CN1613880A - Main of component catalyst of olefin polymer and preparation thereof - Google Patents
Main of component catalyst of olefin polymer and preparation thereof Download PDFInfo
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- CN1613880A CN1613880A CN 200410053790 CN200410053790A CN1613880A CN 1613880 A CN1613880 A CN 1613880A CN 200410053790 CN200410053790 CN 200410053790 CN 200410053790 A CN200410053790 A CN 200410053790A CN 1613880 A CN1613880 A CN 1613880A
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- alcohol
- titanium tetrachloride
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- main catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920000098 polyolefin Polymers 0.000 title description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 48
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229960002337 magnesium chloride Drugs 0.000 claims description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000012442 inert solvent Substances 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 6
- 229940091250 magnesium supplement Drugs 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229940073589 magnesium chloride anhydrous Drugs 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000005662 Paraffin oil Substances 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- -1 ethylene, propylene Chemical group 0.000 abstract description 21
- 238000009826 distribution Methods 0.000 abstract description 17
- 239000004743 Polypropylene Substances 0.000 abstract description 5
- 229920001155 polypropylene Polymers 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 239000004711 α-olefin Substances 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000011859 microparticle Substances 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 22
- 239000010936 titanium Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000000969 carrier Substances 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000002609 medium Substances 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003608 titanium Chemical class 0.000 description 7
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 6
- 125000001475 halogen functional group Chemical group 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 150000002681 magnesium compounds Chemical class 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012809 cooling fluid Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012721 stereospecific polymerization Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000033912 thigmotaxis Effects 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
This invention relates to a primary catalyst component for polymerization of olefins and its preparation. It is prepared from titanium tetrachloride carried on an alcohol carrier that Mg and Li chlorides with molar ratio of 1: (2-20) are dissolved in alcohol, and by: co-dissolving Mg chloride and Li chloride in a low carbon alcohol and stirring at high speed in an inert medium to form micro-particles; reacting the said alcohol with titanium tetrachloride twice, adding organic acid polyester at first time, washing out uncarried titanium tetrachloride, and drying to obtain powdery pruduct. It can be used with auxiliary components, eg, aluminum alkyl to catalyze homopolymerization of ethylene, propylene, butylenes-1 and alpha-olefin or copolymerization of their mixture. Isotactic polypropylene with molecular weight distribution index > 10 can be obtained with the said catalyst.
Description
Technical field
The present invention relates to a kind of main catalyst component that is used for olefinic polymerization and preparation method thereof.
Background technology
The catalyst composition that is used for olefinic polymerization comprises a kind of Primary Catalysts and a kind of promotor usually.For carbonatoms is 3 and the stereospecific polymerization of above alpha-olefin, adds some usually and give electron compound (being called electron donor) in catalyst component.The Primary Catalysts that is most widely used in polyolefin industry is produced is that a class is the titanic halide component of carrier with the magnesium compound at present, and its patent the earliest comes across nineteen sixty for latter stage.The preparation method of this class Primary Catalysts has many kinds, but is broadly divided into polishing and chemical reaction method two classes.The principal character of polishing is magnesium compound and halogenated titanium to be ground altogether obtain catalyst component.The essential characteristic of chemical reaction method is, with magnesium compound or its adducts and excessive halogenated titanium reaction, original position generates the magnesium halide in active particle of high-ratio surface, and partially halogenated titanium is carried on the magnesium halide solid surface simultaneously.At some electron donors of halogenated titanium and magnesium compound reaction the interpolation often (being called internal electron donor, common as organic acid acetic, ethers etc.), its effect is the stereospecificity that improves catalyzer.To can obtain required Primary Catalysts behind the halogenated titanium flush away that load is not got on.This class catalyzer can be used formula M gX
2/ ID/TiX
4Expression, wherein ID is an internal electron donor.The representative patents that reaction method prepares magnesium/titanium loaded catalyst has CN1006071B, CN1036011C, CN1032311C, CN1037609C etc.
The multipolymer (being referred to as polyolefine) of polypropylene (PP), polyethylene (PE) and propylene or ethene and other alpha-olefins is broad-spectrum synthesized polymer materials.The mechanical property of these polyolefine materials, processing rheological property, crystallization behavior, thermal characteristics and material structure are all closely related with the molecular weight distribution of polymkeric substance.Many studies show that, the polyolefine material of wide molecular weight distribution (molecular weight distributing index is greater than 8) has very high using value at the polyolefine that all is better than medium molecular weight distributions (dispersion index 3～8) aspect mechanical property and the processing characteristics two.Regulate polyolefinic molecular weight distribution thereby become a crucial task in the manufacture of polyolefins.The method of the adjusting molecular weight distribution that adopts in industrial practice in the past and the scientific research mainly contains: the composition and the preparation method that change Primary Catalysts, add specific external electron donor to catalyst system, adopt special promotor, two kinds of catalyst mix are become composite catalyst system, adopt the different reactor of placed in-line two or more polymerizing conditions etc.Regulate in the method for molecular weight distribution at these, can prepare the polyolefine of wide molecular weight distribution, but have defectives such as device is complicated, investment increase with a plurality of reactors in series; The scope of regulating molecular weight distribution with the method for adding external electron donor or change promotor is still wide inadequately.
In the past to various MgX
2/ ID/TiX
4-AlR
3Find in the research of ED (wherein ED is an external electron donor) catalyzing propone stereospecific polymerization system, only can in small range, change polyacrylic molecular weight distributing index by the preparation condition that changes Primary Catalysts.The polypropylene molecule amount dispersion index of this class system drops in 4～8 scopes mostly.By change internal electron donor in the Primary Catalysts can make polyacrylic molecular weight distribution have by a relatively large margin broadening (G.Cecchin, G.Morini, A.Pelliconi, Macromol.Symp.2001,173,195-209).
If can be by composition that changes carrier in the Primary Catalysts and character and the distribution situation thereof that structure significantly changes various active centre in the catalyst system, then might change the molecular weight distribution of polymkeric substance greatly, keep the high reactivity of catalyst system, high stereospecificity and good polymer beads form simultaneously.This industrial production for wide molecular weight distribution polyolefin will be very favourable.
At the MgX that openly reported in the past
2/ ID/TiX
4In the class Primary Catalysts, the active centre of most systems all loads on pure MgX
2On the microcrystal.The patent report of Toho Titanium company in catalyst preparation process with magnesium compound and a small amount of CaCl
2As the raw material of carrier, make a kind of CaCl of containing together
2Load-type Titanium catalyzer (US 4,839,321, and US 4,847,227).People such as Garoff T. have reported with a small amount of MnCl that mixes
2MgCl
2For preparing carriers load-type Titanium catalyzer (J Molecular Catalysis, Part A:Chemistry, 1996,104:205).People such as Fregonese D. have then reported with a small amount of ZnCl that mixes
2MgCl
2For preparing carriers load-type Titanium catalyzer (J Molecular Catalysis, Part A:Chemistry, 1999,145:265).So far do not see the report of magnesium halide supported titanium catalyst about containing the LiCl composition and preparation method thereof as yet, do not see report yet with the polyolefinic molecular weight distribution characteristic of this class catalyzer synthetic.
Summary of the invention
The object of the invention provides a kind of catalyst component that is used for olefinic polymerization and preparation method thereof.
It is that titanium tetrachloride is carried on by forming on magnesium chloride, lithium chloride and the pure alcohol adduct carrier that forms, said alcohol adduct carrier is formed with alcohol or pure the contact with the mixture of inert solvent by the mixture of magnesium chloride and lithium chloride, this alcohol adduct carrier and titanium tetrachloride carry out two secondary responses, reaction finishes the back not titanium tetrachloride of load of inert solvent flush away, obtains being pulverous main catalyst component after the drying.
The preparation method of main catalyst component may further comprise the steps:
1) with mol ratio be 2: 1～20: 1 Magnesium Chloride Anhydrous and lithium chloride mixture in magnesium: 1: 2～1: 4 ratio of pure mol ratio is with after low-carbon alcohol is mixed, under 80～140 ℃, be stirred to the formation homogeneous liquid, this liquid is mixed the back high-speed stirring to forming the lactous liquid form mixt with inert solvent, rapidly this liquid form mixt under agitation is cooled to then and is lower than 20 ℃, after filtration, drying obtains the alcohol adduct carrier;
2) carry out two secondary responses with titanium tetrachloride and gained alcohol adduct carrier, wherein also add the polynary ester of a kind of organic acid during first set reaction, during reaction with pure titanium tetrachloride as reaction medium, perhaps use inert solvent as reaction medium, each reaction finishes after-filtration and removes unreacted titanium tetrachloride, reaction for the second time finishes the back not titanium tetrachloride of load of inert solvent flush away, obtains being pulverous main catalyst component after the drying.
The titanium content of gained main catalyst component of the present invention is 2～4.5%, and ester content is 5～20%, and cl content is 55～63%.The main characteristics of this Primary Catalysts are, itself and aluminum alkyls (as: triethyl aluminum, triisobutyl aluminium) and the catalyst system formed of external electron donor (as: dimethoxydiphenylsilane) when being used for catalyzing propone or vinyl polymerization, can synthetic obtain the very wide polymkeric substance of molecular weight distribution, and catalytic activity and stereospecificity are not less than the magnesium chloride load halogenated titanium class Primary Catalysts that does not contain lithium chloride of preparation in kind.When activating with (triethyl aluminum+dimethoxydiphenylsilane), molecular weight distributing index with Primary Catalysts catalyzing propone polymerization gained isotatic polypropylene of the present invention is 9～16, is 5～8 and use the polyacrylic molecular weight distributing index of Primary Catalysts gained that does not contain lithium chloride with the quadrat method preparation.Have polyolefinic mechanical property of medium molecular weight distributions and the processing characteristics that is better than the conventional catalyst preparation with main catalyst component synthetic wide molecular weight distribution polyolefin of the present invention.
Embodiment
The present invention is carried on the solid alcohol compound particulate that is made of magnesium chloride, lithium chloride and low-carbon alcohol by titanium compound to form, said solid alcohol compound particulate is that first mixture with magnesium chloride and lithium chloride is dissolved in carbon number smaller or equal to forming the liquid alcohol compound in 4 the low-carbon alcohol, be dispersed in then in the dispersion medium of forming with the immiscible mineral oil of this alcohol adduct or mineral oil and silicoorganic compound, make the liquid alcohol compound disperse to form the particulate of 5～100 microns of diameters by stirring shearing force, last cooling shaping forms.The mol ratio of lithium chloride and magnesium chloride is 1: 2～1: 20 in this alcohol adduct, and magnesium chloride is 1: 2～1: 4 with the mol ratio of alcohol.
With this solid composite particulate is carrier, earlier with halogenated titanium and internal electron donor reaction, again with pure halogenated titanium reaction, after obtain main catalyst component after the inert solvent washing.
The preparation method of above-mentioned main catalyst component is:
1. the preparation of carrier particles
Earlier Magnesium Chloride Anhydrous, lithium chloride and alcohol are stirred the alcohol adduct melt that forms (magnesium chloride+lithium chloride) down at 80～140 ℃ by a certain percentage, in alcohol adduct, add dispersion agent then, after high-speed stirring is disperseed, quick cooling forms the solia particle of alcohol adduct again, promptly gets carrier granule after washing, drying.
Used alcohol comprises ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol etc., is best with ethanol.Alcohol is 2～4 with the mol ratio of magnesium chloride, with 2.5～3.5 for well.The mol ratio of lithium chloride and magnesium chloride is 1: 2～1: 20, with 1: 4～1: 20 for well.The temperature range of preparation alcohol adduct melt is 80～140 ℃, with 115～130 ℃ for well.Being used to disperse the dispersion agent of alcohol adduct is the inert varsol, as: white oil, white oil, kerosene etc. can also add the part silicoorganic compound.The dispersion agent prescription is the mixture of white oil and methyl-silicone oil preferably.
The melt of alcohol adduct is dispersed into milk sap through high-speed stirring in the mixture of white oil and methyl-silicone oil, is transferred to the solid particle that cooling shaping in the cooling fluid promptly gets alcohol adduct then.Used cooling fluid is a sherwood oil.Gained alcohol adduct particulate is used as the carrier of preparation Primary Catalysts after washing, drying.
2. the preparation of main catalyst component
(magnesium chloride+lithium chloride) alcohol adduct particulate with method for preparing is a carrier, reacts with carrier at twice with excessive titanium tetrachloride, wherein can add a certain amount of internal electron donor during first set reaction.Remove by filter liquid titanium tetrachloride and medium earlier after each reaction finishes, repeatedly wash solid part with inert hydrocarbon solvent then, vacuumize at last and remove residual solvent, can obtain being the main catalyst component of solid powdery.
When titanium tetrachloride and carrier first set reaction, the beginning temperature lower, with-20～0 ℃ for well, progressively be warming up to 100～130 ℃ then.Pure titanium tetrachloride liquid can be joined in the carrier-containing reactor and under agitation react, also can after adding titanium tetrachloride, add a certain amount of inert solvent again, under agitation react.Can add internal electron donor in the reaction, as carboxylic acid esters and ether compound, its effect is the stereotaxis ability of regulating catalyzer.Diisobutyl phthalate and n-butyl phthalate are the most frequently used internal electron donors.When titanium tetrachloride and carrier reacted for the second time, starting temperature was 20～40 ℃, was warming up to 100～130 ℃ then gradually.Total mol ratio of used titanium tetrachloride of two secondary responses and magnesium chloride is 30～100.
The solvent of washing catalyst can be used hydrocarbon compounds such as sherwood oil, normal hexane, normal heptane.
Further specify characteristics of the present invention with embodiment below.
Embodiment 1
(1) preparing carriers
Reflux exchanger, mechanical stirrer and thermometer are being housed, in the 250ml three-necked bottle after argon replaces, are adding dehydrated alcohol 34.6ml, Magnesium Chloride Anhydrous 18g, lithium chloride 1.1g progressively is warming up to 120 ℃ under middling speed stirs, keep 30min.Join in the three-necked bottle being heated to 120 ℃ the 70ml white oil and the mixture of 50ml methyl-silicone oil, then with the speed high-speed stirring 3min of 1000rpm, under agitation rapidly liquid in the bottle being transferred to another contains the 500ml sherwood oil and is chilled in advance in-30 ℃ the 1000ml three-necked bottle, suction filtration, with petroleum ether to remove residual white oil and silicone oil, obtain alcohol adduct particulate 44g after the vacuum-drying.The solid alcohol compound consist of MgCl
20.14LiCl2.87C
2H
5OH.
(2) Preparation of Catalyst
Get above-mentioned alcohol adduct particulate 8g, add and to contain the 100ml titanium tetrachloride and be chilled in advance in-20 ℃ the three-necked bottle, progressively be warming up to 40 ℃, add 1.5ml n-butyl phthalate (DNBP), continue to be warming up to 130 ℃, middling speed stirred 2 hours, suction filtration adds the 100ml titanium tetrachloride again, is warming up to 130 ℃ and kept 2 hours, suction filtration once more washs solid part chloride ion-containing not to the filtrate several times with sherwood oil.The vacuum-drying filter cake obtains Primary Catalysts.
The principal character of Primary Catalysts is: Ti content 3.9%, DNBP content 10.1%.The wide-angle x-ray diffraction spectrum is 28～36 ° at 2 θ a wide and stronger diffuse maximum or " halo ", occurs more weak sharp-pointed diffraction peak to medium tenacity respectively at 15 °, 30 °, 35 °.
(3) propylene polymerization
Under protection of inert gas, in 0.5 a liter reactor that has a mechanical stirring device, add sherwood oil, promotor Al (C successively
2H
5)
3, external electron donor Ph
2Si (OCH
3)
2, making the interior total liquid volume of reactor is 300ml.Under 60 ℃ of constant temperature,, add the Primary Catalysts 0.03g of preparation as stated above at last with the propylene gas of the inert gas replacement in the reactor.In the promotor in aluminium and the Primary Catalysts mol ratio of titanium be 100, the mol ratio of external electron donor and titanium is 5.At the propylene invariablenes pressure of liquid is to carry out polyreaction under 0.3MPa, 400 rev/mins the stirring to stop with ethanol after 1 hour, product 11.6g.The isotactic index that records polymkeric substance with the normal heptane extraction process is 97.2%.The weight-average molecular weight that records polymkeric substance with high temperature gel chromatography is 53.5 ten thousand, and molecular weight distributing index is 11.2.
Embodiment 2
Preparing carriers, Preparation of Catalyst and propene polymerizing method are identical with embodiment 1, and the consumption of lithium chloride changes 1.76g in the time of only will preparing carrier, and the ethanol consumption changes 35.5ml into.Obtain solid alcohol compound 45.8g, it consists of MgCl
20.22LiCl2.99C
2H
5OH.The principal character of gained Primary Catalysts is: Ti content 3.7%, DNBP content 10.0%.The wide-angle x-ray diffraction spectrum is 28～36 ° at 2 θ a wide and stronger diffuse maximum or " halo ", occurs more weak sharp-pointed diffraction peak to medium tenacity respectively at 15 °, 30 °, 35 °.Propylene polymerization obtains product 10.8g.Polyacrylic isotactic index is 97.8%.The weight-average molecular weight of polymkeric substance is 62.7 ten thousand, and molecular weight distributing index is 16.0.
Embodiment 3
Preparing carriers, Preparation of Catalyst and propene polymerizing method are identical with embodiment 1, and the consumption of lithium chloride changes 0.6g in the time of only will preparing carrier, and the ethanol consumption changes 34ml into.Obtain solid alcohol compound 43.2g, it consists of MgCl
20.075LiCl2.83C
2H
5OH.The internal electron donor that adds during the preparation catalyzer changes diisobutyl phthalate (DIBP) into, and consumption is 1.5ml.The principal character of gained Primary Catalysts is: Ti content 3.2%, DIBP content 10.6%.The wide-angle x-ray diffraction spectrum is 28～36 ° at 2 θ a wide and stronger diffuse maximum or " halo ", occurs more weak sharp-pointed diffraction peak to medium tenacity respectively at 15 °, 30 °, 35 °.Propylene polymerization obtains product 10.3g.Polyacrylic isotactic index is 98.2%.The weight-average molecular weight of polymkeric substance is 60.2 ten thousand, and molecular weight distributing index is 10.5.
Embodiment 4
Preparing carriers, Preparation of Catalyst and propene polymerizing method are identical with embodiment 1, and the consumption of lithium chloride changes 3.6g in the time of only will preparing carrier, and the ethanol consumption changes 38ml into.Obtain solid alcohol compound 49.1g, it consists of MgCl
20.45LiCl3.16C
2H
5OH.The principal character of gained Primary Catalysts is: Ti content 3.0%, DNBP content 9.5%.The wide-angle x-ray diffraction spectrum is 28～36 ° at 2 θ a wide and stronger diffuse maximum or " halo ", occurs more weak sharp-pointed diffraction peak to medium tenacity respectively at 15 °, 30 °, 35 °.Propylene polymerization obtains product 9.3g.Polyacrylic isotactic index is 98.0%.The weight-average molecular weight of polymkeric substance is 50.8 ten thousand, and molecular weight distributing index is 10.2.
Embodiment 5
Preparing carriers, Preparation of Catalyst and propene polymerizing method are identical with embodiment 1, and the consumption of lithium chloride changes 0.42g in the time of only will preparing carrier, and the ethanol consumption changes 33.7ml into.Obtain solid alcohol compound 49.1g, it consists of MgCl
20.53LiCl2.89C
2H
5OH.The principal character of gained Primary Catalysts is: Ti content 3.8%, DNBP content 10.6%.Propylene polymerization obtains product 13.6g.Polyacrylic isotactic index is 97.2%.The weight-average molecular weight of polymkeric substance is 53.1 ten thousand, and molecular weight distributing index is 8.9.
Comparative examples 1
Preparing carriers, Preparation of Catalyst and propene polymerizing method are identical with embodiment 1, only do not add lithium chloride when the preparation carrier, and the ethanol consumption changes 33ml into.Obtain solid alcohol compound 41.7g, it consists of MgCl
22.73C
2H
5OH.The principal character of gained Primary Catalysts is: Ti content 4.2%, DNBP content 10.5%.The wide-angle x-ray diffraction spectrum is 28～36 ° at 2 θ a wide and stronger diffuse maximum or " halo ".Propylene polymerization obtains product 12.1g.Polyacrylic isotactic index is 97.0%.The weight-average molecular weight of polymkeric substance is 54.8 ten thousand, and molecular weight distributing index is 7.1.
Comparative examples 2
Preparing carriers, Preparation of Catalyst and propene polymerizing method are identical with embodiment 3, only do not add lithium chloride when the preparation carrier, and the ethanol consumption changes 33ml into.Obtain solid alcohol compound 41.7g, it consists of MgCl
22.73C
2H
5OH.The principal character of gained Primary Catalysts is: Ti content 3.5%, DIBP content 10.8%.The wide-angle x-ray diffraction spectrum is 28～36 ° at 2 θ a wide and stronger diffuse maximum or " halo ".Propylene polymerization obtains product 9.4g.Polyacrylic isotactic index is 98.3%.The weight-average molecular weight of polymkeric substance is 43.5 ten thousand, and molecular weight distributing index is 6.4.
Claims (6)
1. the main catalyst component of a used in alpha-olefines polymerization, it is characterized in that: it is that titanium tetrachloride is carried on the alcohol adduct carrier that magnesium chloride, lithium chloride and alcohol forms and forms, said alcohol adduct carrier is dissolved in the mixture of alcohol or alcohol and inert solvent jointly by magnesium chloride and lithium chloride and forms, this alcohol adduct carrier and titanium tetrachloride carry out two secondary responses, reaction finishes the back not titanium tetrachloride of load of inert solvent flush away, obtains being pulverous main catalyst component after the drying.
2. the main catalyst component of a kind of used in alpha-olefines polymerization according to claim 1 is characterized in that, the mol ratio of magnesium chloride and lithium chloride is 2: 1～20: 1 in the said alcohol adduct carrier.
3. the main catalyst component of a kind of used in alpha-olefines polymerization according to claim 1 is characterized in that, magnesium chloride is 1: 2～1: 4 with the mol ratio of alcohol in the said alcohol adduct carrier.
4. the main catalyst component of a kind of used in alpha-olefines polymerization according to claim 1 is characterized in that, said alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or isopropylcarbinol.
5. the main catalyst component of a kind of used in alpha-olefines polymerization according to claim 1 is characterized in that, said inert solvent is that carbon number is 6～20 saturated alkane, kerosene, paraffin oil, white oil, methyl-silicone oil or their mixture.
6. the preparation method of a main catalyst component as claimed in claim 1 is characterized in that, may further comprise the steps:
1) with mol ratio be 2: 1～20: 1 the mixture of Magnesium Chloride Anhydrous and lithium chloride in magnesium: 1: 2～1: 4 ratio of pure mol ratio is with after alcohol mixes, under 80～140 ℃, be stirred to the formation homogeneous liquid, this liquid is mixed the back high-speed stirring to forming the lactous liquid form mixt with inert solvent, rapidly this liquid form mixt under agitation is cooled to then and is lower than 20 ℃, after filtration, drying obtains the alcohol adduct carrier;
2) carry out two secondary responses with titanium tetrachloride and gained alcohol adduct carrier, wherein also add the polynary ester of a kind of organic acid during first set reaction, during reaction with pure titanium tetrachloride as reaction medium, perhaps use inert solvent as reaction medium, each reaction finishes after-filtration and removes unreacted titanium tetrachloride, reaction for the second time finishes the back not titanium tetrachloride of load of inert solvent flush away, obtains being pulverous main catalyst component after the drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942053A (en) * | 2010-08-16 | 2011-01-12 | 杨波 | High-efficiency catalyst for preparing high-random alpha-olefin copolymer and preparation method thereof |
| CN103788239A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Olefin polymerization catalyst solid component, and olefin polymerization catalyst and its application |
| CN108034014A (en) * | 2017-12-27 | 2018-05-15 | 安徽工业大学 | A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst |
-
2004
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942053A (en) * | 2010-08-16 | 2011-01-12 | 杨波 | High-efficiency catalyst for preparing high-random alpha-olefin copolymer and preparation method thereof |
| CN101942053B (en) * | 2010-08-16 | 2013-04-03 | 辽阳辽化奇达化工有限责任公司 | High-efficiency catalyst for preparing high-random alpha-olefin copolymer and preparation method thereof |
| CN103788239A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Olefin polymerization catalyst solid component, and olefin polymerization catalyst and its application |
| CN103788239B (en) * | 2012-10-29 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of catalyst solid component of olefin polymerization and olefin polymerization catalysis and application thereof |
| CN108034014A (en) * | 2017-12-27 | 2018-05-15 | 安徽工业大学 | A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst |
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