CN112759709A - Dicyclopentadiene-ethylidene norbornene copolymer and preparation method thereof - Google Patents
Dicyclopentadiene-ethylidene norbornene copolymer and preparation method thereof Download PDFInfo
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- CN112759709A CN112759709A CN201910999182.0A CN201910999182A CN112759709A CN 112759709 A CN112759709 A CN 112759709A CN 201910999182 A CN201910999182 A CN 201910999182A CN 112759709 A CN112759709 A CN 112759709A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 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 120
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 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 abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000000465 moulding Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- 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 13
- 239000011986 second-generation catalyst Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 229920001519 homopolymer Polymers 0.000 description 23
- 239000000463 material Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 12
- 238000007711 solidification Methods 0.000 description 10
- 230000008023 solidification Effects 0.000 description 10
- 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 description 9
- 238000007670 refining Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical class C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011985 first-generation catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 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
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (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 dicyclopentadiene-ethylidene norbornene copolymer and a preparation method thereof, wherein the dicyclopentadiene-ethylidene norbornene copolymer comprises the following components in percentage by mass: the mass ratio of dicyclopentadiene monomer to catalyst was 5000-50000: 1, the mass ratio of the dicyclopentadiene monomer to the ethylidene norbornene is 100: 5-50, wherein the mass ratio of the dicyclopentadiene monomer to the antioxidant is 100: 0.01-2. The preparation method comprises the following steps: uniformly mixing the organic solvent for uniformly dissolving dicyclopentadiene, ethylidene norbornene and the antioxidant with the organic solvent for uniformly dissolving the catalyst, immediately injecting into a mold, curing and molding at 40-80 ℃, and performing post-treatment at 120-150 ℃. The invention simplifies the types of the raw materials of the formula of the dicyclopentadiene-ethylidene norbornene copolymer, adjusts the proportion of the raw materials of the formula, reduces the dosage of the catalyst, simplifies the preparation process and obtains the copolymer with good strength, impact toughness and thermal stability.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a dicyclopentadiene-ethylidene norbornene copolymer and a preparation method thereof.
Background
The polydicyclopentadiene engineering plastic is a novel engineering material with good mechanical properties, has high tensile property, bending modulus and good impact strength, also has higher thermal deformation temperature and thermal stability, is acid-resistant and alkali-resistant, is a pure crushed hydrocarbon, does not generate harmful substances during combustion, can be recycled, is energy-saving and environment-friendly, is a good environment-friendly material, is a high and new technology encouraged by the state, and therefore, has wide application prospects in the fields of the automobile industry, the engineering machinery manufacturing industry, medical sports equipment, petrochemical pipelines, civil facilities and the like. PDCPDs have been developed for many years especially by famous companies such as carter, trex, liberhal, sweden walvo, santyvik and japan construction, xiao, etc., in the united states, these technologies and products are on the market, and polydicyclopentadiene products have been sufficient to replace materials such as glass fiber reinforced plastics, polyurethane and aluminum alloys over the past 20 years. Considering environmental reasons, the restriction of China on the glass fiber reinforced plastics is more and more large, and once the domestic polydicyclopentadiene product realizes the localization and forms the competition with foreign countries, the development prospect is very good.
At present, the generation technology of the PDCPD material in China is immature and is still in the exploration and development stage, in order to improve the performance of the PDCPD material, a novel PDCPD material and a preparation process are explored, and a composite material is developed by copolymerizing dicyclopentadiene (DCPD) and other kinds of olefins, so that the generation technology becomes one of the research directions for modifying the PDCPD material. For example, the original polymerized composite material of polydicyclopentadiene/ethylene copolymer and its preparation process (CN101891931A) can increase the impact strength of the polymer from 100J/m to 150J/m to 300J/m, but the ethylene copolymer needs to be dissolved in dicyclopentadiene, which makes the preparation process complicated. The dicyclopentadiene-cyclopentene copolymer and the preparation method (CN105985486A) thereof have high polymerization conversion rate, no odor of products and good heat resistance, and can especially improve the impact strength of the material from the original 100J/m to 300-400J/m. However, the bimetallic catalyst system selected in the above patent is sensitive to water and oxygen, and needs to be carried out under the protection of nitrogen in the whole process, so that the use has certain limitation. A process for preparing the polydicyclopentadiene/modified polystyrene composition (CN106519533A) includes such steps as adding modified polystyrene to dicyclopentadiene to obtain the solution of dicyclopentadiene modified polystyrene, and mixing. The prepared mineral-conforming material has higher impact resistance which is improved from 80J/m to 150-200J/m, but the selected catalyst is a bimetallic catalyst, so that the use still has limitation, and the physical mixing cannot be sufficiently uniform.
Disclosure of Invention
In order to overcome the defects of complicated process and complicated operation of dicyclopentadiene copolymerization caused by the sensitivity of a bimetallic catalyst to water and oxygen and the fact that high-purity dicyclopentadiene is a crystal at normal temperature, the invention provides a dicyclopentadiene-ethylidene norbornene copolymer and a preparation method thereof, which simplify the types of formula raw materials of the dicyclopentadiene-ethylidene norbornene copolymer, adjust the proportion of the formula raw materials, reduce the dosage of the catalyst, simplify the preparation process and obtain the copolymer with good strength, impact toughness and thermal stability.
The technical scheme of the invention is that the dicyclopentadiene-ethylidene norbornene copolymer is prepared by taking dicyclopentadiene monomers and ethylidene norbornene as raw materials and adopting a reaction injection molding process under the action of a catalyst, wherein the mass ratio of the dicyclopentadiene monomers to the catalyst is 5000-50000: 1, preferably 10000: 1; the mass ratio of the dicyclopentadiene monomer to the ethylidene norbornene is 100: 5-50, preferably 100: 5; the mass of the dicyclopentadiene monomer and the antioxidant is 100: 0.01-2, preferably 100: 0.5-1.
The dicyclopentadiene monomer is a polymerization-grade dicyclopentadiene monomer, and the purity is more than 95%.
The purity of the ethylidene norbornene is more than 95%.
The catalyst is ruthenium catalyst, preferably Grubbs second generation catalyst.
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 by means of, but not limited to, mechanical stirring, multi-stage tubular mixing and the like.
A method for preparing a dicyclopentadiene-ethylidene norbornene copolymer comprises the steps of: uniformly mixing the organic solvent for uniformly dissolving dicyclopentadiene, ethylidene norbornene and the antioxidant with the organic solvent for uniformly dissolving the catalyst, immediately injecting into a mold, curing and molding at 40-80 ℃, and performing post-treatment at 120-150 ℃.
Uniformly dissolving dicyclopentadiene, ethylidene norbornene and an antioxidant in an organic solvent, wherein the mass ratio of dicyclopentadiene to ethylidene norbornene is 100: 5-50, preferably 100: 5; the mass of the dicyclopentadiene monomer and the antioxidant is 100: 0.01-2, preferably 100: 0.5 to 1; the mass ratio of dicyclopentadiene to the organic solvent is 100: 2-5, preferably 100: 3-5.
The mass volume concentration of the catalyst in the organic solvent for uniformly dissolving the catalyst is 35-50mg/ml, and preferably 40 mg/ml.
After the organic solvent for uniformly dissolving the dicyclopentadiene, the ethylidene norbornene and the antioxidant is fully and uniformly mixed with the organic solvent for uniformly dissolving the catalyst, the mass ratio of the dicyclopentadiene monomer to the catalyst is 5000-50000: 1, preferably 10000:1.
the organic solvent comprises at least one of dichloromethane, toluene, ethyl acetate or tetrahydrofuran, preferably dichloromethane.
The catalyst is ruthenium catalyst, preferably Grubbs second generation catalyst.
Reacting at 40-80 ℃ for 1-2 h for forming, preferably at 60 ℃ for 1h for forming.
Post-treating at 120-150 deg.c for 1-2 hr, preferably at 140 deg.c for 1 hr.
Compared with the prior art, the invention has the advantages that:
the invention provides a dicyclopentadiene-ethylidene norbornene copolymer and a preparation method thereof, aiming at overcoming the defects of complicated process and complicated operation of dicyclopentadiene copolymerization caused by the fact that a bimetallic catalyst is sensitive to water and oxygen and high-purity dicyclopentadiene is a crystal at normal temperature.
Compared with the prior art, the Grubbs second-generation catalyst selected by the technology is more water-resistant and oxygen-resistant, can keep certain activity in air and a small amount of water before reaction, is more convenient to operate compared with a bimetallic catalyst, and has higher activity compared with a first-generation catalyst, and the ratio of a monomer to the catalyst can be improved by several orders of magnitude, so that the raw material cost can be effectively saved. The solidification point of dicyclopentadiene reaches 33 ℃, so that dicyclopentadiene with relatively high purity is colorless crystals at normal temperature, which is very inconvenient in practical industrial operation.
In the invention, the ethylidene norbornene can be prepared from dicyclopentadiene and 1, 3-butadiene through Diels-Alder reaction, the structure of the ethylidene norbornene is very similar to that of dicyclopentadiene, the freezing point is about-80 ℃, and the ethylidene norbornene can effectively reduce the freezing point when added into dicyclopentadiene. Under the condition of a certain proportion of raw materials and catalyst, 5%, 25% and 50% of ethylidene norbornene are added for copolymerization, and the ethylidene norbornene and dicyclopentadiene can be fully mixed to form a very uniform solution. Proper amount of ethylidene norbornene can not only have the effect of pour point depression, but also have the effects of increasing the strength and toughening of the polymer. The dicyclopentadiene structural unit and the ethylidene norbornene structural unit are combined together through copolymerization, and compared with the method that only dicyclopentadiene homopolymer and ethylidene norbornene homopolymer are simply mixed, the copolymer is more uniform and compact and has better mechanical property. The proper amount of ethylidene norbornene is selected, so that the polymer has higher mechanical strength, especially, the toughness can be improved, and the process operation difficulty is reduced.
According to the method for preparing the dicyclopentadiene-ethylidene norbornene copolymer, the conversion rate of dicyclopentadiene and ethylidene norbornene can reach more than 99%.
The tensile modulus and the flexural modulus of the dicyclopentadiene-ethylidene norbornene copolymer prepared by the invention can reach 1900Mpa, and the impact strength can reach 36.7KJ/m2The heat distortion temperature reaches 149 ℃, and is improved compared with the original homopolymer.
Because the ethylidene norbornene is the derivative of dicyclopentadiene, the dicyclopentadiene raw material can be fully utilized, and the purposes of energy conservation and consumption reduction are achieved.
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 invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
This example illustrates the process of the present invention for producing dicyclopentadiene homopolymer at a ratio of dicyclopentadiene to catalyst material of 5000:1 (about 800:1 by mass)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant (o-di-tert-butyl-p-methylphenol) with the mass of 0.01-2% of that of dicyclopentadiene into the dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring the mixture on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.
(3) Mixed solidification forming
Measuring 3.85ml of A solution and 120g of B solution, quickly mixing the A solution and the B solution through a multi-section tubular mixer under the protection of nitrogen, and mixing uniformly. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer at a 5000:1 ratio of dicyclopentadiene to catalyst material are shown in Table 1.
Example 2
This example illustrates the preparation of a dicyclopentadiene homopolymer according to the invention at a ratio of dicyclopentadiene to catalyst material of 10000:1 (mass ratio of about 1500:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant with the mass of 0.01-2% of dicyclopentadiene into the dicyclopentadiene solution under the protection of nitrogen, and fully and uniformly stirring the mixture on a low-temperature reaction bath, wherein the temperature is controlled at 10-30 ℃.
(3) Mixed solidification forming
Measuring 1.93ml of A solution and 120g of B solution, and quickly mixing the A solution and the B solution through a multi-section tubular mixer under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1 at a ratio of 10000:1 dicyclopentadiene to catalyst material.
Example 3
This example illustrates the preparation of a dicyclopentadiene homopolymer according to the invention at a weight ratio of dicyclopentadiene to catalyst material of 15000:1 (about 2300:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant with the mass of 0.01-2% of dicyclopentadiene into the dicyclopentadiene solution under the protection of nitrogen, and fully and uniformly stirring the mixture on a low-temperature reaction bath, wherein the temperature is controlled at 10-30 ℃.
(3) Mixed solidification forming
Measuring 1.28ml of A solution and 120g of B solution, and mechanically stirring and quickly mixing the A solution and the B solution under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer at a weight ratio of 15000:1 to the catalyst material are shown in Table 1.
Example 4
This example illustrates the preparation of a dicyclopentadiene homopolymer according to the invention at a ratio of amount of dicyclopentadiene to catalyst material of 20000:1 (mass ratio of about 3000:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant with the mass of 0.01-2% of dicyclopentadiene into the dicyclopentadiene solution under the protection of nitrogen, and fully and uniformly stirring the mixture on a low-temperature reaction bath, wherein the temperature is controlled at 10-30 ℃.
(3) Mixed solidification forming
Measuring 0.96ml of A solution and 120g of B solution, and mechanically stirring and quickly mixing the A solution and the B solution under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer at a ratio of 20000:1 to the catalyst material are shown in Table 1.
Example 5
This example illustrates the preparation of a dicyclopentadiene homopolymer according to the invention at a ratio of amount of dicyclopentadiene to catalyst material of 30000:1 (a mass ratio of about 4600:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant with the mass of 0.01-2% of dicyclopentadiene into the dicyclopentadiene solution under the protection of nitrogen, and fully and uniformly stirring the mixture on a low-temperature reaction bath, wherein the temperature is controlled at 10-30 ℃.
(3) Mixed solidification forming
Measuring 0.64ml of A solution and 120g of B solution, and quickly mixing the A solution and the B solution through a multi-section tubular mixer under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer at a 30000:1 ratio of dicyclopentadiene to catalyst material are shown in Table 1.
Example 6
This example illustrates the process of the present invention for producing dicyclopentadiene homopolymer at a ratio of 50000:1 dicyclopentadiene to catalyst material (mass ratio of about 8000:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant with the mass of 0.01-2% of dicyclopentadiene into the dicyclopentadiene solution under the protection of nitrogen, and fully and uniformly stirring the mixture on a low-temperature reaction bath, wherein the temperature is controlled at 10-30 ℃.
(3) Mixed solidification forming
Measuring 0.39ml of A solution and 120g of B solution, and mechanically stirring and quickly mixing the A solution and the B solution under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1 at a 50000:1 ratio of dicyclopentadiene to catalyst material.
Example 7
This example is intended to illustrate the preparation of a dicyclopentadiene-ethylidene norbornene copolymer according to the invention when the ratio of the amount of the dicyclopentadiene-ethylidene norbornene mixed solution to the amount of the catalyst substance is 10000:1 (mass ratio is about 1500:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing a dicyclopentadiene-ethylidene norbornene mixed solution B
Adding excessive calcium hydride into dicyclopentadiene and ethylidene norbornene (purity is higher than 95%), stirring at 80 deg.C under nitrogen protection for 12 hr, and distilling under reduced pressure for refining. Weighing 95% of dicyclopentadiene and 5% of ethylidene norbornene, adding 0.01% -2% of antioxidant (calculated by 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 ℃.
(3) Mixed solidification forming
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, quickly injecting the mixture into a reaction mold after mixing by a multi-section pipeman, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
When the quantitative ratio of dicyclopentadiene to the catalyst substance is 10000:1, the mass ratio of dicyclopentadiene to ethylidene norbornene is 100: at 5, the tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1.
Example 8
This example is intended to illustrate the preparation of a dicyclopentadiene-ethylidene norbornene copolymer according to the invention when the ratio of the amount of the dicyclopentadiene-ethylidene norbornene mixed solution to the amount of the catalyst substance is 10000:1 (mass ratio is about 1500:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing a dicyclopentadiene-ethylidene norbornene mixed solution B
Adding excessive calcium hydride into dicyclopentadiene and ethylidene norbornene (purity is more than 95%) in advance
Stirring at 80 deg.C under nitrogen protection for 12 hr, and refining by reduced pressure distillation. Weighing 75% of dicyclopentadiene and 25% of ethylidene norbornene, adding 0.01% -2% of antioxidant (calculated by 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 ℃.
(3) Mixed solidification forming
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, and mixing uniformly. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
When the quantitative ratio of dicyclopentadiene to the catalyst substance is 10000:1, the mass ratio of dicyclopentadiene to ethylidene norbornene is 75%: at 25%, the tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1.
Example 9
This example is intended to illustrate the preparation of a dicyclopentadiene-ethylidene norbornene copolymer according to the invention when the ratio of the amount of the dicyclopentadiene-ethylidene norbornene mixed solution to the amount of the catalyst substance is 10000:1 (mass ratio is about 1500:1)
(1) Preparing a catalyst solution A
Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.
(2) Preparing a dicyclopentadiene-ethylidene norbornene mixed solution B
Adding excessive calcium hydride into dicyclopentadiene and ethylidene norbornene (purity is higher than 95%), stirring at 80 deg.C under nitrogen protection for 12 hr, and distilling under reduced pressure for refining. Weighing 50% of dicyclopentadiene and 50% of ethylidene norbornene, adding 0.01% -2% of antioxidant (calculated by 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 ℃.
(3) Mixed solidification forming
Measuring 1.93ml of A solution and 120g of B solution, and rapidly mixing the A solution and the B solution by mechanical stirring under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
When the quantitative ratio of dicyclopentadiene to the catalyst substance is 10000:1, the mass ratio of dicyclopentadiene to ethylidene norbornene is 50%: at 50%, the tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1.
TABLE 1 Polymer mechanics at different proportions of monomer and catalyst and at different ENB contents
As can be seen from Table 1, the ratio of the monomer to the catalyst in the invention is different, the mechanical properties of the produced homopolymer are greatly different, the crosslinking density is reduced with the increase of the ratio of the monomer to the catalyst, the tensile and flexural moduli of the polydicyclopentadiene material are reduced, the impact strength is increased, particularly when the amount ratio of the substances reaches 50000:1, the tensile and flexural moduli are reduced greatly, from 1900MPa to 1500MPa, so the ratio of the monomer to the catalyst is not too large, the ratio of the monomer to the catalyst is continuously reduced, the tensile and flexural properties of the polydicyclopentadiene are still continuously increased, but the toughness is deteriorated, when the ratio of the monomer to the catalyst is 10000:1, the moduli and the impact strength can reach a moderate value, and meanwhile, the ratio can be selected to be 10000:1 in order to save raw materials, in addition, the invention focuses on the copolymerization by adding ethylidene norbornene with different contents, compared with the original homopolymer, the performance of the modified ethylene-norbornene homopolymer is also changed, when the content of the ethylidene norbornene is not large, the modified ethylene-norbornene homopolymer is generally less than 10 percent, and not only can the modified ethylene-norbornene homopolymer play a role in pour point depression, but also can the modulus and the impact strength of the modified ethylene-norbornene copolymer be simultaneously increased. When the content of ethylidene norbornene is 5%, the tensile modulus, the flexural modulus and the strength are slightly increased, the impact strength is increased by more than 50%, and the toughness is better.
Claims (7)
1. A dicyclopentadiene-ethylidene norbornene copolymer is characterized by comprising the following components: dicyclopentadiene monomer, ethylidene norbornene, catalyst and antioxidant, wherein the mass ratio of the dicyclopentadiene monomer to the catalyst is 5000-50000: 1, the mass ratio of the dicyclopentadiene monomer to the ethylidene norbornene is 100: 5-50, wherein the mass ratio of the dicyclopentadiene monomer to the antioxidant is 100: 0.01-2.
2. The dicyclopentadiene-ethylidene norbornene copolymer of claim 1, wherein the mass ratio of dicyclopentadiene monomer to catalyst is 10000: 1; the mass ratio of the dicyclopentadiene monomer to the ethylidene norbornene is 100: 5; the mass of the dicyclopentadiene monomer and the antioxidant is 100: 0.5-1.
3. The dicyclopentadiene-ethylidene norbornene copolymer according to claim 1, wherein the catalyst is a ruthenium based catalyst, preferably a Grubbs second generation catalyst.
4. A method for producing the dicyclopentadiene-ethylidene norbornene copolymer according to claim 1 or 3, characterized by comprising the steps of: uniformly mixing the organic solvent for uniformly dissolving dicyclopentadiene, ethylidene norbornene and the antioxidant with the organic solvent for uniformly dissolving the catalyst, immediately injecting into a mold, curing and molding at 40-80 ℃, and performing post-treatment at 120-150 ℃.
5. The method according to claim 4, wherein the dicyclopentadiene, the ethylidene norbornene and the antioxidant are uniformly dissolved in an organic solvent in a mass ratio of 100: 5-50, wherein the mass ratio of the dicyclopentadiene monomer to the antioxidant is 100: 0.01-2, wherein the mass ratio of the dicyclopentadiene to the organic solvent is 100: 2-5; uniformly dissolving the catalyst in an organic solvent, wherein the mass volume concentration of the catalyst is 35-50 mg/ml;
after the organic solvent for uniformly dissolving the dicyclopentadiene, the ethylidene norbornene and the antioxidant is fully and uniformly mixed with the organic solvent for uniformly dissolving the catalyst, the mass ratio of the dicyclopentadiene monomer to the catalyst is 5000-50000: 1.
6. the method of claim 4, wherein the organic solvent comprises at least one of dichloromethane, toluene, ethyl acetate, or tetrahydrofuran.
7. The preparation method according to claim 4, characterized in that the curing is carried out at 40-80 ℃ for 1-2 h for molding, and the post-treatment is carried out at 120-150 ℃ for 1-2 h.
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| CN117866387A (en) * | 2024-03-13 | 2024-04-12 | 江苏基源新材料科技有限公司 | High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof |
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| CN115746204B (en) * | 2022-11-25 | 2023-09-12 | 安徽建筑大学 | Intrinsic flame-retardant polydicyclopentadiene elastomer material and preparation method thereof |
| CN117866387A (en) * | 2024-03-13 | 2024-04-12 | 江苏基源新材料科技有限公司 | High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof |
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