CN103130921A - Catalyst carrier for olefin polymerization and preparation method thereof - Google Patents
Catalyst carrier for olefin polymerization and preparation method thereof Download PDFInfo
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- CN103130921A CN103130921A CN201110386331XA CN201110386331A CN103130921A CN 103130921 A CN103130921 A CN 103130921A CN 201110386331X A CN201110386331X A CN 201110386331XA CN 201110386331 A CN201110386331 A CN 201110386331A CN 103130921 A CN103130921 A CN 103130921A
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Abstract
The invention provides a catalyst carrier for olefin polymerization. The catalyst carrier for the olefin polymerization comprises a reaction product which is formed by at least one compound containing organic-magnesium, at least one compound containing hydroxyl, at least one organic-silicon compound containing chlorine, and at least one furtherance type separating-out agent. The furtherance type separating-out agent is a polystyrene block polybutadiene (SB) copolymer. The invention further correspondingly provides a preparation method of the catalyst carrier. The catalyst carrier which is prepared through the method has good particle morphology and distribution, and therefore using of catalyst in devices of polymerization processes such as gaseous phase and slurry is benefited.
Description
Technical field
The present invention relates to a kind of for the support of the catalyst of the equal polymerization of alkene or copolymerization and preparation method and the purposes of this support of the catalyst.
Background technology
After the 20 efficient polyolefin catalysts of century 70 were succeeded in developing, great change had occured in world's polyolefin industry.Over nearly more than 20 years, follow the development of olefin polymetiation process, the catalyzer that matches with polymerization technique has also been got significant progress, and wherein effective catalyst relies on its good polymerization and ripe utilisation technology still to occupy an important position in the polyolefin catalyst field.Through exploratory development for many years, Mg-Ti be the preparation method of effective catalyst also by common polishing, the Suspension method has developed into pre-forming carrier and has then adopted chemical reaction method.
The pre-forming carrier Kaolinite Preparation of Catalyst has a lot of apparent advantages, as good in the granules of catalyst form, size distribution is narrow etc., but the over-all properties of pre-forming carrier directly affects and determines the performance of gained catalyzer, and the carrier that therefore prepares good over-all properties just becomes the developing important ring of catalyst technology.
Early stage support of the catalyst is to select the magnesium compound milled processed to obtain, and the carrier that obtains like this causes directly that the granules of catalyst form that obtains is bad and size distribution is very wide, and production brings a lot of difficulties to polyolefin device.
There are again subsequently many patents to announce and adopt the whole bag of tricks to prepare the efficient catalytic agent carrier, and the performances such as granules of catalyst form, catalytic efficiency and resulting polymers form thereof have been improved to a certain extent, in producing, polyolefin industry is applied, but the poor morphology of this class carrier gained catalyzer, globulate not, its representational patent are the US4952649 of Mitsui petro-chemical corporation and the US4784983 of Sinopec Beijing Chemical Research Institute.
Just announce in patent US4111835 as far back as middle 1970s Italy Meng Ai company and make magnesium chloride alcohol adduct carrier with spray method, but the yield of the qualified carrier of spray method production is too low, and the gained catalyst efficiency is lower.Another patent of the said firm US4399054 announces and adopts magnesium chloride alcohol adduct melt to disperse in the ejection of dispersion medium mesohigh or high-speed stirring subsequently, then moulding obtains ball type carrier in cryostat, obtain spherical catalyst with this carrier again, but the efficient of catalyzer and orientation property are all relatively poor.The US4293673 of U.S. UCC house journal discloses a kind of catalyzer that adopts silica gel and the preparation of magnesium chloride complex carrier, this catalyzer is applied to have greater activity in gas phase polymerization technique, prepared ethene polymers has good particle form, but this class catalyst preparation process is more loaded down with trivial details.
The objective of the invention is to overcome deficiency of the prior art, adopt more simple and practical preparation method, obtain to be used for the spherical carrier of catalyst of olefinic polymerization.The inventor is by experiment discovery repeatedly, select suitable chemical reaction system, just can make the support of the catalyst synthetic method simple, and can obtain catalyst carrier particle spherical, narrow size-grade distribution, and have higher catalytic activity and hydrogen response preferably with the catalyzer that this carrier prepares.
Summary of the invention
The invention provides a kind of support of the catalyst for olefinic polymerization, it comprises the reaction product that is formed by at least a organo-magnesium compound, at least a hydroxyl compounds, at least a chloride silicoorganic compound and at least a furtherance type precipitation agent; Wherein, described organo-magnesium compound such as general formula (I) MgR
1 nCl
2-nShown in, R in formula
1C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0＜n≤2; Described hydroxyl compounds such as general formula (II) HOR
2Shown in, R in formula
2C
2～C
20Alkyl, can be saturated or undersaturated straight chain, side chain or closed chain; Described chloride silicoorganic compound such as general formula (III) SiR
3 mCl
4-mShown in, R in its Chinese style
3C
2～C
20Alkyl or alkoxyl group, 0≤m in general formula＜4; Described furtherance type precipitation agent is polystyrene block polyhutadiene (SB) analog copolymer.
In preferred organo-magnesium compound general formula of the present invention (I), R
1C
2～C
20Alkyl; More preferably, organo-magnesium compound is selected from least a in dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride, butyl magnesium chloride.Preferred hydroxyl compounds of the present invention is Fatty Alcohol(C12-C14 and C12-C18) or aromatic alcohol, more preferably at least a in propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol and phenylethyl alcohol.
Preferred chloride silicoorganic compound of the present invention are selected from least a in trichlorophenyl silane, trichloromethyl silane, trichloroethyl silane, trichlorine octyl group silane, trichlorine methoxy silane, trichlorine Ethoxysilane, trichlorine butoxy silane, dichloro dimethoxy silane, dichloro diethoxy silane and silicon tetrachloride; Wherein trichloromethyl silane, trichloroethyl silane, trichlorine methoxy silane, trichlorine Ethoxysilane and silicon tetrachloride are most preferred.
In the present invention, preferred described polystyrene block polyhutadiene (SB) analog copolymer comprises diblock and three blocks (SBS, BSB) and derivative thereof, and the block type of optional is linear, band chain or star form.The content of polyhutadiene is 3-97wt%, more preferably 10-90wt% in described polystyrene block polyhutadiene analog copolymer.
The present invention also provides a kind of preparation method who divides for carrier for olefin polymerization catalyst, comprises the steps a: described organo-magnesium compound and the reaction of described hydroxyl compounds are formed clear solution; B: described furtherance type precipitation agent is dispersed in C
4～C
20Alkane is or/and be mixed to get mixed solution in aromatic solvent and with clear solution that step a obtains; C: described chloride silicoorganic compound are mixed under the low temperature of-20～50 ℃ with the mixed solution that step b obtains, and then temperature reaction forms the suspension that contains solid particulate; And d: the described solid particulate of separated and collected is support of the catalyst.
Preferably in preparation method of the present invention, in every mole of organo-magnesium compound, the hydroxyl compounds is 0.1～20 mole, more preferably 0.2～10 mole; Chloride silicoorganic compound are 0.1～50 mole, more preferably 0.5～20 mole; The concentration of furtherance type precipitation agent in reaction system is controlled at 0.001～100 grams per liter, more preferably 0.01～50 grams per liter.
In the step a of Kaolinite Preparation of Catalyst carrier, it is comparatively favourable that magnesium compound and alcohols material react at relatively high temperature, but preferred below the boiling temperature of reactant, namely temperature is not usually higher than 90 ℃, preferably not higher than 70 ℃.The time of reaction is depended on reactant character and operational condition, generally at 5 minutes to 2 hours, and preferred 10 minutes to 1 hour.The clear solution that magnesium compound and alcohols material reaction form can mix use with inert diluent, inert diluent is selected from aliphatic hydrocarbon usually, for example Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, preferably hexane or heptane.
In the step b of Kaolinite Preparation of Catalyst carrier, the clear solution that obtains in the furtherance type precipitation agent solution and the step a that are dissolved in solvent is fully mixed, described solvent is preferably one or more in hexane, heptane and toluene.According to kind and the different in kind of furtherance type precipitation agent, its concentration in solvent is controlled at 0.1～100 grams per liter, preferred 1～50 grams per liter; The add-on of furtherance type precipitation agent solution is so that the concentration of furtherance type precipitation agent in reaction system is controlled at 0.001～100 grams per liter, preferred 0.01～50 grams per liter.The mixing temperature of this step generally will lower than the boiling temperature of system, for simplicity, be typically chosen in 0～90 ℃, preferred 10～50 ℃.The mixing time of two kinds of solution is typically chosen in 0.5 minute to 5 hours, preferred 10 minutes to 1 hour.
In the step c of support of the catalyst preparation, at first the mixed solution that step b is obtained is reduced to certain temperature, solution still keeps clear at this temperature, be unlikely to become turbid or precipitate, temperature can be controlled between-20～50 ℃, preferably between 0～30 ℃, then general formula (III) compound is progressively slowly added, usually stir in reinforced process and be beneficial to abundant mixing, feed rate usually obviously heats up with do not induce reaction obviously aggravation or system and is as the criterion.After fully mixing, can adopt any known suitable method to heat up, as be rapidly heated, slowly heat up, progressively heat up or the temperature programming of gradual change, different temperature-rising methods can obtain the totally different support of the catalyst of performance characteristics, in temperature-rise period, system can become muddiness by clarification, separates out solid particulate and precipitation.In forming settling step, its reaction times should sufficiently long so that precipitation fully, specifically can be 1 minute～10 hours, preferred 3 minutes～5 hours.
Experiment is found, after settling step, reacting at a certain temperature for some time, to carry out maturation process more favourable to the particle shape of support of the catalyst, and it can improve the intensity of carrier particle, thereby reduces the particle fragmentation phenomenon in catalyst cupport and olefin polymerization process.The temperature of maturation process generally is equal to or higher than the outlet temperature of precipitin reaction, and the time of slaking reaction can be controlled at 0.5～10 hour, preferred 1～5 hour.
After carrying out maturation process, first carry out solid-liquid separation, filter or the conventional means such as centrifugal such as selecting, and generally need to wash solid particulate, in order to remove the by product that forms in excessive reactant and preparation process, any inert solvent all can be used for this washing step, such as selecting Trimethylmethane, pentane, hexane, heptane, hexanaphthene, toluene or various aromatic hydrocarbons and composition thereof etc., usually select with after twice of toluene wash in experiment, more fully wash with hexane.After washing, the suspension of carrier in above-mentioned inert solvent carries out drying under nitrogen protection, to obtain support powder.
It is spherical using the carrier granule that the inventive method prepares, and it has controlled globule size and distribution, and median size is at 0.1-200 μ m, preferred 1-100 μ m.The support of the catalyst that the present invention prepares has good particle form and distribution, thereby more is conducive to the use of catalyzer on the polymerization technique devices such as gas phase, slurry.
The support of the catalyst that the present invention relates to can be used according to the load mode that this area olefinic polymerization Ziegler-Natta catalyst and single site catalysts are known, as using, described carrier can also be used for one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalyst mixed load together with transistion metal compound or electron donor.
The catalyzer that carrier component of the present invention obtains is applicable to various any alkene that can carry out the polycoordination reaction, comprise a kind of equal polymerization of alkene or the copolymerization of multiple alkene, the alpha-olefins such as optimal ethylene, propylene, butylene, hexene and octene in alkene, or the mixture of ethene, propylene, butylene and one or more alpha-olefins.Comonomer is C preferably
2-C
12Alkene, preferred C
4-C
10Alkene, as 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methylpentene-1, diene such as divinyl, Isosorbide-5-Nitrae-hexadiene and 1,7-octadiene, cyclenes such as norbornylene, and their any mixture.
The catalyzer that carrier of the present invention prepares can adopt conventional polymerization technique to carry out polyreaction in one or more polymerization reactors, can be gas phase, slurry or bulk polymerization, and polyreaction can be intermittence or continuous polymerization process.
To slurry or bulk reaction device, temperature of reaction is generally at 40-130 ℃, and preferred 60-110 ℃, reactor pressure is generally at 0.2-8MPa, preferred 1-6MPa, and the residence time is generally at 0.2-6 hour, preferred 0.5-3 hour.The general boiling point of selecting uses as thinner at the aliphatic hydrocarbon of-70-100 ℃ scope, and if necessary, polyreaction can be carried out under super critical condition.
For Gas-phase reactor, temperature of reaction is generally at 60-130 ℃, and preferred 70-110 ℃, reactor pressure is generally at 0.5-4MPa, preferred 1-3MPa, and the residence time is generally at 0.5-10 hour, preferred 1-8 hour.If necessary, select suitable aliphatic hydrocarbon to use as thinner, polyreaction can be carried out under the frozen state condition.
Adopt carrier of the present invention and preparation method thereof, can obtain to have the catalyzer of good particle form, and catalyzer has higher catalytic activity and hydrogen response preferably; The polymerisate form that this catalyst olefinic polyreaction obtains is the particle form of replicating vector preferably; Therefore carrier of the present invention has good over-all properties.
Description of drawings
Fig. 1 is the size distribution figure of the support of the catalyst for preparing in embodiment 1.
Embodiment
The size-grade distribution of carrier and catalyzer: adopt the MASTERSIZE particles distribution instrument, normal hexane is as dispersion agent, useful range 0.02～2000 μ m.
The relative weight per-cent of metal in carrier and catalyzer (being mainly titanium, magnesium): adopt plasma emission spectrum (ICP).
The pattern of catalyzer and polymkeric substance: adopt scanning electron microscope (SEM).
The mensuration of melting index: ASTM-D1238.
The mensuration of tap density: DIN-53194.
The embodiment that below provides is only in order to illustrate the present invention, rather than limits the invention; Protection scope of the present invention is as the criterion with claims.
Embodiment 1
Get successively dibutylmagnesium hexane solution (1M) and the 1.0ml isooctyl alcohol of 30ml hexane, 3.15ml, be warming up to 50 ℃ and keep stirring reaction half an hour, obtain clear solution, then add styrene butadiene triblock copolymer (Kraton, FG1901X, wherein polybutadiene content 70%) hexane solution (10g/L) 3ml, be cooled to-10 ℃, add 0.36 milliliter of silicon tetrachloride, naturally slowly heat up, after rising to room temperature, 50 ℃ of reactions 2 hours are kept in heating.Suspension temperature is down to room temperature, standing, sedimentation, with hexane washing three times, the consumption of each hexane is 50 milliliters, after washing is completed, the dry pale solid mobility powder that gets, its particle form is good, and median size is 11.9 microns, and size-grade distribution is seen accompanying drawing 1.
Ultimate analysis: Mg:20.18% (weight), Cl:35.79% (weight).
Under nitrogen protection; spherical carrier particle 3.76 grams that embodiment 1 is obtained join in 250 milliliters of glass reactors; add 50 ml n-hexanes; slurries are made in stirring; bathe with low temperature and be cooled to 0 ℃; slowly drip the hexane solution (containing titanium tetrachloride 2.0ml) of 20.0 milliliters of titanium tetrachlorides, then stirring reaction 1 hour slowly is warming up to 50 ℃ and kept stirring reaction 2 hours.After reaction finishes, standing, leach liquid, with 40 milliliters of hexane washing leaching cakes twice, solid is dried up with nitrogen, obtain having magnesium chloride supported catalyst 3.27 grams of good mobility, its median size is 13.4 microns.
Ultimate analysis (ICP): Ti:2.37% (weight), Mg:16.79% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is as follows:
Vinyl polymerization is estimated A: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in 2L stainless steel stirring tank, then temperature is brought up to 85 ℃, the disposable hydrogen that adds 0.5MPa, then with ethene, the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, the active 5.1kg polymkeric substance of calculating catalyzer/g cat, the tap density of test polyethylene powder is 0.34g/ml, the melting index under the 2.16Kg load is 26.4g/10min.
Vinyl polymerization is estimated B: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in 2L stainless steel stirring tank, then temperature is brought up to 85 ℃, the disposable hydrogen that adds 0.18MPa, then with ethene, the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, the active 11.2kg polymkeric substance of calculating catalyzer/g cat, the tap density of test polyethylene powder is 0.35g/ml, the melting index under the 2.16Kg load is 0.76g/10min.
Embodiment 3
The method for preparing carrier is basic identical with embodiment 1, but " 1.0ml isooctyl alcohol " changed into " 0.6ml propyl carbinol ", and will " add styrene butadiene triblock copolymer (Kraton; FG1901X; wherein polybutadiene content 70%) hexane solution (10g/L) 3ml " and change " adding styrene butadiene triblock copolymer (Kraton; FG1901X, wherein polybutadiene content 70%) hexane solution (10g/L) 1ml " into.Gained carrier median size is 50.8 microns.
Ultimate analysis: Mg:25.79% (weight), Cl:30.16% (weight).
The method for preparing carrier is basic identical with embodiment 1, but will " be cooled to-10 ℃; add 0.36 milliliter of silicon tetrachloride; naturally slowly heat up; after rising to room temperature; 50 ℃ of reactions 2 hours are kept in heating " and change " after adding 0.36 milliliter of silicon tetrachloride to mix half an hour under room temperature, 50 ℃ of reactions 2 hours are kept in heating " into.Gained carrier median size is 8.3 microns.
Ultimate analysis: Mg:16.59% (weight), Cl:29.47% (weight).
Embodiment 5
The method for preparing carrier is basic identical with embodiment 1, changes " adding 0.72 milliliter of silicon tetrachloride " into but will " add 0.36 milliliter of silicon tetrachloride ".Gained carrier median size is 9.2 microns.
Ultimate analysis: Mg:18.34% (weight), Cl:35.27% (weight).
The particle form of gained carrier of the present invention is good as can be seen from the above embodiments, particle is little and narrow diameter distribution, and when being used for the load catalyst for olefines polymerizing, the activity of gained catalyzer is higher and hydrogen response is better.And those skilled in the art as can be known be, if the furtherance type precipitation agent that does not add furtherance type precipitation agent of the present invention or add in the carrier preparation process is also improper, the product granular size that prepares is inhomogeneous, and form is irregular, and median size also is difficult to reach in micro scale; This product generally can not be used as carrier supported catalyst.
Claims (11)
1. be used for the support of the catalyst of olefinic polymerization, it comprises the reaction product that is formed by at least a organo-magnesium compound, at least a hydroxyl compounds, at least a chloride silicoorganic compound and at least a furtherance type precipitation agent;
Described organo-magnesium compound such as general formula (I) MgR
1 nCl
2-nShown in, R in formula
1C
2～C
20Alkyl, 0＜n≤2;
Described hydroxyl compounds such as general formula (II) HOR
2Shown in, in formula, R2 is C
2～C
20Alkyl;
Described chloride silicoorganic compound such as general formula (III) SiR
3 mCl
4-mShown in, R in its Chinese style
3C
2～C
20Alkyl or alkoxyl group, 0≤m in general formula＜4;
Described furtherance type precipitation agent is polystyrene block polyhutadiene analog copolymer.
2. carrier according to claim 1, in wherein said organo-magnesium compound general formula (I), R
1C
2～C
20Alkyl; Preferred described organo-magnesium compound is selected from least a in dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and butyl magnesium chloride; Described hydroxyl compounds is Fatty Alcohol(C12-C14 and C12-C18) or aromatic alcohol, preferably at least a in propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol and phenylethyl alcohol.
3. carrier according to claim 1, described chloride silicoorganic compound are selected from least a in trichlorophenyl silane, trichloromethyl silane, trichloroethyl silane, trichlorine octyl group silane, trichlorine methoxy silane, trichlorine Ethoxysilane, trichlorine butoxy silane, dichloro dimethoxy silane, dichloro diethoxy silane and silicon tetrachloride.
4. the described carrier of any one according to claim 1-3, described polystyrene block polyhutadiene analog copolymer comprises diblock and three blocks and derivative thereof, the block type of optional is linear, band chain or a star form.
5. the described carrier of any one according to claim 1-3, the content of polyhutadiene is 3-97wt% in described polystyrene block polyhutadiene analog copolymer, is preferably 10-90wt%.
6. the preparation method of the support of the catalyst for olefinic polymerization as described in any one in claim 1-5, comprise the steps:
A: described organo-magnesium compound and the reaction of described hydroxyl compounds are formed clear solution;
B: described furtherance type precipitation agent is dispersed in C
4～C
20Alkane is or/and be mixed to get mixed solution in aromatic solvent and with clear solution that step a obtains;
C: described chloride silicoorganic compound are mixed under the low temperature of-20～50 ℃ with the mixed solution that step b obtains, and then temperature reaction forms the suspension that contains solid particulate;
D: the described solid particulate of separated and collected is support of the catalyst.
7. preparation method according to claim 6, is characterized in that, the low temperature in described step c is 0～30 ℃; Described heating mode is to be rapidly heated, slowly to heat up, progressively to heat up or the temperature programming of gradual change.
8. preparation method according to claim 6, is characterized in that, in every mole of organo-magnesium compound, the hydroxyl compounds is 0.1～20 mole, preferred 0.2～10 mole; Chloride silicoorganic compound are 0.1～50 mole, preferred 0.5～20 mole; The concentration of furtherance type precipitation agent in reaction system is controlled at 0.001～100 grams per liter, preferred 0.01～50 grams per liter.
9. preparation method according to claim 6, in described step b, solvent is to be selected from one or more in hexane, heptane and toluene.
10. one kind as carrier as described in any one in claim 1～5 or the carrier for preparing as any one preparation method in claim 6～9, it is characterized in that, carrier granule is spherical, and it has controlled globule size and distribution, median size is at 0.1-200 μ m, preferred 1-100 μ m.
11. one kind as carrier as described in any one in claim 1～5 or the application of carrier in the equal polymerization of alkene or copolymerization that prepare as any one preparation method in claim 6～9, wherein said alkene is ethene, propylene, butylene, hexene and octene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4940682A (en) * | 1987-10-28 | 1990-07-10 | Sumitomo Chemical Company, Limited | Solid catalyst component for olefin polymerization |
| EP1233029B1 (en) * | 2001-02-15 | 2003-11-12 | Saudi Basic Industries Corporation | Supported catalyst composition for polymerization of olefins; method for preparing the same and process for polymerization using the same |
| CN1948351A (en) * | 2006-06-30 | 2007-04-18 | 吉林市朋力科技开发有限公司 | Polymer carrier Ziegler-Natta catalyst for olefin hydrocarbon polymerization and its preparation method |
| CN101260166A (en) * | 2008-04-29 | 2008-09-10 | 郭琦 | Ethene homopolymerization and copolymerization catalyst and preparation method thereof |
-
2011
- 2011-11-29 CN CN201110386331.XA patent/CN103130921B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4940682A (en) * | 1987-10-28 | 1990-07-10 | Sumitomo Chemical Company, Limited | Solid catalyst component for olefin polymerization |
| EP1233029B1 (en) * | 2001-02-15 | 2003-11-12 | Saudi Basic Industries Corporation | Supported catalyst composition for polymerization of olefins; method for preparing the same and process for polymerization using the same |
| CN1948351A (en) * | 2006-06-30 | 2007-04-18 | 吉林市朋力科技开发有限公司 | Polymer carrier Ziegler-Natta catalyst for olefin hydrocarbon polymerization and its preparation method |
| CN101260166A (en) * | 2008-04-29 | 2008-09-10 | 郭琦 | Ethene homopolymerization and copolymerization catalyst and preparation method thereof |
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