CN116854856A - Preparation method of norbornene, long-chain olefin and methyl acrylate ternary polymerization under single-metallocene titanium catalyst - Google Patents
Preparation method of norbornene, long-chain olefin and methyl acrylate ternary polymerization under single-metallocene titanium catalyst Download PDFInfo
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 title claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000010936 titanium Substances 0.000 title claims abstract description 48
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 title claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 29
- 229940078552 o-xylene Drugs 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- -1 aluminum compound Chemical class 0.000 claims description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012968 metallocene catalyst Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 229940069096 dodecene Drugs 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940095068 tetradecene Drugs 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 abstract description 17
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 5
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 5
- XYBSZCUHOLWQQU-UHFFFAOYSA-N 7-bromoquinoline Chemical compound C1=CC=NC2=CC(Br)=CC=C21 XYBSZCUHOLWQQU-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- HLZBYIVAMXUYBW-UHFFFAOYSA-N chloro-cyclopenta-2,4-dien-1-yl-dimethylsilane Chemical compound C[Si](C)(Cl)C1C=CC=C1 HLZBYIVAMXUYBW-UHFFFAOYSA-N 0.000 description 1
- SHWJEWNBZZXDHM-UHFFFAOYSA-N chloro-cyclopenta-2,4-dien-1-yl-diphenylsilane Chemical compound Cl[Si](C1C=CC=C1)(c1ccccc1)c1ccccc1 SHWJEWNBZZXDHM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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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)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the technical field of cycloolefin polymer synthesis, and particularly relates to a preparation method of a norbornene, long-chain olefin and methyl acrylate terpolymer under a single-metallocene titanium catalyst. Norbornene forms copolymers with methyl acrylate and long chain monomers by non-ring opening addition in the presence of a mono-metallocene titanium catalyst-cocatalyst. The single-metallocene titanium catalyst has a structural formula shown in formula I, wherein R 1 Is hydrogen, or C 1 ~C 10 Straight-chain, branched or isomerised alkyl radicals R 2 Is hydrogen, or C 1 ~C 10 Linear, branched or isomerised alkyl groups; alternatively, R 1 Is methyl or phenyl, R 2 Is methyl or phenyl. The invention catalyzes ternary polymerization of norbornene, long-chain olefin and methyl acrylate by using a single-metallocene titanium catalyst, and provides reference for catalyzing the synthesis of cycloolefin polymers.
Description
Technical Field
The invention belongs to the technical field of cycloolefin polymer synthesis, and particularly relates to a preparation method of a norbornene, long-chain olefin and methyl acrylate terpolymer under a single-metallocene titanium catalyst.
Background
Norbornene is a cycloolefin copolymer obtained by polymerizing monomers, has important application value, has excellent properties such as high refractive index, high glass transition temperature, low density, high heat resistance and the like, and is often applied to the fields of optics, electronics, medicine packaging and the like.
However, the polymers still have the defects of poor solubility, poor material performance of the bonding substrate, difficult molding and processing and the like, so that polar monomers such as long-chain olefins, alkyl acrylate and the like can be introduced to chemically modify the cycloolefin polymers, and the rigid structure of the polymers is changed so that the polymers are easy to process and mold.
The metallocene catalyst is a catalyst with a sandwich structure, and is mainly characterized in that: (1) Having a single active site helps to obtain a narrow and uniform distribution of polymer; (2) The catalytic activity is high and is close to the catalytic rate of biological enzyme; (3) The metallocene catalyst structure can be customized according to the substrate type to obtain the polymer with target molecular weight and stereoregularity. The metallocene catalyst can catalyze cycloolefin to introduce functional monomer through non-ring-opening addition polymerization, so as to obtain cycloolefin polymer with high added value.
Disclosure of Invention
The invention aims to provide a preparation method of a norbornene, long-chain olefin and methyl acrylate terpolymer under a single-metallocene titanium catalyst.
The invention is realized by the following technical scheme:
a preparation method of norbornene, long-chain olefin and methyl acrylate terpolymer under a single-metallocene titanium catalyst comprises the following preparation steps: deoxidizing and dewatering the reaction kettle, and introducing nitrogen for protection, wherein the total concentration of monomers is 20 wt%; and (3) placing norbornene, methyl acrylate, a cocatalyst and an o-xylene solution into a reaction kettle, synchronously dropwise adding a certain amount of o-xylene solution containing a single metallocene titanium catalyst and an o-xylene solution containing long-chain olefin, reacting at 20-70 ℃, dropwise adding for about 0.3-0.5 h, preserving heat for 1-6 h, adding a 5% methanol hydrochloric acid solution with mass concentration to terminate the reaction, filtering, and vacuum drying the product at 30-40 ℃.
The single-metallocene titanium catalyst preferably has a structural general formula shown in a formula I:
a method for preparing the compound of formula I,
wherein R is 1 Is hydrogen, or C 1 ~C 10 Straight-chain, branched or isomerised alkyl radicals R 2 Is hydrogen, or C 1 ~C 10 Linear, branched or isomerised alkyl groups; alternatively, R 1 Is methyl or phenyl, R 2 Is methyl or phenyl.
The single-metallocene titanium catalyst is more preferably provided with a structural formula shown in any one of formulas II-IV.
Formula II>Formula III->Formula IV.
The preparation method of the single-metallocene titanium catalyst comprises the following preparation steps.
(1) Preparation of bridging ligand: under the environment of nitrogen protection, 1 part of component A (formula V) and 1 part of component B (formula VI) are dissolved in tetrahydrofuran solution, n-butyllithium is used as a catalyst, the reaction is carried out for 12 to 20 hours at the temperature of minus 60 ℃ to 0 ℃, and the product is cooled and filtered to obtain a ligand;
and (3) a component A:component V, B->A step VI of, in which,
wherein R is 1 Is hydrogen, or C 1 ~C 10 Straight-chain, branched or isomerised alkyl radicals R 2 Is hydrogen, or C 1 ~C 10 Linear, branched or isomerised alkyl groups; alternatively, R 1 Is methyl or phenyl, R 2 Methyl or phenyl;
(2) The ligand and titanium tetrachloride react to obtain the single-metallocene titanium catalyst, and the specific preparation method comprises the following steps: 1 part of ligand is dissolved in petroleum ether under a nitrogen environment, 1 part of titanium tetrachloride dissolved in petroleum ether is slowly added dropwise, and the mixture is reacted for 2 to 6 hours at a temperature of between minus 60 ℃ and minus 40 ℃. And (3) carrying out vacuum suction filtration on the reaction liquid, dissolving the product in toluene for recrystallization, and carrying out vacuum drying to obtain the mono-metallocene titanium catalyst.
The long-chain olefin is an alpha-olefin having 6 to 24 carbon atoms, preferably 1-hexene, 1-octene, 1-decene, dodecene, tetradecene or octadecene.
The norbornene, long-chain olefin and methyl acrylate terpolymer refers to a copolymer having the formula VII:
Ⅶ，
wherein x, y, z and n are integers.
The preparation of the norbornene, long-chain olefin and methyl acrylate terpolymer is to react for 1-6 hours at 20-70 ℃, and more preferably to react for 4-6 hours at 40-60 ℃.
The molar ratio of the norbornene to the long-chain olefin to the methyl acrylate is (2-1) to 1:1-0.5; more preferably, the molar ratio is 1:1:0.5.
The addition amount of the single-metallocene titanium catalyst in the polymer reaction is 0.02-0.3% of the total molar amount of the monomers; more preferably 0.04 to 0.1%.
The single-metallocene titanium catalyst and the cocatalyst form a catalytic system together; the cocatalyst is as follows: methylaluminoxane, ethylaluminoxane, triisobutylaluminum B (C) 6 F 5 ) 3 、[PhMe 2 NH][B(C 6 F 5 ) 4 ]And [ Ph ] 3 C][B(C 6 F 5 ) 4 ]One or more combinations; the molar ratio of the titanium metallocene catalyst to the cocatalyst is preferably: the molar ratio of aluminum in the organic aluminum compound to the cyclopentadienyl titanium compound is (1-300) to 1; the molar ratio of boron in boride to titanocene compound is 10:1.
The single-metallocene titanium catalyst provided by the invention has high catalytic activity, can catalyze non-ring-opening polymerization reaction to obtain cycloolefin copolymer, and in addition, the application of the copolymer is wider due to the incorporation of functional groups.
Compared with other catalysts, the single-metallocene titanium catalyst provided by the invention has better catalytic activity, and the controllability of the single-metallocene titanium catalyst on cycloolefin polymerization is improved through steric hindrance effect and electronic effect.
Description of the embodiments
The features and advantages of the present invention will become more fully apparent from the following detailed description of the invention and examples. It is to be understood that the detailed description and examples, while indicating the invention, are given by way of illustration and not limitation.
The cycloolefin copolymers having the structure of the formula VII in the examples below were prepared by the following processes: the reaction kettle is deoxidized and dehydrated, nitrogen is introduced for protection, and the total concentration of monomers is 20 wt percent. And (3) placing norbornene, methyl acrylate, a cocatalyst and an o-xylene solution into a reaction kettle, synchronously dropwise adding a certain amount of o-xylene solution containing a single-metallocene titanium catalyst and an o-xylene solution containing long-chain olefin, reacting at 40-60 ℃ for about 0.3-0.5 h, preserving heat for 4-h, adding a 5% methanol hydrochloric acid solution with mass concentration to terminate the reaction, filtering, and vacuum drying the product at 30-40 ℃.
Example 1
The synthesis of the single-metallocene titanium catalyst with the structural formula II comprises the following synthesis steps:
(1) Mono-lux titanium bridging ligand V (R) 1 And R is 2 Methyl) is prepared: 1 mmol of 7-bromoquinoline and 1 mmol of cyclopentadienyl dimethylchlorosilane are dissolved in 20 mL tetrahydrofuran solution under the protection of nitrogen, 1 mmol of n-butyllithium 5 mL tetrahydrofuran solution is slowly added dropwise in 0.5 hour, and the reaction is carried out at-60 ℃ for 12 hours. Vacuum filtering, washing with diethyl ether to obtain yellow product with 67% yield;
(2) Under nitrogen atmosphere, 0.5 mmol (1) of the ligand in step (1) was dissolved in 10 mL petroleum ether, and 10 mL petroleum ether solution containing 0.1 mmol of titanium tetrachloride was slowly added dropwise and reacted at-60℃for 3 hours. The reaction solution was filtered under reduced pressure, and the product was dissolved in toluene for recrystallization. The product was a reddish brown powder in 43% yield. The structural formula of the product is shown as formula II. Elemental analysis: found (calculated), C%, 52.39 (52.06), H%, 4.17 (4.37), N%, 3.90 (3.79).
Example 2
The synthesis of the single-metallocene titanium catalyst with the structural formula III comprises the following synthesis steps:
(1) Mono-lux titanium bridging ligand V (R) 1 Is methyl, R 2 Phenyl) preparation: 1 mmol of 7-bromoquinoline and 1 mmol of 1- (chloromethylphenylsilyl) -cyclopentadiene- (1, 3) were dissolved in 20. 20 mL tetrahydrofuran, and a solution containing 1 mmol of n-butyllithium 5 mL in tetrahydrofuran was slowly added dropwise over 0.5 hours and reacted at-60℃for 15 hours. Vacuum filtering, washing with diethyl ether to obtain yellow product with yield of 53%;
(2) Under nitrogen atmosphere, 0.5 mmol of the ligand in step (1) was dissolved in 10 mL petroleum ether, and 10 mL petroleum ether solution containing 0.1 mmol of titanium tetrachloride was slowly added dropwise and reacted at-60℃for 3 hours. The reaction solution was filtered under reduced pressure, and the product was dissolved in toluene for recrystallization. The product was a reddish brown powder with 39% yield. The structural formula of the product is shown as formula III. Elemental analysis: found (calculated), C%, 58.23 (58.49), H%, 4.19 (4.21), N%, 3.46 (3.25).
Example 3
The synthesis of the single-metallocene titanium catalyst with the structural formula IV comprises the following synthesis steps:
(1) Mono-lux titanium bridging ligand V (R) 1 And R is 2 Phenyl) preparation: 1 mmol of 7-bromoquinoline and 1 mmol of cyclopentadienyl diphenylchlorosilane are dissolved in 20 mL tetrahydrofuran solution under the protection of nitrogen, 1 mmol of n-butyllithium 5 mL tetrahydrofuran solution is slowly added dropwise in 0.5 hour, and the reaction is carried out at-60 ℃ for 15 hours. Vacuum filtering, washing with diethyl ether to obtain yellow product with yield of 69%;
(2) Under nitrogen atmosphere, 0.5 mmol of the ligand of step (1) was dissolved in 10 mL petroleum ether, and 10 mL petroleum ether solution containing 0.1 mmol of titanium tetrachloride was slowly added dropwise and reacted at-60℃for 3 hours. The reaction solution was filtered under reduced pressure, and the product was dissolved in toluene for recrystallization. The product was a reddish brown powder with a yield of 47%. The structural formula of the product is shown as formula IV. Elemental analysis: found (calculated), C%, 64.51 (64.30), H%, 3.79 (4.09), N%, 2.90 (2.84).
Example 4
Preparation of norbornene-1-hexene-methyl acrylate terpolymer: deoxidizing and dewatering a reaction kettle, introducing nitrogen for protection, placing 95 g norbornene, 43 g methyl acrylate, 46 g methylaluminoxane and 900 mL o-xylene solution into the reaction kettle, synchronously dropwise adding 100 mL o-xylene solution containing 1 g of the single metallocene titanium catalyst obtained in the example 1 and 115 mL o-xylene solution containing 85 g of 1-hexene, reacting at 50 ℃, dropwise adding time is about 0.3-0.5 h, preserving heat for 4 h, adding 5% methanol hydrochloric acid solution with mass concentration to terminate the reaction, filtering, and vacuum drying the product at 30-40 ℃. Table 1 records the relevant aggregate data of this embodiment.
Example 5
Preparation of norbornene-1-octene-methyl acrylate terpolymer: preparation of norbornene-1-octene-methyl acrylate terpolymer: deoxidizing and dewatering a reaction kettle, introducing nitrogen for protection, placing 95 g norbornene, 43 g methyl acrylate, 60 g methylaluminoxane and 900 mL o-xylene solution into the reaction kettle, synchronously dropwise adding 100 mL o-xylene solution containing 0.8 g of the single metallocene titanium catalyst obtained in the example 2 and 250 mL o-xylene solution containing 112 g of 1-octene into the reaction kettle, reacting at 50 ℃, dropwise adding the reaction kettle for about 0.3-0.5 h, preserving heat for 4 h, adding 5% methanol hydrochloric acid solution with mass concentration to terminate the reaction, filtering, and vacuum drying the product at 30-40 ℃. Table 1 records the relevant aggregate data of this embodiment.
Example 6
Preparation of norbornene-1-decene-methyl acrylate terpolymer: deoxidizing and dewatering a reaction kettle, introducing nitrogen for protection, placing 95 g norbornene, 43 g methyl acrylate, 60 g methylaluminoxane and 900 mL o-xylene solution into the reaction kettle, synchronously dropwise adding 100 mL o-xylene solution containing 1.2 g of the single metallocene titanium catalyst obtained in the example 2 and 390 mL o-xylene solution containing 140 g of 1-decene into the reaction kettle, reacting at 50 ℃, dropwise adding the reaction kettle for about 0.3-0.5 h, preserving heat for 4 h hours, adding 5% methanol hydrochloric acid solution with the mass concentration for terminating the reaction, filtering, and vacuum drying the product at 30-40 ℃. Table 1 records the relevant aggregate data of this embodiment.
Example 7
Preparation of norbornene-dodecene-methyl acrylate terpolymer: preparation of norbornene-dodecene-methyl acrylate terpolymer: deoxidizing and dewatering a reaction kettle, introducing nitrogen for protection, placing 95 g norbornene, 43 g methyl acrylate, 60 g methylaluminoxane and 1000 mL o-xylene solution into the reaction kettle, synchronously dropwise adding 100 mL o-xylene solution containing 1.2 g of the single metallocene titanium catalyst obtained in the example 3 and 530 mL o-xylene solution containing 168 g dodecene into the reaction kettle, reacting at 60 ℃, dropwise adding the reaction kettle for about 0.3-0.5 h, preserving heat for 4 h, adding 5% methanol hydrochloric acid solution with mass concentration to terminate the reaction, filtering, and vacuum drying the product at 30-40 ℃. Table 1 records the relevant aggregate data of this embodiment.
Example 8
Preparation of norbornene-tetradecene-methyl acrylate terpolymer: preparation of norbornene-tetradecene-methyl acrylate terpolymer: deoxidizing and dewatering a reaction kettle, introducing nitrogen for protection, placing 95 g norbornene, 43 g methyl acrylate, 80 g methylaluminoxane and 1000 mL o-xylene solution into the reaction kettle, synchronously dropwise adding 100 mL o-xylene solution containing 1.2 g of the single-metallocene titanium catalyst obtained in the example 3 and 670 mL o-xylene solution containing 196 g tetradecene into the reaction kettle, reacting at 60 ℃, dropwise adding the reaction kettle for about 0.3-0.5 h, preserving heat for 4 h, adding 5% methanol hydrochloric acid solution with the mass concentration for terminating the reaction, filtering, and vacuum drying the product at 30-40 ℃. Table 1 records the relevant aggregate data of this embodiment.
Example 9
Preparation of norbornene-octadecene-methyl acrylate terpolymer: preparation of norbornene-octadecene-methyl acrylate terpolymer: deoxidizing and dewatering a reaction kettle, introducing nitrogen for protection, placing 95 g norbornene, 43 g methyl acrylate, 80 g methylaluminoxane and 1000 mL o-xylene solution into the reaction kettle, synchronously dropwise adding 100 mL o-xylene solution containing 1.5 g of the single metallocene titanium catalyst obtained in the example 3 and 815 mL o-xylene solution containing 225 g octadecene, reacting at 60 ℃, dropwise adding time is about 0.3-0.5 h, preserving heat for 4 h, adding 5% methanol hydrochloric acid solution with mass concentration to terminate the reaction, filtering, and vacuum drying the product at 30-40 ℃. Table 1 records the relevant aggregate data of this embodiment.
Table 1 polymerization data for examples 4 to 9
Note that: the molecular weight and molecular weight distribution of the polymer were both determined by GPC, with polystyrene as standard.
The norbornene-long-chain olefin-methyl acrylate terpolymer obtained by the single-metallocene titanium catalyst provided by the invention has relatively high molecular weight and narrow molecular weight distribution.
Claims (8)
1. The preparation method of ternary polymerization of norbornene, long-chain olefin and methyl acrylate under the single-metallocene titanium catalyst is characterized by comprising the following preparation steps: deoxidizing and dewatering the reaction kettle, and introducing nitrogen for protection, wherein the total concentration of monomers is 20 wt%; and (3) placing norbornene, methyl acrylate, a cocatalyst and an o-xylene solution into a reaction kettle, synchronously dropwise adding a certain amount of o-xylene solution containing a single metallocene titanium catalyst and an o-xylene solution containing long-chain olefin, reacting at 20-70 ℃, dropwise adding for about 0.3-0.5 h, preserving heat for 1-6 h, adding a 5% methanol hydrochloric acid solution with mass concentration to terminate the reaction, filtering, and vacuum drying the product at 30-40 ℃.
2. The method for preparing norbornene, long-chain olefin and methyl acrylate ternary polymerization under the single metallocene titanium catalyst as claimed in claim 1, wherein the single metallocene titanium catalyst has a structural formula shown in formula I:
a method for preparing the compound of formula I,
wherein R is 1 Is hydrogen, or C 1 ~C 10 Straight chain, branched chain of (2)Or isomerized alkyl, R 2 Is hydrogen, or C 1 ~C 10 Linear, branched or isomerised alkyl groups; alternatively, R 1 Is methyl or phenyl, R 2 Is methyl or phenyl.
3. The process for the preparation of a ternary polymerization of norbornene, long-chain olefins and methyl acrylate using a single metallocene catalyst according to claim 1, wherein the single metallocene catalyst is used in combination with an organoaluminide (methylaluminoxane, ethylaluminoxane and triisobutylaluminum) or an organoboride (B (C 6 F 5 ) 3 、[PhMe 2 NH][B(C 6 F 5 ) 4 ]And [ Ph ] 3 C][B(C 6 F 5 ) 4 ]) One or more of the components and the proportions of the cocatalyst are as follows: the molar ratio of aluminum in the organic aluminum compound to the cyclopentadienyl titanium compound is (1-300) to 1; the molar ratio of boron in boride to titanocene compound is 10:1.
4. The method for preparing norbornene, long-chain olefin and methyl acrylate ternary polymerization under the single-metallocene titanium catalyst as claimed in claim 1, wherein the copolymer has a structural formula shown in a formula VII:
a metal oxide semiconductor layer (VII),
wherein x, y, z and n are integers.
5. The method for preparing norbornene, long-chain olefin and methyl acrylate ternary polymerization under the single-metallocene titanium catalyst according to claim 1, wherein the long-chain olefin is alpha-olefin with 6-24 carbon atoms, preferably 1-hexene, 1-octene, 1-decene, dodecene, tetradecene and octadecene.
6. The method for preparing the ternary polymerization of norbornene, long-chain olefin and methyl acrylate under the single-metallocene titanium catalyst according to claim 1, wherein the molar ratio of the norbornene to the long-chain olefin to the methyl acrylate is (2-1) to 1:1-0.5; more preferably, the molar ratio is 1:1:0.5.
7. The preparation method of norbornene, long-chain olefin and methyl acrylate ternary polymerization under the single metallocene titanium catalyst as claimed in claim 1, wherein the addition amount of the single metallocene titanium catalyst in the polymer reaction is 0.02-0.3% of the total molar amount of monomers; more preferably 0.04 to 0.1%.
8. The preparation method of norbornene, long-chain olefin and methyl acrylate ternary polymerization under the single metallocene titanium catalyst according to claim 2, wherein the single metallocene titanium catalyst is prepared by the following steps:
(1) Preparation of bridging ligand: under the environment of nitrogen protection, 1 part of component A (formula V) and 1 part of component B (formula VI) are dissolved in tetrahydrofuran solution, n-butyllithium is used as a catalyst, the reaction is carried out for 12 to 20 hours at the temperature of minus 60 ℃ to 0 ℃, and the product is cooled and filtered to obtain a ligand;
and (3) a component A:component V, B->A step VI of, in which,
wherein R is 1 Is hydrogen, or C 1 ~C 10 Straight-chain, branched or isomerised alkyl radicals R 2 Is hydrogen, or C 1 ~C 10 Linear, branched or isomerised alkyl groups; alternatively, R 1 Is methyl or phenyl, R 2 Methyl or phenyl;
(2) The ligand and titanium tetrachloride react to obtain the single-metallocene titanium catalyst, and the specific preparation method comprises the following steps: 1 part of ligand is dissolved in petroleum ether under a nitrogen environment, 1 part of titanium tetrachloride dissolved in petroleum ether is slowly added dropwise, and the mixture is reacted for 2 to 6 hours at a temperature of between minus 60 ℃ and minus 40 ℃. And (3) carrying out vacuum suction filtration on the reaction liquid, dissolving the product in toluene for recrystallization, and carrying out vacuum drying to obtain the mono-metallocene titanium catalyst.
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