CN113004334B - Preparation method of organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material - Google Patents
Preparation method of organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 41
- 239000011733 molybdenum Substances 0.000 title claims abstract description 40
- 229920001153 Polydicyclopentadiene Polymers 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000001746 injection moulding Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 137
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 68
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 45
- 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 43
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 238000001704 evaporation Methods 0.000 claims abstract description 33
- 230000008020 evaporation Effects 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005086 pumping Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 230000008859 change Effects 0.000 claims description 17
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 16
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical group [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002955 isolation Methods 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 150000001925 cycloalkenes Chemical class 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 11
- 230000032798 delamination Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- -1 cyclic olefin Chemical class 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000012718 coordination polymerization Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010107 reaction injection moulding Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 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
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention provides a preparation method of an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material, which comprises the following steps: s1, introducing nitrogen into a reaction kettle, and then adding a polymerization inhibitor; s2, pumping dicyclopentadiene into a reaction kettle, uniformly mixing, and introducing nitrogen; s3, adding a catalyst into the reaction kettle, and dispersing uniformly; s4, heating the reaction kettle; s5, introducing nitrogen into the evaporation tank for replacement, adding molybdenum pentachloride into the evaporation tank, and heating to melt the molybdenum pentachloride; s6, heating nitrogen, controlling the pressure of the nitrogen to obtain high-temperature nitrogen, converting molybdenum pentachloride into molybdenum pentachloride steam, introducing the high-temperature nitrogen and the molybdenum pentachloride steam into a reaction kettle, and stirring; s7, stopping the stirring device, cooling to below 100 ℃, introducing nitrogen, standing, cooling to room temperature, and discharging. The organic molybdenum catalyst prepared by the method has good catalytic performance, and has good stability, impurity tolerance and miscibility and dispersibility with cycloolefins.
Description
Technical Field
The invention relates to an organic molybdenum catalyst, in particular to a preparation method and application of the organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material.
Background
The polydicyclopentadiene (PDCPD) composite material is a novel engineering material with excellent physical property and balanced physical property. The polydicyclopentadiene is a cyclic olefin material mainly comprising dicyclopentadiene (DCPD), and is formed by a Reaction Injection Molding (RIM) process by utilizing a Ziegler-Natta coordination polymerization mechanism and a catalytic system. Because dicyclopentadiene is a byproduct with larger yield in petrochemical ethylene engineering, the polymerization research on dicyclopentadiene has been widely concerned at home and abroad. Up to now, only two companies such as Japan and the United states have realized the industrial production of polydicyclopentadiene formulation materials all over the world. The industrialization process of China in the field is hindered, and the root cause is the lack of the function of the coordination polymerization catalyst.
Many kinds of compounds constituting the Ziegler-Natta catalyst are used, and most of them use a transition metal compound as a main catalyst and an organometallic compound as a cocatalyst. The accepted cocatalyst is an alkyl aluminum compound, and the main catalyst structure is the key point of coordination polymerization of the cycloolefin material. The main catalyst composing the Ziegler-Natta catalyst system is a transition metal compound, and compounds of tungsten, molybdenum and titanium are mainly selected according to the comprehensive factors of the toxicity, valence, resource amount, price and the like of the transition metal, and the chlorides of the three metals are generally used as original compounds to carry out catalytic function modification.
Related patents and articles at home and abroad report that polar compounds containing oxygen, nitrogen, phosphorus and sulfur and chlorides of tungsten, molybdenum and titanium are subjected to exchange reaction or complex reaction in a solvent, and the catalyst generally has the problems of low activity, high specific gravity, easiness in layering and accumulation, general stability and impurity tolerance, poor miscibility and dispersibility with cycloolefins and the like, and is difficult to industrialize.
Chinese invention with application number CN98122005.3 discloses a "cycloolefine ring-opening metathesis polymerization catalyst", which consists of a main catalyst and an auxiliary catalyst, wherein the ratio of the main catalyst to the auxiliary catalyst is as follows: the molar ratio of the main catalyst to the cocatalyst is 1: 1-4, the main catalyst is a complex compound and can be represented by the following formula:
TiCl4·nL
in the formula: n is 1-2; l is one of Tetrahydrofuran (THF), dioxane, pyridine, picoline, benzophenone or 8-hydroxyquinoline; the cocatalyst is one of RLi or RMgX, wherein: r is one of methyl, ethyl, isopropyl, n-butyl or n-hexyl; x is Cl, Br or I. The invention still has the problems of non-ideal catalytic effect, general stability and impurity tolerance, poor miscibility and dispersibility with cycloolefins and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite materials, wherein the prepared organic molybdenum catalyst has good catalytic performance, and has good stability, impurity tolerance and miscibility and dispersibility with cycloolefins.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material comprises the following steps:
s1, introducing nitrogen into a reaction kettle with a heating device and a stirring device to replace air for 3 times, and then adding a polymerization inhibitor into the reaction kettle;
s2, pumping dicyclopentadiene into a reaction kettle, stirring until the dicyclopentadiene is uniformly mixed, and introducing nitrogen into the reaction kettle to replace air for 3 times;
s3, adding a catalyst into the reaction kettle under the condition of air isolation, and stirring until the catalyst is uniformly dispersed;
s4, starting a heating device of the reaction kettle, and heating the reaction kettle to 120-170 ℃;
s5, introducing nitrogen into an evaporation tank with a heating device to replace air for 3 times, then adding molybdenum pentachloride into the evaporation tank, starting the heating device of the evaporation tank, and heating the temperature of the evaporation tank to 200-280 ℃ to melt the molybdenum pentachloride;
s6, heating nitrogen to 300-400 ℃, controlling the pressure to be 30-35 KPa to obtain high-temperature nitrogen, introducing the high-temperature nitrogen into an evaporation tank to change molten molybdenum pentachloride into molybdenum pentachloride steam, then introducing the high-temperature nitrogen and the molybdenum pentachloride steam into the bottom of a reaction kettle, starting a stirring device of the reaction kettle, and stirring for 10-16 hours at 120-170 ℃;
and S7, stopping a stirring device of the reaction kettle, cooling the temperature of the reaction kettle to be below 100 ℃, introducing nitrogen into the reaction kettle to replace residual waste gas, standing and cooling to room temperature, and discharging to obtain the organic molybdenum catalyst for injection molding of the polydicyclopentadiene composite material.
Further, in step S1 of the present invention, the polymerization inhibitor is a BHT polymerization inhibitor.
Further, in step S1 of the present invention, the volume of the reaction kettle is 3000L.
Further, in step S3 of the present invention, the catalyst is platinum carbon or palladium carbon.
Further, in step S5 of the present invention, the volume of the evaporation tank is 300L.
Further, in the step S6, the stirring speed is 100-150 r/min.
Furthermore, the ratio of the polymerization inhibitor, the dicyclopentadiene, the catalyst and the molybdenum pentachloride is 200kg, 2400L, (2-10) kg and 300 kg.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention fully aims at the molecular structure, physical property characteristics and the like of a cycloolefin compound mainly comprising dicyclopentadiene, selects molybdenum pentachloride with mild catalytic activity as an original compound for functional modification, and prepares the organic molybdenum catalyst-polycyclopentadienyl molybdenum chloride.
2) The invention adopts dicyclopentadiene with small polarity and light specific gravity to carry out functional modification on molybdenum pentachloride and the like, thereby not only reducing the specific gravity and polarity of the catalyst and reducing layering accumulation, but also improving the miscibility and dispersion uniformity between the catalyst and the main material dicyclopentadiene and laying the foundation of industrial application.
3) Molybdenum pentachloride is a difficult-to-dissolve substance, even if the molybdenum pentachloride can be dissolved in some polar solvents, the generated dissolved substance mostly exists in the form of multi-molecular groups, which is very unfavorable for modification reaction, and the modification effect is not ideal, so the invention utilizes the characteristic of high-temperature sublimation of the molybdenum pentachloride, uses high-temperature nitrogen to guide the high-temperature steam of the molybdenum pentachloride to enter dicyclopentadiene liquid containing a catalyst and a polymerization inhibitor, and continuously stirs and disperses for reaction to generate the polycyclopentadienyl molybdenum chloride.
4) The catalyst for the reaction of the molybdenum pentachloride and the dicyclopentadiene is a platinum carbon or palladium carbon catalyst, and the dicyclopentadiene can react with the molybdenum pentachloride to generate the organic molybdenum catalyst of light-weight molecules under the action of the platinum carbon or the palladium carbon; the polymerization inhibitor used in the invention is a BHT polymerization inhibitor which can effectively prevent dicyclopentadiene from polymerizing at high temperature, and both the platinum carbon or palladium carbon catalyst and the BHT polymerization inhibitor can improve the yield of the organic molybdenum catalyst.
5) The catalyst used in the invention, namely platinum carbon and palladium carbon, is ultrafine powder, can automatically sink to the bottom of the reaction kettle after the reaction is finished, and can be sealed by nitrogen for multiple use. Even if trace ultrafine powder is not settled and enters the B component formula, the performance of the combined formula is not influenced.
6) The solvent, the modified reactant and the polymerization object used in the invention are dicyclopentadiene, so the solvent is not required to be removed, the production process is simple, the cost is low, and the BHT polymerization inhibitor can be continuously reserved as the polymerization inhibitor of the component B, becomes a part of the component B catalyst after the production is finished, and directly enters the material preparation procedure.
7) The molecular general formula of the organic molybdenum catalyst modified by molybdenum pentachloride, namely the polycyclopentadienyl molybdenum chloride, prepared by the invention is as follows:
Mo(C5H5)m(C10H11)n(C15H17)kCl5-x
wherein: x is not more than 4; m, n, k is 0-4
Part of polymerization inhibitor will also take part in the modification reaction of molybdenum pentachloride in a specific temperature range, and the generated substance also has similar catalytic activity, and the molecular general formula is:
Mo(ArO)(C5H5)m(C10H11)n(C15H17)kCl4-x
wherein: x is less than or equal to 3; m, n and k are 0-3; ArO is a sterically hindered phenol.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, and the exemplary embodiments and descriptions thereof herein are provided to explain the present invention but not to limit the present invention.
Example 1
Preparing an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material according to the following steps:
s1, introducing nitrogen into a reaction kettle with a volume of 3000L and a heating device and a stirring device to replace air for 3 times, and then adding 200kg of BHT polymerization inhibitor into the reaction kettle;
s2, pumping 2400L dicyclopentadiene into a reaction kettle, stirring until the dicyclopentadiene is uniformly mixed, and introducing nitrogen into the reaction kettle to replace air for 3 times;
s3, adding 5kg of palladium-carbon into the reaction kettle under the condition of air isolation, and stirring until the palladium-carbon is uniformly dispersed;
s4, starting a heating device of the reaction kettle, and heating the temperature of the reaction kettle to 150 ℃;
s5, introducing nitrogen into an evaporation tank with the volume of 300L and a heating device to replace air for 3 times, then adding 300kg of molybdenum pentachloride into the evaporation tank, starting the heating device of the evaporation tank, and heating the temperature of the evaporation tank to 240 ℃ to melt the molybdenum pentachloride;
s6, heating nitrogen to 360 ℃, controlling the pressure to be 32KPa to obtain high-temperature nitrogen, introducing the high-temperature nitrogen into an evaporation tank to change molten molybdenum pentachloride into molybdenum pentachloride vapor, then introducing the high-temperature nitrogen and the molybdenum pentachloride vapor into the bottom of a reaction kettle, starting a stirring device of the reaction kettle, and stirring at the rotating speed of 125r/min and the temperature of 150 ℃ for 12 hours;
s7, stopping a stirring device of the reaction kettle, cooling the temperature of the reaction kettle to be below 100 ℃, introducing nitrogen into the reaction kettle to replace residual waste gas, standing and cooling to room temperature, and discharging to obtain the organic molybdenum catalyst for injection molding of the polydicyclopentadiene composite material; the bottom of the reaction kettle is left about 200L to be paste containing palladium carbon, and the paste is used for the next time after being sealed by nitrogen.
Example 2
Preparing an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material according to the following steps:
s1, introducing nitrogen into a reaction kettle with a volume of 3000L and a heating device and a stirring device to replace air for 3 times, and then adding 200kg of BHT polymerization inhibitor into the reaction kettle;
s2, pumping 2400L dicyclopentadiene into a reaction kettle, stirring until the dicyclopentadiene is uniformly mixed, and introducing nitrogen into the reaction kettle to replace air for 3 times;
s3, adding 10kg of palladium-carbon into the reaction kettle under the condition of air isolation, and stirring until the palladium-carbon is uniformly dispersed;
s4, starting a heating device of the reaction kettle, and heating the temperature of the reaction kettle to 170 ℃;
s5, introducing nitrogen into an evaporation tank with the volume of 300L and a heating device to replace air for 3 times, then adding 300kg of molybdenum pentachloride into the evaporation tank, starting the heating device of the evaporation tank, and heating the temperature of the evaporation tank to 280 ℃ to melt the molybdenum pentachloride;
s6, heating nitrogen to 400 ℃, controlling the pressure to be 35KPa to obtain high-temperature nitrogen, introducing the high-temperature nitrogen into an evaporation tank to change molten molybdenum pentachloride into molybdenum pentachloride vapor, then introducing the high-temperature nitrogen and the molybdenum pentachloride vapor into the bottom of a reaction kettle, starting a stirring device of the reaction kettle, and stirring at the rotating speed of 150r/min and the temperature of 170 ℃ for 10 hours;
s7, stopping a stirring device of the reaction kettle, cooling the temperature of the reaction kettle to be below 100 ℃, introducing nitrogen into the reaction kettle to replace residual waste gas, standing and cooling to room temperature, and discharging to obtain the organic molybdenum catalyst for injection molding of the polydicyclopentadiene composite material; the bottom of the reaction kettle is left about 200L to be paste containing palladium carbon, and the paste is used for the next time after being sealed by nitrogen.
Example 3
Preparing an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material according to the following steps:
s1, introducing nitrogen into a reaction kettle with a volume of 3000L and a heating device and a stirring device to replace air for 3 times, and then adding 200kg of BHT polymerization inhibitor into the reaction kettle;
s2, pumping 2400L dicyclopentadiene into a reaction kettle, stirring until the dicyclopentadiene is uniformly mixed, and introducing nitrogen into the reaction kettle to replace air for 3 times;
s3, adding 6kg of palladium-carbon into the reaction kettle under the condition of air isolation, and stirring until the palladium-carbon is uniformly dispersed;
s4, starting a heating device of the reaction kettle, and heating the temperature of the reaction kettle to 160 ℃;
s5, introducing nitrogen into an evaporation tank with the volume of 300L and a heating device to replace air for 3 times, then adding 300kg of molybdenum pentachloride into the evaporation tank, starting the heating device of the evaporation tank, and heating the temperature of the evaporation tank to 250 ℃ to melt the molybdenum pentachloride;
s6, heating nitrogen to 320 ℃, controlling the pressure to be 34KPa to obtain high-temperature nitrogen, introducing the high-temperature nitrogen into an evaporation tank to change molten molybdenum pentachloride into molybdenum pentachloride vapor, then introducing the high-temperature nitrogen and the molybdenum pentachloride vapor into the bottom of a reaction kettle, starting a stirring device of the reaction kettle, and stirring at the rotation speed of 110r/min and the temperature of 160 ℃ for 11 hours;
s7, stopping a stirring device of the reaction kettle, cooling the temperature of the reaction kettle to be below 100 ℃, introducing nitrogen into the reaction kettle to replace residual waste gas, standing and cooling to room temperature, and discharging to obtain the organic molybdenum catalyst for injection molding of the polydicyclopentadiene composite material; the bottom of the reaction kettle is left about 200L to be paste containing palladium carbon, and the paste is used for the next time after being sealed by nitrogen.
Example 4
Preparing an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material according to the following steps:
s1, introducing nitrogen into a reaction kettle with a volume of 3000L and a heating device and a stirring device to replace air for 3 times, and then adding 200kg of BHT polymerization inhibitor into the reaction kettle;
s2, pumping 2400L dicyclopentadiene into a reaction kettle, stirring until the dicyclopentadiene is uniformly mixed, and introducing nitrogen into the reaction kettle to replace air for 3 times;
s3, adding 2kg of platinum carbon into the reaction kettle under the condition of air isolation, and stirring until the platinum carbon is uniformly dispersed;
s4, starting a heating device of the reaction kettle, and heating the temperature of the reaction kettle to 120 ℃;
s5, introducing nitrogen into an evaporation tank with the volume of 300L and a heating device to replace air for 3 times, then adding 300kg of molybdenum pentachloride into the evaporation tank, starting the heating device of the evaporation tank, and heating the temperature of the evaporation tank to 200 ℃ to melt the molybdenum pentachloride;
s6, heating nitrogen to 300 ℃, controlling the pressure to be 30KPa to obtain high-temperature nitrogen, introducing the high-temperature nitrogen into an evaporation tank to change molten molybdenum pentachloride into molybdenum pentachloride vapor, then introducing the high-temperature nitrogen and the molybdenum pentachloride vapor into the bottom of a reaction kettle, starting a stirring device of the reaction kettle, and stirring at the rotation speed of 100r/min and the temperature of 120 ℃ for 16 hours;
s7, stopping a stirring device of the reaction kettle, cooling the temperature of the reaction kettle to be below 100 ℃, introducing nitrogen into the reaction kettle to replace residual waste gas, standing and cooling to room temperature, and discharging to obtain the organic molybdenum catalyst for injection molding of the polydicyclopentadiene composite material; about 200L of paste containing platinum and carbon is left in the reaction kettle, and the paste is sealed by nitrogen for next use.
Reference example 1
Unlike example 1, the following points are present: step S2 is changed to: pumping 1000L of dicyclopentadiene and 1000L of diphenyl ether into a reaction kettle, stirring until the dicyclopentadiene and the diphenyl ether are uniformly mixed, and introducing nitrogen into the reaction kettle to replace air for 3 times; remove step S5, step S6 changes to: gradually adding 300kg of molybdenum pentachloride into a reaction kettle, and stirring at the rotating speed of 125r/min and the temperature of 150 ℃ for 24 hours; namely: diphenyl ether is used as a solvent, and a step of leading high-temperature steam of molybdenum pentachloride to react by using high-temperature nitrogen is lacked.
Reference example 2
Unlike example 1, the following points are present: step S3 is absent. Namely: no palladium carbon is added, the molybdenum pentachloride and the dicyclopentadiene do not react, the dicyclopentadiene plays the role of a solvent, and the finally prepared catalyst is a reaction product of the molybdenum pentachloride and a BHT polymerization inhibitor.
Comparative example: example 1 of the chinese invention having application number CN 98122005.3.
The first experimental example:
subject: the organomolybdenum catalyst obtained in example 1.
The experimental procedure was as follows:
1) preparing a 25-cubic mixing tank, namely an A material tank, pumping 20 tons of DCPD three-stage raw materials (DCPD + tackifier), adding a modified alkylaluminum compound into the A material tank through a metering pump, wherein the adding amount of the modified alkylaluminum compound is 1.5 percent of the weight of the DCPD three-stage raw materials, and uniformly mixing the modified alkylaluminum compound and the DCPD three-stage raw materials through an internal circulating pump to obtain the component A of the injection formula.
2) Preparing a 25-cubic mixing tank, namely a B tank, pumping 20 tons of DCPD three-level raw materials (DCPD + tackifier), adding the organic molybdenum catalyst into the B tank in batches by a metering pump, wherein the initial addition amount of the organic molybdenum catalyst is 400kg, and uniformly mixing by an internal circulating pump to obtain a component B of the injection formula. The sample is taken on the day and is subjected to an equal amount of mixed curing test with the component A, and the sample is reserved, stored in a nitrogen gas seal mode for 90 days and then subjected to a curing test with the component A.
3) And adding the organic molybdenum catalyst into the material tank B, adding 50kg of the organic molybdenum catalyst in batches each time, and uniformly mixing. The test was done the same day and kept under nitrogen for 90 days. The curing performance of the component B and the component A when the components are mixed and injected in equal amount is determined by the content change of the organic molybdenum catalyst.
The results of the experiment are shown in table 1:
TABLE 1
As can be seen from table 1: when the molybdenum atom content (weight) is about 0.9 per mill, the curing condition of the example 1 is the best, the tensile strength and the exothermic peak are the highest, and the comprehensive cost is only about 1/8 of the ruthenium catalyst system.
Compared with the test of the day, the test after 90 days of storage shows that the performance of the organic molybdenum catalyst in the embodiment 1 is basically not changed, the exothermic peak and the tensile strength are even slightly improved, and the organic molybdenum catalyst prepared by the method has excellent stability and high impurity tolerance.
The initial setting time and the curing time of the organic molybdenum catalyst prepared by the invention are very suitable for the RIM process, have the application characteristics of long mold filling time and long curing time, and are particularly suitable for producing large-scale products.
Experiment example two:
subject: examples 1-4, comparative examples 1-2, and comparative examples.
The experimental procedure was the same as the daily test procedure in experimental example one, and the addition amount of the experimental sample was 500 kg.
The results of the experiment are shown in table 2:
TABLE 2
As can be seen from Table 2, the exothermic peak and the tensile strength of the organomolybdenum catalysts prepared in examples 1-4 of the present invention are significantly higher than those of the comparative examples, indicating that the catalytic performance of the organomolybdenum catalysts prepared in the present invention is better. The difference between the partial steps of the reference examples 1-2 and the example 1 shows that the exothermic peak and the tensile strength of the reference examples 1 and 2 are obviously reduced compared with the example 1, which shows that the catalytic performance of the organic molybdenum catalyst can be improved by using the steps of using high-temperature nitrogen to guide the high-temperature steam of the molybdenum pentachloride to react and using dicyclopentadiene to modify the molybdenum pentachloride.
Experiment example three:
subject: examples 1-4, comparative examples 1-2, and comparative examples.
The experimental procedure was as follows:
respectively adding 500kg of experimental objects into 20 tons of DCPD three-level raw materials (DCPD + tackifier), uniformly mixing to obtain a component B, standing and storing the component B for 90 days at room temperature, and observing that no obvious color difference change and no layering phenomenon occur.
The results of the experiment are shown in table 3:
| example 1 | No obvious color difference change and no delamination phenomenon |
| Example 2 | No obvious color difference change and no delamination phenomenon |
| Example 3 | No obvious color difference change and no delamination phenomenon |
| Example 4 | No obvious color difference change and no delamination phenomenon |
| Reference example 1 | Obvious color difference change and delamination phenomenon appear |
| Reference example 2 | Obvious color difference change and delamination phenomenon appear |
| Comparative example | Obvious color difference change and delamination phenomenon appear |
TABLE 3
As can be seen from Table 3, no obvious color difference change and no delamination occur in any of the examples 1 to 4 of the invention, which indicates that the organic molybdenum catalyst prepared by the invention has good miscibility and dispersion uniformity with the main material dicyclopentadiene. The partial steps of reference examples 1-2 are different from those of example 1, and both reference examples 1 and 2 show obvious layering and color difference changes, which show that the step of using high-temperature nitrogen to guide the high-temperature steam of molybdenum pentachloride to react and using dicyclopentadiene to modify the molybdenum pentachloride can improve the miscibility and the dispersion uniformity between the organic molybdenum catalyst and the main material dicyclopentadiene.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (5)
1. A preparation method of an organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material is characterized by comprising the following steps: the method comprises the following steps:
s1, introducing nitrogen into a reaction kettle with a heating device and a stirring device to replace air for 3 times, and then adding a polymerization inhibitor into the reaction kettle, wherein the polymerization inhibitor is a BHT polymerization inhibitor;
s2, pumping dicyclopentadiene into a reaction kettle, stirring until the dicyclopentadiene is uniformly mixed, and introducing nitrogen into the reaction kettle to replace air for 3 times;
s3, adding a catalyst into the reaction kettle under the condition of air isolation, and stirring until the catalyst is uniformly dispersed, wherein the catalyst is platinum carbon or palladium carbon;
s4, starting a heating device of the reaction kettle, and heating the reaction kettle to 120-170 ℃;
s5, introducing nitrogen into an evaporation tank with a heating device to replace air for 3 times, then adding molybdenum pentachloride into the evaporation tank, starting the heating device of the evaporation tank, and heating the temperature of the evaporation tank to 200-280 ℃ to melt the molybdenum pentachloride;
s6, heating nitrogen to 300-400 ℃, controlling the pressure to be 30-35 KPa to obtain high-temperature nitrogen, introducing the high-temperature nitrogen into an evaporation tank to change molten molybdenum pentachloride into molybdenum pentachloride steam, then introducing the high-temperature nitrogen and the molybdenum pentachloride steam into the bottom of a reaction kettle, starting a stirring device of the reaction kettle, and stirring for 10-16 hours at 120-170 ℃;
and S7, stopping a stirring device of the reaction kettle, cooling the temperature of the reaction kettle to be below 100 ℃, introducing nitrogen into the reaction kettle to replace residual waste gas, standing and cooling to room temperature, and discharging to obtain the organic molybdenum catalyst for injection molding of the polydicyclopentadiene composite material.
2. The method for preparing the organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material according to claim 1, wherein the method comprises the following steps: in the step S1, the volume of the reaction kettle is 3000L.
3. The method for preparing the organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material according to claim 1, wherein the method comprises the following steps: in step S5, the volume of the evaporator is 300L.
4. The method for preparing the organic molybdenum catalyst for injection molding of polydicyclopentadiene composite material according to claim 1, wherein the method comprises the following steps: in the step S6, the stirring speed is 100-150 r/min.
5. The method for preparing the organomolybdenum catalyst for injection molding of polydicyclopentadiene composite material, according to any one of claims 1 to 4, wherein: the proportion of the polymerization inhibitor, the dicyclopentadiene, the catalyst and the molybdenum pentachloride is 200kg, 2400L, (2-10) kg and 300 kg.
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