CN102718901A - Ultrahigh molecular weight polyethylene catalyst preparation method and catalyst prepared by same and application of catalyst - Google Patents
Ultrahigh molecular weight polyethylene catalyst preparation method and catalyst prepared by same and application of catalyst Download PDFInfo
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- CN102718901A CN102718901A CN2012102069572A CN201210206957A CN102718901A CN 102718901 A CN102718901 A CN 102718901A CN 2012102069572 A CN2012102069572 A CN 2012102069572A CN 201210206957 A CN201210206957 A CN 201210206957A CN 102718901 A CN102718901 A CN 102718901A
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Abstract
The invention discloses an ultrahigh molecular weight polyethylene catalyst preparation method. The method includes: reacting magnesium compound with polyalcohol and silica gel to obtain silica gel magnesium alcoholate by separation; using hydroxyl removing agent for hydroxyl removal of the silica gel magnesium alcoholate and obtain an intermediate product by separation; and allowing the intermediate product to react with titaniferous compound and obtaining the ultrahigh molecular weight polyethylene catalyst after separation. The invention further discloses a catalyst prepared by the method and the application of the catalyst to polymerization reaction for preparation of the ultrahigh molecular weight polyethylene. The catalyst is simple in preparation, raw materials are easy to obtain, and product performances can be controlled by adjusting usage of the polyalcohol and the magnesium compound. The catalyst has excellent catalyzing performance and high activity, the ultrahigh molecular weight polyethylene product prepared by the catalyst is high in bulk density, narrow in particle distribution and wide in molecular weight adjusting range.
Description
Technical field
The present invention relates to a kind of olefinic polymerization load catalyst system, relate in particular to the catalyzer that is used to prepare ultrahigh molecular weight polyethylene(UHMWPE).
Background technology
According to ASTM D4020, ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is for having 1.44 or the linear polyethylene of higher relative viscosity, and wherein relative viscosity is measured in 135 ℃ 0.02% perhydronaphthalene solution.UHMWPE has one of flexible plastics most, owing to its own particularity, has the performance of a lot of excellences, has in fields such as transportation, weaving, mining industry, agricultural, electric power, metallurgy and chemical industry widely and uses.The catalyzer that is used for industrial production UHMWPE not only requires to have high catalytic activity, and requires product except the molecular weight with superelevation, can also in the scope of broad, regulate; Also require the tap density of product high simultaneously, can not there be excessive or too small particle in narrow diameter distribution; Preparation of catalysts is simple and with low cost.
Publication number is that the patent of WO0181432 discloses a kind of Catalysts and its preparation method and application that is used to prepare ultrahigh molecular weight polyethylene(UHMWPE); Wherein this Preparation of catalysts method is mixture and the pure contact reacts with magnesium halide and aluminium or boron cpd; Add ester cpds, silicon compound and titanium compound then, make solid titanium catalyst.This catalyzer can obtain the ultrahigh molecular weight polyethylene(UHMWPE) of high-bulk-density and narrow size distribution, but the molecular weight of products therefrom is not high, and does not relate to the regulation and control of molecular weight.
Publication number is that the Chinese patent of CN 102219869A discloses a kind of olefin polymerization catalysis and ultralow degree of branching ultrahigh molecular weight polyethylene(UHMWPE); Described catalyzer is to obtain through metal complexes directly is carried on the magnesium compound, in the time of the ultrahigh molecular weight polyethylene(UHMWPE) of the ultralow degree of branching of preparation, adds aluminum alkyls as promotor.But according to the result of embodiment, in the catalyst preparation process, the part synthetic time is long and productive rate is not high, and this has directly increased cost.
Publication number is that the Chinese patent of CN 101074275A discloses a kind of extra high-molecular polythene catalyst and preparation method thereof; This method is passed through halogenated magnesium compound and alcohol compound, titanate ester compound formation magnesium compound solution earlier; Magnesium compound solution that obtains and chlorination alkyl reactive aluminum obtain intermediate product, and intermediate product finally forms catalyzer with titanium compound, electron donor reaction again.The ultrahigh molecular weight polyethylene(UHMWPE) tap density of this Catalyst Production is high, but the preparation process is complicated, and does not relate to the method for molecular-weight adjusting.
Publication number is that the Chinese patent of CN 101831015A discloses a kind of catalyzer for preparing ultrahigh molecular weight polyethylene(UHMWPE); The characteristics of this catalyzer be in the preparation process, add carbonic acid gas, pure and mild silicon compound is handled the magnesium compound carrier, and regulates the content of titanium and ester in the catalyst system through the add-on of regulating titanic acid ester.The particle diameter of polymerisate is in certain scope, but according to the result of embodiment, this activity of such catalysts is not high, and the regulation range of molecular weight of product is not wide.
Summary of the invention
The invention provides the catalyzer and the application of a kind of extra high-molecular polythene catalyst preparation method and preparation thereof; Prepared catalyzer has excellent catalytic performance; Active high and can regulate the molecular weight of product; The particle form of product is good, and there is not excessive or too small particle in narrow diameter distribution.
A kind of preparation method of extra high-molecular polythene catalyst comprises:
(1) magnesium compound and polyvalent alcohol, silica gel are reacted, separate obtaining silica gel alcohol magnesium compound;
(2) make and spend the silica gel alcohol magnesium compound that hydroxylation reagent obtains step (1) and go hydroxylation to handle, separate obtaining intermediate product, the described hydroxylation reagent that goes is at least a in aluminum alkyls, silicon compound and the titanium compound;
(3) intermediate product and the titanium-containing compound that step (2) are obtained react, and separate to obtain described extra high-molecular polythene catalyst (abbreviation catalyzer);
The usage ratio of described polyvalent alcohol and magnesium compound consumption is 0.01～10ml: 1g.
Being reflected at of above-mentioned steps (1) can be carried out in the organic solvent of dissolved magnesium compound; Be preferably ether solvent; More preferably ether, isopropyl ether, THF, isoamyl oxide, MTBE or dioxane; Most preferably be THF, be reflected at when carrying out in room temperature to the solvent boiling point TR, can both obtain effect preferably.When solvent was THF, temperature of reaction was preferably 40～60 ℃.
Being reflected at of above-mentioned steps (2) and (3) reacted in the hydroxylation reagent organic solvent inert going; Be preferably hydro carbons reagent; More preferably Skellysolve A, normal hexane, hexanaphthene, normal heptane, benzene or toluene; Most preferably be normal hexane, be reflected at when carrying out in room temperature to the solvent boiling point TR, can both obtain effect preferably.When solvent was normal hexane, temperature of reaction was preferably 40～65 ℃.
Among the present invention; Method through step (1) and step (2) activated magnesium compound is called the recrystallize method again; This method with forming complex compound sediment in the solution of compounds such as ester, alcohol, ethers as complex-precipitation agent adding magnesium compound, removes above-claimed cpd again and obtains active magnesium compound crystal earlier.The complex-precipitation agent of using among the present invention is polyvalent alcohol, compares with monohydroxy-alcohol, and polyvalent alcohol has two or above hydroxyl, has better complex ability with mg ion, and crystallization effect is better, and the carrier specific surface area that obtains is higher.As the complex-precipitation agent of magnesium compound, polyvalent alcohol requires stable in properties, and complex ability is strong, and experiment shows that the magnesium chloride support that the polyhydric alcohol complex deposition obtains has unordered structure, and unordered degree strengthens along with the growth of carbochain; The particle diameter of catalyzer and specific surface area also receive the influence of carbon chain lengths, and carbochain is long more, and particle diameter is big more, and specific surface area is more little; Carbochain increases, and the polymerization activity of catalyzer appears increases earlier the trend that afterwards reduces; The polymer molecular weight that the alcohol of long carbochain makes catalyzer is higher than the alcohol of short carbon chain.Described multi-alcohol is preferably C
2～C
10Multi-alcohol, more preferably C
2～C
6Multi-alcohol, more preferably from terepthaloyl moietie, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol and 1, at least a in the 6-pinakon.
Said magnesium compound forms pure magnesium compound in the silica gel surface under the strong complexing action of polyvalent alcohol.The form of alcohol magnesium compound is relevant with the additional proportion of polyvalent alcohol and magnesium compound, and follow-up catalytic activity and product form are had very big influence, and the poly molecular weight of product that can telo merization.The ratio of polyvalent alcohol is excessive, will not play the effect of complexing crystalline by some polyvalent alcohol, is a kind of catalyzer poison in follow-up process, thereby reduces catalytic performance.The ratio of polyvalent alcohol is too small, will make the magnesium compound crystallization incomplete, and can not be dispersed in the silica gel surface well.The polyvalent alcohol described in the step (1) and the usage ratio of magnesium compound are preferably 0.01～3ml: 1g; Under preferred ratio; The crystallization effect of magnesium compound is good; And the binding substances of magnesium compound and polyvalent alcohol can be dispersed in the silica gel surface well, and this provides bigger specific surface for the load of follow-up titanium compound, and active specy is disperseed on the silica gel surface well.
The particle diameter of used silica gel can provide bigger specific surface area in the passive while between 15～30 μ m.The mass ratio of magnesium compound and silica gel is preferably 0.01～1 described in the step (1): 1, and under preferred ratio, the crystallisate mass-energy of magnesium compound is dispersed in the silica gel surface well.
Hydroxyl groups is an avtive spot, need before the effective species of supported catalyst, be removed.The described hydroxylation reagent that goes is preferably at least a in aluminum alkyls, silicon compound and the titanium compound; These three kinds of reagent can react with hydroxyl groups; Thereby reach hydroxylated effect, wherein said aluminum alkyls is preferably at least a in trimethylaluminium, triethyl aluminum and the triisobutyl aluminium; Said silicon compound is preferably at least a in silicon tetrachloride, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, trimethylaluminium silane and the di-isopropyl dichlorosilane; Said titanium compound is preferably at least a in titanous chloride, titanium tetrachloride and the titanium tetrabromide.
Described go hydroxylation reagent can with hydroxyl groups reaction, remove resultant through washing, make most of polyvalent alcohols from magnesium or silica gel disengaging, some is residual but still understand.Residual polyvalent alcohol meeting and go hydroxylation reagent generation complex reaction, the complex compound of generation and magnesium compound effect, the effect of serving as internal electron donor not only helps improving the polymeric activity, and helps improving the molecular weight of polymerisate.Go the ratio of hydroxylation reagent excessive, residual polyvalent alcohol with go the complex compound of hydroxylation reagent to reduce, thereby do not have above-mentioned effect.Go the ratio of hydroxylation reagent too small, polyvalent alcohol is residual too much can to form nonactive site, thereby reduces activity of such catalysts, goes the mol ratio of hydroxylation reagent and polyvalent alcohol to be preferably 0.1～10: 1.When the mol ratio of removing hydroxylation reagent and polyvalent alcohol is 0.1～10: 1, the kind of removing hydroxylation reagent is carried out when preferred according to such scheme, and the catalyst performance that obtains is better.
Titanium-containing compound described in the step (3) is preferably at least a in titanous chloride, titanium tetrachloride and the titanium tetrabromide, most preferably is titanium tetrachloride.Wherein the special coordination relation of titanium tetrachloride and magnesium compound can load on the magnesium compound titanium tetrachloride well, and the step of preparation is chemical process, so gained catalyzer uniform form.
The present invention also provides the extra high-molecular polythene catalyst that is obtained by method for preparing; This catalyzer has excellent catalytic performance, and is active high, high with the ultrahigh molecular weight polyethylene(UHMWPE) product bulk density of its preparation; Particle distribution is narrow, and the molecular-weight adjusting wide ranges.
The present invention also provides the application of described catalyzer in the polyreaction of preparation ultrahigh molecular weight polyethylene(UHMWPE).Described polymeric reaction temperature is 40～80 ℃, and polymerization pressure is high more, and the molecular weight that obtains is high more, but pressure is high more, and is also higher to the requirement of equipment, takes all factors into consideration, and polymerization pressure is preferably 0.3～2.0MPa.In reaction, add aluminum alkyls simultaneously as promotor, the mol ratio of add-on and catalyzer is 20～250: 1.
Among the present invention, the molecular weight of polyethylene product can be regulated through the ratio and the polymerizing condition of polyvalent alcohol and magnesium compound, and regulation range is 100～7,000,000.The result shows that along with the reduction of polyvalent alcohol in the catalyzer and magnesium compound ratio, the molecular weight of polyethylene product increases; Along with the rising of polymeric reaction temperature, the molecular weight of polyethylene product reduces; Along with the rising of polymerization pressure, molecular weight of polyethylene increases.
Compare with prior art, beneficial effect of the present invention is embodied in:
1, Preparation of catalysts of the present invention need not add electron donor, adopts polyvalent alcohol recrystallize activation method, and a certain amount of polyvalent alcohol serves as electron donor with the complex compound that goes hydroxyl agent and magnesium compound to form, and used raw material and step are simpler.
When 2, catalyzer of the present invention was used for preparing ultrahigh molecular weight polyethylene(UHMWPE), the molecular weight of the ultrahigh molecular weight polyethylene(UHMWPE) that obtains can be regulated.
3, the prepared ultrahigh molecular weight polyethylene(UHMWPE) that obtains of the present invention has good particle form, and tap density is high, and narrow diameter distribution does not have excessive or too small particle, helps processing.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.
The measuring method of each data is following in the instance:
Particle size analysis: the MASTERSIZE/E type laser granulometry that adopts Britain MALVERN company to produce is measured.
Bulk density: according to the GB1639-79 standard test.
Viscosity-average molecular weight: according to the ASTM-D4020 standard test, calculation formula is M
η=5.37 * 10
4[η]
1.37
Embodiment 1
1, catalyzer synthetic (butyleneglycol and magnesium chloride amount ratio are 0.88ml/g): reaction flask is carried out vacuum bakeout also fully replace with high purity nitrogen.Get 2g silica gel and 30ml THF, add 1 of 0.5ml, the 4-butyleneglycol, magnetic agitation is until being uniformly dispersed.Get 0.57g magnesium chloride and 30ml THF, 60 ℃ of lower magnetic forces are stirred to dissolving fully, and it slowly is transferred in the silica gel tetrahydrofuran solution, deposition occurs; Behind the stirring reaction 2h, isolate deposition,, be scattered in the normal hexane after the vacuum-drying with normal hexane washing four times; Add the isopentane solution (0.57mol/L) of 8ml triethyl aluminum, stirring reaction 1h isolates deposition in the time of 60 ℃; Be scattered in the normal hexane after the washing drying, add the titanium tetrachloride of 2ml again, stirring reaction 2h in the time of 60 ℃; More than three times, carry out vacuum-drying with the normal hexane washing, obtain solid catalyst 2.5g.
2, vinyl polymerization: volume be the Buchi reaction kettle of 1L after high pure nitrogen is fully taken out roasting displacement, add above-mentioned solid catalyst 25mg, normal heptane 300ml; Triethyl aluminum 5ml; Feed ethylene gas, make reaction pressure maintain 3bar, rotating speed of agitator 300rpm; At 50 ℃ of following polymerization 1h of temperature, polymerization result is seen attached list.
Embodiment 2
1, catalyzer synthetic (butyleneglycol and magnesium chloride amount ratio are 1.3ml/g): the add-on of removing magnesium chloride changes 0.38g into, and all the other preparation processes obtain solid catalyst 2.3g with embodiment 1.
2, vinyl polymerization: polymerization process is with embodiment 1, and polymerization result is seen attached list.
Embodiment 3
1, catalyzer synthetic (butyleneglycol and magnesium chloride amount ratio are 2.6ml/g): the add-on of removing magnesium chloride changes 0.19g into, and all the other preparation processes obtain solid catalyst 2.2g with embodiment 1.
2, vinyl polymerization: polymerization process is with embodiment 1, and polymerization result is seen attached list.
Embodiment 4
1, catalyzer synthetic (terepthaloyl moietie and magnesium chloride amount ratio are 0.88ml/g): remove 1 of adding 0.5ml, the 4-butyleneglycol changes the terepthaloyl moietie that adds 0.3ml into, and all the other preparation processes obtain solid catalyst 2.3g with embodiment 1.
2, vinyl polymerization: polymerization process is with embodiment 1, and polymerization result is seen attached list.
Embodiment 5
1, catalyzer synthetic (USP Kosher and magnesium chloride amount ratio are 0.88ml/g): remove 1 of adding 0.5ml, the 4-butyleneglycol changes the USP Kosher that adds 0.4ml into, and all the other preparation processes obtain solid catalyst 2.5g with embodiment 1.
2, vinyl polymerization: polyreaction is with comparative example 1, and polymerization result is seen attached list.
Embodiment 6
1, catalyzer synthetic (terepthaloyl moietie and magnesium chloride amount ratio are 0.88ml/g): remove 1 of adding 0.5ml, the 4-butyleneglycol changes into and adds 1 of 0.67g, the 6-pinakon, and all the other preparation processes obtain solid catalyst 2.6g with embodiment 1.
2, vinyl polymerization: polyreaction is with comparative example 1, and polymerization result is seen attached list.
Embodiment 7
1, catalyzer synthetic (going the hydroxyl agent is silicon tetrachloride): remove adding 8ml triethyl aluminum (0.57mol/L) and change adding 0.5ml silicon tetrachloride solution into, all the other preparation processes obtain solid catalyst 2.4g with embodiment 1.
2, vinyl polymerization: polyreaction is with comparative example 1, and polymerization result is seen attached list.
Embodiment 8
1, catalyzer synthetic (removing hydroxylation reagent is titanium tetrachloride): remove adding 8ml triethyl aluminum (0.57mol/L) and change adding 0.5ml titanium tetrachloride solution into, all the other preparation processes obtain solid catalyst 2.3g with embodiment 1.
2, vinyl polymerization: polyreaction is with comparative example 1, and polymerization result is seen attached list.
Embodiment 9
1, catalyzer is synthetic: the preparation process is with embodiment 1.
2, vinyl polymerization: remove triethyl aluminum 5ml, pressure maintains 3bar, changes triethyl aluminum 3ml at 50 ℃ of following polymerization 1h, and pressure maintains 8bar, and at 40 ℃ of following polymerization 2h, all the other are with embodiment 1, and polymerization result is seen attached list.
Embodiment 10
1, catalyzer is synthetic: the preparation process is with embodiment 1.
2, vinyl polymerization: remove triethyl aluminum 5ml, pressure maintains 3bar, changes triethyl aluminum 3ml at 50 ℃ of following polymerization 1h, and pressure maintains 10bar, and at 40 ℃ of following polymerization 2h, all the other are with embodiment 1, and polymerization result is seen attached list.
Embodiment 11
1, catalyzer is synthetic: the preparation process is with embodiment 1.
2, vinyl polymerization: remove triethyl aluminum 5ml, pressure maintains 3bar, changes triethyl aluminum 3ml at 50 ℃ of following polymerization 1h, and pressure maintains 8bar, and at 50 ℃ of following polymerization 2h, all the other are with embodiment 1, and polymerization result is seen attached list.
Embodiment 12
1, catalyzer is synthetic: the preparation process is with embodiment 1.
2, vinyl polymerization: remove triethyl aluminum 5ml, pressure maintains 3bar, changes triethyl aluminum 3ml at 50 ℃ of following polymerization 1h, and pressure maintains 8bar, and at 60 ℃ of following polymerization 2h, all the other are with embodiment 1, and polymerization result is seen attached list.
Subordinate list:
Claims (10)
1. the preparation method of an extra high-molecular polythene catalyst is characterized in that, comprising:
(1) magnesium compound and polyvalent alcohol, silica gel are reacted, separate obtaining silica gel alcohol magnesium compound;
(2) make and spend the silica gel alcohol magnesium compound that hydroxylation reagent obtains step (1) and go hydroxylation to handle, separate obtaining intermediate product, the described hydroxylation reagent that goes is at least a in aluminum alkyls, silicon compound and the titanium compound;
(3) intermediate product and the titanium-containing compound that step (2) are obtained react, and separate to obtain described extra high-molecular polythene catalyst;
The usage ratio of polyvalent alcohol described in the step (1) and magnesium compound is 0.01～10ml: 1g.
2. the preparation method of extra high-molecular polythene catalyst according to claim 1 is characterized in that, the usage ratio of polyvalent alcohol described in the step (1) and magnesium compound is 0.01～3ml: 1g.
3. the preparation method of extra high-molecular polythene catalyst according to claim 1 and 2 is characterized in that, the polyvalent alcohol described in the step (1) is C
2～C
10Multi-alcohol.
4. the preparation method of extra high-molecular polythene catalyst according to claim 3 is characterized in that, described C
2～C
10Multi-alcohol is selected from terepthaloyl moietie, 1, ammediol, USP Kosher, 1,4-butyleneglycol, 1,5-pentanediol and 1, at least a in the 6-pinakon.
5. the preparation method of extra high-molecular polythene catalyst according to claim 1 is characterized in that, the described magnesium compound of step (1) is selected from least a in magnesium chloride, magnesium bromide and the magnesium iodide.
6. according to the preparation method of claim 1 or 5 described extra high-molecular polythene catalysts, it is characterized in that the mass ratio of magnesium compound described in the step (1) and silica gel consumption is 0.01～1: 1.
7. the preparation method of extra high-molecular polythene catalyst according to claim 1 is characterized in that, the aluminum alkyls described in the step (2) is selected from least a in trimethylaluminium, triethyl aluminum, the triisobutyl aluminium;
Described silicon compound is selected from least a in silicon tetrachloride, dimethyldichlorosilane(DMCS), diethyl dichlorosilane, diphenyl dichlorosilane, trimethylaluminium silane and the di-isopropyl dichlorosilane;
Said titanium compound is selected from least a in titanous chloride, titanium tetrachloride and the titanium tetrabromide.
8. the preparation method of extra high-molecular polythene catalyst according to claim 1 is characterized in that, the mol ratio of removing hydroxylation reagent and polyvalent alcohol consumption described in the step (2) is 0.1～10: 1.
9. the extra high-molecular polythene catalyst for preparing according to the preparation method of the arbitrary described extra high-molecular polythene catalyst of claim 1～8.
10. the application of extra high-molecular polythene catalyst according to claim 9 in the polyreaction of preparation ultrahigh molecular weight polyethylene(UHMWPE).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108359033A (en) * | 2018-01-31 | 2018-08-03 | 公安县瑞凯高分子材料股份有限公司 | A kind of High molecular weight polyethylene and preparation method thereof and corrosion-resistant sand streak wax |
| CN114478879A (en) * | 2022-02-25 | 2022-05-13 | 江苏扬农化工集团有限公司 | Method for adjusting molecular weight of ultrahigh molecular weight polyethylene |
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| CN101654492A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Super-high molecular polyethylene and preparation method and application thereof |
| CN101831015A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene |
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- 2012-06-19 CN CN2012102069572A patent/CN102718901A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654492A (en) * | 2008-08-21 | 2010-02-24 | 中国石化扬子石油化工有限公司 | Super-high molecular polyethylene and preparation method and application thereof |
| CN101831015A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108359033A (en) * | 2018-01-31 | 2018-08-03 | 公安县瑞凯高分子材料股份有限公司 | A kind of High molecular weight polyethylene and preparation method thereof and corrosion-resistant sand streak wax |
| CN114478879A (en) * | 2022-02-25 | 2022-05-13 | 江苏扬农化工集团有限公司 | Method for adjusting molecular weight of ultrahigh molecular weight polyethylene |
| CN114478879B (en) * | 2022-02-25 | 2023-12-19 | 江苏扬农化工集团有限公司 | Molecular weight regulating method of ultra-high molecular weight polyethylene |
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Application publication date: 20121010 |