CN110105400A - A kind of temperature sensitive type ruthenium carbene complex and its preparation method and application - Google Patents
A kind of temperature sensitive type ruthenium carbene complex and its preparation method and application Download PDFInfo
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- CN110105400A CN110105400A CN201910472333.7A CN201910472333A CN110105400A CN 110105400 A CN110105400 A CN 110105400A CN 201910472333 A CN201910472333 A CN 201910472333A CN 110105400 A CN110105400 A CN 110105400A
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- catalyst
- sensitive type
- temperature sensitive
- carbene complex
- ruthenium carbene
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 48
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 150000001336 alkenes Chemical group 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 17
- 239000011984 grubbs catalyst Substances 0.000 claims description 12
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- -1 cyclic olefin Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 4
- 239000004913 cyclooctene Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000001514 detection method Methods 0.000 description 15
- 238000005452 bending Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 239000003446 ligand Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 206010001497 Agitation Diseases 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 2
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011987 hoveyda–grubbs catalyst Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- 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
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
-
- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
-
- 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
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
-
- 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
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to a kind of temperature sensitive type ruthenium carbene complex and its preparation method and application, preparation method is to take Grubbs three generations's catalyst, by the Grubbs three generations catalyst and NR3It is added in solvent, is reacted；Material after reaction is subjected to separating-purifying, is dried to obtain the temperature sensitive type ruthenium carbene complex；The temperature sensitive type ruthenium carbene complex is particularly suitable for catalyzed alkene ring opening metathesis polymerization reaction applied to the metathesis reaction of catalyzed alkene for the catalyst with temperature-sensitive.Compared with prior art, catalyst preparation process of the invention is simple, and raw material is easy to get, and when for the polymerization of alkene ring opening metathesis, dosage is few, and temperature-controllable has many advantages, such as wide prospects for commercial application, it can be achieved that the temperature control of alkene polymerize.
Description
Technical field
The present invention relates to a kind of ruthenium carbene complexs and its preparation method and application, belong to organo-metallic catalyst preparation skill
Art field, more particularly, to a kind of temperature sensitive type ruthenium carbene complex and its preparation method and application.
Background technique
In recent decades, the research of olefin metathesis reaction and its substantial worth in fields such as medicine, materials obtain it
Obtained rapid development.Ring opening metathesis polymerize (Ring-opening metathesis polymerization, abbreviation ROMP)
Reaction is the important reaction type of one of olefin metathesis reaction, and the research in the field is concentrated mainly on preparation and is suitable for phase
Answer the special catalyst of condition, and the functional material based on reaction preparation.And pass through the development of many years, it is different to be suitable for open loop
The catalyst of position polymerization produces the dispersion of different types of structure, wherein it is most important be also study at present it is most commonly used for Cabbeen
Type catalyst.In this kind of catalyst, what is be most widely used is Grubbs catalyst, and similar there are also Schrock to urge
Agent, Hoveyda-Grubbs catalyst, Grela catalyst and ZhanShi catalyst derived from Grubbs catalyst.These
Catalyst all has that catalytic rate is fast, the high feature of catalytic activity.
For specific contour machining procedure, whole process is prepared from feed liquid, arrives feed liquid injection molding, then arrive hot briquetting, should
Process requires certain operating time in each stage.Its injection molding, which is formulated into, from feed liquid completes the stage for the stabilization with system
Property require it is very high, catalyst efficiently make instead its in processing and forming application greatly restricted.It is current to solve to be somebody's turn to do
There are mainly two types of the modes of problem.First way is the catalytic activity added different types of additive and inhibit catalyst, real
The controllable adjustment of existing polymerization process.It should be noted that the introducing of additive also affects while inhibiting catalyst activity
The final performance of material.The second way is the catalyst using lower/medium activity, and the major defect of this method is to need greatly
Catalyst is measured to participate in, and the cost of polymeric material is mainly controlled by catalyst amount.
Therefore, how to prepare that a kind of catalytic activity is higher, while the temperature control that can be realized the polymerization of alkene ring opening metathesis is adjusted
Catalyst for alkene ring opening metathesis polymerize it is significant.Van der Schaaf etc. [J.Organomet.Chem., 2000,
606:65-74] it is prepared for causing the Latence catalyst of alkene ring opening metathesis polymerization, although passing through the substituent group for changing pyridine ring
Adjust initiation temperature, but catalyst activity is not high.Then, Ung etc. [Organometallics, 2004,23:5399-
5401] catalyst activity is adjusted by the moiety isomerization of structure, still, these catalyst cannot be long-term stored at olefinic monomer
In, polymerization process is just completed in 25min.Verpoort etc. [J.Mol.Cat.A:Chem., 2006,260:221-226] to O,
N- bidentate schiff bases combination ruthenium carbone catalyst is studied, which can store the several months in alkene, but active phase
To poor.At present, slower for the progress of temperature control type catalyst, catalyst is only capable of realizing partial function,
Most of catalyst or activity are lower, or structure is complicated, or with certain corrosion type.
Summary of the invention
The purpose of the present invention is by ruthenium carbene complex ligand it is preferred, prepare that a kind of to be suitable for alkene ring opening metathesis poly-
The ruthenium carbene complex of conjunction, the ruthenium carbene complex structure is simple, and preparation process is simple, has one in alkene temperature control catalytic field
Fixed potentiality.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of temperature sensitive type ruthenium carbene complex, chemical general formula are as follows:
R in its chemical general formula is straight chained alkyl or aryl.
The R is straight chained alkyl, carbon atom number 1-16.
The R is aryl, and the general formula of the aryl is as follows:
Wherein, R1、R2、R3、R4And R5Being selected from alkyl, carbon atom number that hydrogen, amino, carbon atom number are 1~16 is 1~16
Alkoxy or carbon atom number be 1~16 one of alkane phosphorus base.
Temperature sensitive type ruthenium carbene complex of the invention mainly solves bis- generation of Grubbs catalyst and polymerize in alkene ring opening metathesis
The too fast problem of middle Catalysis Rate realizes that alkene does not polymerize under cryogenic, when system is increased to certain temperature, system
It being capable of rapid polymerization.
From the mechanism of the reaction of olefin metathesis it is found that in catalytic reaction process, the activated centre of catalyst is metal
Alkene (C=C) double bond is unfolded into metal cyclobutane structure by Cabbeen (M=CHR), the activated centre, then resets realization catalysis
Process.Therefore, in this catalyst system, how to adjust activated centre is released to core of the invention point.The present invention select compared with
The ligand of strong electron and activated centre are coordinated to obtain final catalyst, it is intended that make catalyst temperature compared with
When low, the strong coordination effect based on ligand makes catalyst structure keep stablizing, it is not easy to form activated centre, and temperature
Ligand can be separated with activated centre after raising, realize the temperature control catalytic effect of catalyst.It is therefore preferable that electron proper properties
Ligand be the key that realize temperature control catalysis, if electron performance is too strong, catalyst is also difficult to discharge in activity in very high temperature
The heart realizes catalysis, if weaker to electrical property, the trigger rate of catalyst may overrun.
The present invention also provides a kind of preparation method of temperature sensitive type ruthenium carbene complex, preparation step is as follows: taking
Grubbs three generations's catalyst, by the Grubbs three generations catalyst and NR3It is added in solvent, is reacted；By the material after reaction
It carries out separating-purifying, be dried to obtain the temperature sensitive type ruthenium carbene complex.
Wherein, the general formula of the Grubbs three generations catalyst is as follows:
In the present invention, the Grubbs three generations catalyst is prepared using bis- generation of Grubbs catalyst and pyridine as reaction raw materials
It obtains；The general formula of bis- generation of the Grubbs catalyst is as follows:
The preparation method of the Grubbs three generations catalyst specifically:
Bis- generation of Grubbs catalyst and pyridine are mixed, is reacted under the conditions of being stirred at room temperature, is obtained the Grubbs three generations and urge
Agent；Wherein the reaction time be 12~for 24 hours, preferably 20-24h.
The NR3Molar ratio with Grubbs three generations's catalyst is 1/1~20/1, and reaction temperature is 25~60 DEG C, reaction
Time is 12~48h；The solvent is selected from tetrahydrofuran, ethyl acetate, ether, acetone, acetonitrile, toluene or 1,4- dioxane
One or more of.
The synthetic route of temperature sensitive type ruthenium carbene complex of the invention is prepared using bis- generation of Grubbs catalyst as raw material are as follows:
The present invention obtains final catalyst through two-step reaction, after separating-purifying, obtains from Grubbs bis- generations catalyst
The chemical purity of the final catalyst arrived is up to 99.0% or more.
For the synthesis technology, the ratio that the most important factor of composite result is reaction dissolvent and reactant is influenced.At this
In synthesis process, select solvent polarity for medium or low pole solvent, in the case where guaranteeing reaction substrate dissolution, choosing
The weak solvent of coordination ability is selected, to ensure that target ligand can be effectively coordinated with activated centre, while guaranteeing catalyst structure
Stablize.In addition, the dosage of ligand determines that can ligand be coordinated with metal, the weaker ligand dosage bigger than normal one of coordination ability
A bit, it to guarantee to obtain final catalyst, if ligands ability is slightly strong, can be obtained less using some ligands intended catalyzed
Agent.If being pointed out that ligand dosage is excessive, it may result in catalyst structure and be destroyed, be unfavorable for final catalyst
Generation.
The present invention also provides a kind of applications of temperature sensitive type ruthenium carbene complex, and the temperature sensitive type ruthenium carbene complex is as tool
There is the catalyst of temperature-sensitive, the metathesis reaction applied to catalyzed alkene；The alkene is selected from norbornene, cyclohexene, double
Cyclopentadiene, cyclo-octene, ring penta 2 be dilute, one of the derivative of 1- octene, 1- hexene, styrene or any of the above-described alkene or
It is several.
Preferably, the temperature sensitive type ruthenium carbene complex carries out ring opening metathesis polymerization reaction for being catalyzed cyclic olefin；Institute
Temperature sensitive type ruthenium carbene complex and cyclic olefin is stated to be mixed according to the proportion that molar ratio is 1/30000~1/200000, when
When temperature is 25~35 DEG C, the cyclic olefin not can be carried out ring opening metathesis polymerization reaction, when temperature is 80~200 DEG C, institute
It states cyclic olefin and ring opening metathesis polymerization reaction occurs；The polymerization time of the ring opening metathesis polymerization reaction is 5~20min.
Can be seen that the formation that activated centre during the reaction is metal carbene (M=CHR) from the mechanism of catalysis is to protect
Demonstrate,prove the basis that catalyst has preferable catalytic activity.For the present invention, temperature sensitive type ruthenium carbene complex is kept in low temperature
Stable structure, after temperature is increased to a certain degree, ligand is separated with activated centre in the metal carbene activity to form high activity
The heart, to realize alkene rapid polymerization.
Compared with prior art, the invention has the following advantages that
(1) the temperature sensitive type ruthenium carbene complex that the present invention is prepared has temperature-sensing property, which can realize
The temperature control of alkene polymerize, i.e., does not cause olefinic polymerization at room temperature, and when the system that catalyst is added is increased to certain temperature
Degree, is able to achieve system rapid polymerization；Therefore, in production process, advantageously ensure that feed liquid is formulated into its injection molding and completes rank
The stability of section material system, again can be with efficient catalytic polymerization reaction after the stage of reaction, raising temperature；Guarantee entire technique mistake
Cheng Gaoxiao, safe and stable operation；With wide prospects for commercial application.
(2) preparation method of temperature sensitive type ruthenium carbene complex has preparation process simple in the present invention, easy to operate etc. excellent
Point；In preparation process, reaction condition is mild, and raw material is easy to get, and synthetic route is short, prepares high income, is easy industry amplification and life
It produces and implements.
(3) in the present invention temperature sensitive type ruthenium carbene complex can effective catalyzed alkene temperature control polymerization reaction, catalytic activity is high,
Catalyst amount is few, and the reaction time is short, and temperature-controllable, polymer yield is up to 95~99%.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is a kind of preparation method of temperature sensitive type ruthenium carbene complex, and synthetic route is as follows:
Specific preparation process are as follows:
(1) it takes bis- generation of 20.0g Grubbs catalyst to 250mL flask, 100mL pyridine is added and (is used as solvent and reaction
Object), it is stirred at room temperature for 24 hours, then obtains 16.0g Grubbs three generations's catalyst, yield 93% through separating-purifying；The preparation process
In: the preparation process of Grubbs three generations's catalyst refers to [Organometallics, 2001,20,5314-5318] document.
Nuclear magnetic resonance characterization is carried out to the Grubbs three generations's catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) 19.67 (s, 1H, CH=Ph), 8.84 (s, 2H, pyridine), 8.39 (s, 2H,
pyridine),8.07(d,2H,ortho CH),7.15(t,1H,para CH),6.83-6.04(m,9H,pyridine,Mes-
CH),3.37(d,4H,CH2CH2),2.79(s,6H,Mes-CH3),2.45(s,6H,Mes-CH3),2.04(s,6H,Mes-CH3).
(2) temperature sensitive type ruthenium carbene complex is further prepared using the Grubbs three generations catalyst that step (1) is prepared；
Specifically the preparation method comprises the following steps: by 1.0g Grubbs three generations catalyst and 0.081g N (CH3)35mL tetrahydro furan is added in (1.0 equivalent)
It mutters, 25 DEG C of magnetic agitation 12h；After reaction, it through separating-purifying, dry 0.76g temperature sensitive type ruthenium carbene complex, is denoted as and urges
Agent Cat.-1, the yield of the catalyst are 88%.
Nuclear magnetic resonance characterization is carried out to the agent Cat.-1 catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) δ (ppm)=2.12 (s, 12H, Mes-CH3),2.26(s,6H,Mes-CH3),2.27(s,9H,
N-CH3),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.23(t,2H,Ar-H),7.54(t,1H,
), ArH 7.75 (d, 2H, Ar-H), 19.03 (d, Ru=CH-Ph)
Wherein, the structure of Cat.-1 catalyst is as follows:
(3) polymerization for the Cat.-1 catalyst 5- ethylidene -2- norbornene being prepared using step (2) is anti-
It answers: in reaction flask, 100.0g 5- ethylidene -2- norbornene and 17.4mg Cat.-1 (alkene/cat.=30000/ is added
1, molar ratio), then 25 DEG C of stirring 1h.80 DEG C are then heated to, 10min polymerize, the yield 98% of polymer.
Obtained polymer is tested for the property, detection data is as follows: tensile strength 56MPa, yield elongation rate
8.35%, stretch modulus 1425MPa, bending strength 71MPa, bending modulus 1130MPa, impact strength 11.5KJ/m2。
Embodiment 2
Grubbs three generations's catalyst that this implementation is obtained using step (1) in embodiment 1, further prepares temperature sensitive type ruthenium card
Guest's complex, catalyst Cat.-2；And the catalyst being prepared to be used to be catalyzed the polymerization of 2,5- dimethyl -2,4- hexadiene
Reaction.
(1) by 1.0g Grubbs three generations catalyst and 4.86gN (C8H17)3It is molten that 5mL ethyl acetate is added in (10.0 equivalent)
In agent, 40 DEG C of magnetic agitation 12h；After reaction, through separating-purifying, dry 1.04g catalyst Cat.-2, catalyst yield
It is 82%.
Nuclear magnetic resonance characterization is carried out to the agent Cat.-2 catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) δ (ppm)=0.88 (t, 9H, CH2-CH3),1.26(t,36H,-CH2-),2.12(s,12H,
Mes-CH3),2.26(s,6H,Mes-CH3),2.34(t,6H,N-CH2),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,
), Mes-CH 7.23 (t, 2H, Ar-H), 7.54 (t, 1H, ArH), 7.75 (d, 2H, Ar-H), 19.03 (d, Ru=CH-Ph)
Wherein, the structure of Cat.-2 catalyst is as follows:
(2) in reaction flask, it is added 100.0g 2,5- dimethyl-2,4-hexadiene and 16.8mg Cat.-2 (alkene/
Cat.=50000/1, molar ratio), then 30 DEG C of stirring 1h.100 DEG C are then heated to, 15min polymerize, the receipts of polymer
Rate is 99%.
Obtained polymer is tested for the property, detection data is as follows: tensile strength 49MPa, yield elongation rate
6.9%, stretch modulus 1380MPa, bending strength 78MPa, bending modulus 1070MPa, impact strength 9.7KJ/m2。
Embodiment 3
Grubbs three generations's catalyst that this implementation is obtained using step (1) in embodiment 1, further prepares temperature sensitive type ruthenium card
Guest's complex, catalyst Cat.-3；And the catalyst being prepared to be used to be catalyzed the polymerization reaction of dicyclopentadiene.
(1) by 1.0gGrubbs three generations catalyst and 18.95g N (C16H33)320mL ether solvent is added in (20.0 equivalent)
In, 60 DEG C of magnetic agitation 48h；After reaction, through separating-purifying, dry 1.19g catalyst Cat.-3, yield 69%.
Nuclear magnetic resonance characterization is carried out to the agent Cat.-3 catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) δ (ppm)=0.88 (t, 9H, CH2-CH3),1.27(t,84H,-CH2-),2.12(s,12H,
Mes-CH3),2.26(s,6H,Mes-CH3),2.34(t,6H,N-CH2),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,
), Mes-CH 7.23 (t, 2H, Ar-H), 7.54 (t, 1H, ArH), 7.75 (d, 2H, Ar-H), 19.03 (d, Ru=CH-Ph)
Wherein, the structure of Cat.-3 catalyst is as follows:
(2) in reaction flask, be added 100.0g dicyclopentadiene and 9.5mg Cat.-3 (alkene/cat.=100000/1,
Molar ratio), then 35 DEG C of stirring 1h.150 DEG C are then heated to, 20min polymerize, polymer yield 95%.
Obtained polymer is tested for the property, detection data is as follows: tensile strength 46MPa, yield elongation rate
10.2%, stretch modulus 1580MPa, bending strength 73MPa, bending modulus 1250MPa, impact strength 8.5KJ/m2。
Embodiment 4
Grubbs three generations's catalyst that this implementation is obtained using step (1) in embodiment 1, further prepares temperature sensitive type ruthenium card
Guest's complex, catalyst Cat.-4；And the catalyst being prepared to be used to be catalyzed the polymerization reaction of bicyclo hexene.
(1) by 1.0gGrubbs three generations catalyst and 0.67gN (C6H5)35mL acetone, 30 DEG C of magnetic force are added in (2.0 equivalent)
Stir 15h；After reaction, through separating-purifying, dry 0.95g catalyst Cat.-4, the yield 85% of catalyst.
Nuclear magnetic resonance characterization is carried out to the agent Cat.-4 catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) δ (ppm)=2.12 (s, 12H, Mes-CH3),2.26(s,6H,Mes-CH3),4.04(s,4H,
N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.02(t,3H,Ar-H),7.18(d,6H,Ar-H),7.29(t,6H,Ar-
), H 7.23 (t, 2H, Ar-H), 7.54 (t, 1H, ArH), 7.75 (d, 2H, Ar-H), 19.03 (d, Ru=CH-Ph)
Wherein, the structure of Cat.-4 catalyst is as follows:
(2) in reaction flask, be added 100.0g cyclohexene and 4.9mg Cat.-4 (alkene/cat.=200000/1, mole
Than), then 30 DEG C of stirring 1h.180 DEG C are then heated to, 10min polymerize, polymer yield 96%.
Obtained polymer is tested for the property, detection data is as follows: tensile strength 38MPa, yield elongation rate
5.6%, stretch modulus 980MPa, bending strength 57MPa, bending modulus 990MPa, impact strength 6.5KJ/m2。
Embodiment 5
Grubbs three generations's catalyst that this implementation is obtained using step (1) in embodiment 1, further prepares temperature sensitive type ruthenium card
Guest's complex, catalyst Cat.-5；And the catalyst being prepared to be used to be catalyzed the polymerization reaction of cyclo-octene.
(1) by 1.0gGrubbs three generations catalyst and 1.98g N (C7H7)35mL acetonitrile, 50 DEG C of magnetic are added in (5.0 equivalent)
Power stirs for 24 hours；After reaction, through separating-purifying, dry 0.93g catalyst Cat.-5, catalyst yield 79%.
Nuclear magnetic resonance characterization is carried out to the agent Cat.-5 catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) δ (ppm)=2.12 (s, 12H, Mes-CH3),2.26(s,6H,Mes-CH3),2.32(t,9H,
Ar-CH3),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.18(d,6H,Ar-H),7.29(t,6H,Ar-
), H 7.23 (t, 2H, Ar-H), 7.54 (t, 1H, ArH), 7.75 (d, 2H, Ar-H), 19.03 (d, Ru=CH-Ph)
Wherein, the structure of Cat.-5 catalyst is as follows:
(2) in reaction flask, be added 100.0g cyclo-octene and 7.7mg Cat.-5 (alkene/cat.=100000/1, mole
Than), then 30 DEG C of stirring 1h.200 DEG C are then heated to, 10min polymerize, polymer yield 97%.
Obtained polymer is tested for the property, detection data is as follows: tensile strength 42MPa, yield elongation rate
6.2%, stretch modulus 910MPa, bending strength 61MPa, bending modulus 960MPa, impact strength 6.2KJ/m2。
Embodiment 6
Grubbs three generations's catalyst that this implementation is obtained using step (1) in embodiment 1, further prepares temperature sensitive type ruthenium card
Guest's complex, catalyst Cat.-6；And the catalyst being prepared is used for styrene catalyzed anti-with dicyclopentadiene polymerization
It answers.
(1) by 1.0gGrubbs three generations catalyst and 4.0g N (C6H4N3)3(10.0 equivalent) addition 10mL toluene, 50
DEG C magnetic agitation is for 24 hours；After reaction, through separating-purifying, dry that 0.97g catalyst Cat.-6, the yield of catalyst are
82%.
Nuclear magnetic resonance characterization is carried out to the agent Cat.-6 catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) δ (ppm)=2.12 (s, 12H, Mes-CH3),2.26(s,6H,Mes-CH3),4.04(s,4H,
N-CH2-CH2-N),4.52(s,6H,NH2),6.63(s,4H,Mes-CH),7.18(d,6H,Ar-H),7.29(t,6H,Ar-H),
7.23 (t, 2H, Ar-H), 7.54 (t, 1H, ArH), 7.75 (d, 2H, Ar-H), 19.03 (d, Ru=CH-Ph)
Wherein, the structure of Cat.-6 catalyst is as follows:
(2) in reaction flask, be added 50.0g styrene, 63.5g dicyclopentadiene and 15.6mg Cat.-6 (alkene/
Cat.=50000/1, molar ratio), then 25 DEG C of stirring 1h.150 DEG C are then heated to, 10min polymerize, yield 98%.
Obtained polymer is tested for the property, detection data is as follows: tensile strength 38MPa, yield elongation rate
4.8%, stretch modulus 880MPa, bending strength 56MPa, bending modulus 790MPa, impact strength 4.5KJ/m2。
Embodiment 7
Grubbs three generations's catalyst that this implementation is obtained using step (1) in embodiment 1, further prepares temperature sensitive type ruthenium card
Guest's complex, catalyst Cat.-7；And it is dilute and norbornene by the catalyst being prepared to be used to be catalyzed 1- hexene, ring penta 2
Polymerization reaction.
(1) by 1.0g Grubbs three generations catalyst and 9.24g N (C7H7O3)310mL1,4- dioxy is added in (20.0 equivalent)
Six rings, 50 DEG C of magnetic agitations are for 24 hours；After reaction, through separating-purifying, dry 0.81g catalyst Cat.-7, the receipts of catalyst
Rate is 65%；
Nuclear magnetic resonance characterization is carried out to the agent Cat.-7 catalyst being prepared, detection data is as follows:
1H NMR(CDCl3) δ (ppm)=2.12 (s, 12H, Mes-CH3),2.26(s,6H,Mes-CH3),3.81(s,9H,
CH3-O-),4.04(s,4H,N-CH2-CH2-N),6.63(s,4H,Mes-CH),7.18(d,6H,Ar-H),7.29(t,6H,Ar-
), H 7.23 (t, 2H, Ar-H), 7.54 (t, 1H, ArH), 7.75 (d, 2H, Ar-H), 19.03 (d, Ru=CH-Ph)
Wherein, the structure of Cat.-7 catalyst is as follows:
(2) in reaction flask, be added dilute 20.0g 1- hexene, 31.4g ring penta 2,44.8g norbornene and
18.0mgCat.-7 (alkene/cat.=70000/1, molar ratio), then 25 DEG C of stirring 1h.120 DEG C are then heated to, 15min
It polymerize, polymer yield 99%.
Obtained polymer is tested for the property, detection data is as follows: tensile strength 31MPa, yield elongation rate
3.5%, stretch modulus 780MPa, bending strength 55MPa, bending modulus 760MPa, impact strength 4.5KJ/m2。
Examples 1 to 7 provides a kind of preparation method of ruthenium carbene complex and its in alkene ring opening metathesis polymerization reaction
Application, mainly solve the problems, such as bis- generation of Grubbs catalyst alkene ring opening metathesis polymerization in Catalysis Rate it is too fast, realize exist
Alkene does not polymerize under cryogenic conditions, and when system is increased to certain temperature, system being capable of rapid polymerization.The present invention is from Grubbs
Two generation catalyst set out, and obtain final catalyst through two-step reaction, after separating-purifying, chemical purity up to 99.0% or more, with
The prior art is compared, and catalyst process of the present invention is simple, and raw material is easy to get, and when for the polymerization of alkene ring opening metathesis, dosage is few, temperature
Controllably, it can be achieved that the temperature control of alkene polymerize, there is wide prospects for commercial application.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of temperature sensitive type ruthenium carbene complex, which is characterized in that its chemical general formula is as follows:
2. a kind of temperature sensitive type ruthenium carbene complex according to claim 1, which is characterized in that the R in its chemical general formula is
Straight chained alkyl or aryl.
3. a kind of temperature sensitive type ruthenium carbene complex according to claim 2, which is characterized in that the R is straight chained alkyl,
Carbon atom number is 1-16.
4. a kind of temperature sensitive type ruthenium carbene complex according to claim 2, which is characterized in that the R is aryl, the aryl
General formula it is as follows:
Wherein, R1、R2、R3、R4And R5It is selected from the alkane that alkyl, carbon atom number that hydrogen, amino, carbon atom number are 1~16 are 1~16
One of the alkane phosphorus base that oxygroup or carbon atom number are 1~16.
5. a kind of preparation method of temperature sensitive type ruthenium carbene complex as described in claim 1, which is characterized in that its preparation step is such as
Under: Grubbs three generations's catalyst is taken, by the Grubbs three generations catalyst and NR3It is added in solvent, is reacted；After reacting
Material carry out separating-purifying, be dried to obtain the temperature sensitive type ruthenium carbene complex.
6. a kind of preparation method of temperature sensitive type ruthenium carbene complex according to claim 5, which is characterized in that the NR3With
The molar ratio of Grubbs three generations's catalyst is 1/1~20/1, and reaction temperature is 25~60 DEG C, and the reaction time is 12~48h；It is described
Solvent is selected from one or more of tetrahydrofuran, ethyl acetate, ether, acetone, acetonitrile, toluene or 1,4- dioxane.
7. a kind of preparation method of temperature sensitive type ruthenium carbene complex according to claim 5, which is characterized in that described
The general formula of Grubbs three generations's catalyst is as follows:
8. a kind of preparation method of temperature sensitive type ruthenium carbene complex according to claim 5, which is characterized in that described
Grubbs three generations's catalyst is prepared using bis- generation of Grubbs catalyst and pyridine as reaction raw materials；
The general formula of bis- generation of the Grubbs catalyst is as follows:
The reaction temperature of bis- generation of the Grubbs catalyst and pyridine be room temperature, the reaction time be 12~for 24 hours.
9. a kind of application of temperature sensitive type ruthenium carbene complex as described in claim 1, which is characterized in that the temperature sensitive type ruthenium Cabbeen is matched
Conjunction object is the catalyst with temperature-sensitive, the metathesis reaction applied to catalyzed alkene；The alkene is selected from norbornene, ring
Hexene, dicyclopentadiene, cyclo-octene, ring penta 2 be dilute, in the derivative of 1- octene, 1- hexene, styrene or any of the above-described alkene
One or more.
10. a kind of application of temperature sensitive type ruthenium carbene complex according to claim 9, which is characterized in that the temperature sensitive type
Ruthenium carbene complex carries out ring opening metathesis polymerization reaction for being catalyzed cyclic olefin；The temperature sensitive type ruthenium carbene complex and ring-type
Alkene is mixed according to the proportion that molar ratio is 1/30000~1/200000, when temperature is 25~35 DEG C, the ring-type alkene
Hydrocarbon not can be carried out ring opening metathesis polymerization reaction, and when temperature is 80~200 DEG C, it is anti-that ring opening metathesis polymerization occurs for the cyclic olefin
It answers；The polymerization time of the ring opening metathesis polymerization reaction is 5~20min.
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| CN105728046A (en) * | 2016-03-25 | 2016-07-06 | 上海克琴化工科技有限公司 | Ruthenium metallic olefin metathesis catalyst and preparation and application methods thereof |
| CN108299506A (en) * | 2018-01-29 | 2018-07-20 | 中国科学院成都有机化学有限公司 | N- heterocycle carbine ruthenium complexs and its preparation method and application |
| CN109651598A (en) * | 2019-01-31 | 2019-04-19 | 上海交通大学 | A kind of ruthenium metal composite catalyst and its application |
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| CN105728046A (en) * | 2016-03-25 | 2016-07-06 | 上海克琴化工科技有限公司 | Ruthenium metallic olefin metathesis catalyst and preparation and application methods thereof |
| CN108299506A (en) * | 2018-01-29 | 2018-07-20 | 中国科学院成都有机化学有限公司 | N- heterocycle carbine ruthenium complexs and its preparation method and application |
| CN109651598A (en) * | 2019-01-31 | 2019-04-19 | 上海交通大学 | A kind of ruthenium metal composite catalyst and its application |
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| GERALD O. WILSON等: "Stability of Second Generation Grubbs’ Alkylidenes to Primary Amines: Formation of Novel Ruthenium-Amine Complexes", 《ADV. SYNTH. CATAL.》 * |
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