CN112210030A - Preparation method of broad-distribution hyperbranched polyethylene - Google Patents
Preparation method of broad-distribution hyperbranched polyethylene Download PDFInfo
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- CN112210030A CN112210030A CN201910618388.4A CN201910618388A CN112210030A CN 112210030 A CN112210030 A CN 112210030A CN 201910618388 A CN201910618388 A CN 201910618388A CN 112210030 A CN112210030 A CN 112210030A
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- -1 polyethylene Polymers 0.000 title claims abstract description 50
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 46
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000413 hydrolysate Substances 0.000 claims abstract description 7
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- QQTGJVBUIOTPGZ-UHFFFAOYSA-N CCC[Zn]CCC Chemical compound CCC[Zn]CCC QQTGJVBUIOTPGZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 15
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 claims description 4
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 claims description 4
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 claims description 2
- DFGSACBYSGUJDZ-UHFFFAOYSA-M chloro(dihexyl)alumane Chemical compound [Cl-].CCCCCC[Al+]CCCCCC DFGSACBYSGUJDZ-UHFFFAOYSA-M 0.000 claims description 2
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- VMLUVDHAXSZZSR-UHFFFAOYSA-L hexylaluminum(2+);dichloride Chemical compound CCCCCC[Al](Cl)Cl VMLUVDHAXSZZSR-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- 229920000642 polymer Polymers 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000012711 chain transfer polymerization Methods 0.000 description 2
- 238000010516 chain-walking reaction Methods 0.000 description 2
- FRLYMSHUDNORBC-UHFFFAOYSA-N diisopropylzinc Chemical compound [Zn+2].C[CH-]C.C[CH-]C FRLYMSHUDNORBC-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- AFRZIGPEPSJSAM-UHFFFAOYSA-N 2-chloroethylalumane Chemical compound ClCC[AlH2] AFRZIGPEPSJSAM-UHFFFAOYSA-N 0.000 description 1
- SMUZAWTUJOJXQK-UHFFFAOYSA-N C1=CC2=CC=CC3=CC=CC1=C23.C=C Chemical group C1=CC2=CC=CC3=CC=CC1=C23.C=C SMUZAWTUJOJXQK-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Abstract
The invention discloses a preparation method of widely distributed hyperbranched polyethylene, which takes an alpha-nickel diimine catalyst as a main catalyst; ethylene polymerization is carried out by taking at least one of alkyl aluminum, alkyl aluminum hydrolysate or halogenated alkyl aluminum as a cocatalyst and at least one of diethyl zinc, dimethyl zinc, dipropyl zinc or dibutyl zinc as an auxiliary agent. The obtained hyperbranched polyethylene has wider molecular weight distribution and controllable distribution.
Description
Technical Field
The invention relates to hyperbranched polyethylene, in particular to a preparation method of widely distributed hyperbranched polyethylene.
Background
The hyperbranched polyethylene (HBPE) has a compact dendritic spherical structure, less molecular entanglement and difficult crystallization, and the hydrodynamic properties show typical Newtonian fluid behavior. Thus, HBPE has superior processability, better film-forming properties, film light transmission, and the like, relative to High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), and Linear Low Density Polyethylene (LLDPE). Moreover, when the branching degree is increased, the glass transition temperature Tg is reduced, and at normal temperature, the polyethylene is in a rubbery state, is an elastomer and has great industrial application value.
The best way to obtain hyperbranched polyethylenes at present is to use late transition metal catalysts. Professor Brookhart, north kauri university in the united states in 1995, first reported that an (alpha-diimine) nickel catalyst with chain walking (chain walking) capability, such as formula I, can produce high molecular weight, branched polyethylene. Subsequent researchers have synthesized catalysts of other structures (Catal. Sci. Technol.2013, 3, 1172; Macromolecules 42, 2009, 7789; Angew. chem. int. Ed. 2004, 43, 1821; J.Am. chem. Soc.2013, 135, 16316; Organometallics 23, 2004, 3276-doped 3283), such as the (alpha-diimine) nickel catalysts shown in formulas II-VII, which have certain improvements in thermal stability.
Chinese patent CN104877054A discloses a terminal hydroxyl functionalized hyperbranched polyethylene and a preparation method thereof, ethylene acenaphthylene (alpha-diimine) nickel catalyst is used as a main catalyst, alkyl aluminum is used as a cocatalyst, and diethyl zinc is used as a chain transfer agent to catalyze ethylene to homopolymerize, and the diethyl zinc end-capped hyperbranched polyethylene is obtained through coordination chain transfer polymerization. In the invention, the catalyst does not need noble metal, thereby greatly reducing the synthesis cost of HBPE; the HBPE is prepared by using diethyl zinc as a chain transfer agent and adopting a coordination chain transfer polymerization method, so that the polymerization activity is high and the process is simple; the method for obtaining the terminal hydroxyl is simple, low in cost and high in practical value; in the hydroxyl-terminated HBPE, the reactivity of hydroxyl is high, and various polymer chains with different properties can be introduced into HBPE through condensation reaction, coupling reaction, click chemical reaction and the like, so that polymers with various properties and different functions can be prepared.
Chinese patent CN106478848A discloses a nickel diimine catalyst and its application in preparing branched polyethylene, wherein the nickel diimine catalyst is used as main catalyst, aluminum catalyst is used as cocatalyst, and ethylene polymerization is carried out in organic solvent; the number average molecular weight of the branched polyethylene prepared is 200000-550000, the molecular weight distribution is 2.5-4.5, and the branching degree is 60-106/1000C. The invention can obtain the branched polyethylene material with high molecular weight, narrow molecular weight distribution and high branching degree. The material can be used for film materials and molding materials.
The molecular weight and molecular weight distribution of polyethylene have a significant impact on the rheological properties of its melt and the mechanics of the product. In the molten state, the melt viscosity is a function of molecular weight, and is increased along with the increase of molecular weight, and the increase of the molecular weight distribution index can increase the melt index and improve the processability of polyethylene, which is particularly important for processing high molecular weight polyethylene. However, the molecular weight distribution of the above catalysts is generally weak, and it is difficult to control the molecular weight by the catalyst itself. Therefore, it is very important to find a method capable of regulating the molecular weight distribution of the hyperbranched polyethylene. However, the prior art has few researches related to the molecular weight distribution width of the hyperbranched polyethylene.
Disclosure of Invention
The invention aims to provide a preparation method of broad-distribution hyperbranched polyethylene.
The present inventors have conducted studies based on the prior art and found that the molecular weight distribution of hyperbranched polyethylene can be controlled by adding a certain amount of an auxiliary agent during the polymerization process, thereby completing the present invention. Therefore, the technical scheme adopted by the invention is as follows:
a preparation method of broad-distribution hyperbranched polyethylene takes an alpha-nickel diimine catalyst as a main catalyst; ethylene polymerization is carried out by taking at least one of alkyl aluminum, alkyl aluminum hydrolysate or halogenated alkyl aluminum as a cocatalyst and at least one of diethyl zinc, dimethyl zinc, dipropyl zinc or dibutyl zinc as an auxiliary agent;
the chemical structural formula of the alpha-diimine nickel catalyst is shown as formula 1:
in the formula 1, R1And R4Is hydrogen, C1-4Straight-chain or branched-chain hydrocarbon groups, which may form a ring with each other; r3-R12Selected from hydrogen, C1-4A straight or branched chain hydrocarbon group; x is halogen.
In order to further improve the molecular weight distribution index of the obtained hyperbranched polyethylene, the molar ratio of the auxiliary agent to the main catalyst is preferably 100-500: 1, and the molar ratio of the auxiliary catalyst calculated by aluminum to the main catalyst calculated by metal M is preferably 20-1000: 1. further preferably, the molar ratio of the auxiliary agent to the main catalyst is 300-500: 1, excluding 300.
In order to further improve the processability of the obtained hyperbranched polyethylene, the polymerization conditions are preferably as follows: the reaction temperature is 0-100 ℃, and the reaction pressure is 0.1-6.0 Mpa. Further preferably, the reaction pressure is 2.3 to 6.0 MPa.
To further increase the polymerization activity, the aluminum alkyl is preferably selected from trimethylaluminum (Al (CH)3)3) Triethylaluminum (Al (CH)2CH3)3) Tri-n-propylaluminum (Al (C)3H7)3) Triisobutylaluminum (Al (i-C)4H9)3) Tri-n-butylaluminum (Al (C)4H9)3) Triisopentylaluminum (Al (i-C)5H11)3) Tri-n-pentylaluminum (Al (C)5H11)3) Tri-n-hexylaluminum (Al (C)6H13)3) Triisohexylaluminum (Al (i-C)6H13)3) Diethyl methyl aluminum (Al (CH)3)(CH3CH2)2) Or dimethyl ethyl aluminum (Al (CH)3CH2)(CH3)2) At least one of (1).
In order to further enhance the polymerization activity, it is preferable that the alkyl aluminum hydrolysate is trimethyl aluminum (Al (CH)3)3) Triethylaluminum (Al (CH)2CH3)3) Tri-n-propylaluminum (Al (C)3H7)3) Triisobutylaluminum (Al (i-C)4H9)3) Tri-n-butylaluminum (Al (C)4H9)3) Triisopentylaluminum (Al (i-C)5H11)3) Tri-n-pentylaluminum (Al (C)5H11)3) Tri-n-hexylaluminum (Al (C)6H13)3) Triisohexylaluminum (Al (i-C)6H13)3) Diethyl methyl aluminum (Al (CH)3)(CH3CH2)2) Or dimethyl ethyl aluminum (Al (CH)3CH2)(CH3)2) A hydrolysate obtained after reaction with water; in the reaction, the molar ratio of the alkyl aluminum to the water is 3-0.5: 1.
In order to further improve the polymerization activity, the alkyl aluminum halide is preferably at least one selected from the group consisting of diethylaluminum monochloride, ethylaluminum dichloride, di-n-butylaluminum monochloride, n-butylaluminum dichloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, di-n-hexylaluminum monochloride and n-hexylaluminum dichloride.
The hyperbranched polyethylene prepared by any one of the polymerization methods has a weight average molecular weight Mw of 10-22 ten thousand and a molecular weight distribution index DIP (Mw/Mn) of 6-14.
The invention has the beneficial effects that:
1. compared with the prior art, the hyperbranched polyethylene obtained by the invention has wider molecular weight distribution and controllable distribution.
2. The invention can control the molecular weight distribution index of the obtained hyperbranched polyethylene by adding the reaction auxiliary agent, controlling the molar ratio of the reaction auxiliary agent to the main catalyst and selecting proper reaction conditions, and has mild and controllable reaction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention, however, should be pointed out that the scope of the present invention is not limited by these embodiments.
The starting materials used in the following examples and comparative examples are commercially available, unless otherwise specified.
The molecular weight of the polyethylene obtained in the following examples and comparative examples was measured by:
polymer molecular weights were determined using Polymer Laboratories, model PL-220 gel permeation chromatography. 1,2, 4-trichlorobenzene is used as a mobile phase, polystyrene is used as a standard sample, a differential detector is adopted, the flow rate is 1.0mL/min, the measurement temperature is 150 ℃, and the sample concentration is 2.0 mg/mL.
The chemical structure of the alpha-diimine nickel catalyst used in the following examples is shown in M1:
application example 1
0.014mmol of alpha-diimine nickel catalyst, 0.17mmol of diethyl zinc, 15ml of toluene and 3.96mmol of ethyl aluminum dichloride were sequentially added to a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 79.6g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 16.88 ten thousand, and the molecular weight distribution index DIP was 3.07.
Application example 2
0.016mmol of alpha-diimine nickel catalyst, 1.6mmol of diethyl zinc, 15ml of toluene and 4.32mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 45.8g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 15.72 ten thousand, and the molecular weight distribution index DIP was 3.57.
Application example 3
0.013mmol of alpha-diimine nickel catalyst, 4.5mmol of diethyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 4.9g of a polymer. The weight average molecular weight Mw of the obtained hyperbranched polyethylene is 15.02 ten thousand, and the molecular weight distribution index DIP is 11.98.
Application example 4
0.016mmol of alpha-diimine nickel catalyst, 8.0mmol of diethyl zinc, 15ml of toluene and 4.32mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to obtain 2.43g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 13.85 ten thousand, and the molecular weight distribution index DIP was 13.57.
Application example 5
0.013mmol of alpha-diimine nickel catalyst, 4.0mmol of dimethyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for later use. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 1.6g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 11.97 ten thousand, and the molecular weight distribution index DIP was 9.82.
Application example 6
0.013mmol of alpha-nickel diimine catalyst, 4.2mmol of diisopropyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 1.46g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene is 14.77 ten thousand, and the molecular weight distribution index DIP is 7.45.
Application example 7
0.013mmol of alpha-nickel diimine catalyst, 4.2mmol of diisopropyl zinc, 15ml of toluene and 3.6mmol of diethyl aluminum monochloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 1.36g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was Mw of 12.39 ten thousand and the molecular weight distribution index DIP of 6.58.
Application example 8
0.013mmol of alpha-diimine nickel catalyst, 4.5mmol of diethyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 40 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 1.79g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 21.78 ten thousand, and the molecular weight distribution index DIP was 11.17.
Application example 9
0.013mmol of alpha-diimine nickel catalyst, 4.5mmol of diethyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 20 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with ethanol containing 5% hydrochloric acid, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 1.74g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 85.42 ten thousand, and the molecular weight distribution index DIP was 9.28.
Application example 10
0.013mmol of alpha-diimine nickel catalyst, 8.5mmol of diethyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 80 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to obtain 0.89g of a polymer. The weight average molecular weight Mw of the obtained hyperbranched polyethylene is 10.16 ten thousand, and the molecular weight distribution index DIP is 14.01.
Application example 11
0.013mmol of alpha-diimine nickel catalyst, 4.5mmol of diethyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 4.00MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 1.9g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 13.57 ten thousand, and the molecular weight distribution index DIP was 10.66.
Application example 12
0.013mmol of alpha-diimine nickel catalyst, 4.5mmol of diethyl zinc, 15ml of toluene and 3.6mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 3.5MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid-containing ethanol, and the polymer was filtered, washed, and vacuum-dried at 50 ℃ to constant weight to give 1.48g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene is 12.67 ten thousand, and the molecular weight distribution index DIP is 12.15.
Application example 13
0.013mmol of alpha-diimine nickel catalyst, 4.5mmol of diethyl zinc, 15ml of toluene and 12mmol of ethyl aluminum dichloride are sequentially added into a 50ml triangular flask in a glove box and mixed for standby. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 3.5MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid in ethanol, and the polymer was filtered, washed, and vacuum dried at 50 ℃ to constant weight to give 0.85g of polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was Mw of 10.91 ten thousand and the molecular weight distribution index DIP of 8.82.
Comparative example 1
0.014mmol of alpha-diimine nickel catalyst, 15ml of toluene and two 3.96mmol of chloroethylaluminum were sequentially added to a 50ml triangular flask in a glove box, and mixed for later use. 1L of hexane and the catalyst solution prepared above were sequentially charged into a 2L high pressure polymerization vessel purged with nitrogen, 2.3MPa of ethylene was introduced at 60 ℃ and polymerization was carried out for 0.5hr with stirring at 300 rpm. The polymerization solution was quenched with 5% hydrochloric acid in ethanol, and the polymer was filtered, washed, and vacuum dried at 50 ℃ to constant weight to give 79.6g of a polymer. The weight average molecular weight of the obtained hyperbranched polyethylene was 19.64 ten thousand, and the molecular weight distribution index DIP was 2.39.
TABLE 1 comparative table for each example and comparative example
As can be seen from the above examples and comparative examples, the hyperbranched polyethylene having a large molecular weight distribution can be obtained by adding the reaction assistant in the present invention. The practice proves that the molecular weight distribution index increases with the addition amount of the auxiliary agent, when the addition amount is more than 300 mol ratio, the molecular weight distribution width has a qualitative leap, but when the addition amount reaches 500 mol ratio, the molecular weight distribution index increases little.
Claims (9)
1. A preparation method of broad-distribution hyperbranched polyethylene is characterized in that an alpha-nickel diimine catalyst is used as a main catalyst; ethylene polymerization is carried out by taking at least one of alkyl aluminum, alkyl aluminum hydrolysate or halogenated alkyl aluminum as a cocatalyst and at least one of diethyl zinc, dimethyl zinc, dipropyl zinc or dibutyl zinc as an auxiliary agent;
the chemical structural formula of the alpha-diimine nickel catalyst is shown as formula 1:
in the formula 1, R1And R4Is hydrogen, C1-4Straight-chain or branched-chain hydrocarbon groups, which may form a ring with each other; r3-R12Selected from hydrogen, C1-4A straight or branched chain hydrocarbon group; x is halogen.
2. The preparation method according to claim 1, wherein the molar ratio of the auxiliary agent to the main catalyst is 100-500: 1, and the molar ratio of the auxiliary catalyst calculated by aluminum to the main catalyst calculated by the metal M is 20-1000: 1.
3. the preparation method according to claim 2, wherein the molar ratio of the auxiliary agent to the main catalyst is preferably 300 to 500:1, excluding 300.
4. The process according to claim 1,2 or 3, wherein the polymerization conditions are: the reaction temperature is 0-100 ℃, and the reaction pressure is 0.1-6.0 Mpa.
5. The method according to claim 4, wherein the reaction pressure is preferably 2.1 to 4.0 MPa.
6. The method according to claim 1, wherein the alkyl aluminum is preferably at least one selected from the group consisting of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, triisopentyl aluminum, tri-n-pentyl aluminum, tri-n-hexyl aluminum, triisohexyl aluminum, diethyl methyl aluminum and dimethyl ethyl aluminum.
7. The method according to claim 6, wherein the alkylaluminum hydrolysate is a hydrolysate obtained by reacting trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, triisohexylaluminum, diethylmethylaluminum, or dimethylethylaluminum with water; in the reaction, the molar ratio of the alkyl aluminum to the water is 3-0.5: 1.
8. The process according to claim 1, wherein the alkylaluminum halide is at least one member selected from the group consisting of diethylaluminum monochloride, ethylaluminum dichloride, di-n-butylaluminum monochloride, n-butylaluminum dichloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, di-n-hexylaluminum monochloride and n-hexylaluminum dichloride.
9. A hyperbranched polyethylene prepared by the polymerization process according to any one of claims 1 to 8, wherein the hyperbranched polyethylene has a weight average molecular weight Mw of 10 to 22 ten thousand and a molecular weight distribution index DIP of 6 to 14.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104877054A (en) * | 2015-05-22 | 2015-09-02 | 浙江大学 | HBPE (hyperbranched polyethylene) functionalized with terminal hydroxyl groups and preparation method thereof |
| CN107663257A (en) * | 2016-07-28 | 2018-02-06 | 中国石油化工股份有限公司 | A kind of method of carbon monoxide-olefin polymeric and its catalysis long-chain alpha-olefin polymerization for long-chain alpha-olefin polymerization |
| CN109593150A (en) * | 2017-09-30 | 2019-04-09 | 中国石化扬子石油化工有限公司 | A kind of preparation method of wide distribution hyperbranched polyethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877054A (en) * | 2015-05-22 | 2015-09-02 | 浙江大学 | HBPE (hyperbranched polyethylene) functionalized with terminal hydroxyl groups and preparation method thereof |
| CN107663257A (en) * | 2016-07-28 | 2018-02-06 | 中国石油化工股份有限公司 | A kind of method of carbon monoxide-olefin polymeric and its catalysis long-chain alpha-olefin polymerization for long-chain alpha-olefin polymerization |
| CN109593150A (en) * | 2017-09-30 | 2019-04-09 | 中国石化扬子石油化工有限公司 | A kind of preparation method of wide distribution hyperbranched polyethylene |
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