reaction conditions prepared required for Schiff base intermediate is:
Temperature of reaction is 40 DEG C ~ 180 DEG C;
Reaction times is 6h ~ 48h;
The mol ratio meeting general formula 4 and general formula 5 compound is 1:0.5 – 1:2;
In reaction process, solvent for use is ethanol, methyl alcohol, dimethylbenzene, toluene, methylene dichloride or its mixed solution;
In general formula 3, R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical; R '
1, R '
2, R '
3, R '
4, R
1, R
2, R
3, R
4h, C
1~ C
10aliphatic group, wherein any two substituting groups are identical or different;
R in general formula 4
1, R
2, R
3, R
4h, C
1~ C
10aliphatic group, wherein any two substituting groups are identical or different;
In general formula 5, R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical; R '
1, R '
2, R '
3, R '
4h, C
1~ C
10aliphatic group, wherein any two substituting groups can be the same or different;
(2) preparation of part:
General formula 3 and diphenyl phosphorus chloride Reactive Synthesis meet the part of general formula 2;
In general formula 2, R is H, C
1~ C
10aliphatic group, C
6~ C
20aryl radical; R '
1, R '
2, R '
3, R '
4, R
1, R
2, R
3, R
4h, C
1~ C
10aliphatic group, wherein any two substituting groups are identical or different;
The reaction conditions prepared required for part is:
Temperature of reaction is 0 DEG C ~ 90 DEG C;
Reaction times is 0.5h ~ 24h;
The mol ratio of the compound and diphenyl phosphorus chloride that meet general formula 3 is 1:0.5 – 1:1.5;
In reaction process, solvent for use is toluene, methylene dichloride, dimethylbenzene or its mixed solution;
(3) preparation of general formula (1) bridge type Nonmetallocene is met:
Meet part and the metal halide MX of general formula 2
nreaction preparation meets the non-metallocene catalyst of general formula (1), and wherein M is Ti, Zr, Ni, Nd, Y, Rh, Hf, Sc, La or Sm; X is halogen atom; N=3 or 4;
The reaction conditions of synthesis general formula (1) is:
Temperature of reaction is 10 DEG C ~ 80 DEG C;
Reaction times is 2h ~ 12h;
Meet part and the metal halide MX of general formula 2
nmol ratio be 1:0.5 – 1:3;
Solvent in reaction process is tetrahydrofuran (THF), toluene or normal hexane.
3. an application for bridge type Nonmetallocene according to claim 1, is characterized in that: the polymerization of catalysis nonpolar olefinic or copolymerization or nonpolar olefinic and polar olefin copolymerization;
Described promotor adopts methylaluminoxane or modified methylaluminoxane, and the mol ratio of Primary Catalysts and promotor is 1:(100-5000);
Described nonpolar olefinic is selected from C
2~ C
15alpha-olefin;
Described polar olefin is methyl methacrylate, methyl acrylate, butyl acrylate or vinyl trifluoro dimethylsilane.
4. the application of bridge type Nonmetallocene according to claim 3, is characterized in that: the polymerization of catalysis nonpolar olefinic or copolymerization or nonpolar olefinic and polar olefin copolymerization, the reaction conditions required for described copolymerization:
Polymerization temperature is 30 DEG C-90 DEG C;
Gaseous tension is 0.2-2MPa;
Polymerization reaction time is 5min-240min.
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