CN1273502C - Multinuclear acenaphthene diimine nickle catalyst for synthesis of branched polyethylene - Google Patents

Multinuclear acenaphthene diimine nickle catalyst for synthesis of branched polyethylene Download PDF

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CN1273502C
CN1273502C CN 200410027498 CN200410027498A CN1273502C CN 1273502 C CN1273502 C CN 1273502C CN 200410027498 CN200410027498 CN 200410027498 CN 200410027498 A CN200410027498 A CN 200410027498A CN 1273502 C CN1273502 C CN 1273502C
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multinuclear
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王海华
胡扬剑
江洪流
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Sun Yat Sen University
National Sun Yat Sen University
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Abstract

The present invention relates to a multinuclear acenaphthene diimine nickel chloride catalyst for the synthesis of branched polyethylene, and a preparation method thereof. The catalyst is characterized in that a multinuclear acenaphthene diimine nickel complex loaded on a compound carrier of SiO2 and MgCl2 is used as a main catalyst, and AlEt2Cl is used as a cocatalyst. An impregnating reaction method is used for the preparation method. The obtained catalyst has a spheroidal particle shape, and a branched low-density polyethylene plastic body and an elastic body can be prepared without single ethylene polymerization catalysis by MAO.

Description

Polynuclear nickel (II) acenaphthenequinonedcatalyst catalyst of synthesizing branched polyethylene and preparation method thereof
Technical field
The present invention relates to a kind of synthesizing branched polyethylene plastomer, elastomeric multinuclear acenaphthene diimine nickelous chloride composition catalyst and preparation method thereof.
Background technology
Reaction has catalytic activity preferably to traditional Z-N (Z-N) catalyzer to ethene and alpha-olefin copolymer, can make the different degrees of branching in, new LDPE (film grade); But its body can not make polyethylene produce side chain, obtain branched polyethylene, just needs to use expensive alpha-olefin, and this has increased poly cost, simultaneously, also is difficult to obtain the polyethylene of the high degree of branching with this class catalyzer.The diimine ligand compound of the rear transition metal nickel of middle nineteen nineties in last century discovery, palladium etc. can be from the polyethylene plastomers and the elastomerics of single ethylene oligomerisation, the synthetic various high degrees of branching of in-situ copolymerization at the catalyst system that makes with methylaluminoxane (MAO) or boron compound, this has opened up a frontier for olefinic polymerization, have important application prospects (J.K.Johnson is arranged, C.M.Killian and M.Brookhart, J Am.Chem.Soc, 1995,117:6414).Yet this catalyzer need adopt expensive MAO or boron compound to make promotor, and cost is higher; And the prepared product degree of branching is wayward, and product form is irregular, promotes the use of in industrial production and still has bigger difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of setting out and prepare supported catalyst---the multinuclear acenaphthene diimine nickelous chloride composition catalyst of branched polyethylene by single ethylene.This catalyzer only need be with general AlEt 2Cl makes promotor, need not to use expensive MAO or boron compound, can the poly-polymerization of catalysis single ethylene make high degree of branching polyethylene plastomers of low density and elastomerics.Contain branch chain of different length in the polymer molecular chain, help improving the over-all properties of polymkeric substance.The preparation of this series catalyst is simple, is easy to suitability for industrialized production, and some technical problems that above-mentioned prior art is existed can solve preferably.
Catalyzer of the present invention, its component comprises Primary Catalysts and promotor; Load on MgCl with multinuclear acenaphthene diimine nickelous chloride title complex 2And SiO 2On the complex carrier, constitute compound primary catalysts; With AlEt 2Cl is a promotor; Multinuclear acenaphthene diimine nickelous chloride title complex is (Ni) N+2Cl 2 (n+2), wherein L is a multinuclear acenaphthene diimine compound, is selected from L shown in the following structural formula I 1To L 4In arbitrary compound:
Figure C20041002749800041
Among the formula I: n is 2～10;
L 1: R 1=R 2=R 3=sec.-propyl;
L 2: R 1=R 2=ethyl, R 3=sec.-propyl;
L 3: R 1=ethyl, R 2=R 3=sec.-propyl;
L 4: R 1=H, R 2=methoxyl group, R 3=sec.-propyl;
Corresponding multinuclear acenaphthene diimine nickelous chloride complex structure is as shown in the formula shown in the II:
Figure C20041002749800051
N is 2～10 among the formula II.
The catalyzer of the invention described above, the each component proportioning is generally by weight: MgCl 2: SiO 2: (Ni) N+2LCl 2 (n+2)=1: (2～8): (0.5～3), all the other each components are with (Ni) N+2LCl 2 (n+2)Mole number calculate its mol ratio and be: (Ni) N+2LCl 2 (n+2): AlEt 2Cl=1.0: (20～200).
The used multinuclear acenaphthene diimine nickelous chloride title complex of the invention described above catalyzer can obtain by the following method: under nitrogen protection; anhydrous chlorides of rase nickel was dissolved in dehydrated alcohol 2～3 hours; after waiting to have dissolved, join the CH that is dissolved with multinuclear acenaphthene diimine compounds L 2l 2In the solution, back flow reaction 12～16 hours is drained and is sloughed solvent, and with the anhydrous diethyl ether washing, vacuum-drying promptly gets required multinuclear acenaphthene diimine nickel complex (Ni) N+2LCl 2 (n+2)
The invention described above catalyzer can adopt dipping-reaction method preparation, and concrete steps are as follows:
(1) with microspheroidal SiO 2Place tube furnace, the heating down of logical nitrogen is warming up to 600 ℃, and 4～6 hours postcooling of calcining at constant temperature in the nitrogen protection bottom discharge, place reaction flask again, add 10 times of SiO 2The heptane of volume, nitrogen protection and stirring add and contain AlR down 3Hexane solution, maintain 25～30 ℃ the reaction 30 minutes, vacuumize drying and remove heptane, pre-treatment SiO 2AlR 3Middle R is C 2～C 4Alkyl contains AlR 3Hexane solution concentration be 2.5mol/LAlR 3
Under (2) 60～65 ℃, with MgCl 2Be dissolved in alcohol, the ether mixing solutions, stir mother liquor; Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), MgCl 2: alcohol=1: (3～5), MgCl 2: ether=1: (24～40);
(3) N 2Protection is following, above-mentioned mother liquor is added enter pretreated SiO 2In, 60～65 ℃ of stirring reaction 1～2h remove by filter mother liquor, 50～60 ℃ of controlled temperature, and vacuum tightness 30～35kPa drains liquid, gets active SiO 2-MgCl 2Complex carrier;
(4) N 2Protection adds alkane down in (3) products therefrom, be warming up to 60～70 ℃, adds title complex (Ni) under agitation condition N+2LCl 2 (n+2)CH 2Cl 2Solution, reaction 1.5～3h; Used alkane is hexane, heptane or octane, and consumption is every gram complex carrier 8～15ml alkane; (Ni) N+2LCl 2 (n+2): CH 2Cl 2=1: (10～20) W/W;
(5)) solvent in above-mentioned (4) reactant is drained, with alkane washing three times, vacuum is drained under 60 ℃ condition again, promptly gets Primary Catalysts; Wherein, alkane is hexane or heptane, and consumption is every gram complex carrier 8～15ml; Primary Catalysts and promotor AlEt 2Cl forms the poly composite catalyst of ethylene polymerization for preparing branched, and its mol ratio is: (Ni) N+2LCl 2 (n+2): AlEt 2Cl=1: (20～200).
The present invention is by (Ni) N+2LCl 2 (n+2)Component and above-mentioned specific dipping reaction method for preparing make the catalyzer that makes only need general AlEt 2Cl makes promotor, need not expensive MAO or boron compound, can the highly active catalytic vinyl polymerization, make high degree of branching new LDPE (film grade) plastomer and elastomerics; Owing to adopt MgCl 2And SiO 2Form complex carrier, make to make polyethylene product and have good particle form.Catalyzer of the present invention has above-mentioned excellent comprehensive performance, is beneficial to aborning and promotes the use of, and has significant superiority.
Catalyzer of the present invention is 106.7kPa at pressure, 50～60 ℃ of polymerization temperatures, and slurry polymerization 1.5 hours, to vinyl polymerization, catalytic efficiency is 45～58kgLLDPE/molNi, making density is 0.879～0.912g/cm 3, the degree of branching is 18.9～86.4 polyethylene plastomers and elastomerics.
Embodiment
The invention will be further described below by embodiment:
Embodiment one:
1. nickel complex (Ni) N+2L 1Cl 2 (n+2)Preparation: multinuclear acenaphthene diimine nickel complex can obtain by the following method: under nitrogen protection; 0.5354g (4.14mmol) anhydrous chlorides of rase nickel was dissolved in the 20ml dehydrated alcohol 2～3 hours; after waiting to have dissolved, join and be dissolved with 2.005g (4.14mmol) ligand L 130 the gram CH 2Cl 2In the solution, back flow reaction 12～16 hours is drained and is sloughed solvent, and with 30ml anhydrous diethyl ether washing three times, vacuum-drying promptly gets required nickel complex (Ni) N+2L 1Cl 2 (n+2)
2. Preparation of Catalyst:
2-1. with 5 gram microspheroidal SiO 2Put in the tube furnace, the heating down of logical nitrogen is warming up to 600 ℃, the calcining at constant temperature dehydration, and 6 hours postcooling get 4 gram SiO in the nitrogen protection bottom discharge 2, place reaction flask, add the 40ml heptane, under nitrogen protection and under constantly stirring, add and contain 2.5mol/LAlEt 3Hexane solution 3ml, maintain 25～30 ℃ the reaction 30 minutes, vacuumize drying and remove heptane, pre-treatment SiO 2
2-2. with 1.2 gram MgCl 2Be dissolved in alcohol, the ether mixing solutions, stir mother liquor.Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), MgCl 2: alcohol=1: 3, MgCl 2: ether=1: (24～40).
2-3. at N 2Protection is following, above-mentioned mother liquor is added enter pretreated SiO 2In, 60～65 ℃ of stirring reaction 2h remove by filter mother liquor, 50～60 ℃ of controlled temperature, and vacuum tightness 30～35kPa drains liquid, promptly gets active SiO 2-MgCl 2Complex carrier.
2-4. at N 2Under the protection, with SiO 2-MgCl 2Complex carrier is added in the reaction flask, adds alkane again, is warming up to 60～70 ℃, adds 1.624g nickel complex (Ni) under agitation condition N+2L 1Cl 2 (n+2)CH 2Cl 2Solution, reaction 1.5h.Used alkane can be hexane, heptane or octane, and consumption is every gram complex carrier 8～15ml alkane.
2-5. solvent is drained, use hexane wash three times, vacuum is drained under 60 ℃ condition again, promptly gets body of catalyst.Wherein the hexane consumption is every gram complex carrier 8～15ml.Body of catalyst and AlEt 2Cl forms ethylene rolymerization catalyst.
3. the ethene slurry polymerization prepares low-density branched polyethylene:
Reaction flask was vacuumized under 100 ℃ dry 1 hour, use N 2Replace three times, at N 2Protection down, add 50ml exsiccant toluene and by Al/Ni than the AlR that are 100 calculating 2Cl, under agitation add 0.5～15mg Primary Catalysts then, after continuation is stirred and catalyzer was uniformly dispersed in 5 minutes, feeding ethylene gas, is under the 106.7kPa at the pressure that keeps ethylene gas, is warming up to 30 ℃, carry out polyreaction, write down the ethene of polyreaction consumption in per 5 minutes, reaction 1.5h, stopped reaction.With acidic alcohol mixing solutions termination reaction thing, use washing with alcohol again, weigh after the drying, calculate catalyst efficiency.
Under above-mentioned polymerizing condition, the density of gained branched polyethylene is 0.881g/cm 3, be the degree of branching (elastomerics of number of branches/1000C) that is 69.4.The catalytic efficiency of catalyzer is 63kg LLDPE/molNi.
Embodiment two:
1. in embodiment one step 1, with the 4.14mmol ligand L 1Change the 4.14mmol ligand L into 2, the remaining reaction condition is identical, gets title complex (Ni) N+2L 2Cl 2 (n+2)
2. in embodiment one step 2-4, will add 1.624g nickel complex (Ni) N+2L 1Cl 2 (n+2)CH 2Cl 2Solution changes adding 1.486g (Ni) into N+2L 2Cl 2 (n+2)CH 2Cl 2Solution, all the other conditions and operation are with embodiment one, and the catalyzer that makes is polyreaction under embodiment one the same terms.
The density of gained branched polyethylene is 0894g/cm under above-mentioned polymerizing condition 3, the degree of branching is 68.0 elastomericss.The catalytic efficiency of catalyzer is 65kgLLDPE/molNi.
Embodiment three:
1. in embodiment one step 1, with 2.005g (4.14mmol) ligand L 1Change 1.788 (4.14mmol) ligand L into 3, the remaining reaction condition is identical, gets title complex (Ni) N+2L 3Cl 2 (n+2)
2. in embodiment one step 2-4, with 1.624g nickel complex (Ni) N+2L 1Cl 2 (n+2)Change 1.577g (Ni) into N+2L 3Cl 2 (n+2), all the other conditions and operation are with embodiment one, and the catalyzer that makes is polyreaction under embodiment one the same terms.
Under above-mentioned polymerizing condition the density of prepared branched polyethylene be, 0.887g/cm 3, the degree of branching is 50.2 elastomericss.The catalytic efficiency of catalyzer is 65kgLLDPE/molNi.
Embodiment four
1. in embodiment one step 1, with 2.005g (4.14mmol) ligand L 1Change 1.788 (4.14mmol) ligand L into 4, the remaining reaction condition is identical, gets title complex (Ni) N+2L 4Cl 2 (n+2)
2. in embodiment one step 2-4, with 1.624g nickel complex (Ni) N+2L 1Cl 2 (n+2)Change 1.455g (Ni) into N+2L 4Cl 2 (n+2), all the other conditions and operation are with embodiment one, and the catalyzer that makes is polyreaction under embodiment one the same terms.
The density of prepared branched polyethylene is 0915g/cm under above-mentioned polymerizing condition 3, the degree of branching is 18.9 plastomeies.The catalytic efficiency of catalyzer is 13kgLLDPE/molNi.

Claims (4)

1. the multinuclear acenaphthene diimine nickelous chloride composition catalyst of a synthesizing branched polyethylene comprises Primary Catalysts and promotor; It is characterized in that loading on MgCl with multinuclear acenaphthene diimine nickelous chloride title complex 2And SiO 2On the complex carrier, constitute compound primary catalysts; With AlEt 2Cl is a promotor; Multinuclear acenaphthene diimine nickelous chloride title complex is (Ni) N+2LCl 2 (n+2), wherein L is for being selected from L shown in the following structural formula I 1To L 4The multinuclear acenaphthene diimine compound of one of compound:
Among the formula I: n is 2～10;
L 1: R 1=R 2=R 3=sec.-propyl;
L 2: R 1=R 2=ethyl, R 3=sec.-propyl;
L 3: R 1=ethyl, R 2=R 3=sec.-propyl;
L 4: R 1=H, R 2=methoxyl group, R 3=sec.-propyl;
Corresponding multinuclear acenaphthene diimine nickelous chloride complex structure is as shown in the formula shown in the II:
N is 2～10 among the formula II.
2. according to the described catalyzer of claim 1; it is characterized in that described multinuclear acenaphthene diimine nickelous chloride title complex obtains by the following method: under nitrogen protection; anhydrous chlorides of rase nickel was dissolved in dehydrated alcohol 2～3 hours; after waiting to have dissolved, join the CH that is dissolved with multinuclear acenaphthene diimine compounds L 2Cl 2In the solution, back flow reaction 12～16 hours is drained and is sloughed solvent, and with the anhydrous diethyl ether washing, vacuum-drying promptly gets required multinuclear acenaphthene diimine nickel complex (Ni) N+2LCl 2 (n+2)
3. according to claim 1 or 2 described catalyzer, it is characterized in that the each component proportioning is by weight: MgCl 2: SiO 2: (Ni) N+2LCl 2 (n+2)=1: (2～8): (0.5～3.0), all the other each components are with (Ni) N+2LCl 2 (n+2)Mole number calculate its mol ratio and be: (Ni) N+2LCl 2 (n+2): AlEt 2Cl=1.0: (20～200).
4. the described Preparation of catalysts method of claim 1,2 or 3 is characterized in that adopting the dipping reaction method, and concrete steps are as follows:
(1) with microspheroidal SiO 2Place tube furnace, the heating down of logical nitrogen is warming up to 600 ℃, and 4～6 hours postcooling of calcining at constant temperature in the nitrogen protection bottom discharge, place reaction flask again, add 10 times of SiO 2The heptane of volume, nitrogen protection and stirring add and contain AlR down 3Hexane solution, maintain 25～30 ℃ the reaction 30 minutes, vacuumize drying and remove heptane, pre-treatment SiO 2AlR 3Middle R is C 2～C 4Alkyl contains AlR 3Hexane solution concentration be 2.5mol/L AlR 3
Under (2) 60～65 ℃, with MgCl 2Be dissolved in alcohol, the ether mixing solutions, stir mother liquor; Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), MgCl 2: alcohol=1: (3～5), MgCl 2: ether=1: (24～40);
(3) N 2Protection is following, above-mentioned mother liquor is added enter pretreated SiO 2In, 60～65 ℃ of stirring reaction 1～2h remove by filter mother liquor, 50～60 ℃ of controlled temperature, and vacuum tightness 30～35kPa drains liquid, gets active SiO 2-MgCl 2Complex carrier;
(4) N 2Protection adds alkane down in (3) products therefrom, be warming up to 60～70 ℃, adds title complex (Ni) under agitation condition N+2LCl 2 (n+2)CH 2Cl 2Solution, reaction 1.5～3h; Used alkane is hexane, heptane or octane, and consumption is every gram complex carrier 8～15ml alkane; (Ni) N+2LCl 2 (n+2): CH 2Cl 2=1: (10～20) W/W;
(5)) solvent in above-mentioned (4) reactant is drained, with alkane washing three times, vacuum is drained under 60 ℃ condition again, promptly gets Primary Catalysts; Wherein, alkane is hexane or heptane, and consumption is every gram complex carrier 8～15ml; Primary Catalysts and promotor aluminum alkyls AlEt 2Cl forms the poly composite catalyst of ethylene polymerization for preparing branched, and its mol ratio is: (Ni) N+2LCl 2 (n+2): AlEt 2Cl=1: (20～200).
CN 200410027498 2004-06-09 2004-06-09 Multinuclear acenaphthene diimine nickle catalyst for synthesis of branched polyethylene Expired - Fee Related CN1273502C (en)

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CN101531724A (en) * 2009-04-17 2009-09-16 南昌航空大学 Polynuclear nickel(II) acenaphthenequinonediimine catalyst for synthesizing branched polyethylene and preparation method thereof
CN109553710B (en) * 2017-09-27 2021-08-06 中国石化扬子石油化工有限公司 Branched polyethylene and preparation method thereof
CN107827935B (en) * 2017-11-29 2020-04-28 常州大学 α -diimine nickel complex with butanedione skeleton and preparation method and application thereof
CN109456814B (en) * 2018-12-29 2022-01-07 江苏奥克化学有限公司 Transformer oil composition and preparation method thereof
CN109852452B (en) * 2018-12-29 2022-01-07 江苏奥克化学有限公司 Low-temperature-resistant synthetic engine oil and preparation method thereof
CN110105478B (en) * 2019-05-24 2021-08-24 重庆理工大学 Plate-type dual-core alpha-diimine catalyst and preparation method and application thereof

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