CN112759690B - Polydicyclopentadiene composite material and preparation method thereof - Google Patents
Polydicyclopentadiene composite material and preparation method thereof Download PDFInfo
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- 229920001153 Polydicyclopentadiene Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 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 54
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 10
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 claims description 9
- 239000011986 second-generation catalyst Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 238000010107 reaction injection moulding Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000005205 Pinus Nutrition 0.000 description 1
- 241000218602 Pinus <genus> Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- YBVNFKZSMZGRAD-UHFFFAOYSA-N pentamidine isethionate Chemical class OCCS(O)(=O)=O.OCCS(O)(=O)=O.C1=CC(C(=N)N)=CC=C1OCCCCCOC1=CC=C(C(N)=N)C=C1 YBVNFKZSMZGRAD-UHFFFAOYSA-N 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/45—Mixing liquids with liquids; Emulsifying using flow mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/30—Micromixers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F232/00—Copolymers 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
- C08F232/08—Copolymers 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)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a polydicyclopentadiene composite material and a preparation method thereof. The polydicyclopentadiene composite material comprises the following components in percentage by mass: the mass ratio of dicyclopentadiene monomer to catalyst is 5000-50000:1, the mass of dicyclopentadiene monomer and antioxidant is 100:0.01-2. The preparation method comprises the following steps: the organic solvent dissolved with dicyclopentadiene and antioxidant and the organic solvent dissolved with catalyst are mixed by a multi-section tubular mixer and then immediately injected into a mould, and after reaction molding at 40-80 ℃, the post-treatment is carried out at 120-150 ℃. The multi-section tube type micro-flow channel mixed polymerization process is adopted, so that the mixing effect is greatly improved, the catalyst consumption is reduced, the production process is simple, and the obtained polydicyclopentadiene composite material has excellent performance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polydicyclopentadiene composite material and a preparation method thereof.
Background
Polydicyclopentadiene (PDCPD) is a novel engineering plastic, is polymerized by dicyclopentadiene (DCPD) under the action of a ring-opening metathesis catalyst, and has the characteristics of good heat resistance, creep resistance, dimensional stability, corrosion resistance, abrasion resistance and the like. At present, a catalyst system adopted for preparing polydicyclopentadiene comprises tungsten-molybdenum complex or a carbene catalyst of molybdenum and ruthenium, and the adopted process is a Reaction Injection Molding (RIM) process, so that the catalyst system has the advantages of high molding speed, high efficiency, low energy consumption and the like, and can be used for manufacturing various large-sized thin-wall products with complex shapes.
The PDCPD material processed and molded by the RIM technology has excellent mechanical property, thermal stability, ageing resistance and the like, and can be widely applied to the aspects of automobile parts, industrial equipment, medical appliances and the like. At present, only a few enterprises in China use foreign core technology to produce and sell PDCPD materials, and the foreign technology is mature, and particularly, PDCPD has been developed for many years by famous companies such as Katretahler, terex, germany Libohaier, swedish Walker, mountain Twik, japanese construction machine, pinus and the like. In the united states, PDCPD materials are mainly used for containers for hazardous waste, side beams for large trucks, bumpers, fenders, and the like. PDCPD is mainly used in japan for producing automobile bumpers and large water treatment containers. Representative brands of polydicyclopentadiene engineering plastics are METTON developed by Hercules corporation and Japanese imperial corporation, and TELENE, PENTAM series developed by Goodrich corporation and Rayleigh Weng Zhushi corporation. The Langfang Senhui New Material Co., ltd, of Japanese Utility in 2006, produced and promoted PDCPD products in China first and had a certain production capacity.
The main research and development institutions in China are Tianjin university, shanghai chemical industry institute Limited company, henan university, keqin new material science and technology Limited company and the like, but are still in a state of immature technology.
The RIM process conventionally adopts A, B materials to be mixed and injected at a ratio of 1:1, but when a ruthenium carbene catalyst is adopted, the proportion of A, B materials is 1000-10000:1, and the mixing effect is difficult to achieve by adopting the traditional process, so that the product performance is influenced. The polydicyclopentadiene composite material (CN 105199290B) is prepared with dicyclopentadiene, styrene, silicon dioxide, triphenylphosphine, p-tert-butylphenol, toluene and curing agent, and through mixing the materials, forming slurry with the curing agent solution and injecting into forming mold.
The invention aims to provide a polydicyclopentadiene composite material and a process thereof, which adopt a multi-section tube type micro-flow channel mixed polymerization process, are suitable for a ruthenium carbene catalyst system, can greatly improve the mixing effect, reduce the catalyst consumption, and have simple production process and excellent product performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the polydicyclopentadiene composite material, which greatly reduces the catalyst consumption, simplifies the formula component types and contents, gradually increases the mechanical properties such as tensile modulus, tensile strength, bending strength and the like along with the gradual reduction of the catalyst consumption, gradually reduces the notch impact and elongation at break, gradually increases the thermal deformation temperature, and has excellent overall performance.
The invention provides a preparation method of a polydicyclopentadiene composite material, which adopts a multistage tube type micro-channel mixed polymerization process, is suitable for a ruthenium carbene catalyst system, greatly improves the mixing effect, reduces the catalyst consumption, and has simple production process and excellent product performance.
The technical scheme of the invention is that the polydicyclopentadiene composite material comprises the following components in percentage by mass: the mass ratio of dicyclopentadiene monomer to catalyst is 5000-50000:1, preferably 10000:1, a step of; if ethylidene norbornene is added as a modifier, the mass ratio of dicyclopentadiene monomer to ethylidene norbornene is 100:5-50, preferably 100:5, a step of; the mass of dicyclopentadiene monomer and antioxidant is 100:0.01-2, preferably 100:0.5-1.
The catalyst is a ruthenium catalyst, preferably a Grubbs second generation catalyst.
The dicyclopentadiene monomer is a polymerization grade dicyclopentadiene monomer, and the purity is more than 95%.
The antioxidant is a high molecular antioxidant which can be dissolved in dichloromethane or toluene, and preferably o-di-tert-butyl p-methylphenol.
The raw materials are mixed in a multi-section tubular micro-channel mode.
A preparation method of polydicyclopentadiene composite material comprises the following steps: the organic solvent dissolved with dicyclopentadiene and antioxidant and the organic solvent dissolved with catalyst are mixed evenly by a multi-section tubular mixer, and then are immediately injected into a die, and after curing and forming at 40-80 ℃, the post-treatment is carried out at 120-150 ℃.
In an organic solvent dissolved with dicyclopentadiene and an antioxidant, the mass ratio of the dicyclopentadiene to the organic solvent is 100:2-5, preferably 100:3-5; the mass ratio of dicyclopentadiene to the antioxidant is 100:0.01-2, preferably 100:1-2.
In an organic solvent for dissolving dicyclopentadiene and an antioxidant, the mass ratio of a modifier ethylidene norbornene is 100:5-50, preferably 100:5.
In the organic solvent in which the catalyst is dissolved, the mass volume concentration of the catalyst is 35-50mg/ml, preferably 40mg/ml.
The organic solvent comprises at least one of dichloromethane, toluene, ethyl acetate or tetrahydrofuran, preferably dichloromethane.
The catalyst is a ruthenium catalyst, preferably a Grubbs second generation catalyst.
The reaction is carried out for 1 to 2 hours at 40 to 80 ℃ and is preferably carried out for 1 hour at 60 ℃.
The post-treatment is carried out at 120-150 ℃ for 1-2 hours, preferably at 140 ℃ for 1 hour.
Compared with the prior art, the invention has the advantages that:
Compared with a bimetallic catalyst, the Grubbs second generation catalyst has higher activity, can improve the proportion of monomers to the catalyst by several orders of magnitude, and can effectively save the raw material cost.
The RIM technology of the invention has simple technological operation, even material mixing, small catalyst consumption, even and compact product prepared by copolymerization and better mechanical property.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
This example illustrates the preparation of a dicyclopentadiene homopolymer with a ratio of dicyclopentadiene to catalyst material of 5000:1 (about 800:1 by mass) in accordance with the present invention
(1) Preparation of catalyst solution A
Grubbs second generation catalyst (424.5 mg,0.5 mmol) was weighed out in a glove box and dissolved in 10.6ml dichloromethane to prepare a 40mg/ml catalyst solution.
(2) Preparation of dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%) in advance, stirring for 12h under the protection of nitrogen at 80 ℃, distilling under reduced pressure for refining, and then adding dichloromethane solvent with the mass of 2% -5% of dicyclopentadiene for fully dissolving in advance. Adding 0.01% -2% of antioxidant o-di-tert-butyl p-methylphenol by mass of dicyclopentadiene into dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring in a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.
(3) Mixing, solidifying and shaping
3.85Ml of A solution and 120g of B solution are measured, the A solution and the B solution are uniformly mixed by a multi-section tubular mixer under the protection of nitrogen, the mixture is injected into a reaction mould, the temperature of the mould is programmed, the reaction temperature is kept at 60 ℃, the temperature is kept for 1h, the post-treatment temperature is 140 ℃, and the temperature is kept for 1h.
After the mold is cooled, the product is demolded, and two mold cavities, 60g of product respectively, are obtained.
The stretching, bending properties, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1 at a ratio of dicyclopentadiene to catalyst material of 5000:1.
Example 2
This example is a description of the preparation method of dicyclopentadiene homopolymer when the amount ratio of dicyclopentadiene to catalyst substance is 10000:1 (mass ratio of about 1500:1)
(1) Preparation of catalyst solution A
Grubbs second generation catalyst (424.5 mg,0.5 mmol) was weighed out in a glove box and dissolved in 10.6ml dichloromethane to prepare a 40mg/ml catalyst solution.
(2) Preparation of dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%) in advance, stirring for 12h under the protection of nitrogen at 80 ℃, distilling under reduced pressure for refining, and then adding dichloromethane solvent with the mass of 2% -5% of dicyclopentadiene for fully dissolving in advance. Adding 0.01% -2% of antioxidant o-di-tert-butyl p-methylphenol by mass of dicyclopentadiene into dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring in a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.
(3) Mixing, solidifying and shaping
1.93Ml of A solution and 120g of B solution are measured, and the A solution and the B solution are quickly mixed by a multi-section tubular mixer under the protection of nitrogen, and are uniformly mixed. And (3) quickly injecting the mixture into a reaction mould, starting to perform programmed heating of the mould, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, and keeping the post-treatment temperature at 140 ℃ for 1h.
After the mold is cooled, the product is demolded, and two mold cavities, 60g of product respectively, are obtained.
The stretching, bending properties, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1 at a ratio of dicyclopentadiene to catalyst substance of 10000:1.
Example 3
This example is a description of the preparation method of dicyclopentadiene homopolymer when the amount ratio of dicyclopentadiene to catalyst substance is 20000:1 (mass ratio of about 3000:1)
(1) Preparation of catalyst solution A
Grubbs second generation catalyst (424.5 mg,0.5 mmol) was weighed out in a glove box and dissolved in 10.6ml dichloromethane to prepare a 40mg/ml catalyst solution.
(2) Preparation of dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%) in advance, stirring for 12h under the protection of nitrogen at 80 ℃, distilling under reduced pressure for refining, and then adding dichloromethane solvent with the mass of 2% -5% of dicyclopentadiene for fully dissolving in advance. Adding 0.01% -2% of antioxidant o-di-tert-butyl p-methylphenol by mass of dicyclopentadiene into dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring in a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.
(3) Mixing, solidifying and shaping
Measuring 0.96ml of A solution and 120g of B solution, rapidly mixing the A solution and the B solution by a multi-section tubular mixer under the protection of nitrogen, and uniformly mixing. And (3) quickly injecting the mixture into a reaction mould, starting to perform programmed heating of the mould, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, and keeping the post-treatment temperature at 140 ℃ for 1h.
After the mold is cooled, the product is demolded, and two mold cavities, 60g of product respectively, are obtained.
The stretching, bending properties, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1, with the amount ratio of dicyclopentadiene to catalyst substance being 20000:1.
Example 4
This example is a description of the preparation method of the dicyclopentadiene-ethylidene norbornene copolymer according to the present invention, when the ratio of the dicyclopentadiene-ethylidene norbornene mixed solution to the catalyst substance is 10000:1 (the mass ratio is about 1500:1)
(1) Preparation of catalyst solution A
Grubbs second generation catalyst (424.5 mg,0.5 mmol) was weighed out in a glove box and dissolved in 10.6ml dichloromethane to prepare a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene-ethylidene norbornene mixed solution B
The dicyclopentadiene and ethylidene norbornene (the purity is more than 95%) are respectively added with excessive calcium hydride in advance, stirred for 12 hours under the protection of nitrogen at 80 ℃ and distilled under reduced pressure for refining. Weighing 95% dicyclopentadiene and 5% ethylidene norbornene, adding 0.01% -2% antioxidant o-di-tert-butyl p-methylphenol (based on dicyclopentadiene mass) under the protection of nitrogen, fully and uniformly stirring on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.
(3) Mixing, solidifying and shaping
Measuring 1.93ml of A solution and 120g of B solution, quickly mixing the A solution and the B solution under the protection of nitrogen by a multi-section tubular mixer, injecting the mixture into a reaction mould, starting the temperature programming of the mould, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1h.
After the mold is cooled, the product is demolded, and two mold cavities, 60g of product respectively, are obtained.
When the mass ratio of dicyclopentadiene to catalyst substance is 10000:1, the mass ratio of dicyclopentadiene to ethylidene norbornene is 95%: at 5%, the elongation, bending properties, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1.
TABLE 1 Polymer mechanics at different monomer to catalyst ratios and different ENB content
Claims (1)
1. The preparation method of the polydicyclopentadiene composite material is characterized by comprising the following steps of:
(1) Preparing a catalyst solution A: weighing Grubbs second generation catalyst in a glove box, and dissolving the Grubbs second generation catalyst in dichloromethane to prepare 40mg/ml catalyst solution;
(2) Preparing dicyclopentadiene-ethylidene norbornene mixed solution B: adding excessive calcium hydride into dicyclopentadiene and ethylidene norbornene respectively in advance, stirring for 12h at 80 ℃ under the protection of nitrogen, and distilling under reduced pressure to refine; weighing 95% dicyclopentadiene and 5% ethylidene norbornene, adding 0.01% -2% antioxidant o-di-tert-butyl p-methylphenol based on the mass of dicyclopentadiene under the protection of nitrogen, fully and uniformly stirring on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃;
The purities of dicyclopentadiene and ethylidene norbornene are both more than 95 percent; (3) mixing, curing and forming: according to the mass ratio of dicyclopentadiene monomer to catalyst is 10000:1, measuring a solution A and a solution B, quickly mixing the solution A and the solution B under the protection of nitrogen by a multi-section tubular mixer, injecting the mixture into a reaction mould, starting the temperature programming of the mould, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1h;
(4) And after the mold is cooled, demolding to obtain the polydicyclopentadiene composite material.
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| Guang Yang.Cure kinetics and physical properties of poly(dicyclopentadiene/5-ethylidene-2-norbornene) initiated by different Grubbs' catalysts.RSC Adv.2015,第5卷59120–59130. * |
| 采用Grubbs催化剂的双环戊二烯开环移位聚合速率调控;孙春水;谢家明;傅建松;周立武;姚臻;曹堃;化学反应工程与工艺;第27卷(第003期);第251-256页 * |
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