CN102617763A - Preparation method of ultrahigh molecular weight polyethylene - Google Patents
Preparation method of ultrahigh molecular weight polyethylene Download PDFInfo
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Abstract
The invention discloses a preparation method of ultrahigh molecular weight polyethylene, which includes conducting polymerization reaction on ethylene monomers under catalyst effect of a ziegler natta catalyst to obtain ultrahigh molecular weight polyethylene. Compared with the prior art, a sulfonic acid class compound is introduced in the ziegler natta catalyst, and a cation metal activity center is formed due to introduction of the sulfonic acid class compound, so that the polyethylene can be favorable for being coordinated with the ethylene monomer with alkalescence, chain increment speed is increased, and polymerization activity is improved. Simultaneously, acceleration of the chain increment speed reduces effect of chain transfer on polymer molecular weight and improves polymer molecular weight. Experiment result shows that the viscosity average molecular weight (Mv) of the ultrahigh molecular weight polyethylene prepared by the method is more than 3*106, and the adopted ziegler natta catalyst has high catalytic activity.
Description
Technical field
The present invention relates to technical field of polymer, more particularly, relate to a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE).
Background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is a kind of thermoplastic engineering plastic of linear structure.Although the molecular structure of ultrahigh molecular weight polyethylene(UHMWPE) and common high density polyethylene(HDPE) are identical; But; The molecular weight of common high density polyethylene(HDPE) is lower; Be merely 5～300,000, and the molecular weight of ultrahigh molecular weight polyethylene(UHMWPE) is greater than 1,000,000, thereby ultrahigh molecular weight polyethylene(UHMWPE) have common high density polyethylene(HDPE) and the unexistent special performance of some other engineering plastics; Shock resistance, wearability, chemical resistance, lower temperature resistance, stress cracking resistance, anti-adhesive and self-lubricity etc. like excellence have the title of " surprised plastics ".Superhigh molecular weight polyethylene fibers is owing to have numerous excellent specific properties; Thereby on high-performance fiber market; For example aspects such as the mooring rope of offshore oilfield and high-performance light matrix material all demonstrate great advantage, change fields such as war and Aeronautics and Astronautics, marine site defend equipment in modern times and are bringing into play very important effect.
At present, the preparation method of ultrahigh molecular weight polyethylene(UHMWPE) has obtained extensive studies, and wherein, the catalyzer of preparation ultrahigh molecular weight polyethylene(UHMWPE) is mainly metallocene catalyst and ziegler natta catalyst.According to bibliographical information, metallocene catalyst is extremely responsive to temperature, for example, and with Cp
2ZrCl
2Catalyzed ethylene polymerization, when temperature when 20 ℃ are raised to 70 ℃, polymericular weight drops to 120,000 [Macromol.Chem.Phys., 2007,208,938] from 600,000.Simultaneously; Metallocene catalyst is if will reach sufficiently high catalytic activity; Need a large amount of expensive MAOs (MAO) as promotor, thereby increased the product prepn cost, on the other hand; Promotor MAO is not the single compound of composition, and production process causes product performance unstable easily.
Ziegler natta catalyst is the industrializeding catalyst of preparation ultrahigh molecular weight polyethylene(UHMWPE); For example, [Polym.Bull., 2011 such as Zhang H.X.; 66; 627] reported the method for utilizing the ziegler natta catalyst that contains internal electron donor to prepare ultrahigh molecular weight polyethylene(UHMWPE), yet the internal electron donor in this ziegler natta catalyst has reduced activity of such catalysts.The inventor considers, a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE) is provided, and this method further improves the molecular weight of the ultrahigh molecular weight polyethylene(UHMWPE) of preparation, and guarantees that the catalytic activity of catalyzer is higher.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE), and the catalytic activity of the catalyzer that this method adopts is higher, and the ultrahigh molecular weight polyethylene(UHMWPE) molecular weight for preparing is higher.
In order to solve above technical problem, the present invention provides a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE), may further comprise the steps:
Vinyl monomer is carried out polyreaction under the katalysis of ziegler natta catalyst, obtain ultrahigh molecular weight polyethylene(UHMWPE), said ziegler natta catalyst prepares according to following method:
In magnesium alcoholate, add transition metal halide, obtain catalyst precursor after the reaction;
With said catalyst precursor and sulfonic compound back flow reaction in solvent, obtain ziegler natta catalyst.
Preferably, the general formula of said transition metal halide is suc as formula shown in the I:
M (R)
nX
(4-n)Formula I
Wherein, M is Ti, Zr, Hf, V or Nd, and R is the alkyl of C1～C20, and X is a halogen, and n is 0,1,2 or 3.
Preferably, the general formula of said sulfonic compound is suc as formula shown in the II:
R
1-SO
3-R
2Formula II
Wherein, R
1And R
2Independent separately is alkyl, aromatic base, aralkyl or the haloalkyl of C1～C20.
Preferably, said sulfonic compound is selected from methylsulfonic acid, ethyl sulfonic acid, Phenylsulfonic acid, trifluoromethanesulfonic acid; P-methyl benzenesulfonic acid, perfluoro butyl sulfonic acid, perfluoro octyl sulfonic acid, penta fluoro benzene sulfonic acid, methyl mesylate; Ethyl methane sulfonate, methylsulfonic acid isobutyl, methylsulfonic acid trifluoroethyl ester, ethyl sulfonic acid methyl esters, ethyl sulfonic acid ethyl ester; The ethyl sulfonic acid isobutyl, ethyl sulfonic acid trifluoroethyl ester, methyl benzenesulfonate, ethyl benzenesulfonat, Phenylsulfonic acid isobutyl; Phenylsulfonic acid trifluoroethyl ester, trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid isobutyl, trifluoromethanesulfonic acid trifluoroethyl ester; The p-methyl benzenesulfonic acid methyl esters, p-methyl benzenesulfonic acid ethyl ester, p-methyl benzenesulfonic acid isobutyl, p-methyl benzenesulfonic acid trifluoroethyl ester, perfluoro butyl methylmesylate; Perfluoro butyl sulfonic acid ethyl ester, perfluoro butyl sulfonic acid isobutyl, perfluoro butyl sulfonic acid trifluoroethyl ester, perfluoro octyl sulfonic acid methyl esters, perfluoro octyl sulfonic acid ethyl ester; The perfluoro octyl sulfonic acid isobutyl, perfluoro octyl sulfonic acid trifluoroethyl ester, penta fluoro benzene methylmesylate, penta fluoro benzene sulfonic acid ethyl ester, one or more in penta fluoro benzene sulfonic acid isobutyl and the penta fluoro benzene sulfonic acid trifluoroethyl ester.
Preferably, the said temperature of reaction that obtains catalyst precursor is 100～120 ℃, and the reaction times is 0.5～8 hour.
Preferably, said magnesium alcoholate prepares as follows:
Magnesium compound and alcohol compound are mixed in organic solvent, obtain mixing solutions after intensification and the insulation;
Said mixing solutions is added in the ethane, obtain magnesium alcoholate.
Preferably, the general formula of magnesium compound is shown in formula III:
Mg (OR`)
mX
(2-m)Formula III
Wherein, R` is alkyl, aralkyl or the aryl of C1～C20, and X is a halogen, and m is 0 or 1.
Preferably, said alcohol compound is selected from cycloalkanol compounds and in C6～C15 aromatic alcohol compound one or more of aliphatic alcohols compound, the C3～C15 of C1～C15.
Preferably; Said alcohol compound is selected from methyl alcohol, ethanol, propyl alcohol, terepthaloyl moietie, n-propyl alcohol, Virahol, 1, one or more in ammediol, butanols, isopropylcarbinol, hexanol, enanthol, n-Octanol, isooctyl alcohol, nonyl alcohol, decyl alcohol, sorbyl alcohol, hexalin and the benzylalcohol.
Preferably, the time of said polyreaction is 50～80 minutes.
The present invention provides a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE), vinyl monomer is carried out polyreaction obtained ultrahigh molecular weight polyethylene(UHMWPE) under the katalysis of ziegler natta catalyst.Compared with prior art, introduced sulfonic compound in the ziegler natta catalyst that the present invention adopts, because the introducing of sulfonic compound; Formed the cationic metal active site, helped and be weakly alkaline vinyl monomer coordination, chain growth speed is accelerated; Improved polymerization activity; Simultaneously, the quickening of chain growth speed has reduced the influence of chain transfer to polymericular weight, has improved the molecular weight of polymkeric substance.Experimental result shows that the viscosity-average molecular weight (Mv) of the ultrahigh molecular weight polyethylene(UHMWPE) of the present invention's preparation is 3 * 10
6More than, and the ziegler natta catalyst that adopts has advantages of high catalytic activity.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE); May further comprise the steps: vinyl monomer is carried out polyreaction under the katalysis of ziegler natta catalyst; Obtain ultrahigh molecular weight polyethylene(UHMWPE); Said ziegler natta catalyst prepares according to following method: in magnesium alcoholate, add transition metal halide, obtain catalyst precursor after the reaction; With said catalyst precursor and sulfonic compound back flow reaction in solvent, obtain ziegler natta catalyst.
Ziegler natta catalyst is the key of preparation ultrahigh molecular weight polyethylene(UHMWPE); In the preparation process of this ziegler natta catalyst; At first, magnesium alcoholate and transition metal halide reaction, generation is that the transition metal halide catalyst of carrier is a catalyst precursor with the magnesium halide; Then, the reaction of sulfonic compound described in catalyst precursor and the present invention generation final product is a ziegler natta catalyst.
According to the present invention, said magnesium alcoholate is preferably according to following method preparation: magnesium compound and alcohol compound are mixed in organic solvent, obtain mixing solutions after intensification and the insulation; Said mixing solutions is added in the ethane, obtain magnesium alcoholate.The present invention does not have special restriction for the organic solvent that adopts in the above-mentioned preparation magnesium alcoholate, can adopt organic solvent well known to those skilled in the art.Said alcohol compound is selected from cycloalkanol compounds and in C6～C15 aromatic alcohol compound one or more of aliphatic alcohols compound, the C3～C15 of C1～C15; More preferably methyl alcohol, ethanol, propyl alcohol, terepthaloyl moietie, n-propyl alcohol, Virahol, 1, one or more in ammediol, butanols, isopropylcarbinol, hexanol, enanthol, n-Octanol, isooctyl alcohol, nonyl alcohol, decyl alcohol, sorbyl alcohol, hexalin and the benzylalcohol.As preferably, the general formula of magnesium compound is shown in formula III:
Mg (OR`)
mX
(2-m)Formula III
Wherein, R` is alkyl, aralkyl or the aryl of C1～C20, and X is a halogen, and m is 0 or 1.
In the present invention; Magnesium compound has the effect of carrier in the ziegler natta catalyst of preparation, for one of composition of traditional ziegler natta catalyst, can make the catalyzer of preparation have suitable shape, size and physical strength; Simultaneously; Carrier can make active ingredient be dispersed on the carrier surface, obtains higher specific surface area, improves the catalytic efficiency (of unit mass active ingredient.In addition, the effect of said alcohol compound is that with carrier be the magnesium compound dissolving.
In the preparation process of magnesium alcoholate, the said temperature that obtains mixing solutions is preferably 100～130 ℃, and more preferably 120 ℃, said soaking time is preferably 1～3 hour, more preferably 2～3 hours; The temperature of the said hexane solvent that obtains adopting in the magnesium alcoholate step is preferably-20～-40 ℃, more preferably-30 ℃.Therefore, magnesium compound at high temperature by the alcohol compound dissolving, has obtained magnesium alcoholate.
Then, generate the reaction of magnesium alcoholate and transition metal halide, alcohol compound is removed, and has generated catalyst precursor.The said temperature of reaction that obtains catalyst precursor is preferably 100～120 ℃, more preferably 110 ℃; Reaction times is preferably 0.5～8 hour, and more preferably 0.5～5 hour, more preferably 1.5～5 hours.Through the reaction of above-mentioned transition metal halide and magnesium alcoholate, realized transition metal halide is loaded on the magnesium compound polymerization of catalyzed ethylene after the activation.The general formula of said transition metal halide is suc as formula shown in the I:
M (R)
nX
(4-n)Formula I
Wherein, M is Ti, Zr, Hf, V or Nd, and R is the alkyl of C1～C20, and X is a halogen, and n is 0,1,2 or 3.
The step that the present invention obtains catalyst precursor is preferably: in first magnesium alcoholate, add first transition metal halide, obtain first catalyst precursor after the reaction; In second transition metal halide, add first catalyst precursor, the reaction after scouring obtains catalyst precursor.Therefore; The present invention preferably carries out twice load-reaction; When adding first transition metal halide carried out the first pass load, transition metal halide and magnesium alcoholate generated the phthalate compound, and the transition metal halide that is added during second time load filters out the phthalate compound dissolution.In addition, the present invention preferably adopts hexane to wash, and more preferably adopts 50～70 ℃ hexane solvent to wash.
At last, catalyst precursor and sulfonic compound back flow reaction in solvent has obtained ziegler natta catalyst.Wherein, the temperature of said back flow reaction is preferably 60～80 ℃, more preferably 70 ℃; The time of back flow reaction is preferably 2～5 hours, more preferably 3 hours.And, preferably utilize hexane with the ziegler natta catalyst washing that obtains 2～5 times after the back flow reaction, dry then.The general formula of the sulfonic compound that the present invention adopts is preferably suc as formula shown in the II:
R
1-SO
3-R
2
Formula II
Wherein, R
1And R
2Independent separately is the alkyl of C1～C20, aromatic base, aralkyl or haloalkyl.Preferred, said sulfonic compound is a methylsulfonic acid, ethyl sulfonic acid, Phenylsulfonic acid, trifluoromethanesulfonic acid; P-methyl benzenesulfonic acid, perfluoro butyl sulfonic acid, perfluoro octyl sulfonic acid, penta fluoro benzene sulfonic acid, methyl mesylate; Ethyl methane sulfonate, methylsulfonic acid isobutyl, methylsulfonic acid trifluoroethyl ester, ethyl sulfonic acid methyl esters, ethyl sulfonic acid ethyl ester; The ethyl sulfonic acid isobutyl, ethyl sulfonic acid trifluoroethyl ester, methyl benzenesulfonate, ethyl benzenesulfonat, Phenylsulfonic acid isobutyl; Phenylsulfonic acid trifluoroethyl ester, trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid isobutyl, trifluoromethanesulfonic acid trifluoroethyl ester; The p-methyl benzenesulfonic acid methyl esters, p-methyl benzenesulfonic acid ethyl ester, p-methyl benzenesulfonic acid isobutyl, p-methyl benzenesulfonic acid trifluoroethyl ester, perfluoro butyl methylmesylate; Perfluoro butyl sulfonic acid ethyl ester, perfluoro butyl sulfonic acid isobutyl, perfluoro butyl sulfonic acid trifluoroethyl ester, perfluoro octyl sulfonic acid methyl esters, perfluoro octyl sulfonic acid ethyl ester; The perfluoro octyl sulfonic acid isobutyl, perfluoro octyl sulfonic acid trifluoroethyl ester, penta fluoro benzene methylmesylate, penta fluoro benzene sulfonic acid ethyl ester, one or more in penta fluoro benzene sulfonic acid isobutyl and the penta fluoro benzene sulfonic acid trifluoroethyl ester.
With the transition metal halide is TiCl
4Be example, the reaction formula of sulfonic compound and transition metal halide is following:
Be elaborated below in conjunction with the preparation process of chemical formula to ziegler natta catalyst provided by the invention:
The magnesium compound general formula of preparation magnesium alcohol adducts is Mg (OR`)
mX
(2-m), R` is alkyl, aralkyl or the aryl of C1～C20 in the formula, and X is a halogen, and m is 0 or 1.
When m=0, reaction formula is following:
MgCl
2+ROH-----→MgCl
2·(ROH)
MgCl
2(ROH)+TiCl
4(excessive)-----→ MgCl
2TiCl
4+ Ti (OR)
4
MgCl
2·TiCl
4+R
1SO
3R
2-----→MgCl
2·TiCl
(4-m)(O
3SR1)
m+R
2Cl
When m=1, reaction formula is following:
Mg(OR`)Cl+ROH-----→Mg(OR`)Cl·ROH
Mg (OR`) ClROH+TiCl
4(excessive)--→ MgCl
2TiCl
4+ Ti (OR`)
4+ Ti (OR)
4...
MgCl
2·TiCl
4+R
1SO
3R
2----→MgCl
2·TiCl
(4-m)(O
3SR
1)m+R
2Cl
Can find out that from above-mentioned reaction formula at first, magnesium compound at high temperature by the alcohol compound dissolving, obtains magnesium alcoholate, secondly, the magnesium alcoholate of generation and transition metal halide are (like TiCl
4) reaction, alcohol compound is removed, and has generated traditional with MgCl
2TiCl for carrier
4Catalyzer, last, with MgCl
2TiCl for carrier
4It is ziegler natta catalyst that catalyzer and sulfonic compound reaction generate final product.
In addition, the condition of polyreaction influences the carrying out of reaction to a certain extent, and as preferred version, said temperature of reaction is 20～80 ℃, and more preferably 40～70 ℃, more preferably 60～70 ℃; Reaction times is preferably 50～80 minutes, and more preferably 50～70 minutes, more preferably 60 minutes; Reaction pressure is preferably 0.5～1MPa, more preferably 0.6～0.8MPa, more preferably 0.7MPa.
Can find out from such scheme, introduce sulfonic compound in the ziegler natta catalyst that the present invention adopts, because the introducing of sulfonic compound; Formed the cationic metal active site, helped and be weakly alkaline vinyl monomer coordination, chain growth speed is accelerated; Improved polymerization activity, simultaneously, the quickening of chain growth speed; Reduced the influence of chain transfer, improved the molecular weight of polymkeric substance polymericular weight.Experimental result shows, the prepared ultrahigh molecular weight polyethylene(UHMWPE) molecular weight of the ziegler natta catalyst of the present invention after with the sulfonic compound modification is far above the ziegler natta catalyst without the sulfonic compound modification, and has advantages of high catalytic activity.In addition, this ziegler natta catalyst is applicable to slurry, gas phase and bulk technique.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Embodiment 1
In through the abundant metathetical reactor drum of high pure nitrogen, add anhydrous magnesium dichloride (MgCl successively
2) 10g, white oil 100ml, silicone oil 80ml; Be warming up to 50 ℃ under stirring, add ethanol 20ml, continue to be warming up to 120 ℃; And kept 2.5 hours, form homogeneous transparent solution, then solution is changed over to fast in the hexane solution of-30 ℃ of high-speed stirring; Filter the back and use the hexane solvent washed twice, obtain white magnesium dichloride alcohol adduct;
The 100ml TiCl that the magnesium dichloride alcohol adduct that generates is added-30 ℃ of high-speed stirring
4In, slowly be warming up to 110 ℃ after, kept 2 hours at 110 ℃, be cooled to room temperature, filter, add 100ml TiCl once more
4, be warming up to 110 ℃, be incubated 1 hour, filter, with hexane solvent washing five times, obtain the ziegler natta catalyst presoma;
The ziegler natta catalyst presoma of above-mentioned preparation is placed the 200ml hexane solvent; Add a certain amount of (Ti: S=1: 1; Mol ratio) behind the methylsulfonic acid 70 ℃ of refluxed 3 hours; Filter the back with hexane solvent washing 3 times, obtain ziegler natta catalyst, catalyzer titaniferous amount is 2.5wt%.
In high pure nitrogen protection down, 70 ℃ of recirculated waters of adding in the reacting kettle jacketing after 2 liters of dry deoxygenations are furnished with and add normal hexane 1000ml in the churned mechanically high-pressure reactor successively, triethyl aluminum (Al (C
2H
5)
3) ziegler natta catalyst of 2mmol and the above-mentioned preparation of 25mg, adding the ethylene gas post-polymerization and begin, the system total pressure is 0.7MPa, and the reaction times is 60 minutes, and polymerization result is seen table 1.
Embodiment 2～7
With embodiment 1 same catalyst treatment condition and polymerizing condition under, as shown in table 1ly change different sulfonic compounds successively, polymerization result is seen table 1.
Comparative example 1
In through the abundant metathetical reactor drum of high pure nitrogen, add anhydrous magnesium dichloride (MgCl successively
2) 10g, white oil 100ml, silicone oil 80ml; Be warming up to 50 ℃ under stirring, add ethanol 20ml, continue to be warming up to 120 ℃; And kept 2.5 hours, form homogeneous transparent solution, then solution is changed over to fast in the hexane solution of-30 ℃ of high-speed stirring; Filter the back and use the hexane solvent washed twice, obtain white magnesium dichloride alcohol adduct;
The 100ml TiCl that the magnesium dichloride alcohol adduct that generates is added-30 ℃ of high-speed stirring
4In, slowly be warming up to 110 ℃ after, kept 2 hours at 110 ℃, be cooled to room temperature, filter, add 100ml TiCl once more
4, be warming up to 110 ℃, be incubated 1 hour, filter, with hexane solvent washing five times, obtain ziegler natta catalyst, catalyzer titaniferous amount is 3.0wt%.
In high pure nitrogen protection down, 70 ℃ of recirculated waters of adding in the reacting kettle jacketing after 2 liters of dry deoxygenations are furnished with and add normal hexane 1000ml in the churned mechanically high-pressure reactor successively, triethyl aluminum (Al (C
2H
5)
3) ziegler natta catalyst of 2mmol and the above-mentioned preparation of 25mg, adding the ethylene gas post-polymerization and begin, the system total pressure is 0.7MPa, the reaction times is 60 minutes.
The polymerization result of table 1 embodiment 1～7 and the ziegler natta catalyst of comparative example 1 preparation
Embodiment 8
Fully clean the reaction flask that has whisking appliance with high-purity nitrogen, in reaction flask, add the 0.1mol tributyl phosphate afterwards, under agitation, add 0.05mol solid water-free magnesium dichloride; Be warming up to 80 ℃ gradually, stirred 2 hours, the solid dissolving, shape liquid is translucent; Treat that solution cooling back adds 0.03mol ethanol, stir half a hour, solution is transparence; Add the 0.0075mol Tetra hydro Phthalic anhydride again and be warming up to 80 ℃, constant temperature 1 hour obtains the magnesium dichloride solution of stable uniform;
Above-mentioned homogeneous solution is moved in the gauge line, splashes in advance the TiCl of the 0.9mol that is cooled to-5 ℃
4In, heat up after dripping, there is solid to separate out thereupon, be warming up to 80 ℃ and stirred 3 hours, filtered while hot goes out mother liquor then, with hexane wash 6 times, obtains the ziegler natta catalyst presoma;
The ziegler natta catalyst presoma of above-mentioned preparation is placed the 200ml hexane solvent; Add a certain amount of (Ti: S=1: 1; Mol ratio) behind the methylsulfonic acid 70 ℃ of refluxed 3 hours; Filter the back with hexane solvent washing 3 times, obtain ziegler natta catalyst, catalyzer titaniferous amount is 6.8wt%.Polymerizing condition is with embodiment 1, and polymerization result is seen table 2.
Embodiment 9
Other conditions change the methylsulfonic acid among the embodiment 8 into trifluoromethanesulfonic acid with embodiment 8, and the ziegler natta catalyst titaniferous amount that obtains is 6.5wt%.
Comparative example 2
Fully clean the reaction flask that has whisking appliance with high-purity nitrogen, in reaction flask, add the 0.1mol tributyl phosphate afterwards, under agitation, add 0.05mol solid water-free magnesium dichloride; Be warming up to 80 ℃ gradually, stirred 2 hours, the solid dissolving, shape liquid is translucent; Treat that solution cooling back adds 0.03mol ethanol, stir half a hour, solution is transparence; Add the 0.0075mol Tetra hydro Phthalic anhydride again and be warming up to 80 ℃, constant temperature 1 hour obtains the magnesium dichloride solution of stable uniform;
Above-mentioned homogeneous solution is moved in the gauge line, splashes in advance the TiCl of the 0.9mol that is cooled to-5 ℃
4In, heat up after dripping, there is solid to separate out thereupon, be warming up to 80 ℃ and stirred 3 hours, filtered while hot goes out mother liquor then, with hexane wash 6 times, obtains the ziegler natta catalyst that titanium content is 7.4wt%.Polymerizing condition is with comparative example 1, and polymerization result is seen table 2.
Embodiment 10
In the abundant metathetical reactor drum of high pure nitrogen, add the anhydrous MgCl of 0.042mol successively
2, 60ml toluene, 0.032mol epoxy chloropropane, 0.022mol tributyl phosphate, 0.017mol ethanol, be warming up to 80 ℃ under stirring, and keep 15 minutes solids and dissolve fully; Form homogeneous solution, add Tetra hydro Phthalic anhydride 0.0074mol then, kept again 1 hour; This solution is cooled to-25 ℃, again the 0.5mol titanium tetrachloride is splashed into wherein, slowly be warming up to 80 ℃ then; Reacted 3 hours, and used toluene wash 6 times after the filtration respectively, obtain the ziegler natta catalyst presoma;
The ziegler natta catalyst presoma of above-mentioned preparation is placed the 200ml hexane solvent; Add a certain amount of (Ti: S=1: 1; Mol ratio) behind the methylsulfonic acid 70 ℃ of refluxed 3 hours; Filter the back with hexane solvent washing 3 times, obtain ziegler natta catalyst, catalyzer titaniferous amount is 5.0wt%.Polymerizing condition is with comparative example 1, and polymerization result is seen table 2.
Embodiment 11
Other conditions just change the methylsulfonic acid among the embodiment 10 into trifluoromethanesulfonic acid with embodiment 10, and the ziegler natta catalyst titaniferous amount after the modification that obtains is 4.8wt%.
Comparative example 3
In the abundant metathetical reactor drum of high pure nitrogen, add the anhydrous MgCl of 0.042mol successively
2, 60ml toluene, 0.032mol epoxy chloropropane, 0.022mol tributyl phosphate, 0.017mol ethanol, be warming up to 80 ℃ under stirring, and keep 15 minutes solids and dissolve fully.Form homogeneous solution, add Tetra hydro Phthalic anhydride 0.0074mol then, kept again 1 hour; This solution is cooled to-25 ℃; Again the 0.5mol titanium tetrachloride is splashed into wherein, slowly be warming up to 80 ℃ then, reacted 3 hours; Use toluene wash 6 times after the filtration respectively, obtain the ziegler natta catalyst that titanium content is 5.2wt%.Polymerizing condition is with comparative example 1, and polymerization result is seen table 2.
Embodiment 12
Under nitrogen protection, in the reaction kettle that whisking appliance, TM and reflux exchanger are housed, add 4.76g (0.05mol) Magnesium Chloride Anhydrous, 150ml decane and 31ml 2-Ethylhexyl Alcohol (0.20mol); Be heated with stirring to 120 ℃, be incubated 2 hours, obtain uniform clear solution; This solution is cooled to 70 ℃; Add 0.6ml (0.005mol) 2-hydroxyethyl methacrylate, keep reaction after 1 hour, be cooled to 20 ℃ at 70 ℃.In above-mentioned solution, slowly drip 33ml TiCl
4, be warming up to 80 ℃ in 1 hour then, be incubated 2 hours, make to react completely, obtain solid catalyst.Stop to stir, the upper strata stillness of night is filtered in sedimentation, with hexane wash 6 times, obtains the ziegler natta catalyst presoma;
The ziegler natta catalyst presoma of above-mentioned preparation is placed the 200ml hexane solvent, add behind the methylsulfonic acid of a certain amount of (Ti: S=1: 1, mol ratio) 70 ℃ of refluxed 3 hours.Filter the back with hexane solvent washing 3 times, obtain ziegler natta catalyst, catalyzer titaniferous amount is 5.6wt%.Polymerizing condition is with comparative example 1, and polymerization result is seen table 2.
Embodiment 13
Other conditions just change the methylsulfonic acid among the embodiment 12 into trifluoromethanesulfonic acid with embodiment 12, and the ziegler natta catalyst titaniferous amount after the modification that obtains is 5.2wt%.
Comparative example 4
Under nitrogen protection; In the reaction kettle that whisking appliance, TM and reflux exchanger are housed, add 4.76g (0.05mol) Magnesium Chloride Anhydrous, 150ml decane and 31ml 2-Ethylhexyl Alcohol (0.20mol) are heated with stirring to 120 ℃; Be incubated 2 hours, obtain uniform clear solution; This solution is cooled to 70 ℃, adds 0.6ml (0.005mol) 2-hydroxyethyl methacrylate, keep reaction after 1 hour, be cooled to 20 ℃ at 70 ℃; In above-mentioned solution, slowly drip 33ml TiCl
4, be warming up to 80 ℃ in 1 hour then, be incubated 2 hours, make to react completely, obtain solid catalyst; Stop to stir, the upper strata stillness of night is filtered in sedimentation, with hexane wash 6 times, obtains the ziegler natta catalyst that titanium content is 5.9wt%.Polymerizing condition is with comparative example 1, and polymerization result is seen table 2.
The polymerization result of table 2 embodiment 8～13 and the ziegler natta catalyst of comparative example 2～4 preparations
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a ultrahigh molecular weight polyethylene(UHMWPE) is characterized in that, may further comprise the steps:
Vinyl monomer is carried out polyreaction under the katalysis of ziegler natta catalyst, obtain ultrahigh molecular weight polyethylene(UHMWPE), said ziegler natta catalyst prepares according to following method:
In magnesium alcoholate, add transition metal halide, obtain catalyst precursor after the reaction;
With said catalyst precursor and sulfonic compound back flow reaction in solvent, obtain ziegler natta catalyst.
2. preparation method according to claim 1 is characterized in that, the general formula of said transition metal halide is suc as formula shown in the I:
M (R)
nX
(4-n)Formula I
Wherein, M is Ti, Zr, Hf, V or Nd, and R is the alkyl of C1～C20, and X is a halogen, and n is 0,1,2 or 3.
3. preparation method according to claim 1 is characterized in that, the general formula of said sulfonic compound is suc as formula shown in the II:
R
1-SO
3-R
2Formula II
Wherein, R
1And R
2Independent separately is alkyl, aromatic base, aralkyl or the haloalkyl of C1～C20.
4. preparation method according to claim 1 is characterized in that said sulfonic compound is selected from methylsulfonic acid, ethyl sulfonic acid, Phenylsulfonic acid, trifluoromethanesulfonic acid; P-methyl benzenesulfonic acid, perfluoro butyl sulfonic acid, perfluoro octyl sulfonic acid, penta fluoro benzene sulfonic acid, methyl mesylate; Ethyl methane sulfonate, methylsulfonic acid isobutyl, methylsulfonic acid trifluoroethyl ester, ethyl sulfonic acid methyl esters, ethyl sulfonic acid ethyl ester; The ethyl sulfonic acid isobutyl, ethyl sulfonic acid trifluoroethyl ester, methyl benzenesulfonate, ethyl benzenesulfonat, Phenylsulfonic acid isobutyl; Phenylsulfonic acid trifluoroethyl ester, trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid isobutyl, trifluoromethanesulfonic acid trifluoroethyl ester; The p-methyl benzenesulfonic acid methyl esters, p-methyl benzenesulfonic acid ethyl ester, p-methyl benzenesulfonic acid isobutyl, p-methyl benzenesulfonic acid trifluoroethyl ester, perfluoro butyl methylmesylate; Perfluoro butyl sulfonic acid ethyl ester, perfluoro butyl sulfonic acid isobutyl, perfluoro butyl sulfonic acid trifluoroethyl ester, perfluoro octyl sulfonic acid methyl esters, perfluoro octyl sulfonic acid ethyl ester; The perfluoro octyl sulfonic acid isobutyl, perfluoro octyl sulfonic acid trifluoroethyl ester, penta fluoro benzene methylmesylate, penta fluoro benzene sulfonic acid ethyl ester, one or more in penta fluoro benzene sulfonic acid isobutyl and the penta fluoro benzene sulfonic acid trifluoroethyl ester.
5. preparation method according to claim 1 is characterized in that, the said temperature of reaction that obtains catalyst precursor is 100～120 ℃, and the reaction times is 0.5～8 hour.
6. preparation method according to claim 1 is characterized in that, said magnesium alcoholate prepares as follows:
Magnesium compound and alcohol compound are mixed in organic solvent, obtain mixing solutions after intensification and the insulation;
Said mixing solutions is added in the ethane, obtain magnesium alcoholate.
7. preparation method according to claim 6 is characterized in that, the general formula of magnesium compound is shown in formula III:
Mg (OR`)
mX
(2-m)Formula III
Wherein, R` is alkyl, aralkyl or the aryl of C1～C20, and X is a halogen, and m is 0 or 1.
8. preparation method according to claim 6 is characterized in that, said alcohol compound is selected from cycloalkanol compounds and in C6～C15 aromatic alcohol compound one or more of aliphatic alcohols compound, the C3～C15 of C1～C15.
9. preparation method according to claim 6; It is characterized in that; Said alcohol compound is selected from methyl alcohol, ethanol, propyl alcohol, terepthaloyl moietie, n-propyl alcohol, Virahol, 1, one or more in ammediol, butanols, isopropylcarbinol, hexanol, enanthol, n-Octanol, isooctyl alcohol, nonyl alcohol, decyl alcohol, sorbyl alcohol, hexalin and the benzylalcohol.
10. preparation method according to claim 1 is characterized in that, the time of said polyreaction is 50～80 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772547A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and catalyst thereof |
| 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 |
| CN116063597A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of ultra-high molecular weight polyethylene and ultra-high molecular weight polyethylene |
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| CN101864013A (en) * | 2010-06-24 | 2010-10-20 | 东北石油大学 | Catalyst for gas-phase polymerization or copolymerization of ethylene and preparation method thereof |
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| CN101864013A (en) * | 2010-06-24 | 2010-10-20 | 东北石油大学 | Catalyst for gas-phase polymerization or copolymerization of ethylene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772547A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and catalyst thereof |
| CN103772547B (en) * | 2012-10-23 | 2016-04-27 | 中国石油化工股份有限公司 | For catalyst component and the catalyzer thereof of ethylene polymerization |
| CN116063597A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of ultra-high molecular weight polyethylene and ultra-high molecular weight polyethylene |
| 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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Effective date of registration: 20161214 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130000 Jilin City, Changchun province people's street, No. 5625 Patentee before: Changchun Applied Chemistry Inst., Chinese Academy of Sciences |