CN102627712B - Preparation method and application of Ziegler Natta catalyst for propylene polymerization - Google Patents
Preparation method and application of Ziegler Natta catalyst for propylene polymerization Download PDFInfo
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Abstract
The invention discloses a preparation method of a Ziegler Natta catalyst for propylene polymerization, which comprises the following steps of adding a transition metal halide and an electron donor compound into a magnesium alcohol compound, and obtaining a catalysis precursor after a reaction; and enabling the catalysis precursor and a sulfonic acid compound to have a reflux reaction in a solvent, and obtaining the Ziegler Natta catalyst for propylene polymerization. Due to the fact that the sulfonic acid compound is introduced and has the function of destroying the random active center in the catalyst, random polypropylene produced when propylene is catalyzed by the catalyst in polymerization is reduced, so that isotacticity of propylene is improved. The preparation method of the Ziegler Natta catalyst is simple in process and easy to produce in industrialized mode. An experiment result presents that the isotacticity of propylene prepared by the Ziegler Natta catalyst is 98.2wt% above. Correspondingly, application of the Ziegler Natta catalyst in the aspect of catalytic propylene monomer polymerization is provided.
Description
Technical field
The present invention relates to olefin polymerization technology field, more particularly, relate to a kind of preparation method and application of the ziegler natta catalyst for propylene polymerization.
Background technology
Polypropylene is a kind of thermoplastic resin that propylene polymerization obtains, and by methyl arrangement position, is divided into isotatic polypropylene (isotaetic-PolyProlene), Atactic Polypropelene (atactic-PolyPropylene) and syndiotactic polypropylene (syndiotatic-PolyPropylene).The isotactic structural content (degree of isotacticity) of the acrylic resin that general technology is produced is about 95%, and all the other are Atactic Polypropelene or syndiotactic polypropylene.Along with the raising of degree of isotacticity, polyacrylic mechanical property constantly strengthens, and when polypropylene degree of isotacticity surpasses or approaches 99%, even can substitute the engineering plastics such as ABS.
Propylene polymerization generally adopts Z-N (Ziegler-Natta) catalyzer, wherein, Ziegler-Natta catalyst is a kind of organo-metallic catalyst, for the synthesis of the polyolefine of non-branching, high tacticity, claim again ziegler-natta initiator, belong to polycoordination initiator.Within 1956, German organic chemist Ziegler finds TiCl first
4/ Et
3al system catalyzed ethylene polymerization effectively under lower pressure, the scholar Natta that Italianizes has subsequently developed this catalyst system for propylene, divinyl, the isotaxy of isopentene etc., these catalyzer were referred to as Ziegler-Natta catalyst afterwards.From invention decades till now of ziegler natta catalyst the 1950's, ziegler natta catalyst is constantly updated and is regenerated, by the TiCl of the conventional δ crystal formation of the initial first-generation
3and AlCl
3eutectic, develops into present high reactivity, high performance with MgCl
2and/or SiO
2for the 4th generation of carrier and the 5th generation catalyzer, not only the catalytic activity of catalyzer is the raising of hundreds of and even several thousand times, and degree of isotacticity is also greatly improved.
Yet traditional ziegler natta catalyst is difficult to prepare the polypropylene of high isotactic.For example, publication number is that the Chinese patent literature of CN1071934 discloses a kind of method that mixture with magnesium source compound and zinc source compound forms the Kaolinite Preparation of Catalyst of carrier, catalyzer prepared by the method has improved olefin polymerizating activity, and the molecular weight distribution of alkene can change according to the variation of carrier ingredients ratio.But the catalyzer of above-mentioned bibliographical information is only applicable to the polymerization of vinyl monomer, is difficult to prepare the polypropylene of high isotactic.Gao Futang etc. [polymer material science and engineering, 07 phase in 2010] have reported that composite internal electron donor prepares isotatic polypropylene, and the polypropylene degree of isotacticity of preparing by the method is still lower than 99%.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method and application of the ziegler natta catalyst for propylene polymerization, ziegler natta catalyst prepared by the method can synthesize high isotatic polypropylene, and this ziegler natta catalyst has the purposes of catalyzing propone monomer polymerization.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of the ziegler natta catalyst for propylene polymerization, comprise the following steps:
In magnesium alcoholate, add transition metal halide and electron donor compound, after reaction, obtain catalyst precursor;
The back flow reaction in solvent by described catalyst precursor and sulfonic compound, obtains the ziegler natta catalyst for propylene polymerization.
Preferably, the general formula of described transition metal halide is suc as formula shown in I:
M (R)
nx
(4-n)formula I
Wherein, M is Ti, Zr, Hf, V or Nd, the alkyl that R is C1～C20, and X is halogen, n is 0,1,2 or 3.
Preferably, described electron donor compound is lipid internal electron donor compound or succinate compound internal electron donor compound.
Preferably, the general formula of described sulfonic compound is suc as formula shown in II:
R
1-SO
3-R
2formula II
Wherein, R
1and R
2independent is separately alkyl, aromatic base, aralkyl or the haloalkyl of C1～C20.
Preferably, described 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, 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, 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, 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 penta fluoro benzene sulfonic acid trifluoroethyl ester.
Preferably, described in obtain catalyst precursor temperature of reaction be 100～120 ℃, the reaction times is 0.5～8 hour.
Preferably, described magnesium alcoholate is prepared as follows:
Magnesium compound and alcohol compound are mixed in organic solvent, heat up and be incubated after obtain mixing solutions;
Described mixing solutions is added in ethane, obtain magnesium alcoholate.
Preferably, the general formula of magnesium compound is as shown in formula III:
Mg (OR`)
mx
(2-m)formula III
Wherein, the alkyl that R` is C1～C20, aralkyl or aryl, X is halogen, m is 0 or 1.
Preferably, described alcohol compound is selected from the aliphatic alcohols compound of C1～C15, one or more in the cycloalkanol compounds of C3～C15 and C6～C15 aromatic alcohol compound.
Accordingly, the present invention also provides ziegler natta catalyst prepared by a kind of above-mentioned preparation method application aspect catalyzing propone monomer polymerization.
The preparation method who the invention provides a kind of ziegler natta catalyst for propylene polymerization, comprises the following steps: in magnesium alcoholate, add transition metal halide and electron donor compound, obtain catalyst precursor after reaction; The back flow reaction in solvent by described catalyst precursor and sulfonic compound, obtains the ziegler natta catalyst for propylene polymerization.Compared with prior art, because the present invention has introduced sulfonic compound, this sulfonic compound has the effect that destroys random active centre in catalyzer, and the Atactic Polypropelene generating while making catalyst propylene polymerization reduces, thereby improves polyacrylic degree of isotacticity.Secondly, preparation method's technique of ziegler natta catalyst provided by the invention is simple, is easy to suitability for industrialized production.Experimental result shows, utilizes polyacrylic degree of isotacticity prepared by ziegler natta catalyst that the present invention obtains more than 98.2wt%.Accordingly, the present invention also provides the application of a kind of above-mentioned ziegler natta catalyst aspect catalyzing propone monomer polymerization.
Embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The preparation method who the invention discloses a kind of ziegler natta catalyst for propylene polymerization, comprises the following steps: in magnesium alcoholate, add transition metal halide and electron donor compound, obtain catalyst precursor after reaction; The back flow reaction in solvent by described catalyst precursor and sulfonic compound, obtains the ziegler natta catalyst for propylene polymerization.
In the preparation process of above-mentioned catalyzer, first, magnesium alcoholate reacts with transition metal halide and electron compound, it is catalyst precursor that the transition metal halide catalyst that magnesium halide is carrier is take in generation, then, catalyst precursor reacts with sulfonic compound described in the present invention and generates final product for the ziegler natta catalyst of propylene polymerization.
According to the present invention, described magnesium alcoholate is preferably prepared as follows: magnesium compound and alcohol compound are mixed in organic solvent, heat up and be incubated after obtain mixing solutions; Described mixing solutions is added in ethane, obtain magnesium alcoholate.The present invention prepares the organic solvent adopting in magnesium alcoholate there is no particular restriction for above-mentioned, can adopt organic solvent well known to those skilled in the art.Described alcohol compound is preferably selected from the aliphatic alcohols compound of C1～C15, one or more in the cycloalkanol compounds of C3～C15 and C6～C15 aromatic alcohol compound, one or more in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, n-propyl alcohol, Virahol, 1,3-PD, butanols, isopropylcarbinol, hexanol, enanthol, n-Octanol, isooctyl alcohol, nonyl alcohol, decyl alcohol, sorbyl alcohol, hexalin and benzylalcohol more preferably.As preferably, the general formula of magnesium compound is as shown in formula III:
Mg (OR`)
mx
(2-m)formula III
Wherein, the alkyl that R` is C1～C20, aralkyl or aryl, X is halogen, m is 0 or 1.
In the present invention, magnesium compound has the effect of carrier in preparing ziegler natta catalyst, for one of composition of traditional ziegler natta catalyst, can make the catalyzer of preparation there is suitable shape, size and physical strength, simultaneously, carrier can make active ingredient be dispersed on carrier surface, obtains higher specific surface area, improves the catalytic efficiency of unit mass active ingredient.In addition, the effect of described alcohol compound is by carrier to be that magnesium compound dissolves.
In the preparation process of magnesium alcoholate, described in obtain mixing solutions temperature be preferably 100～130 ℃, more preferably 120 ℃, described soaking time is preferably 1～3 hour, more preferably 2～3 hours; The described temperature that obtains the hexane solvent that adopts in magnesium alcoholate step is preferably-20～-40 ℃, more preferably-30 ℃.Therefore, magnesium compound is at high temperature dissolved by alcohol compound, has obtained magnesium alcoholate.
Then, the magnesium alcoholate generating reacts with transition metal halide and electron compound, electron donor compound and carrier and transition-metal coordination, alcohol compound is removed, and generates that to take the transition metal halide catalyst that magnesium halide is carrier be catalyst precursor.The described 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.By reacting of above-mentioned transition metal halide and magnesium alcoholate, realized transition metal halide has been loaded on magnesium compound, meanwhile, in the process of transition metal load, introduced electron donor compound, it is loaded on catalyzer, the polymerization of propylene after activation.The general formula of described transition metal halide is suc as formula shown in I:
M (R)
nx
(4-n)formula I
Wherein, M is Ti, Zr, Hf, V or Nd, the alkyl that R is C1～C20, and X is halogen, n is 0,1,2 or 3.
The step that the present invention obtains catalyst precursor is preferably: in the first magnesium alcoholate, add First Transition metal halide, be warming up to 100～120 ℃ after stirring, add electron donor compound, obtain the first catalyst precursor after reaction; In Second Transition halogenide, add the first catalyst precursor, after reaction, washing, obtains catalyst precursor.Therefore, the present invention preferably carries out twice load-reaction, when adding First Transition metal halide to carry out first pass load, transition metal halide and magnesium alcoholate generate phthalate compound, and the transition metal halide adding during second time load filters out phthalate compound dissolution.In addition, the present invention preferably adopts hexane to wash, and more preferably adopts the hexane solvent of 50～70 ℃ to wash.
Electron donor compound is also one of ziegler natta catalyst component for conventional polypropylene, mainly contains and improves polymkeric substance degree of isotacticity, controls the distribution of carrying Ti amount and Ti of carried catalyst, and the random active centre of catalyzer is converted into isotactic active centre.As preferably, the electron donor compound that the present invention adopts is lipid internal electron donor compound or succinate compound internal electron donor compound, and wherein, described lipid internal electron donor compound is preferably methyl benzoate, ethyl benzoate, butyl benzoate, Bisphthalate (for example: dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, amyl phthalate, phthalic acid two (2-methyl butyl) ester, phthalic acid two (3-methyl butyl) ester, phthalic acid two peopentyl esters, the just own ester of phthalic acid two, phthalic acid two (2-methyl amyl) ester, phthalic acid two (3-methyl amyl) ester, o-phthalic acid ester, the new own ester of phthalic acid two, phthalic acid two (2,3-dimethylbutyl) ester, heptyl phthalate ester, phthalic acid two (2-methyl hexyl) ester, phthalic acid two (2-ethyl pentyl group ester, diisoheptyl phthalate, the new heptyl ester of phthalic acid two, dinoctyl phthalate, phthalic acid two (2-methylheptyl) ester, dimixo-octyl phthalate, phthalic acid two (3-ethylhexyl) ester, the new monooctyl ester of phthalic acid two, 2-nonyl-phthalate ester, diisononyl phthalate, phthalate ester decanoate or Di Iso Decyl Phthalate.Described succinate compound internal electron donor compound is preferably suc as formula shown in IV:
Formula IV
In chemicals described in its Chinese style IV, R
7and R
8be same to each other or different to each other, independent is separately C1～C20 line style or branched-alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group; R
3, R
4, R
5and R
6be same to each other or different to each other, independent is separately hydrogen or C1-C20 line style or branched-alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl group.R
1and R
2independent is separately methyl, ethyl, n-propyl, normal-butyl, isobutyl-, neo-pentyl or 2-ethylhexyl.Particularly, succinate compound internal electron donor compound is sec-butyl ethyl succinate more preferably, hexyl ethyl succinate, cyclopropyl ethyl succinate, norcamphyl ethyl succinate, perhydro-ethyl succinate, trimethyl-succinic acid diethyl ester, methoxyl group ethyl succinate, p-methoxyphenyl ethyl succinate, phenylsuccinic acid diethyl ester, cyclohexyl ethyl succinate, benzyl ethyl succinate, cyclohexyl methyl ethyl succinate, tertiary butyl ethyl succinate, isobutyl-ethyl succinate, sec.-propyl ethyl succinate, neo-pentyl ethyl succinate or isopentyl ethyl succinate.
Take electron donor compound as Bisphthalate be example, the structure of electron donor compound in catalyzer is as follows:
Finally, catalyst precursor and sulfonic compound back flow reaction in solvent, has obtained the ziegler natta catalyst for propylene polymerization.Wherein, the temperature of described 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, after back flow reaction, preferably utilize hexane by the ziegler natta catalyst washing obtaining 2～5 times, then dry.The general formula of the sulfonic compound that the present invention adopts is preferably suc as formula shown in II:
R
1-SO
3-R
2
Formula II
Wherein, R
1and R
2independent is separately the alkyl of C1～C20, aromatic base, aralkyl or haloalkyl.Preferred, described sulfonic compound is 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, 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, 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, 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 penta fluoro benzene sulfonic acid trifluoroethyl ester.
Take transition metal halide as TiCl
4for example, the reaction formula of sulfonic compound and transition metal halide is as follows:
Below in conjunction with chemical formula, the preparation process of ziegler natta catalyst provided by the invention is elaborated:
The magnesium compound general formula of preparing magnesium alcohol adducts is Mg (OR`)
mx
(2-m), the alkyl that in formula, R` is C1～C20, aralkyl or aryl, X is halogen, m=0 or 1.
ID is the abbreviation of Internal Donor (interior to electronics)
When m=0, reaction formula is as follows:
MgCl
2+ROH-----→MgCl
2·(ROH)
MgCl
2(ROH)+TiCl
4(excessive)+ID-----→ MgCl
2iDTiCl
4+ Ti (OR)
4
MgCl
2·ID·TiCl
4+R
1SO
3R
2-----→MgCl
2·ID·TiCl
(4-m)(O
3SR
1)
m+R
2Cl
When m=1, reaction formula is as follows:
Mg(OR`)Cl+ROH-----→Mg(OR`)Cl·ROH
Mg (OR`) ClROH+TiCl
4(excessive)+ID → MgCl
2iDTiCl
4+ Ti (OR`)
4+ Ti (OR)
4
MgCl
2·ID·TiCl
4+R
1SO
3R
2----→MgCl
2·ID·TiCl
(4-m)(O
3SR
1)m+R
2Cl
From above-mentioned reaction formula, can find out, first, magnesium compound is at high temperature dissolved by alcohol, obtains magnesium alcoholate, and secondly, the magnesium alcoholate of generation and transition metal are (as TiCl
4) and electron donor compound reaction, alcohol is removed, and has generated traditional with MgCl
2tiCl for carrier
4catalyzer, electron donor and carrier and transition-metal coordination, last, generation with MgCl
2tiCl for carrier
4catalyzer reacts with the sulfonic compound of mentioning in the present invention and generates final product-high isotatic polypropylene catalyzer.
Because the present invention has introduced sulfonic compound, this sulfonic compound has destroyed random active centre in catalyzer, and the Atactic Polypropelene generating while making catalyst propylene polymerization reduces, and improves polyacrylic degree of isotacticity.
From such scheme, can find out, preparation method's technique of ziegler natta catalyst involved in the present invention is simple, is easy to suitability for industrialized production.And ziegler natta catalyst prepared by the present invention can synthesize high isotatic polypropylene, its polypropylene degree of isotacticity of preparing is higher than traditional ziegler natta catalyst.Experimental result shows, utilizes polyacrylic degree of isotacticity prepared by ziegler natta catalyst that the present invention obtains more than 98.2wt%.
The present invention also provides the application of a kind of above-mentioned ziegler natta catalyst aspect catalyzing propone monomer polymerization, and this ziegler natta catalyst can be applicable to the polymerization of propylene monomer, is applicable to slurry, gas phase and bulk technique.
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
Embodiment 1
In the reactor of fully replacing through high pure nitrogen, add successively anhydrous magnesium dichloride (MgCl
2) 10g, white oil 100ml, silicone oil 80ml, is warming up to 50 ℃ under stirring, add ethanol 20ml, continue to be warming up to 120 ℃, and maintain 2.5 hours, and form homogeneous transparent solution, then solution is proceeded to fast in the hexane solution of-30 ℃ of high-speed stirring, after filtering, use hexane solvent washed twice, obtain white magnesium dichloride alcohol adduct;
The 100ml TiCl that the magnesium dichloride alcohol adduct of generation is added to-30 ℃ of high-speed stirring
4in, be slowly warming up to after 110 ℃, add 1.5ml diisobutyl phthalate, at 110 ℃, maintain 2 hours, be cooled to room temperature, filter, again add 100ml TiCl
4, be warming up to 110 ℃, be incubated 1 hour, filter, add 100ml hexane solvent, at 70 ℃ of 0.12g Phenylsulfonic acids, reflux 3 hours;
After filtration, with hexane solvent washing 3 times, obtain the polypropylene ziegler natta catalyst that contains sulfonic compound and diisobutyl phthalate, catalyzer titaniferous amount is 2.5wt%.
Under high pure nitrogen protection, to 2 liters of dry deoxygenations, be furnished with and in churned mechanically high-pressure reactor, add successively propylene 1500ml, triethyl aluminum (Al (C
2h
5)
3) 4mmol, the polypropylene ziegler natta catalyst that contains sulfonic compound and diisobutyl phthalate that external electron donor dimethoxydiphenylsilane 0.008mol and 30mg are above-mentioned; In reacting kettle jacketing, add 70 ℃ of recirculated waters, polyreaction starts; Reaction was carried out after 60 minutes, and by unreacted propylene monomer flash distillation in reaction system, polymerization result is in Table 1.
Embodiment 2
Other conditions, with embodiment 1, only change the Phenylsulfonic acid in embodiment 1 into trifluoromethanesulfonic acid in embodiment 2, and other conditions are constant, and polymerization result is in Table 1.
Embodiment 3～11
Under catalyst treatment condition and polymerizing condition similarly to Example 1, as shown in table 1ly change successively different sulfonic compounds, polymerization result is in Table 1.
Embodiment 12～13
Under catalyst treatment condition and polymerizing condition similarly to Example 1, just the diisobutyl phthalate in embodiment 1 is changed to sec.-propyl ethyl succinate, change successively different sulfonic compounds, polymerization result is in Table 1.
Comparative example 1
In the reactor of fully replacing through high pure nitrogen, add successively anhydrous magnesium dichloride (MgCl
2) 10g, white oil 100ml, silicone oil 80ml, is warming up to 50 ℃ under stirring, add ethanol 20ml, continue to be warming up to 120 ℃, and maintain 2.5 hours, and form homogeneous transparent solution, then solution is proceeded to fast in the hexane solution of-30 ℃ of high-speed stirring, after filtering, use hexane solvent washed twice, obtain white magnesium dichloride alcohol adduct.The 100ml TiCl that the magnesium dichloride alcohol adduct of generation is added to-30 ℃ of high-speed stirring
4in, be slowly warming up to after 110 ℃, add 1.5ml diisobutyl phthalate, at 110 ℃, maintain 2 hours, be cooled to room temperature, filter, again add 100ml TiCl
4, be warming up to 110 ℃, be incubated 1 hour, filter, with hexane solvent washing five times, the polyolefin catalyst that to obtain take diisobutyl phthalate be internal electron donor, catalyzer titaniferous amount is 3.0wt%.
Under high pure nitrogen protection, to 2 liters of dry deoxygenations, be furnished with and in churned mechanically high-pressure reactor, add successively propylene 1500ml, triethyl aluminum (Al (C
2h
5)
3) 4mmol, external electron donor dimethoxydiphenylsilane 0.008mol and 30mg are above-mentioned take the polypropylene ziegler natta catalyst that diisobutyl phthalate is internal electron donor.In reacting kettle jacketing, add 70 ℃ of recirculated waters, polyreaction starts; Reaction was carried out after 60 minutes, and by unreacted propylene monomer flash distillation in reaction system, polymerization result is in Table 1.
Comparative example 2
Other conditions, with comparative example 1, only change the diisobutyl phthalate in comparative example 1 into sec.-propyl ethyl succinate in comparative example 2, and other conditions are constant, and polymerization result is in Table 1.
Ziegler natta catalyst prepared by table 1 embodiment of the present invention and comparative example polymerization result
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. for a preparation method for the ziegler natta catalyst of propylene polymerization, it is characterized in that, comprise the following steps:
In magnesium alcoholate, add transition metal halide and electron donor compound, after reaction, obtain catalyst precursor;
The back flow reaction in solvent by described catalyst precursor and sulfonic compound, obtains the ziegler natta catalyst for propylene polymerization;
Described 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, 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, 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, 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 penta fluoro benzene sulfonic acid trifluoroethyl ester.
2. preparation method according to claim 1, is characterized in that, the general formula of described transition metal halide is suc as formula shown in I:
M(R)
nx
(4-n)formula I
Wherein, M is Ti, Zr, Hf, V or Nd, the alkyl that R is C1 ~ C20, and X is halogen, n is 0,1,2 or 3.
3. preparation method according to claim 1, is characterized in that, described electron donor compound is methyl benzoate, ethyl benzoate, butyl benzoate, dimethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, amyl phthalate, phthalic acid two (2-methyl butyl) ester, phthalic acid two (3-methyl butyl) ester, phthalic acid two peopentyl esters, the just own ester of phthalic acid two, phthalic acid two (2-methyl amyl) ester, phthalic acid two (3-methyl amyl) ester, o-phthalic acid ester, the new own ester of phthalic acid two, phthalic acid two (2,3-dimethylbutyl) ester, heptyl phthalate ester, phthalic acid two (2-methyl hexyl) ester, phthalic acid two (2-ethyl pentyl group) ester, diisoheptyl phthalate, the new heptyl ester of phthalic acid two, dinoctyl phthalate, dimixo-octyl phthalate, phthalic acid two (3-ethylhexyl) ester, the new monooctyl ester of phthalic acid two, 2-nonyl-phthalate ester, diisononyl phthalate, phthalate ester decanoate, Di Iso Decyl Phthalate, sec-butyl ethyl succinate, hexyl ethyl succinate, cyclopropyl ethyl succinate, norcamphyl ethyl succinate, perhydro-ethyl succinate, trimethyl-succinic acid diethyl ester, methoxyl group ethyl succinate, p-methoxyphenyl ethyl succinate, phenylsuccinic acid diethyl ester, cyclohexyl ethyl succinate, benzyl ethyl succinate, cyclohexyl methyl ethyl succinate, tertiary butyl ethyl succinate, isobutyl-ethyl succinate, sec.-propyl ethyl succinate, neo-pentyl ethyl succinate or isopentyl ethyl succinate.
4. preparation method according to claim 1, is characterized in that, described in obtain catalyst precursor temperature of reaction be 100 ~ 120 ℃, the reaction times is 0.5 ~ 8 hour.
5. preparation method according to claim 1, is characterized in that, described magnesium alcoholate is prepared as follows:
Magnesium compound and alcohol compound are mixed in organic solvent, heat up and be incubated after obtain mixing solutions;
Described mixing solutions is added in hexane, obtain magnesium alcoholate.
6. preparation method according to claim 5, is characterized in that, the general formula of magnesium compound is suc as formula shown in III:
Mg (OR`)
mx
(2-m)formula III
Wherein, the alkyl that R` is C1 ~ C20, aralkyl or aryl, X is halogen, m is 0 or 1.
7. preparation method according to claim 5, is characterized in that, described alcohol compound is selected from the aliphatic alcohols compound of C1 ~ C15, one or more in the cycloalkanol compounds of C3 ~ C15 and C6 ~ C15 aromatic alcohol compound.
8. the application of the ziegler natta catalyst that prepared by claim 1 ~ 7 any one preparation method aspect catalyzing propone monomer polymerization.
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| CN102336851A (en) * | 2010-07-14 | 2012-02-01 | 中国石油天然气股份有限公司 | Propylene polymerization catalyst |
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