CN113185673B - Carbon-based catalyst, preparation method thereof and catalyst system for dicyclopentadiene polymerization - Google Patents
Carbon-based catalyst, preparation method thereof and catalyst system for dicyclopentadiene polymerization Download PDFInfo
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- CN113185673B CN113185673B CN202110549849.4A CN202110549849A CN113185673B CN 113185673 B CN113185673 B CN 113185673B CN 202110549849 A CN202110549849 A CN 202110549849A CN 113185673 B CN113185673 B CN 113185673B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 166
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 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 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 title abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 68
- 239000003446 ligand Substances 0.000 claims description 58
- 239000000178 monomer Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 31
- -1 aluminum compound Chemical class 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 26
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 18
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 17
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 13
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 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
- 238000005470 impregnation Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 2
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 150000008442 polyphenolic compounds Chemical class 0.000 claims 1
- 235000013824 polyphenols Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 8
- 230000001976 improved effect Effects 0.000 abstract description 7
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- 230000009920 chelation Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 85
- 239000000203 mixture Substances 0.000 description 46
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 31
- 229910052721 tungsten Inorganic materials 0.000 description 31
- 239000010937 tungsten Substances 0.000 description 31
- 238000002474 experimental method Methods 0.000 description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 22
- 229910052750 molybdenum Inorganic materials 0.000 description 22
- 239000011733 molybdenum Substances 0.000 description 22
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 19
- 229920006132 styrene block copolymer Polymers 0.000 description 18
- 239000000725 suspension Substances 0.000 description 18
- 239000003085 diluting agent Substances 0.000 description 17
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 16
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 13
- 230000002522 swelling effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 10
- 239000002808 molecular sieve Substances 0.000 description 10
- 229910052707 ruthenium Inorganic materials 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
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- 238000010790 dilution Methods 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
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- 239000012467 final product Substances 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
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- 238000007865 diluting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008093 supporting effect Effects 0.000 description 3
- WHICWXAKVSVOAT-UHFFFAOYSA-N 2,6-dipentylbenzene-1,4-diol Chemical compound CCCCCC1=CC(O)=CC(CCCCC)=C1O WHICWXAKVSVOAT-UHFFFAOYSA-N 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
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- WDFZWSZNOFELJY-OLQVQODUSA-N (1R,6S)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=C[C@H]2O[C@H]21 WDFZWSZNOFELJY-OLQVQODUSA-N 0.000 description 1
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical group O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- QFLMVSNWSBDYNQ-UHFFFAOYSA-N CCCCCC1=CC=C(C(C)(C)C)C(CCCCC)=C1O Chemical compound CCCCCC1=CC=C(C(C)(C)C)C(CCCCC)=C1O QFLMVSNWSBDYNQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
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- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- 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]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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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)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of dicyclopentadiene polymerization catalysts, and provides a carbon-based catalyst, a preparation method thereof and a catalyst system for dicyclopentadiene polymerization. The invention adopts acid to carry out activation pretreatment on the carbon carrier, so that a large amount of phenolic hydroxyl groups are formed on the surface of the carbon carrier, and then the active component is loaded on the carbon carrier through chelation of transition metal ions and the phenolic hydroxyl groups, thereby improving the activity and stability of the catalyst. The carbon-based catalyst provided by the invention has higher activity and stability and is stable to air, and the mechanical property of a product can be improved by taking the carbon-based catalyst as a main catalyst for dicyclopentadiene polymerization, so that the polymerization reaction has a proper operation window, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the technical field of dicyclopentadiene polymerization catalysts, in particular to a carbon-based catalyst, a preparation method thereof and a catalyst system for dicyclopentadiene polymerization.
Background
The dicyclopentadiene is a byproduct of ethylene preparation by petroleum cracking and coal coking, has a structure shown in formula I, contains two unsaturated double bonds, can generate ring-opening metathesis polymerization reaction on two rings containing the unsaturated double bonds, and can easily generate self-polymerization reaction on a dicyclopentadiene monomer. The dicyclopentadiene has wide application prospects in the fields of fine chemistry and polymer chemistry, has great scientific research values and economic benefits, and the polymer is widely applied to the industries such as agriculture, automobiles, chemical engineering and the like by virtue of excellent performance.
The dicyclopentadiene reaction injection molding process was a technology developed by Hercules and Goodrich in the United states in the 80 th century and allows the rapid preparation of complex shaped articles from low viscosity monomers. At present, the technology is widely applied to the preparation of automobile covering parts, and the technology must replace glass fiber reinforced plastic products to become a main body of light weight materials of vehicles.
The ring-opening metathesis polymerization is the key for preparing polydicyclopentadiene and is also the key link of the dicyclopentadiene reaction injection molding process. The catalyst is the core of ring-opening metathesis polymerization, and the structure and performance of the product can be influenced by the factors such as activity, stability and the like of the catalyst, so that the industrial application value of the catalyst is determined. At present, dicyclopentadiene ring-opening metathesis polymerization catalysts are mainly classified into two types, two-component catalysts and single-component catalysts. The single-component catalyst is metal carbene and metal alkyl alkene, and the catalyst has high activity and good environmental stability, but has high price and poor manufacturability, and is not widely applied in industry.
The bi-component catalyst consists of a main catalyst and an auxiliary catalyst, wherein the main catalyst is a complex of transition metals such as tungsten, molybdenum, ruthenium and the like, and the auxiliary catalyst is a metal organic matter such as aluminum, magnesium, tin, zinc and the like. The main catalyst plays a determining role in the formation of the metal carbene, and the cocatalyst can promote the formation of the metal carbene and improve the catalytic activity. WCl 6 And MoCl 5 The complex with the substituted hindered phenol is a main catalyst applied in the industry at present, and the benzene oxide or the phenol salt of tungsten can well catalyze the ring opening metathesis polymerization of dicyclopentadiene under the action of a metal organic cocatalyst. The electronic effect and steric hindrance of the substituted hindered phenolic ligands are key factors in determining the activity and stability of the catalyst. WCl 6 And MoCl 5 The stability of the catalyst can be improved after the catalyst is coordinated with substituted sterically hindered phenol, the electron donating performance of the phenol ligand increases the electron cloud density of metal ions, and the stability of the metal carbene complex is improved, so that the catalytic efficiency of the catalyst is improved.
The steric hindrance effect of the ligand also has great influence on the activity of the catalyst, and researches show that the larger the steric hindrance around the metal central ion, the higher the catalytic activity is. Loading the transition metal central ion on the solid surface undoubtedly increases the steric hindrance around the metal ion. Currently, researchers have catalyzed dicyclopentadiene polymerization with polystyrene and molecular sieve supported tungsten catalysts. Researches show that the activity of the polystyrene supported catalyst is higher than that of the unsupported catalyst, the stability is better, and the catalyst supported by the molecular sieve also shows higher activity. However, the polystyrene supported tungsten catalyst belongs to physical embedding, the specific surface area is small, the utilization rate of the catalyst is low, the molecular sieve has large specific surface area, but the coordination group on the surface of the molecular sieve is not as good as the phenoxy group in the aspect of power supply, and the dispersion of the molecular sieve in dicyclopentadiene has some problems, which can affect the properties of polydicyclopentadiene.
Disclosure of Invention
In view of the above, the present invention aims to provide a carbon-based catalyst, a preparation method thereof and a catalyst system for dicyclopentadiene polymerization. The carbon-based catalyst is used as a main catalyst for catalyzing the polymerization of dicyclopentadiene, and an obtained catalyst system has high activity, good stability, high utilization rate of the catalyst and good dispersibility in the dicyclopentadiene.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a carbon-based catalyst comprises the following steps:
(1) activating and pretreating the carbon carrier by using acid to obtain an activated carbon carrier;
(2) mixing the activated carbon carrier and the active component mixed solution for impregnation to obtain a carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex.
Preferably, the preparation method of the active component mixed solution comprises the following steps:
mixing a first ligand, a transition metal chloride and a solvent for reaction to obtain a reaction solution;
sequentially adding a second ligand and a third ligand into the reaction solution to obtain an active component mixed solution;
the transition metal chloride comprises WCl 6 、MoCl 5 And RuCl 4 One or more of the above; the first ligand comprises tert-butyl alcohol and/or di-tert-butyl-p-cresol; the second ligand comprises one or more of nonyl phenol, 4-dimethyl-6-tert-butyl phenol, 2, 6-diamyl hydroquinone, 2, 6-diamyl tert-butyl phenol, 4' -ethylidene bis (6-tert-butyl-o-cresol), polyhydric phenol ligand, bisphenol ligand, tert-butyl catechol, hydrogen phenol, resorcinol and 1,2, 3-benzenetriol; the third ligand comprises one or more of 2, 4-pentanedione and acetylacetone ester ligands;
the molar ratio of the first ligand to the transition metal chloride is 0.1-1: 1; the molar ratio of the second ligand to the transition metal chloride is 1-5: 1; the molar ratio of the third ligand to the transition metal chloride is 1-5: 1.
Preferably, in the reaction solution, the molar ratio of the transition metal chloride to the transition metal oxychloride is 0.5-5: 1.
Preferably, after adding the second ligand, the method comprises the step of adding the obtained feed liquid N 2 Bubbling for 1-2 h; after the third ligand is added, the method also comprises the step of adding the obtained feed liquid N 2 Bubbling for 1-2 h.
Preferably, the acid comprises one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid; the weight ratio of the carbon carrier to the acid is 1: 2-3, the temperature of the activation pretreatment is 30-80 ℃, and the treatment time is 3-8 hours.
Preferably, the dosage ratio of the activated carbon carrier to the active component mixed solution is 1g: 20-200 mL, and the impregnation time is 20-30 h.
The invention also provides a carbon-based catalyst prepared by the preparation method in the scheme, which comprises an activated carbon carrier and an active component loaded on the activated carbon carrier, wherein the active component comprises a transition metal oxychlorid complex.
The invention also provides a catalyst system for dicyclopentadiene polymerization, which comprises a main catalyst and a cocatalyst which are independently and separately packaged, wherein the main catalyst is the carbon-based catalyst in the claim 7, and the cocatalyst is an organic aluminum compound.
The invention also provides a method for preparing dicyclopentadiene polymeric material by using the catalyst system in the scheme, which comprises the following steps:
(1) respectively dispersing a main catalyst and a cocatalyst in materials to be polymerized with the same volume under a protective atmosphere to obtain a component A and a component B;
the material to be polymerized is a dicyclopentadiene monomer, or the material to be polymerized comprises a cyclopentadiene monomer and a composite component;
(2) and mixing the component A and the component B under a protective atmosphere, and carrying out heat treatment to obtain the dicyclopentadiene polymeric material.
Preferably, the molar ratio of the total molar quantity of the dicyclopentadiene in the component A and the component B to the main catalyst and the cocatalyst is (1200-1500): 1 (10-30); the molar weight of the main catalyst is calculated by the molar weight of a transition metal element, and the molar weight of the auxiliary catalyst is calculated by the mass of an Al element.
The invention provides a preparation method of a carbon-based catalyst, which comprises the steps of carrying out activation pretreatment on a carbon carrier by using acid, mixing the obtained activated carrier and an active component mixed solution, and impregnating to obtain the carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex. According to the invention, the carbon carrier is subjected to activation pretreatment by using acid, so that a large amount of phenolic hydroxyl groups are formed on the surface of the carbon carrier, and the phenolic hydroxyl groups can be chelated and coordinated with transition metal ions to form a stable complex, thereby being beneficial to improving the stability and catalytic activity of the catalyst; in addition, carbonyl and pyrone groups on the surface of the carbon carrier can play a role of Lewis base and control the electron cloud density around the active center of the transition metal, so that the activity of the catalyst is regulated, a polymerization reaction has a proper operation window, and the industrial production is facilitated.
Compared with a polystyrene supported tungsten catalyst, the transition metal ions in the carbon-based catalyst provided by the invention form coordination bonds with phenolic hydroxyl groups on the surface of a carbon carrier, the obtained complex has a stable structure, the polystyrene supported tungsten catalyst is only physically embedded and does not have a chemical bond effect, and the structure of the catalyst is unstable; furthermore, the carbon carrier adopted by the invention has higher specific surface area, can load more active components, and has high utilization rate of the catalyst, smaller specific surface area of polystyrene and lower utilization rate of the catalyst.
Compared with a molecular sieve supported catalyst, although the molecular sieve has a larger specific surface area, coordination groups on the surface of the molecular sieve have poor electricity supply performance and poor regulation and control effect on the electron density of transition metal ions, and the activated carbon carrier can play a role in regulating and controlling the electron cloud density and increase an operation window; further, only mesopores and no pores with other pore diameters exist in the molecular sieve, which can affectThe catalyst promoter and the monomer are influenced to transmit to central ions, the utilization rate of the central ions is reduced, and the carbon carrier adopted by the invention has larger pore size distribution (0.8-1.1 cm) 3 /g) and has some through holes to facilitate the transport of cocatalyst and monomer; in addition, the dispersibility of the carbon carrier in the dicyclopentadiene monomer is much better than that of the inorganic molecular sieve, and the property of the polydicyclopentadiene product cannot be influenced.
The invention also provides a catalyst system for dicyclopentadiene polymerization, which comprises a main catalyst and a cocatalyst which are independently and separately packaged, wherein the main catalyst is the carbon-based catalyst in the scheme. The carbon-based catalyst provided by the invention has higher activity and stability, is stable to air, can be used as a main catalyst for polymerization of dicyclopentadiene, can enable polymerization reaction to have a proper operation window, is convenient for production operation, and is convenient for industrial production.
The invention also provides a method for preparing the dicyclopentadiene polymeric material, which comprises the steps of respectively dispersing the main catalyst and the cocatalyst into a material to be polymerized containing dicyclopentadiene monomers with the same volume to obtain a component A and a component B, and then mixing the component A and the component B for polymerization reaction. The method provided by the invention is convenient to operate, and the obtained product has high mechanical property.
Detailed Description
The invention provides a preparation method of a carbon-based catalyst, which comprises the following steps:
(1) activating and pretreating the carbon carrier by using acid to obtain an activated carbon carrier;
(2) mixing the activated carbon carrier and the active component mixed solution for impregnation to obtain a carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex.
The invention uses acid to carry out activation pretreatment on the carbon carrier to obtain the activated carbon carrier. The invention uses acid to carry out activation pretreatment on the carbon carrier to obtain the activated carbon carrier. In the invention, the carbon carrier is preferably one or more of activated carbon, carbon black and mesoporous carbon; the specific surface area of the carbon carrier is preferably 500-3000 m 2 Per g, morePreferably 1500 to 2000m 2 The particle size is preferably 1 to 20 μm, more preferably 1 to 5 μm.
In the invention, the acid preferably comprises one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid; the concentration of the nitric acid is preferably 0.5-7 mol/L, more preferably 1-6 mol/L, the concentration of the acetic acid is preferably 0.1-5 mol/L, more preferably 1-4 mol/L, the concentration of the hydrochloric acid is preferably 0.1-5 mol/L, more preferably 1-4 mol/L, and the concentration of the sulfuric acid is preferably 0.1-3 mol/L, more preferably 1-2 mol/L; the weight ratio of the carbon carrier to the acid is preferably 1: 2-3, more preferably 1:2.5, the temperature of the activation pretreatment is preferably 30-80 ℃, more preferably 40-70 ℃, and the treatment time of the activation pretreatment is preferably 3-8 hours, more preferably 4-7 hours. In the invention, the activation pretreatment is to soak the carbon carrier in acid, take out the carbon carrier after the soaking is finished, wash the carbon carrier for 3 times by distilled water, and then dry the carbon carrier to constant weight at 120 ℃. The carbon carrier has high specific surface area and proper pore diameter, a large number of phenolic hydroxyl groups are formed on the surface after activation pretreatment, the phenolic hydroxyl groups can be chelated and coordinated with transition metal ions to form stable complexes, and the formed complexes are stable and have higher steric hindrance than micromolecular phenolic ligands.
After the activated carbon carrier is obtained, the activated carbon carrier and the active component mixed solution are mixed and impregnated to obtain the carbon-based catalyst. In the present invention, the active component in the active component mixture solution includes a transition metal oxychloride complex.
In the present invention, the preparation method of the active ingredient mixed solution preferably includes the steps of:
mixing a first ligand, a transition metal chloride and a solvent for reaction to obtain a reaction solution;
and sequentially adding a second ligand and a third ligand into the reaction solution to obtain an active component mixed solution.
The invention is toThe first ligand, the transition metal chloride and the solvent are mixed for reaction to obtain reaction liquid. In the present invention, the transition metal chloride preferably comprises WCl 6 、MoCl 5 And RuCl 4 One or more of the above; the first ligand comprises tert-butyl alcohol and/or di-tert-butyl-p-cresol; the molar ratio of the first ligand to the transition metal chloride is 0.1-1: 1, and more preferably 0.25: 1; the solvent is preferably toluene and/or xylene; the toluene and xylene are preferably used after drying; the ratio of the amount of the transition metal chloride to the amount of the solvent is preferably 2 g: 7 mL. In the present invention, the reaction is preferably carried out in a protective atmosphere, preferably N 2 (ii) a The reaction time is preferably 5-25 h, and the reaction temperature is preferably room temperature; taking tungsten chloride and tert-butyl alcohol as an example, the reaction process is as follows:
WCl 6 +ROH→ROWCl 5 →WOCl 4 +RCl
in the present invention, the molar ratio of the transition metal chloride to the transition metal oxychloride in the reaction solution is preferably 0.5 to 5:1, and more preferably 3: 1.
After the reaction solution is obtained, the second ligand and the third ligand are sequentially added into the reaction solution to obtain the active component mixed solution. In the present invention, the second ligand preferably includes one or more of nonylphenol, 4-dimethyl-6-tert-butylphenol, 2, 6-dipentylhydroquinone, 2, 6-di-tert-butylphenol, 4' -monoethylene bis (6-tert-butyl-o-cresol), polyhydric phenol ligands, bisphenol ligands, tert-butylcatechol, hydroquinone, resorcinol and 1,2, 3-benzenetrisol; the molar ratio of the second ligand to the transition metal chloride is preferably 1-5: 1, and more preferably 2-3: 1; in the invention, a second ligand is preferably dissolved in a solvent to obtain a second ligand solution, and then the second ligand solution is added into the reaction solution, wherein the solvent is consistent with the solvent used in the scheme in kind, and is not described herein again; the concentration of the second ligand solution is preferably 0.3-0.4 g/mL; according to the invention, it is preferred that a solution of the second ligand is added to the reaction solution, and then N 2 Bubbling for 1-2 h to remove HCl generated in the coordination process. In the present invention, the nonanol is used asThe ligand can coordinate with transition metal chloride and transition metal oxychloride in the reaction solution, and the nonyl phenol can also play a role in resisting oxidation and preventing the catalyst from being inactivated.
In the invention, the third ligand preferably comprises one or more of 2, 4-pentanedione and acetylacetone ester ligands, and the molar ratio of the third ligand to the transition metal chloride is preferably 1-5: 1, and more preferably 2-3: 1. The invention preferably uses a syringe to add 2, 4-pentanedione into the feed liquid; after the addition of the 2, 4-pentanedione is complete, N is again preferred in the invention 2 Bubbling for 1-2 h to remove HCl generated in the coordination process. In the present invention, the 2, 4-monopentanedione can coordinate with the transition metal chloride and the transition metal oxychloride in the reaction liquid, and at the same time, it functions to stabilize the complex.
In the present invention, the components of the active component mixed solution finally obtained by the above method are transition metal oxychloride with different coordination numbers. The ligand is adopted for coordination, so that the activity of the transition metal chloride can be reduced, the main catalyst is prevented from directly initiating monomer polymerization in the application process, and the stability of the catalyst is improved.
After the active component mixed solution is obtained, the activated carbon carrier and the active component mixed solution are mixed and impregnated. In the invention, the dosage ratio of the activated carbon carrier to the active component mixed solution is preferably 1g: 20-200 mL, and more preferably 1g: 50-150 mL; the dipping time is preferably 20-30 h, and more preferably 24 h; the impregnation is preferably carried out with stirring and under nitrogen protection. In the dipping process, the transition metal ions and the phenolic hydroxyl on the carbon carrier are chelated and coordinated, so that the carbon-based catalyst with high activity and high stability is obtained.
In the invention, the feed liquid obtained after impregnation is the suspension of the carbon-based catalyst, and the suspension is directly used as the catalyst without any treatment.
The invention provides a carbon-based catalyst prepared by the preparation method in the scheme, which comprises an activated carbon carrier and an active component loaded on the activated carbon carrier, wherein the active component comprises a transition metal oxychlorid complex; the ligands in the transition metal oxychloride complex preferably include the first ligand, the second ligand and the third ligand described in the above scheme, and the metal central ion in the active component and the phenolic hydroxyl group on the surface of the activated carbon support form a stable chelate. In the invention, the loading amount of the transition metal element in the carbon-based catalyst is preferably 5-50 wt%, and more preferably 10-40 wt%.
The invention also provides a catalyst system for dicyclopentadiene polymerization, which comprises a main catalyst and a cocatalyst which are independently and separately packaged, wherein the main catalyst is the carbon-based catalyst in the scheme, and the cocatalyst is an organic aluminum compound; the organic aluminum compound is preferably diethyl aluminum chloride, triethyl aluminum or ethyl aluminum dichloride.
The invention also provides a method for preparing dicyclopentadiene polymeric material by using the catalyst system in the scheme, which comprises the following steps:
(1) respectively dispersing a main catalyst and a cocatalyst in materials to be polymerized with the same volume under a protective atmosphere to obtain a component A and a component B;
(2) and mixing the component A and the component B under a protective atmosphere, and carrying out heat treatment to obtain the dicyclopentadiene polymeric material.
In the invention, under the protective atmosphere, a main catalyst and a cocatalyst are respectively dispersed in a material to be polymerized with the same volume to obtain a component A and a component B. In the present invention, the protective atmosphere is preferably an inert gas or nitrogen; the material to be polymerized is dicyclopentadiene monomer, or the material to be polymerized comprises cyclopentadiene monomer and a composite component, wherein the composite component preferably comprises one or more of vinyl norbornene monomer, methacryloyl norbornene monomer and butadiene-styrene block copolymer.
In the invention, when the material to be polymerized is a dicyclopentadiene monomer, the finally obtained product is polydicyclopentadiene; when the material to be polymerized is a mixture of cyclopentadiene monomers and vinyl norbornene monomers, the mass fraction of the vinyl norbornene monomers in the mixture is preferably 5%, and the final product is a copolymer of dicyclopentadiene and vinyl norbornene; when the material to be polymerized is a mixture of cyclopentadiene monomers and methacryloyl norbornene monomers, the mass fraction of the methacryloyl norbornene monomers in the mixture is preferably 5%, and the final product is a copolymer of dicyclopentadiene and methacryloyl norbornene; when the material to be polymerized is a mixture of cyclopentadiene monomers and butadiene-styrene block copolymers, the mass fraction of the butadiene-styrene block copolymers in the mixture is preferably 6%, and the final product is a composite material of dicyclopentadiene and butadiene-styrene block copolymers; when the material to be polymerized is a mixture of cyclopentadiene monomer, vinyl norbornene monomer and butadiene-styrene block copolymer, the mass fraction of vinyl norbornene monomer in the mixture is preferably 5%, the mass fraction of butadiene-styrene block copolymer is preferably 6%, and the final product is a composite material of dicyclopentadiene-methacryloyl norbornene copolymer and butadiene-styrene block copolymer. In the present invention, the butadiene-styrene block copolymer functions as a reinforcing material.
In the invention, when the material to be polymerized is dicyclopentadiene, a main catalyst and a cocatalyst are directly and respectively added into the dicyclopentadiene with the same volume for mixing; when the material to be polymerized comprises cyclopentadiene monomers and a composite component, the cyclopentadiene monomers and the composite component are preferably mixed and then divided into two parts with equal volumes, then a main catalyst and a cocatalyst are respectively added, and particularly, when the composite component comprises a butadiene-styrene block copolymer, the dicyclopentadiene and the butadiene-styrene block copolymer are preferably mixed and then stirred for 30-60 min at 60 ℃ to obtain a uniform and transparent solution, then the solution is divided into two parts with equal volumes, and then the subsequent steps are carried out.
In the present invention, the main catalyst is preferably directly added in the form of a carbon-supported catalyst suspension obtained in the above scheme, and the co-catalyst is preferably dissolved in toluene and then added in the form of a diethylaluminum chloride solution.
In the invention, the molar ratio of the total molar amount of dicyclopentadiene in the component A and the component B to the main catalyst and the cocatalyst is preferably (1200-1500): 1 (10-30), more preferably (1300-1400): 1 (15-25); the molar weight of the main catalyst is calculated by the molar weight of a transition metal element, and the molar weight of the auxiliary catalyst is calculated by the mass of an Al element.
After the component A and the component B are obtained, the component A and the component B are mixed and subjected to heat treatment under a protective atmosphere to obtain the dicyclopentadiene polymeric material. In the present invention, the temperature of the heat treatment is preferably 70 ℃; the component A and the component B are preferably quickly mixed together, the viscosity of the mixture is increased within 10-30 s, the mixture is transferred into a preheated mold, and the mixture is quickly cured within 60-200 s to form a crosslinked solid, so that the dicyclopentadiene polymeric material is obtained.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
In the following examples, activated carbon is used as a carrier, and the specific surface area of the activated carbon is 500 to 2000m 2 (iii) a particle size of 0.02 to 20 μm/g.
Example 1: preparation of carbon-supported tungsten catalyst
(1) Under the protection of nitrogen, tert-butyl alcohol and WCl are added 6 Mixing with dry toluene, and stirring for 10 hr, wherein WCl 6 In an amount of 20g, toluene in a volume of 70mL, tert-butanol and WC1 6 The molar ratio was 0.25 to obtain a reaction solution in which WC1 was present 6 And WOC1 4 Has a total concentration of 0.73mol/L, WC1 6 With WOCl 4 Is 3: 1.
(2) Adding 11.1g of nonylphenol to 30 ml of toluene to obtain a nonylphenol solution, adding the nonylphenol solution to the reaction solution of step (1), and then adding N 2 The HCl was removed by bubbling for 1 hour, after which 10.1g of 2, 4-pentanedione were added by syringe and the mixture was again purged with N 2 Bubbling for 1h to remove HCl, and a mixed active ingredient solution was obtained.
(3) The activated carbon is subjected to activation pretreatment by using 1mol/L nitric acid, the weight ratio of the carbon carrier to the nitric acid is 1:3, the treatment temperature is 30 ℃, the treatment time is 3 hours, the treated carbon carrier is washed three times by using distilled water, and the carbon carrier is dried to constant weight at the temperature of 120 ℃ to obtain the activated carbon carrier.
(4) And (3) adding 5g of the activated carbon carrier prepared in the step (3) into the mixed active component solution in the step (2), and stirring for 24 hours under the protection of nitrogen to form uniform and stable black suspension, namely the carbon-supported tungsten catalyst.
Example 2: preparation of carbon-supported molybdenum catalyst
(1) Under the protection of nitrogen, adding di-tert-butyl-p-cresol and MoCl 5 Mixing with dry toluene, stirring for 10h, wherein MoCl 5 The amount of the compound (B) is 10g, the volume of the methylbenzene is 50mL, and the di-tert-butyl-p-cresol and MoCl are 5 The molar ratio was 0.25 to obtain a reaction solution in which MoC1 was present 5 And MoOC1 3 Has a total concentration of 0.73mol/L and MoC1 5 With MoOCl 4 Is about 3: 1.
(2) Adding 11.1g of nonylphenol to 30 ml of toluene to obtain a nonylphenol solution, adding the nonylphenol solution to the reaction solution obtained in the step (1), and then adding N 2 The HCl was removed by bubbling for 1 hour, after which 10.1g of 2, 4-pentanedione were added by syringe and the mixture was again purged with N 2 Bubbling for 1h to remove HCl and obtain a mixed active ingredient solution.
(3) Activating and pretreating activated carbon by using 1mol/L acetic acid, wherein the weight ratio of a carbon carrier to nitric acid is 1:3, the treatment temperature is 30 ℃, the treatment time is 3 hours, the treated carbon carrier is washed by using distilled water for three times, and the carbon carrier is dried to constant weight at the temperature of 120 ℃. Obtaining the activated carbon carrier.
(4) And (3) adding 5g of the activated carbon carrier prepared in the step (3) into the mixed active component solution in the step (2), and stirring for 24 hours under the protection of nitrogen to form uniform and stable black suspension, namely the carbon-supported molybdenum catalyst.
Example 3: preparation of carbon-supported ruthenium catalyst:
(1) under the protection of nitrogen, di-tert-butyl-p-cresol and RuCl are added 4 Mixing with dry toluene and stirring for 10h, wherein RuCl 6 In an amount of 10g, toluene volume of 70mL, di-t-butyl-p-cresol and MoCl 6 The molar ratio was 0.25, and a reaction solution was obtained.
(2) Adding 11.1g of nonylphenol to 30 ml of toluene to obtain a nonylphenol solution, adding the nonylphenol solution to the reaction solution obtained in the step (1), and then adding N 2 The HCl was removed by bubbling for 1 hour, after which 10.1g of 2, 4-pentanedione were added by syringe and the mixture was again purged with N 2 Bubbling for 1h to remove HCl and obtain a mixed active ingredient solution.
(3) Activating and pretreating activated carbon by using 1mol/L hydrochloric acid, wherein the weight ratio of a carbon carrier to nitric acid is 1:3, the treatment temperature is 30 ℃, the treatment time is 3 hours, the treated carbon carrier is washed three times by using distilled water, and the carbon carrier is dried to constant weight at the temperature of 120 ℃. Obtaining the activated carbon carrier.
(4) And (3) adding 5g of the activated carbon carrier prepared in the step (3) into the mixed active component solution in the step (2), and stirring for 24 hours under the protection of nitrogen to form a uniform and stable black suspension, namely the carbon-supported ruthenium catalyst.
Example 4: preparation of polydicyclopentadiene
Experiment one: the catalyst suspension solution of carbon-supported tungsten prepared in example 1 was diluted with dicyclopentadiene liquid to a tungsten concentration of 0.1mol/L to obtain a catalyst diluent of carbon-supported tungsten, and 5g of dicyclopentadiene liquid was added to a glass test tube, and 0.19mL (tungsten content: 0.019mmol) of the catalyst diluent of carbon-supported tungsten was added to obtain a component a. In another tube, 5g of dicyclopentadiene liquid was added, and 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. Based on the total amount of the component A and the component B, the concentration of the active aluminum is 0.07mol/L, and the concentration of the tungsten is 0.0019 mol/L.
The component A and the component B are rapidly mixed together, the viscosity of the mixture becomes large in a short time, and the mixture is transferred to a mold preheated to 70 ℃ and rapidly cured to form a crosslinked solid, so that the polydicyclopentadiene is obtained.
Experiment two: the catalyst suspension solution of carbon-supported molybdenum prepared in example 2 was diluted with dicyclopentadiene liquid to a molybdenum concentration of 0.1mol/L to obtain a catalyst dilution of carbon-supported molybdenum, and 5g of dicyclopentadiene liquid was added to a glass test tube, and 0.15mL (molybdenum content: 0.015mmol) of the catalyst dilution of carbon-supported molybdenum was added to obtain component a. In another tube, 5g of dicyclopentadiene liquid was added, and 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. Based on the total amount of the component A and the component B, the total molar concentration of the active aluminum is 0.07mol/L, and the concentration of the molybdenum is 0.0015 mol/L.
The component A and the component B are rapidly mixed together, the viscosity of the mixture becomes large in a short time, and the mixture is transferred to a mold preheated to 70 ℃ and rapidly cured to form a crosslinked solid, so that the polydicyclopentadiene is obtained.
Experiment three: the catalyst suspension solution of ruthenium on carbon prepared in example 3 was diluted with dicyclopentadiene liquid to a ruthenium concentration of 0.1mol/L to obtain a catalyst dilution of ruthenium on carbon, and 5g of dicyclopentadiene liquid was added to a glass test tube, and 0.10mL (ruthenium content: 0.010mmol) of the catalyst dilution of ruthenium on carbon was added to obtain a component a. In another tube, 5g of dicyclopentadiene liquid was added, and 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. The total molar concentration of the active aluminum is 0.07mol/L and the concentration of the ruthenium is 0.0010mol/L based on the total amount of the component A and the component B.
And (3) rapidly mixing the component A and the component B together, transferring the mixture into a preheated 70 ℃ mold with the viscosity increased within 10-30 s, and forming a crosslinked solid within 60-200 s to obtain the polydicyclopentadiene.
The physical properties of the polydicyclopentadiene obtained and the swelling properties in toluene are shown in Table 1.
TABLE 1 Performance test results for polydicyclopentadiene
| Kind of main catalyst | Gel/% | Swelling/% | Tg/℃ | Tensile strength/MPa |
| Tungsten (W) | 96 | 67 | 116 | 37 |
| Molybdenum (Mo) | 95 | 77 | 114 | 43 |
| Ruthenium (II) | 97 | 64 | 109 | 41 |
In table 1: the gel% represents the crosslinking degree of the cured resin and is tested by a dynamic mechanical tester; swelling represents the swelling property of polydicyclopentadiene in toluene, and the test method is as follows: soaking the obtained polydicyclopentadiene in toluene for 10-24 h until swelling is stable, and calculating the volume change rate before and after swelling; tg denotes the glass transition temperature.
Example 5: preparation of polydicyclopentadiene
Other conditions were the same as in the first experiment in example 4, and the amount of the catalyst diluent only containing tungsten supported on carbon was changed to 0.098mL and 0.38mL, respectively.
The physical properties of the polydicyclopentadiene obtained and the swelling properties in toluene are shown in Table 2.
TABLE 2 Performance test results for polydicyclopentadiene
| Amount of main catalyst | Gel/% | Swelling/% | Tg/℃ | Tensile strength/MPa |
| 0.098mL | 95 | 50 | 105 | 29 |
| 0.19mL | 96 | 67 | 116 | 37 |
| 0.38mL | 97 | 92 | 119 | 45 |
The test methods for% gel and swelling properties in table 2 are consistent with those in table 1.
As can be seen from Table 2, polydicyclopentadiene prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
Example 6: preparation of copolymer of dicyclopentadiene and vinyl norbornene
Experiment one: the catalyst suspension solution of tungsten supported on carbon prepared in example 1 was diluted with dicyclopentadiene liquid to a tungsten concentration of 0.1mol/L to obtain a catalyst dilution solution of tungsten supported on carbon, and 5g of a mixture of dicyclopentadiene liquid and a vinyl norbornene monomer, the mass fraction of which was 5%, was added to a glass test tube. Adding 0.19mL of catalyst diluent (the tungsten content is 0.019mmol) loaded with tungsten to prepare a component A. In another test tube, 5g of a mixture of dicyclopentadiene liquid and a vinyl norbornene monomer, wherein the mass fraction of the vinyl norbornene monomer was 5%, was added 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) to obtain a B component. The total molar concentration of the active aluminum is 0.07mol/L and the concentration of the tungsten is 0.0019mol/L based on the total amount of the component A and the component B.
And (3) rapidly mixing the component A and the component B together, transferring the mixture into a preheated 70 ℃ mold within 10-30 s when the viscosity of the mixture is increased, and curing the mixture within 60-200 s to form a crosslinked solid, thus obtaining the dicyclopentadiene and vinyl norbornene copolymer.
Experiment two: other conditions and experiment one were the same, and the amount of catalyst diluent loaded with tungsten alone was changed to 0.098 mL.
Experiment three: other conditions and experiment one were the same, except that the amount of the catalyst diluent supporting tungsten was changed to 0.38 mL.
The physical properties of the resulting copolymer of dicyclopentadiene and vinyl norbornene and the swelling properties in toluene are shown in Table 3.
TABLE 3 Performance test results for copolymers of Dicyclopentadiene and vinyl norbornene
| Amount of main catalyst | Gel% | Swelling of the composition | Tg | Tensile strength/MPa | Flexural Strength/MPa | Impact Strength/KJ/m 2 |
| 0.098mL | 97 | 55 | 110 | 39 | 49 | 81 |
| 0.19mL | 98 | 77 | 121 | 41 | 52 | 77 |
| 0.38mL | 99 | 93 | 125 | 45 | 50 | 76 |
The test methods for% gel and swelling properties in table 3 are consistent with those in table 1.
As can be seen from Table 3, the copolymer of dicyclopentadiene and vinyl norbornene prepared using the catalyst system of the present invention has excellent physical properties and high strength.
Example 7: preparation of dicyclopentadiene and methacryloyl norbornene copolymer composition
Experiment one: the catalyst suspension solution of tungsten supported on carbon prepared in example 1 was diluted with dicyclopentadiene liquid to a tungsten concentration of 0.1mol/L to obtain a catalyst dilution solution of tungsten supported on carbon, and 5g of a mixture of dicyclopentadiene liquid and a methacryloyl norbornene monomer, in which the mass fraction of the vinyl norbornene monomer was 5%, was added to a glass test tube. 0.19mL (tungsten content: 0.019mmol) of the tungsten-supporting catalyst suspension solution prepared in example 1 was added to obtain component A. In another test tube, 5g of a mixture of dicyclopentadiene liquid and a vinyl norbornene monomer, wherein the mass fraction of the methacryloyl norbornene monomer was 5%, was added. 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. The total molar concentration of the active aluminum is 0.07mol/L and the concentration of the tungsten is 0.0019mol/L based on the total amount of the component A and the component B.
And (3) rapidly mixing the dicyclopentadiene and the methacryloyl norbornene together, transferring the mixture into a mold preheated to 70 ℃ within 10-30 s when the viscosity of the mixture is increased, and curing the mixture within 60-200 s to form a crosslinked solid, namely the dicyclopentadiene and methacryloyl norbornene copolymer.
Experiment two: other conditions were the same as in the first experiment, except that the amount of the catalyst diluent supporting tungsten was changed to 0.098 mL.
Experiment three: other conditions and experiment one were the same, except that the amount of the catalyst diluent supporting tungsten was changed to 0.38 mL.
The physical properties of the resulting copolymer of dicyclopentadiene and methacryloyl norbornene and the swelling properties in toluene are shown in Table 4.
TABLE 4 Performance test results for copolymers of Dicyclopentadiene and methacryloyl norbornene
| Amount of main catalyst | Gel% | Swelling of the composition | Tg | Tensile strength/MPa | Flexural Strength/MPa | Impact Strength/KJ/m 2 |
| 0.098mL | 99 | 45 | 116 | 41 | 61 | 40 |
| 0.19mL | 99 | 66 | 124 | 44 | 63 | 37 |
| 0.38mL | 98 | 73 | 131 | 47 | 70 | 39 |
The test methods for% gel and swelling properties in table 4 are consistent with those in table 1.
As can be seen from Table 4, the copolymer of dicyclopentadiene and methacryloyl norbornene prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
Example 8: preparation of dicyclopentadiene and butadiene-styrene block copolymer (SBS) composite material
Experiment one: diluting the catalyst suspension solution of the carbon-supported molybdenum prepared in the example 2 with dicyclopentadiene liquid until the concentration of molybdenum is 0.1mol/L to obtain a catalyst diluent of the carbon-supported molybdenum; a glass test tube was charged with 10g of a mixture of dicyclopentadiene liquid and SBS, a butadiene-styrene block copolymer, wherein the SBS block polymer was present in a mass fraction of 6%. Stirring at 60 deg.C for 30min to obtain a uniform transparent solution, and uniformly dividing into two parts. 0.19mL of catalyst diluent of carbon-supported molybdenum (the molybdenum content is 0.019mmol) is added into one part of the mixture to obtain a component A. In another tube, 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. Based on the total amount of the component A and the component B, the total molar concentration of the active aluminum is 0.07mol/L, and the concentration of the molybdenum is 0.0019 mol/L.
Quickly mixing the component A and the component B together, increasing the viscosity of the mixture within 10-30 s, transferring the mixture into a mold preheated to 70 ℃, and curing within 60-200 s to form a cross-linked solid.
Experiment two: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.098 mL.
Experiment three: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.38 mL.
The physical properties of the resulting composite as well as the swelling properties in toluene are shown in table 5.
TABLE 5 Performance test results for Dicyclopentadiene and butadiene-styrene Block copolymer composites
The test methods for% gel and swelling properties in table 5 are consistent with those in table 1.
As can be seen from Table 5, the dicyclopentadiene and butadiene-styrene block copolymer composites prepared by using the catalyst system of the present invention have excellent physical properties and high strength.
Example 9: preparation of dicyclopentadiene-vinylnorbornene-butadiene-styrene block copolymer (SBS) composite material
Experiment one: diluting the catalyst suspension solution of the carbon-supported molybdenum prepared in the example 2 with dicyclopentadiene liquid until the concentration of molybdenum is 0.1mol/L to obtain a catalyst diluent of the carbon-supported molybdenum; a glass test tube was charged with 10g of a mixture of dicyclopentadiene liquid, a vinyl norbornene monomer and a butadiene-styrene block copolymer, wherein the mass fraction of the vinyl norbornene monomer was 5% and the mass fraction of the SBS block copolymer was 6%. Stirring at 60 deg.C for 30min to form a uniform transparent solution. The mixture was uniformly divided into two portions, and 0.15mL (molybdenum content: 0.015mmol) of the molybdenum-supported catalyst diluent prepared in example 2 was added to one portion to obtain component A. In another tube, 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a component B. Based on the total amount of the component A and the component B, the total molar concentration of the active aluminum is 0.07mol/L, and the concentration of the molybdenum is 0.0015 mol/L.
The two are quickly mixed together, the viscosity of the mixture is increased within 10-30 s, the mixture is transferred to a mold preheated to 70 ℃, and the mixture is cured within 60-200 ℃ to form a cross-linked solid.
Experiment two: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.098 mL.
Experiment three: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.38 mL.
The physical properties of the resulting composite as well as the swelling properties in toluene are shown in Table 6.
TABLE 6 dicyclopentadiene-vinylnorbornene-SBS composite Performance test results
The test method for% gel in table 6 is consistent with that in table 1.
As can be seen from Table 6, the dicyclopentadiene-vinylnorbornene-SBS composite prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
Example 10: preparation of dicyclopentadiene-vinylnorbornene-butadiene-styrene block copolymer (SBS) composite material
Experiment one: diluting the catalyst suspension solution of carbon-supported ruthenium prepared in example 3 with dicyclopentadiene liquid to a ruthenium concentration of 0.1mol/L to obtain a catalyst diluent of carbon-supported molybdenum; a glass test tube was charged with 10g of a mixture of dicyclopentadiene liquid, vinyl norbornene monomer and SBS, a butadiene-styrene block copolymer, wherein the mass fraction of the vinyl norbornene monomer was 5% and the mass fraction of the SBS block polymer was 6%. Stirring was carried out at 60 ℃ for 30min to form a uniform and transparent solution, which was divided into two portions, and 0.10mL (ruthenium content: 0.010mmol) of the ruthenium-supported catalyst suspension prepared in example 3 was added to one portion to obtain component A. In another tube, 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a component B. Based on the total amount of the component A and the component B, the total molar concentration of the active aluminum is 0.07mol/L, and the concentration of the ruthenium is 0.0010 mol/L.
The two are rapidly mixed together, the viscosity of the mixture is increased within 10-30 s, the mixture is transferred to a mold preheated to 70 ℃, and the mixture is cured within 60-200 s to form a crosslinked solid.
Experiment two: other conditions were the same as in the first experiment, except that the amount of the diluted ruthenium-supported catalyst solution was changed to 0.05 mL.
Experiment three: other conditions were the same as in the first experiment, except that the amount of the diluted ruthenium-supported catalyst solution was changed to 0.20 mL.
The physical properties of the resulting composite as well as the swelling properties in toluene are shown in Table 7.
TABLE 7 Performance test results of dicyclopentadiene-vinylnorbornene-SBS composite
The test method for% gel in table 7 is consistent with that in table 1.
As can be seen from Table 7, the dicyclopentadiene-vinylnorbornene-SBS composite prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
In addition, as can be seen from the data in tables 1 to 7, the gel% of the material is higher when the catalyst system of the present invention is used for preparing dicyclopentadiene polymeric materials, which indicates that the catalyst system of the present invention can improve the monomer conversion rate.
And (3) testing the stability of the catalyst:
the catalyst suspension solutions prepared in examples 1 to 3 were exposed to air for 24 hours, then dicyclopentadiene was prepared using 3 catalyst suspensions according to the method of example 4, the reaction gel condition was observed, and finally the gelation time was recorded, and the results showed that the gelation time was substantially unchanged from that of example 4 after exposure to air for 24 hours, indicating that it had excellent stability.
The embodiments show that the carbon-based catalyst provided by the invention has high activity and stability, and can be used as a main catalyst for initiating the ring-opening metathesis polymerization of dicyclopentadiene, so that the monomer conversion rate and the product performance can be improved, and the process performance of a polymerization system can be improved; in addition, the carbon-based catalyst provided by the invention has the advantages of simple preparation method, low production cost, mass production and good application prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method of preparing a dicyclopentadiene polymeric material, comprising the steps of:
(1) respectively dispersing a main catalyst and a cocatalyst in materials to be polymerized with the same volume under a protective atmosphere to obtain a component A and a component B; the main catalyst is a carbon-based catalyst, and the cocatalyst is an organic aluminum compound; the molar ratio of the total molar amount of dicyclopentadiene in the component A and the component B to the main catalyst and the cocatalyst is (1200-1500) to 1 (10-30); the molar weight of the main catalyst is calculated by the molar weight of a transition metal element, and the molar weight of the auxiliary catalyst is calculated by the mass of an aluminum element;
the material to be polymerized is a dicyclopentadiene monomer, or the material to be polymerized comprises a cyclopentadiene monomer and a composite component;
(2) mixing the component A and the component B in a protective atmosphere, and carrying out heat treatment to obtain a dicyclopentadiene polymeric material;
the preparation of the carbon-based catalyst comprises the following steps:
(1) activating and pretreating the carbon carrier by using acid to obtain an activated carbon carrier;
(2) mixing the activated carbon carrier and the active component mixed solution for impregnation to obtain a carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex;
the preparation method of the active component mixed solution comprises the following steps:
mixing a first ligand, a transition metal chloride and a solvent for reaction to obtain a reaction solution;
sequentially adding a second ligand and a third ligand into the reaction solution to obtain an active component mixed solution;
the transition metal chloride comprises WCl 6 、MoCl 5 And RuCl 4 One or more of the above; the first ligand comprises tert-butyl alcohol and/or di-tert-butyl-p-cresol; the second ligand comprises one or more of nonylphenol, 2, 4-dimethyl-6-tert-butylphenol, 2, 6-di-tert-butylphenol, polyphenol ligands and bisphenol ligands; the third ligand comprises one or more of 2, 4-pentanedione and acetylacetone ester ligands;
the molar ratio of the first ligand to the transition metal chloride is 0.1-1: 1; the molar ratio of the second ligand to the transition metal chloride is 1-5: 1; the molar ratio of the third ligand to the transition metal chloride is 1-5: 1.
2. The method according to claim 1, wherein the molar ratio of the transition metal chloride to the transition metal oxychloride in the reaction solution is 0.5 to 5: 1.
3. The method according to claim 1, wherein the adding of the second ligand comprises adding N to the resulting solution 2 Bubbling for 1-2 h; and after the third ligand is added, bubbling the obtained feed liquid with nitrogen for 1-2 hours.
4. The preparation method according to claim 1, wherein the acid comprises one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid; the weight ratio of the carbon carrier to the acid is 1: 2-3, the temperature of the activation pretreatment is 30-80 ℃, and the treatment time is 3-8 hours.
5. The preparation method according to claim 1, wherein the amount of the activated carbon carrier and the active component mixed solution is 1 g/20-200 mL, and the immersion time is 20-30 h.
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| US4918039A (en) * | 1988-09-21 | 1990-04-17 | Hercules Incorporated | Binuclear metathesis polymerization catalyst system |
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