CN104558049A - Preparation method and application of ruthenium-carbene catalyst - Google Patents
Preparation method and application of ruthenium-carbene catalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 title claims abstract description 10
- 229920001153 Polydicyclopentadiene Polymers 0.000 claims abstract description 57
- 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 abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 54
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 53
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 25
- 239000012043 crude product Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000643 oven drying Methods 0.000 claims description 12
- 150000003384 small molecules Chemical class 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 7
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 6
- 101150065749 Churc1 gene Proteins 0.000 claims description 6
- 102100038239 Protein Churchill Human genes 0.000 claims description 6
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical group BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000009466 transformation Effects 0.000 abstract description 18
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 17
- 238000005865 alkene metathesis reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003708 ampul Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 transition metal W Chemical class 0.000 description 2
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a preparation method and application of a ruthenium-carbene catalyst. According to the invention, a ruthenium-carbene complex is prepared by a method of olefin metathesis, the device and technology used for preparation are simple, only two-step reaction is needed, the cost is lower, and the production rate can reach 95%. According to the invention, the ruthenium-carbene complex is used as a catalyst for a ring-opening metathesis polymerization reaction of dicyclopentadiene so as to prepare polydicyclopentadiene. The activity of the ring-opening metathesis polymerization reaction is high, the transformation rate to the polymerization of the dicyclopentadiene is 99.8%, the reaction condition is moderate, high temperature and high pressure are not needed, resources are reasonably utilized, the reaction has no bad influence on the environment, and therefore, the method disclosed by the invention is a green process route, and is suitable for industrial popularization.
Description
Technical field
The present invention relates to a kind of ruthenium carbene complex preparation method and for dicyclopentadiene ring opening metathesis polymerization, belong to polymerization catalyzed reaction field.
Background technology
Dicyclopentadiene derives from the C of cracking of ethylene
5cut, abundance, cheap, space structure is divided into endocyclic and hanging ring type, and endocyclic is comparatively common, and it has two unsaturated double-bonds, and chemical property is relatively more active, has a wide range of applications in macromolecular material and fine chemistry industry.
Polydicyclopentadiene is a kind of important novel hot setting macromolecule engineering material.It has excellent mechanical property, resistance to medium and thermostability, has been widely used at field tools such as traffic, Sports facilities, material of construction, electric installation and communications.
The ring-opening metathesis polymerization catalyst of dicyclopentadiene (DCPD) is divided into two classes, and a class is two-pack catalyst system, and the first component is Primary Catalysts, for compounds such as transition metal W, Mo, Ti, Ru, Ta, second component is promotor, is generally strong lewis base class material, as aluminum alkyls (AlEt
2cl) etc.This kind of catalyzer is more responsive to empty G&W, and component is more, limits it and applies.Another kind of is single component catalyst system containing Cabbeen structure, and after Chauvin in 1971 illustrates metal ring butane mechanism, various carbene catalyst obtains and develops rapidly.Nineteen ninety-five, Grubbs etc. have synthesized single component ruthenium carbene complex, and its chemical formula is (PCy
3)
2cl
2ru=CHPh, is named as Grubbs generation catalyzer.It advances the development of olefin metathesis reaction greatly.This catalyzer is insensitive to air, and catalytic activity is higher, also has good compatibility to functional group.Strong electron-donating group N-heterocyclic ligand replaces a Phosphine ligands subsequently, has invented another kind of ruthenium carbene complex, i.e. (PCy
3) (SIMes) Cl
2ru=CHPh, is named as Grubbs s-generation catalyzer, and its catalytic activity has had and significantly improves.The introducing of chelation group can make Grubbs catalyzer thermostability improve, by changing the electronegativity of catalyzer and the sterically hindered modification realized catalyzer.At present, domestic Zhan Zhengyun professor utilizes advanced chemical synthesising technology, on Nobel prize achievement in research basis, the New Ruthenium Carbene Complexes with high catalytic activity has been synthesized in research, this catalyzer is named as Zhan Shi catalyzer, its structure is different from the catalyzer of all reports, has broken the monopoly position of Grubbs catalyzer monopolistic market.But because synthesis step is many, complex process, expensive etc., limit range of application industrially.(reference: [1] Yan Yinan, Yuqin etc. polydicyclopentadiene catalyst system and forming method [J]. New Chemical Materials,
2009, 37(10): 17-20
[2] recklessly have an area of, Zheng Yubin. the synthesis of ring-opening metathesis polymerization polydicyclopentadiene and the progress [J] of Structure and Properties. polymer is circulated a notice of,
2011, (9): 139-150.
[3]Paul A.van der Schaaf*,Roman Kolly,Hans-Jürg Kirner,Francois Rime,Andreas Mühlebach,Andreas Hafner.Synthesis and reactivity of novel ruthenium carbine catalysts.X-ray structure of [RuCl
2(CHSC
6H
5)(P
iPr
3)
2] and [RuCl
2(CHCH
2CH
2-C,N-2-C
5H
4N)(P
iPr
3)
2] [J].
J.Org.Chem.,
2000，606：65-74.
[4] Schwab P，Grubbs R H，Ziller J W. Synthesis and applications of RuCl
2(=CHR')(PR
3)
2:The influence of the alkylidene moiety on metathesis activity［J］．
J.Am.Chem.Soc.,
1996，118(1)：100－110.）
[5] Zhan Zhengyun. ruthenium complex part, ruthenium complex, solid carrying ruthenium complex catalyst and its production and use: China, 200610100377.X.2006-07-03.
Summary of the invention
The invention provides a kind of preparation and application thereof of ruthenium carbene complex.
1, the invention provides a kind of preparation method of ruthenium carbene complex, described ruthenium carbene complex is that two-triphenylphosphine-styrene ether-dichloro closes ruthenium complexe, and its chemical formula is (PCy
3)
2cl
2ru=CHCH
2oPh, it is characterized in that step and condition as follows:
(1) in three mouthfuls of reactors, solvent acetone is added, then phenol, 3-bromopropylene and Anhydrous potassium carbonate is added successively by the mol ratio of 1:1-2:1-2, the proportioning of the quality g of phenol and the volume mL of acetone is 4.7:50, temperature of reaction 40-60 DEG C, reaction times 4-7 h, react under the condition of backflow, after reaction terminates, obtain allyl phenyl ether C through suction filtration, underpressure distillation
9h
10o.
(2) under nitrogen protection, in three mouthfuls of reactors, add methylene chloride, then add Grubbs generation catalyzer and allyl phenyl ether C successively by the mol ratio of 1:1-15
9h
10the proportioning of the quality g of O, Grubbs generation catalyzer and the volume mL of methylene dichloride is 0.21:10, and temperature of reaction-30-0 DEG C, obtains ruthenium carbene complex, and its chemical formula is as follows:
The chemical formula of described Grubbs generation catalyzer is (PCy
3)
2cl
2ru=CHPh.
Product is through characterizing.
2, the invention provides the application of ruthenium carbene complex, it is as preparing polydicyclopentadiene catalyzer.
The invention provides ruthenium carbene complex as catalyzer, step and the condition of preparing the method for polydicyclopentadiene are as follows:
In reactor, add dicyclopentadiene and ruthenium carbene complex, its mol ratio is 500-1000:1; Reactor cooling, is placed on ultrasonic 5-10min in frozen water by reactor; Be placed on by reactor in water-bath, temperature of reaction is 40-70 DEG C, and the reaction times is 5-40 min, and gel time 35-85 s, obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, calculated the transformation efficiency of monomer.
beneficial effect:(1) ruthenium carbene complex of the present invention adopts the method preparation of olefin metathesis, and simply, only need two-step reaction, cost is lower, and productive rate is up to 95% for equipment used and technique.(2) ruthenium carbene complex of the present invention prepares polydicyclopentadiene catalyzer as dicyclopentadiene ring opening metathesis polymerization.This reactive behavior is high, and to the transformation efficiency of dicyclopentadiene polymerization up to 99.8%, reaction conditions is gentle, does not need High Temperature High Pressure, makes rational use of resources, have no adverse effects to environment, be a friendly process route, be suitable for industrialization promotion.
Accompanying drawing explanation
Fig. 1 is the RuCH of ruthenium carbene complex prepared by the present invention
1h NMR.
Fig. 2 is the RuCH of Grubbs generation catalyzer
1h NMR.
Fig. 3 is the infrared spectrogram of ruthenium carbene complex prepared by the present invention.
Fig. 4 is the X-ray diffraction of polydicyclopentadiene prepared by the present invention.
Fig. 5 is the infrared spectrogram of polydicyclopentadiene prepared by the present invention.
embodiment:
embodiment 1a preparation method for ruthenium carbene complex, described ruthenium carbene complex is that two-triphenylphosphine-styrene ether-dichloro closes ruthenium complexe, and its chemical formula is (PCy
3)
2cl
2ru=CHCH
2oPh, condition and the step of the preparation method of described ruthenium carbene complex are as follows:
(1)allyl phenyl ether C
9h
10the preparation of O: add solvent acetone 50 mL in there-necked flask, then add phenol 4.71 g(0.05 mol successively for 1:1.2:1.1 in molar ratio), 3-bromopropylene 7.26 g(0.06 mol) and Anhydrous potassium carbonate 7.60 g(0.055 mol), temperature of reaction 50 DEG C, reaction times 6 h, react under the condition of backflow, after reaction terminates, obtain allyl phenyl ether C through suction filtration, underpressure distillation
9h
10o is 6.37 g, and the productive rate of the product be obtained by reacting is 95%, and product characterizes through following nuclear-magnetism:
1h-NMR (400MHz CDCl
3): δ=7.38-7.36(m, 2H, Ar), 7.07-7.01(m, 3H, Ar), 6.21-6.11(m, 1H), 5.54-5.36 (m, 2H), 4.62-4.60 (m, 2H).
(2)the preparation of ruthenium carbene complex: under nitrogen protection, adds methylene chloride 10 mL, then adds Grubbs generation catalyzer 0.2056 g, allyl phenyl ether C successively for 1:10 in molar ratio in there-necked flask
9h
10o0.3347 g, temperature of reaction-20 DEG C, reaction times 20 min, after reaction terminates, obtain ruthenium carbene complex 0.2028 g through underpressure distillation, washing, suction filtration, drying, its chemical formula is as follows:
The chemical formula of described Grubbs generation catalyzer is (PCy
3)
2cl
2ru=CHPh, Cabbeen is structural
1h NMR as shown in Figure 2.
The productive rate of the product be obtained by reacting is 95%, and product characterizes through following nuclear-magnetism:
1h-NMR (400MHz, CDCl
3): δ=19.30-19.28 (t, Ru=CH), 7.32-6.86 (m, Ar), 4.58 (d, CH
2oPh), 2.53-2.47,1.81.1.70,1.59-1.53, and 1.26-1.22 (all m, P (C
6h
11)
3), Cabbeen is structural
1h NMR as shown in Figure 1.Infrared spectrum characterization as shown in Figure 3.
embodiment 2a preparation method for ruthenium carbene complex, described ruthenium carbene complex is that two-triphenylphosphine-styrene ether-dichloro closes ruthenium complexe, and its chemical formula is (PCy
3)
2cl
2ru=CHCH
2oph, condition and the step of the preparation method of described ruthenium carbene complex are as follows:
(1)allyl phenyl ether C
9h
10the preparation of O: add solvent acetone 50 mL in there-necked flask, then add phenol 4.71 g(0.05 mol successively for 1:1:1 in molar ratio), 3-bromopropylene 6.05 g(0.05 mol) and Anhydrous potassium carbonate 6.91 g(0.05 mol), temperature of reaction 40 DEG C, reaction times 7 h, react under the condition of backflow, after reaction terminates, obtain allyl phenyl ether C through suction filtration, underpressure distillation
9h
10o is 6.00 g, and the productive rate of the product be obtained by reacting is 90%.
(2)the preparation of ruthenium carbene complex: under nitrogen protection, adds methylene chloride 10 mL, then adds Grubbs generation catalyzer 0.2056 g, allyl phenyl ether C successively for 1:1 in molar ratio in there-necked flask
9h
10o0.0335 g, temperature of reaction-30 DEG C, reaction times 5 min, after reaction terminates, obtain ruthenium carbene complex 0.1833 g through underpressure distillation, washing, suction filtration, drying, its chemical formula is as follows:
The chemical formula of described Grubbs generation catalyzer is (PCy
3)
2cl
2ru=CHPh.
The productive rate of the product be obtained by reacting is 86%, and product characterizes through nuclear-magnetism.
embodiment 3a preparation method for ruthenium carbene complex, described ruthenium carbene complex is that two-triphenylphosphine-styrene ether-dichloro closes ruthenium complexe, and its chemical formula is (PCy
3)
2cl
2ru=CHCH
2oph, condition and the step of the preparation method of described ruthenium carbene complex are as follows:
(1)allyl phenyl ether C
9h
10the preparation of O: add solvent acetone 50 mL in there-necked flask, then add phenol 4.71 g(0.05 mol successively for 1:2:2 in molar ratio), 3-bromopropylene 12.10 g(0.1 mol) and Anhydrous potassium carbonate 13.82 g(0.1 mol), temperature of reaction 60 DEG C, reaction times 4 h, react under the condition of backflow, after reaction terminates, obtain allyl phenyl ether C through suction filtration, underpressure distillation
9h
10o is 5.90 g, and the productive rate of the product be obtained by reacting is 88%.
(2)the preparation of ruthenium carbene complex: under nitrogen protection, adds methylene chloride 10 mL, then adds Grubbs generation catalyzer 0.2056 g, allyl phenyl ether C successively for 1:15 in molar ratio in there-necked flask
9h
10o0.5021 g, temperature of reaction 0 DEG C, reaction times 30 min, after reaction terminates, obtain ruthenium carbene complex 0.1705 g through underpressure distillation, washing, suction filtration, drying, its chemical formula is as follows:
The chemical formula of described Grubbs generation catalyzer is (PCy
3)
2cl
2ru=CHPh.
The productive rate of the product be obtained by reacting is 80%.
embodiment 4the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 6.5 mg successively for 1000:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 5 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 30 min, and gel time 85 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 83.3% of monomer.X-ray diffraction characterizes as shown in Figure 4.Infrared spectrum characterization as shown in Figure 5.
embodiment 5the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 7.2 mg successively for 900:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 5 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 30 min, and gel time 80 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 85.2% of monomer.
embodiment 6the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 8.1 mg successively for 800:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 8 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 30 min, and gel time 70 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 88.8% of monomer.
embodiment 7the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 9.2 mg successively for 700:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 8 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 30 min, and gel time 55 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 93.6% of monomer.
embodiment 8the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 10.8 mg successively for 600:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 10 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 30 min, and gel time 40 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 99.8% of monomer.
embodiment 9the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 12.9 mg successively for 500:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 10 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 30 min, and gel time 35 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 99.8% of monomer.
embodiment 10the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 10.8 mg successively for 600:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 10 min in frozen water, reactor is placed in water-bath, temperature of reaction is 40 DEG C, reaction times is 30 min, and gel time 160 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 97.5% of monomer.
embodiment 11the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 10.8 mg successively for 600:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 10 min in frozen water, reactor is placed in water-bath, temperature of reaction is 70 DEG C, reaction times is 30 min, and gel time 30 s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 96% of monomer.
embodiment 12the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 10.8 mg successively for 600:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 10 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 5 min, and gel time 35s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 84.7% of monomer.
embodiment 13the application of ruthenium carbene complex, it is as catalyzer, polydicyclopentadiene is prepared for dicyclopentadiene ring opening metathesis polymerization, step and the condition of its preparation method are as follows: in ampoule, add dicyclopentadiene 1000 mg, catalyzer 10.8 mg successively for 600:1 in molar ratio, reactor cooling, reactor is placed on ultrasonic 10 min in frozen water, reactor is placed in water-bath, temperature of reaction is 60 DEG C, reaction times is 40 min, and gel time 35s obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.Dried to constant weight, the transformation efficiency 99.8% of monomer.
The transformation efficiency of monomer and gel time are in table 1.Table 1 shows, contrasts (see comparative example and table 2) with Grubbs generation catalyzer, and dicyclopentadiene ring opening metathesis polymerization transformation efficiency of the present invention is up to 99.8%, transformation efficiency is the highest can improve 7.7%, the highest prolongation 100% of gel time, is beneficial to operation, is applicable to industrialization promotion and uses.
Table 1
comparative example
With under embodiment 4-9 equal conditions, adopt Grubbs generation catalyzer to carry out polyreaction to dicyclopentadiene, the transformation efficiency of monomer and gel time are in table 2.
Table 2
| Embodiment | Dicyclopentadiene transformation efficiency/% | Gel time/s |
| 4 | 80.6 | 60 |
| 5 | 82.2 | 45 |
| 6 | 88.4 | 35 |
| 7 | 90.5 | 30 |
| 8 | 92.6 | 25 |
| 9 | 94.8 | 22 |
Claims (3)
1. a preparation method for ruthenium carbene complex, described ruthenium carbene complex is that two-triphenylphosphine-styrene ether-dichloro closes ruthenium complexe, and its chemical formula is (PCy
3)
2cl
2ru=CHCH
2oPh, it is characterized in that step and condition as follows:
(1) in three mouthfuls of reactors, solvent acetone is added, then phenol, 3-bromopropylene and Anhydrous potassium carbonate is added successively by the mol ratio of 1:1-2:1-2, the proportioning of the quality g of phenol and the volume mL of acetone is 4.7:50, temperature of reaction 40-60 DEG C, reaction times 4-7 h, react under the condition of backflow, after reaction terminates, obtain allyl phenyl ether C through suction filtration, underpressure distillation
9h
10o;
(2) under nitrogen protection, in three mouthfuls of reactors, add methylene chloride, then add Grubbs generation catalyzer and allyl phenyl ether C successively by the mol ratio of 1:1-15
9h
10the proportioning of the quality g of O, Grubbs generation catalyzer and the volume mL of methylene dichloride is 0.21:10, and temperature of reaction-30-0 DEG C, obtains ruthenium carbene complex, and its chemical formula is as follows:
The chemical formula of described Grubbs generation catalyzer is (PCy
3)
2cl
2ru=CHPh.
2. an application for ruthenium carbene complex, described ruthenium carbene complex is that two-triphenylphosphine-styrene ether-dichloro closes ruthenium complexe, and its chemical formula is (PCy
3)
2cl
2ru=CHCH
2oPh, is characterized in that, it is as preparing polydicyclopentadiene catalyzer.
3. the application of a kind of ruthenium carbene complex as claimed in claim 2, is characterized in that, its step as the method for catalyst preparing polydicyclopentadiene and condition as follows:
In reactor, add dicyclopentadiene and ruthenium carbene complex, its mol ratio is 500-1000:1; Reactor cooling, is placed on ultrasonic 5-10 min in frozen water by reactor; Be placed on by reactor in water-bath, temperature of reaction is 40-70 DEG C, and the reaction times is 5-40 min, and gel time 35-85 s, obtains polydicyclopentadiene crude product; Polydicyclopentadiene crude product will be obtained and be placed in vacuum drying oven drying, and remove unreacted small molecule monomer, obtain polydicyclopentadiene product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670194A (en) * | 2016-03-31 | 2016-06-15 | 上海东杰高分子材料有限公司 | Polydicyclopentadiene/high-polymer elastomer IPN (interpenetrating polymer network) high-polymer alloy material and preparation method thereof |
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| CN107722243A (en) * | 2017-11-02 | 2018-02-23 | 克琴新材料科技（上海）有限公司 | A kind of lightweight is modified dicyclopentadiene material and preparation method thereof |
| CN111468191A (en) * | 2020-05-26 | 2020-07-31 | 上海化工研究院有限公司 | Synthetic method of ruthenium carbene catalyst |
| CN111732681A (en) * | 2020-07-02 | 2020-10-02 | 张玉清 | Bi-component latent metal carbene catalytic system, dicyclopentadiene polymeric bi-material system and polydicyclopentadiene composite material |
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- 2014-12-30 CN CN201410835058.8A patent/CN104558049A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670194A (en) * | 2016-03-31 | 2016-06-15 | 上海东杰高分子材料有限公司 | Polydicyclopentadiene/high-polymer elastomer IPN (interpenetrating polymer network) high-polymer alloy material and preparation method thereof |
| CN105884947A (en) * | 2016-05-11 | 2016-08-24 | 武汉理工大学 | Emergency material repair system |
| CN107722243A (en) * | 2017-11-02 | 2018-02-23 | 克琴新材料科技（上海）有限公司 | A kind of lightweight is modified dicyclopentadiene material and preparation method thereof |
| CN111468191A (en) * | 2020-05-26 | 2020-07-31 | 上海化工研究院有限公司 | Synthetic method of ruthenium carbene catalyst |
| CN111732681A (en) * | 2020-07-02 | 2020-10-02 | 张玉清 | Bi-component latent metal carbene catalytic system, dicyclopentadiene polymeric bi-material system and polydicyclopentadiene composite material |
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