CN100560613C - A kind of preparation method of olefin polymerization catalyst - Google Patents
A kind of preparation method of olefin polymerization catalyst Download PDFInfo
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- CN100560613C CN100560613C CNB2007101773863A CN200710177386A CN100560613C CN 100560613 C CN100560613 C CN 100560613C CN B2007101773863 A CNB2007101773863 A CN B2007101773863A CN 200710177386 A CN200710177386 A CN 200710177386A CN 100560613 C CN100560613 C CN 100560613C
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Abstract
本发明涉及烯烃聚合催化剂的制备方法，按1mmol∶2.5mmol∶0.013g∶10mL配比加入苊醌、3，5-二甲基-4-氨基苯酚、对甲苯磺酸和甲苯得α-双亚胺配体；按1g∶0.25g或0.34g∶30mL∶0.21g的配比加入α-双亚胺配体、二氯化镍或二溴化镍、二氯甲烷和乙二醇二甲醚，得到α-双亚胺镍烯烃聚合催化剂；按1g∶60mL∶0.5～3g配比加入三甲基铝处理过的硅胶、二氯甲烷和α-双亚胺镍烯烃聚合催化剂，温度为20～30℃，得到硅胶负载α-双亚胺镍烯烃聚合催化剂；该催化剂在低助催化剂用量条件下，可催化乙烯高效聚合，能得到具有良好形态的高分子量聚乙烯。The present invention relates to the preparation method of olefin polymerization catalyst, add acenaphthylquinone, 3,5-dimethyl-4-aminophenol, p-toluenesulfonic acid and toluene according to the ratio of 1mmol: 2.5mmol: 0.013g: 10mL to obtain α-bis(2) Amine ligand; add α-bisimine ligand, nickel dichloride or nickel dibromide, dichloromethane and ethylene glycol dimethyl ether according to the ratio of 1g: 0.25g or 0.34g: 30mL: 0.21g, Obtain α-bisimine nickel olefin polymerization catalyst; add trimethylaluminum-treated silica gel, dichloromethane and α-bisimine nickel olefin polymerization catalyst at a ratio of 1g: 60mL: 0.5-3g, and the temperature is 20-30 ℃ to obtain a silica gel-supported α-bisimine nickel olefin polymerization catalyst; the catalyst can catalyze the high-efficiency polymerization of ethylene under the condition of low cocatalyst dosage, and can obtain high molecular weight polyethylene with good morphology.
Description
Technical field
The present invention relates to a kind of silica gel-supported alpha-diimine nickel olefine polymerization Preparation of catalysts method.
Background technology
Polyolefine is a class output maximum, the synthesized polymer material that is most widely used.Alkene is under the effect of catalyzer, and polymerization reaction take place generates macromolecular compound, i.e. polyolefine.Catalyzer is the core of polyolefin industry development, is the key of control polyolefin structure and performance.Traditional Ziegler-Natta catalyst is widely used in the industrial production of isotatic polypropylene, high density polyethylene(HDPE) and linear low density polyethylene, but its structural controllability and copolymerized ability are relatively poor.In order to overcome above-mentioned shortcoming, people have been developed the metallocene catalyst of a class high reactivity, high structural controllability.Metallocene catalyst is the agent of monomer reactivity centers catalyse, be widely used in the industrial production of syndiotactic polypropylene, syndiotactic polystyrene, linear low density polyethylene and long-chain branched polyethylene, but the copolymerized ability of metallocene catalyst still awaits improving, for example when metallocene catalysis ethene and styrene copolymerized poor effect, catalyzed ethylene and norbornylene copolymerization, the reactivity ratio of norbornylene is lower etc.Therefore, " luxuriant back " (post-metallocene) olefin polymerization catalysis causes people's great interest, wishes to develop the better or stronger olefin polymerization catalysis of copolymerized ability of structural controllability.Nineteen ninety-five, discovery alpha-diimine nickels such as Brookhart show advantages of high catalytic activity to ethene and alpha-olefine polymerizing, can prepare high-molecular weight controllable structure polymkeric substance, make that late transition metal catalyst obtains paying attention to.
The key of polymerization in homogeneous phase catalyzer application and development is a catalyst cupportization, makes it to be adapted to gas-phase fluidized-bed or slurry polymerization processes.But the loadization of late transition metal catalyst is difficulty relatively, is difficult for obtaining the ideal effect.It must be out-phase that the existing technical process of polyolefin industry requires catalyzer, loadization, if catalyzer without load, then the polyolefin particles form is bad, influence the product conveying, even causes the polymer lumps wall sticking phenomenon.In addition, the loadization of catalyzer can reduce the consumption of promotor greatly, increases the stability in active centre etc.Therefore, the colleague has carried out many trials both at home and abroad, mainly contains two kinds of methods, and the one, utilize the method for physical adsorption rear transition metal to be loaded on (Macromol.Chem.Phys.2003,204,1653-1659 on the inorganic carriers such as silica gel and magnesium chloride; Macromol.Chem.Phys.2001,202,3237-3247), advantage is that polyolefinic form is good, but load efficiency is lower, and activity of such catalysts can descend one more than the order of magnitude usually; The 2nd, utilize so-called " high molecular technology " late transition metal catalyst to be fixed on (Appl.Catal.A 2004,262,13-18 on the polystyrene; New J.Chem.2002,10,1485-1489), advantage is active higher, but the polyolefine form is relatively poor.
Summary of the invention
The objective of the invention is to utilize the mode of chemical bond connection, with the alpha-diimine nickel catalyst cupport on silica gel, obtain the high-efficient carrier alpha-diimine nickel olefine polymerization catalyst, under the condition of low promotor consumption, but the catalyzed ethylene high-efficiency polymerization, the High molecular weight polyethylene that obtains having good form.
Silica gel-supported alpha-diimine nickel olefine polymerization catalyzer disclosed by the invention has following structure:
In the formula, X is Br or Cl.
The pore volume of used silica gel is 1.55～1.90mL/g, and surface-area is 280～355m
2/ g.
Silica gel-supported alpha-diimine nickel olefine polymerization catalyzer disclosed by the invention is under the effect of modified methylaluminoxane (MMAO) or other aluminum alkyls class promotor, but the efficient catalytic vinyl polymerization, the polyethylene of the high molecular controllable structure that the generation form is good.
For achieving the above object, the invention provides silica gel-supported alpha-diimine nickel olefine polymerization Preparation of catalysts method, its step and condition are as follows:
Preparation Schiff's base: in reactor, add acenaphthenequinone, 3,5-dimethyl-4-amino-phenol, tosic acid and toluene, its proportion relation is: 1mmol: 2.5mmol: 0.013g: 10mL, reflux 10～18h, steam toluene, add dehydrated alcohol then, the mole number of acenaphthenequinone and the volume ratio of dehydrated alcohol are 1mmol: 16mL, and reheat refluxes, heat filtering, with filtrate placement overnight, there is red solid to generate, uses the dehydrated alcohol recrystallization again, thereby obtain the alpha-diimine part of structure as follows:
The preparation alpha-diimine nickel olefine polymerization catalyst:
Under the anhydrous and oxygen-free condition, in the exsiccant reactor, add alpha-diimine part, Nickel Chloride or Nickel Bromide, methylene dichloride and glycol dimethyl ether, its proportion relation is: 1g: 0.25g or 0.34g: 30mL: 0.21g, stirred 18 hours at 20～30 ℃, filter, it is inferior to give a baby a bath on the third day after its birth with anhydrous diethyl ether, drying obtains alpha-diimine nickel olefine polymerization catalyst as shown below at last:
In the formula, X is Br or Cl.
The alpha-diimine nickel olefine polymerization catalyst of preparation silica gel load:
A) handle silica gel with trimethyl aluminium: under the condition of anhydrous and oxygen-free, in the exsiccant reactor, add silica gel, toluene, reactor is placed ice-water bath, the pentane solution that extracts trimethyl aluminium with syringe slowly joins in the middle of the system, stirred 1 hour when slowly temperature of reaction system being risen to 20～30 ℃ again after emitting, under-100kpa condition, filter after drying, obtain the silica gel that trimethyl aluminium was handled-50 Deng no gas.Proportionlity wherein is, in every 8.5g silica gel, and toluene 40mL, concentration is the hexane solution 15mL of 2mol/L trimethyl aluminium.
B) under the condition of anhydrous and oxygen-free, in the exsiccant reactor, add silica gel, methylene dichloride and alpha-diimine nickel olefine polymerization catalyst that trimethyl aluminium was handled, its proportion relation is: 1g: 60mL: 0.5～3g, 20～30 ℃ were stirred 2～4 hours, filter under-100kpa condition-50, drying obtains the alpha-diimine nickel olefine polymerization catalyst of silica gel load as follows at last:
In the formula, X is Br or Cl.
This catalyzer is (Al/Ni mol ratio 50～400) under the effect of a spot of modified methylaluminoxane (MMAO), but the efficient catalytic vinyl polymerization generates the High molecular weight polyethylene with good form.
Concrete application method is as follows:
This silica gel-supported alpha-diimine nickel olefine polymerization catalyzer is used for ethylene oligomerization prepared in reaction High molecular weight polyethylene, adds modified methylaluminoxane, Al/Ni mol ratio 50～400; Add the normal hexane through refining processed, the amount that adds normal hexane makes catalyst concn between 0.001～0.15g/L; Ethylene reaction pressure is 0.1～5.0MPa, and temperature of reaction is 25～30 ℃, 30～60 minutes reaction times.
Beneficial effect of the present invention:
This catalyzer is (Al/Ni mol ratio 50～400) under the effect of modified methylaluminoxane (MMAO), but the efficient catalytic vinyl polymerization, and activity can reach 966～4800gPE/g
CatH generates the High molecular weight polyethylene with good form.
Embodiment
Embodiment 1
Preparation of catalysts:
In the 250mL round-bottomed flask, add acenaphthenequinone 2.73g, be equivalent to 15mmol; 3,5-dimethyl-4-amino-phenol 5.15g is equivalent to 37.5mmol; tosic acid 0.2g, toluene 150mL, heating reflux reaction is 18 hours under the nitrogen protection; steam toluene, add dehydrated alcohol 240mL then, reheat refluxes; heat filtering with filtrate placement overnight, has red solid to generate; with red solid dehydrated alcohol recrystallization, obtain wine-colored lenticular alpha-diimine part 4.8g, productive rate: 76%.Nmr analysis:
1HNMR (CDCl
3): δ 8.12 (d, 2H, Nap-H
o), 7.95 (d, 2H, Nap-H
p), 7.39 (t, 2H, Nap-H
m), 6.60 (s, 4H, Ar-H), 4.63 (s, 2H, OH), 1.95 (s, 12H, CH
3).
In the reaction flask of 100ml; add alpha-diimine ligand 1 .00g; Nickel Bromide 0.34g, methylene dichloride 30mL, glycol dimethyl ether 0.21g; stirring at room is 18 hours under nitrogen protection; filter, wash 3 times drying with anhydrous diethyl ether 20mL; obtain the alpha-diimine nickel complex 0.94g of brown, productive rate: 92%.Mass spectroscopy, molecular ion peak m/e is 639.Ultimate analysis measured value: C, 52.58%; H, 3.83%; N, 4.41%; Theoretical value (C
28H
24Br
2N
2NiO
2): C, 52.63%; H, 3.79%; N, 4.38%.
In the 100mL reactor, add silica gel (200 ℃ of bakings 6 hours) 8.5g, toluene 40mL, reactor is placed ice-water bath, extracting concentration with syringe is that the pentane solution 15mL of the trimethyl aluminium of 2mol/L slowly joins in the middle of the system, slowly temperature of reaction system is risen to 20～30 ℃ again after emitting Deng no gas, stirred 1 hour, and under condition of negative pressure, filtered after drying, obtain the silica gel that trimethyl aluminium was handled.
Under the condition of anhydrous and oxygen-free, in the exsiccant reactor, add the silica gel 0.5g that trimethyl aluminium was handled, alpha-diimine nickel olefine polymerization catalyst 0.5g, methylene dichloride 30mL was in stirring at room 4 hours, filter, drying obtains the alpha-diimine nickel olefine polymerization catalyst of silica gel load at last.Through ultimate analysis, contain the nickel of 35.0mg in the alpha-diimine nickel olefine polymerization catalyst of every gram silica gel load.
With the catalyzer that embodiment 1 makes, its vinyl polymerization gets the class spherical polymer, and activity is 2510gPE/g
CatH, the ethene polymers weight-average molecular weight is 35.5 ten thousand g/mol.
Embodiment 2
Preparation of catalysts: the silica gel consumption of handling except that trimethyl aluminium is 0.3g, and the alpha-diimine nickel olefine polymerization catalyst consumption is outside the 0.6g, and all the other are with embodiment 1.Obtain the alpha-diimine nickel olefine polymerization catalyst of silica gel load at last,, contain the nickel of 43.4mg in the alpha-diimine nickel olefine polymerization catalyst of every gram silica gel load through ultimate analysis.
With the catalyzer that embodiment 2 makes, its vinyl polymerization gets the class spherical polymer, and activity is 3620gPE/g
CatH.
Embodiment 3
Preparation of catalysts: the silica gel consumption of handling except that trimethyl aluminium is 0.3g, and the alpha-diimine nickel olefine polymerization catalyst consumption is outside the 0.9g, and all the other are with embodiment 1.Obtain the alpha-diimine nickel olefine polymerization catalyst of silica gel load at last,, contain the nickel of 55.1mg in the alpha-diimine nickel olefine polymerization catalyst of every gram silica gel load through ultimate analysis.
With the catalyzer that embodiment 3 makes, its vinyl polymerization gets the class spherical polymer, and activity is 4800gPE/g
CatH.
Embodiment 4
Preparation of catalysts: the silica gel consumption of handling except that trimethyl aluminium is 0.6g, the alpha-diimine nickel olefine polymerization catalyst consumption is outside the 0.3g, all the other are with embodiment 1, obtain the alpha-diimine nickel olefine polymerization catalyst of silica gel load at last, through ultimate analysis, contain the nickel of 21.3mg in the alpha-diimine nickel olefine polymerization catalyst of every gram silica gel load.
With the catalyzer that embodiment 4 makes, its vinyl polymerization gets the class spherical polymer, and activity is 1612gPE/g
CatH.
Embodiment 5
The preparation of alpha-diimine part is with embodiment 1.
In the reaction flask of 100ml; add alpha-diimine ligand 1 .00g; Nickel Chloride 0.25g, methylene dichloride 30mL, glycol dimethyl ether 0.21g; stirring at room is 18 hours under nitrogen protection; filter, wash 3 times drying with anhydrous diethyl ether 20mL; obtain the alpha-diimine nickel complex 0.88g of brown, productive rate: 92%.
Under the condition of anhydrous and oxygen-free, in the exsiccant reactor, add the silica gel 0.5g that trimethyl aluminium was handled, above-mentioned synthetic alpha-diimine nickel olefine polymerization catalyst 0.5g, methylene dichloride 30mL in stirring at room 4 hours, filters, drying obtains the alpha-diimine nickel olefine polymerization catalyst of silica gel load at last.Through ultimate analysis, contain the nickel of 35.0mg in the alpha-diimine nickel olefine polymerization catalyst of every gram silica gel load.
With the catalyzer that embodiment 5 makes, its vinyl polymerization gets the class spherical polymer, and activity is 1523gPE/g
CtH.The ethene polymers weight-average molecular weight is 11.4 ten thousand g/mol.
Claims (1)
1. the preparation method of an olefin polymerization catalysis, it is characterized in that: step and condition are as follows:
Preparation Schiff's base: in reactor, press 1mmol: 2.5mmol: 0.013g: the 10mL proportioning adds acenaphthenequinone, 3,5-dimethyl-4-amino-phenol, tosic acid and toluene, reflux 10～18h, steam toluene, press the 1mmol acenaphthenequinone then: 16mL dehydrated alcohol proportioning adds dehydrated alcohol, and reheat refluxes, heat filtering, with filtrate placement overnight, there is red solid to generate, uses the dehydrated alcohol recrystallization again, obtain the alpha-diimine part of following structure:
The preparation alpha-diimine nickel olefine polymerization catalyst:
Under the anhydrous and oxygen-free condition, in the exsiccant reactor, press 1g: the proportioning of 0.25g or 0.34g: 30mL: 0.21g adds alpha-diimine part, Nickel Chloride or Nickel Bromide, methylene dichloride and glycol dimethyl ether, stirred 18 hours at 20～30 ℃, filter, give a baby a bath on the third day after its birth time with anhydrous diethyl ether, drying obtains the alpha-diimine nickel olefine polymerization catalyst of following structure at last:
In the formula, X is Br or Cl;
The alpha-diimine nickel olefine polymerization catalyst of preparation silica gel load:
A) handle silica gel with trimethyl aluminium: under the condition of anhydrous and oxygen-free, in the exsiccant reactor, add silica gel, toluene, reactor is placed ice-water bath, the pentane solution that extracts trimethyl aluminium with syringe slowly joins in the middle of the system, slowly temperature of reaction system is risen to 20～30 ℃ again after emitting Deng no gas, stirred 1 hour, under-100kpa condition, filter after drying-50, obtain the silica gel that trimethyl aluminium was handled, proportionlity wherein is, in every 8.5g silica gel, toluene 40mL, concentration is the hexane solution 15mL of 2mol/L trimethyl aluminium;
B) under the condition of anhydrous and oxygen-free, in the exsiccant reactor, press 1g: 60mL: 0.5～3g proportioning adds silica gel, methylene dichloride and the alpha-diimine nickel olefine polymerization catalyst that trimethyl aluminium was handled, stirred 2～10 hours at 20～30 ℃, filter, drying obtains the silica gel-supported alpha-diimine nickel olefine polymerization catalyzer of following structure at last:
X is Br or Cl.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619111B (en) * | 2008-07-03 | 2012-05-09 | 中国石油天然气股份有限公司 | Silica gel loaded alpha-nickel diimine olefin polymerization catalyst, preparation method and application |
| CN102675496B (en) * | 2011-03-09 | 2015-10-21 | 中国科学院长春应用化学研究所 | A kind of method preparing class ball-type double peak weight distributing polyethylene |
| CN102773078A (en) * | 2012-07-16 | 2012-11-14 | 武汉纺织大学 | Solid complexation extractant capable of simultaneously adsorbing cation and anion, and preparation and application thereof |
| CN102827312B (en) * | 2012-08-03 | 2014-04-09 | 浙江大学 | Ethylidene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof |
| CN112679635B (en) * | 2019-10-18 | 2024-03-26 | 中国石油化工股份有限公司 | Preparation method of supported metallocene catalyst and catalyst prepared by preparation method |
| CN112094303B (en) * | 2020-11-02 | 2021-03-26 | 江苏欣诺科催化剂有限公司 | Solid-supported metal organic complex and preparation method and application thereof |
| CN114192192B (en) * | 2021-12-28 | 2022-09-09 | 卫星化学股份有限公司 | Catalyst composition for ethylene oligomerization and preparation method and application thereof |
| CN114797989B (en) * | 2022-05-30 | 2024-02-23 | 卫星化学股份有限公司 | Supported catalyst and preparation method and application thereof |
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| US6002034A (en) * | 1996-07-23 | 1999-12-14 | E. I. Du Pont De Nemours And Company | Bis(arylimino)acenaphthene nickel(II) complexes |
| CN1527849A (en) * | 2001-03-28 | 2004-09-08 | ��Ļ���Ű˾ | Supported Catalysts for Olefin Polymerization |
| CN1884312A (en) * | 2006-06-06 | 2006-12-27 | 中山大学 | Nickel acenaphthenequinonediimine/ Fe3O4 carried magnetic nano catalyst for ethene in situ polymerization and its preparation method |
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| US6002034A (en) * | 1996-07-23 | 1999-12-14 | E. I. Du Pont De Nemours And Company | Bis(arylimino)acenaphthene nickel(II) complexes |
| CN1527849A (en) * | 2001-03-28 | 2004-09-08 | ��Ļ���Ű˾ | Supported Catalysts for Olefin Polymerization |
| CN1884312A (en) * | 2006-06-06 | 2006-12-27 | 中山大学 | Nickel acenaphthenequinonediimine/ Fe3O4 carried magnetic nano catalyst for ethene in situ polymerization and its preparation method |
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