CN1410457A - Preparation method of solid titanium catalyst component used for olefine polymerization - Google Patents
Preparation method of solid titanium catalyst component used for olefine polymerization Download PDFInfo
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Abstract
A process for preparing solid titanium catalyst used for polymerizing olefine includes such steps as preparing the alkoxide of magnesium chloride from alcohol and magnesium chloride in hydrocarbon solvent under the presence of ester complex, further low-temp contact of the said alkoxide solution with the liquid Ti compound, heating to reaction temp., reaction while adding organic carboxylate, filtering, washing, and drying to obtain the solid titanium catalyst. When it is used for polymerizing olefine, it is further added with co-catalyst alkyl aluminium and organic siloxane to obtain the polymer of olefine. Its advantage are high catalytic effect and simple process.
Description
Technical field the present invention relates to a kind of preparation method who is used for the olefinic polyreaction solid catalytic ingredient.
Background technology is since Ziegler-Natta catalyst comes out, the preparation method and the correlation technique that are used for olefin polymerization catalysis have obtained very big progress, some olefin polymerization catalysis have successfully been realized suitability for industrialized production, and successfully are applied on the various polymerization techniques.Worldwide synthetic resins production and scientific research are opened and have all been reached higher level.At present, olefin polymerization catalysis in the world develops into metalloscene catalyst and late transition metal catalyst by the Z-N catalyzer, but on industrial application prevailing still Z-N high-effective carrier catalyst.
The Z-N catalyst component that propylene polymerization uses mostly adopts magnesium chloride to be carrier, earlier it and some solvent reaction are formed homogeneous solution, be added drop-wise in the titanium tetrahalide then, separate out precipitation, handle precipitation with the multi-carboxylate, it is loaded on the solid precipitation, obtains solid titanium catalyst through titanium tetrahalide and inert diluent washing again, as Chinese patent CN85100997A.When being used for propylene polymerization, catalyzer also must add external electron donor and just can obtain high isotactic product under promotor.
Also useful 1,3-third diether compound replaces the polycarboxylic acid purport to handle, and as the internal electron donor of Z-N catalyzer, improves activity of such catalysts and performance.For example: Chinese patent CN1087094A.
The high-effective carrier catalyst development though some industrialization products are arranged, mostly exists polymer morphology bad so far, and polymkeric substance performance density is not high, problems such as course of industrialization complexity.
Summary of the invention the present invention is a kind of preparation method of solid titanium catalyst component.When being used for olefinic polymerization, solid titanium catalyst also need add promotor aluminum alkyls B component and external electron donor organo-siloxane C component as the A component.The proportioning of A, B, C three components, during by polymerization, the different of the monomer of use, polymerisate and reaction conditions are determined.
The preparation method of solid titanium Primary Catalysts A component of the present invention is achieved like this:
Solid titanium catalyst A component is the preparation by (1) alcohol adduct; (2) two steps of preparation of solid titanium catalyst component finish.
(1) preparation of alcohol adduct:
With the compound of Magnesium Chloride Anhydrous and alcohols and varsol in the presence of ester class complex compound, the molar ratio of alcohol compound and magnesium chloride is 1-6: 1, the mole of ester class complex compound and magnesium chloride is 0.01-0.80: 1 o'clock, 50-180 ℃ of reaction 0.5-5.0 hour, then, homogeneous complex solution with titanate ester compound and internal electron donor formation, be added in the magnesium chloride alcohol adduct, keep said temperature, to the reaction end, be cooled to room temperature, obtain stabilized uniform alcohol adduct solution.
Above-mentioned alcohol compound comprises Fatty Alcohol(C12-C14 and C12-C18), alicyclic ring alcohol and aromatic alcohol.Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, octanol, hexanol, enanthol, decyl alcohol, 2-ethyl butanol, 2-Ethylhexyl Alcohol and ethylene glycol; Alicyclic ring alcohol is a hexalin etc.; Aromatic alcohol is phenylcarbinol, phenylethyl alcohol and phenol compound.
Above-mentioned ester class complex compound mainly contains the polynary ester of organic carboxyl acid and tetraethyl titanate, tetrabutyl titanate and metatitanic acid four monooctyl ester compounds such as organic carboxyl acid monoesters such as ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, methyl acrylate, ethyl propenoate, ethyl benzoate, methoxybenzoic acid ethyl ester or diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate (DOP), dimixo-octyl phthalate.
Above-mentioned varsol is aliphatic hydrocarbon, alicyclic hydrocarbon and aromatic hydrocarbon, as: hexane, heptane, octane, decane, kerosene, 200
#Oil, pentamethylene, hexanaphthene, methylcyclohexane, ethylcyclohexane, benzene,toluene,xylene etc.
(2) preparation of solid titanium catalyst component:
The alcohol adduct homogeneous solution of above-mentioned preparation is added to through nitrogen fully replaces, be equipped with-reactor of 40-+40 ℃ liquid titanium compound in, the mol ratio of alcohol adduct homogeneous solution and liquid titanium compound is 5-60: 1, make their fully contacts at low temperatures by stirring, after 3-5 hour, be warming up to 50-150 ℃ then, add internal electron donor, the mol ratio of its add-on and alcohol adduct homogeneous solution is 0.005-0.200, reacts 0.5-6 hour, after reaction finishes, filter out liquid, add liquid titanium compound again, under same temperature, continue reaction 1-6 hour, reaction filters out liquid after finishing, and uses solvent wash, drying makes solid titanium catalyst component (when being applied to polyreaction as the A component).
The solid titanium catalyst component is a pale yellow powder, and its tap density is 0.60-0.65g/cm
3, specific surface area is 135-320m
2/ g, titanium content 1.5-3.5% (weight), Mg content 15.0-20.0% (weight).
The general formula of above-mentioned used liquid titanium compound is Ti (OR)
nX
4-n, wherein: R is an alkyl; X is a halogen; 0≤n≤4; Liquid titanium compound comprises: titanium tetrahalide, as: titanium tetrachloride, titanium tetrabromide etc.; Alkoxyl group three halogenated titaniums, as: methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, butoxy titanous chloride, methoxyl group titanium tribromide, oxyethyl group titanium tribromide, butoxy titanium tribromide etc.; Dialkoxy dihalide titanium, as: dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diethoxy dibrominated titanium etc.; The tri-alkoxy halogenated titanium is triethoxy titanium chloride, three butoxy titanium chlorides, triethoxy titanium bromide etc.
Above-mentioned described internal electron donor is ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, methyl acrylate, ethyl propenoate, ethyl benzoate, methoxybenzoic acid ethyl ester, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid n-caprylic acid, dimixo-octyl phthalate etc.
B component alkylaluminium cpd when using olefinic polymerization comprises: trialkylaluminium, as: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, trioctylaluminum etc.; Dialkylaluminum halides, as: dimethylaluminum chloride, diethyl aluminum chloride, diisobutyl aluminum chloride etc.; Alkyl dihalide aluminium, as: methylaluminum dichloride, ethylaluminum dichloride, propyl group al dichloride, buty laluminum dichloride, isobutyl-al dichloride etc.
C component external electron donor when using olefinic polymerization is an organosilicone compounds, and general formula is
R in the formula
1, R
2Be the alkyl of 1-18 carbon atom, cycloalkyl and aryl.R
3Be the alkyl of 1-4 carbon atom, n=1 or 2,0≤L≤2,0≤H≤2, L=0 or H=0 when n=1.The example of silicoorganic compound comprises: dimethyldimethoxysil,ne, diethyl dimethoxy silane, dipropyl dimethoxy silane, dibutyl dimethoxy silane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane, dicyclohexyl dimethoxy silane, dimethoxydiphenylsilane, methyltrimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silicane, the sec.-propyl Trimethoxy silane, butyl trimethoxy silane, isobutyl-Trimethoxy silane, Union carbide A-162, ethyl triethoxysilane, propyl-triethoxysilicane, sec.-propyl triethoxyl silane, the butyl triethoxyl silane, the cyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclopentyl triethoxyl silane, the cyclohexyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, cyclohexyl methyl dimethoxy silane etc.
The invention provides a kind of technology method for preparing catalyst simple, with short production cycle, the catalyzer that makes has catalytic efficiency height, good, the good characteristics of polymkeric substance apparent density height, particularly polymer morphology of polymer performance.
It can be slurry polymerization, vapour phase polymerization and mass polymerization that the present invention is used for olefin polymetiation process.Itself make solvent with the liquid alkane class during mass polymerization.During polymerization, earlier propylene and promotor and organo-siloxane are added in the autoclave, and then with the solid titanium catalyst component of preparation, add in the autoclave by certain aluminium/titanium mol ratio, the still temperature rise is safeguarded isothermal reaction to temperature of reaction behind the hydrogenation, finishes until polyreaction.
Third polymerizing condition is: aluminium/titanium (mol ratio) 1: 50-1000, and aluminium/silicon (mol ratio) is 1: 4-15, polymerization temperature are 40-150 ℃, polymerization time is 1-6 hour.
Embodiment
Embodiment 1
1) alcohol adduct preparation
In the there-necked flask that agitator and thermometer are housed, after fully replacing, nitrogen adds anhydrous MgCl
25 grams, decane 30ml and 2-Ethylhexyl Alcohol 23.0ml.Warming while stirring to 130 ℃, and reaction 2 hours under this temperature.In advance 1.5ml tetrabutyl titanate and 2ml diisobutyl phthalate are added in the 5ml toluene,, obtain all-complex solution stirring at room reaction 0.5 hour.Toluene solution is added in the there-necked flask, and continues reaction 1 hour at 130 ℃.Reaction finishes, and is cooled to room temperature and forms stabilized uniform alcohol adduct solution.
2) preparation of solid titanium catalyst component
With the homogeneous solution of above-mentioned preparation, in 30 minutes, be added drop-wise to and agitator and thermometer are housed and fully replace through nitrogen, fill and add in advance and remain in the reactor of-20 ℃ of 200ml titanium tetrachlorides, dropwise, be warming up to 110 ℃ through 3.5 hours.Add diisobutyl phthalate 1.2ml down at 110 ℃, reaction is 2 hours under this temperature.After reaction finishes filter liquide, add the 200ml titanium tetrachloride again 110 ℃ of reactions 1.5 hours.Leach reaction solution after reaction finishes, use the purified trichloromethane 60 ℃ of washings 60 minutes, be washed till in the filtrate till the no free chlorion with dry hexane then, the remaining solid product gets the solid titanium catalyst component through vacuum-drying.
Solid titanium catalyst compositional analysis result:
Titanium content: 1.96% (wt)
Mg content: 16.32% (wt)
Cl content: 55.81% (wt)
3) polyreaction
2 liters of stainless steel cauldrons, the agitator that changes 600 rev/mins of scooters is housed, after nitrogen is fully replaced, add 1.5 liters of refining propylene and 3.2ml triethyl (concentration is the hexane solution of 1moL/L) and 0.1ml methylcyclohexyl dimethoxy silane, and the catalyst component 0.015 that adds embodiment 1 preparation restrains (0.00645 mmole is pressed titanium and calculated).Then, being warming up to 70 ℃ of adding dividing potential drops is the hydrogen of 0.2Mpa.Polyreaction is 2 hours under this temperature, and temperature of reaction remains on 70 ℃ in the reaction process.After reaction finished, logical water coolant to room temperature, stopped the still temperature drop to stir, and gets rid of unreacting gas, obtains reaction product, got 585 gram white polymer through vacuum-drying.Catalytic efficiency 42,000gPP/gCat; Polymkeric substance apparent density 0.44g/cm
3
Embodiment 2-3
Change the mol ratio that 2-Ethylhexyl Alcohol and magnesium chloride feed intake, with embodiment 1, its result lists table 1 in as the preparation of solid titanium catalyst component and propylene polymerization condition for other
Table 1
| Embodiment | Alcohol/magnesium (mol ratio) | Catalytic efficiency gPP/gCat | Polymkeric substance apparent density g/cm 3 | Titanium content % (wt) |
| ????2 ????3 | ????2.74 ????2.97 | ????37,000 ????38,000 | ????0.44 ????0.45 | ????2.22 ????2.34 |
Embodiment 4-5
Change the kind that adds ester class complex compound in the preparation process.Embodiment 4 usefulness tetraethyl titanates replace metatitanic acid four butyric acid of embodiment 1, and other is with embodiment 1.Embodiment 5 usefulness phthalic acids two isocaprylic acids replace phthalic acid two isopropylformic acids in the example 1, and other is with embodiment 1.Its result lists table 2 in
Table 2
| Embodiment | Titanium content % (wt) | Catalytic efficiency gPP/gCat | Polymkeric substance apparent density g/cm 3 |
| ????4 ????5 | ????2.31 ????2.37 | ????31,500 ????29,000 | ????0.45 ????0.46 |
Embodiment 6
The preparation of solid titanium catalyst component
In the there-necked flask that agitator and thermometer are housed, after nitrogen is fully replaced, add anhydrous MgCl
25 grams, decane 30ml and 2-Ethylhexyl Alcohol 22.5ml.Being warming up to 130 ℃ under whipped state kept 2 hours.Then, add the homogeneous complex solution that 2.5ml phthalic acid two isopropylformic acids and 1ml metatitanic acid four butyric acid form in the 5ml chlorinated benzene, continued insulation reaction 1.5 hours, be cooled to room temperature and obtain stable magnesium chloride alcohol adduct homogeneous solution, with above-mentioned homogeneous solution, in 30 minutes, be added drop-wise to and agitator and thermometer are housed and fully replace, fill and add in advance and remain in-20 ℃ the reactor of 200ml titanium tetrachloride through nitrogen.Dropwise, be warming up to 110 ℃ through 3.5 hours.Add the 1.0ml dinoctyl phthalate, reaction is 2 hours under this temperature.After reaction finishes, filter reaction mixture.Again add the 200ml titanium tetrachloride, be warming up to 110 ℃, reaction is 1.5 hours under this temperature, filters out reaction liquid then, and is washed till in the filtrate till the no free chlorion with dry hexane, and the remaining solid product gets solid titanium catalyst component through vacuum-drying.Its titanium content 2.21% (wt) is pressed embodiment 1 polymerization result:
Catalyst activity 33,700gPP/gCat
Polymkeric substance apparent density 0.45g/cm
3
Embodiment 7
The preparation of solid titanium catalyst component
In the there-necked flask that agitator and thermometer are housed, after nitrogen is fully replaced, add anhydrous MgCl
25 grams, decane 30ml, and 2-Ethylhexyl Alcohol 23ml.Under whipped state, be warming up to 130 ℃ and under this temperature the reaction 2 hours.Then, add 0.5ml tetrabutyl titanate and 2ml phthalic acid two n-caprylic acid, the homogeneous complex solution that in 5ml toluene, forms, and under this temperature, reacted 1 hour, be cooled to room temperature and obtain stable alcohol adduct homogeneous solution.With above-mentioned homogeneous solution, in 30 minutes, be added drop-wise to and agitator and thermometer are housed and fully replace through nitrogen, fill and add in advance and remain in-20 ℃ the reactor of 200ml titanium tetrachloride.Dropwise, be warming up to 110 ℃ through 3.5 hours.Add 0.75ml diisobutyl phthalate and 0.25ml dimixo-octyl phthalate, reaction is 2 hours under this temperature.Leach reaction solution, add the 200ml titanium tetrachloride again, be warming up to 110 ℃, with reaction under this temperature 2 hours, filter out reaction solution then, and be washed till in the filtrate till the no free chlorion with dry hexane, the remaining solid product gets solid titanium catalyst component through vacuum-drying.Its titanium content 2.80% (wt)
Press embodiment 1 polymerization result:
Catalyst activity 35,500gPP/gCat
Polymkeric substance apparent density 0.44g/cm
3
Comparative example 1
Trichloromethane washing step in the washing process of embodiment 1 is saved, and other is constant.
Catalyst Ti content 2.35%.Polymerization result:
Catalytic efficiency 39,000gPP/gCat
Polymkeric substance apparent density 0.44g/cm
3
Comparative example 2
In the there-necked flask that agitator and thermometer are housed, after nitrogen is fully replaced, add anhydrous MgCl
25 grams, decane 40ml, and 2-Ethylhexyl Alcohol 24ml.Under whipped state, be warming up to 130 ℃, kept 2 hours.Then, add the 1.5ml tetrabutyl titanate, react adding 2ml diisobutyl phthalate after 0.5 hour, continue to form uniform solution in 1 hour in this thermotonus.Reaction finishes, and it is standby that alcohol adduct is cooled to room temperature.With the above-mentioned alcohol adduct homogeneous solution for preparing, in 30 minutes, be added drop-wise to and agitator and thermometer are housed and fully replace through nitrogen, fill and add in advance and remain in-20 ℃ the reactor of 200ml titanium tetrachloride.Dropwise, be warming up to 110 ℃ through 3.5 hours.Add the 1.0ml diisobutyl phthalate, react and leach reaction solution after 2 hours, again add the 200ml titanium tetrachloride, be warming up to 110 ℃, under this temperature, continue reaction 2 hours, leach reaction liquid then, and be washed till in the filtrate till the no free chlorion with dry hexane, the remaining solid product gets solid titanium catalyst component through vacuum-drying.Its titanium content 2.85% (wt).
Press embodiment 1 step polymerization result:
Catalyst activity 32,000gPP/gCat
Polymkeric substance apparent density 0.45g/cm
3
Claims (6)
1, a kind of when being used for olefinic polymerization, by solid titanium Primary Catalysts A component, aluminum alkyl catalyst B component and organo-siloxane C component are formed, the preparation method of solid titanium Primary Catalysts A component wherein, it is characterized in that Magnesium Chloride Anhydrous and alcohol compound and varsol in the presence of ester class complex compound, when the molar ratio of alcohol compound and magnesium chloride is 1-6: 1, the mol ratio of ester class complex compound and magnesium chloride is 0.01-0.80: 1 o'clock, 50-180 ℃ of reaction 0.5-5.0 hour, with the even complex solution of titanate ester compound and internal electron donor formation, be added in the magnesium chloride alcohol adduct then; Continue to keep said temperature, question response is cooled to room temperature after finishing, and obtains stable and uniform alcohol adduct solution; Again it is added to through nitrogen replacement and be equipped with-reactor of 40-+40 ℃ liquid titanium compound in, the mol ratio of alcohol adduct homogeneous solution and liquid titanium compound is 5-60: 1, stirring under above-mentioned low temperature fully contacts them, after 3-5 hour, be warming up to 50-150 ℃, add internal electron donor, the mol ratio of its add-on and alcohol adduct homogeneous solution is 0.005-0.200, reacted 0.5-6 hour, reaction filters out liquid after finishing, and adds liquid titanium compound again, under same temperature, continue reaction 1-6 hour, filter out liquid, use solvent wash, drying makes solid titanium Primary Catalysts A component.
2,, it is characterized in that alcohol compound is a Fatty Alcohol(C12-C14 and C12-C18): methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, decyl alcohol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, ethylene glycol according to the preparation method of the described solid titanium catalyst component of claim 1; Alicyclic ring alcohol is a hexalin; Aromatic alcohol is phenylcarbinol, phenylethyl alcohol and phenol compound.
3,, it is characterized in that varsol is that aliphatic hydrocarbon is hexane, heptane, octane, decane, kerosene, 200 according to the preparation method of the described solid titanium catalyst component of claim 1
#Oil; Alicyclic hydrocarbon is pentamethylene, hexanaphthene, methylcyclohexane, ethylcyclohexane; Aromatic hydrocarbon is benzene,toluene,xylene.
4,, it is characterized in that ester class complex compound is that the organic carboxyl acid monoesters is: ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, methyl acrylate, ethyl propenoate, ethyl benzoate, methoxybenzoic acid ethyl ester according to the preparation method of the described solid catalytic ingredient of claim 1; The polynary ester of organic carboxyl acid is diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid n-caprylic acid, dimixo-octyl phthalate and tetraethyl titanate, tetrabutyl titanate, metatitanic acid four monooctyl esters.
5,, it is characterized in that liquid titanium compound is that titanium tetrahalide is titanium tetrachloride, titanium tetrabromide according to the preparation method of the described solid catalytic ingredient of claim 1; Alkoxyl group three halogenated titaniums are methoxyl group titanous chloride, oxyethyl group titanous chloride, propoxy-titanous chloride, butoxy titanous chloride, methoxyl group titanium tribromide, oxyethyl group titanium tribromide, butoxy titanium tribromide; Dialkoxy dihalide titanium is dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diethoxy dibrominated titanium; The tri-alkoxy halogenated titanium is triethoxy titanium chloride, three butoxy titanium chlorides, three ethoxy titanium bromides.
6,, it is characterized in that internal electron donor is ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, methyl acrylate, ethyl propenoate, ethyl benzoate, methoxybenzoic acid ethyl ester, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid n-caprylic acid, dimixo-octyl phthalate according to the preparation method of the described solid catalytic ingredient of claim 1.
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| CN106317274A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst compound for preparing polyolefin for fibers, and preparation method and application thereof, catalyst system, application of catalyst system, and olefin polymerization method |
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| CN106317275A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst component for preparing fiber polyolefin, preparation method and application thereof, catalyst system, application of catalyst system, and olefin polymerization method |
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| CN108495874B (en) * | 2015-12-02 | 2021-01-15 | Sabic环球技术有限责任公司 | Procatalyst for olefin polymerization |
| CN114456288A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization reaction, and preparation method and application thereof |
| CN114456289A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization, and preparation method and application thereof |
| CN114456289B (en) * | 2020-10-22 | 2024-02-13 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization, preparation method and application thereof |
| CN114456288B (en) * | 2020-10-22 | 2024-02-13 | 中国石油化工股份有限公司 | Titanium-containing catalyst, catalyst for olefin polymerization reaction, preparation method and application thereof |
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