CN101724103A - Preparation method of catalyst component for ethylene polymerization - Google Patents
Preparation method of catalyst component for ethylene polymerization Download PDFInfo
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- CN101724103A CN101724103A CN200810224880A CN200810224880A CN101724103A CN 101724103 A CN101724103 A CN 101724103A CN 200810224880 A CN200810224880 A CN 200810224880A CN 200810224880 A CN200810224880 A CN 200810224880A CN 101724103 A CN101724103 A CN 101724103A
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Abstract
The invention relates to a prepration method of a catalyst component for ethylene polymerization, which comprises the following steps: (1) leading an alkoxy titanium compound to be reacted with a magnesium compound for obtaining reaction solution; and (2) leading the obtained reaction solution to be in direct contact reaction with a liquid titanium compound for obtaining a solid catalyst component. The preparation method is simple, the activity of the obtained catalyst is high, and the content of fine powder in an obtained ethylene polymer is low.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the catalyst component of ethylene polymerization.In particular, relate to a kind of preparation method who reacts the catalyst component that makes by titan-alkoxide, magnesium compound and liquid titanium compound.
Technical background
As everyone knows, in the polyvinyl technology of industrialized preparation at present, all require employed catalyzer to have advantages of high catalytic activity, high reactivity not only can improve output, can also reduce the catalyst residue problem (halogen in the residual catalyzer may cause the problem that mould gets rusty in the polymkeric substance post-treatment moulding technology) in the unit polymkeric substance.Simultaneously, in existing polymerization technique, also require prepared ethene polymers to have performances such as good flowability, fine powder be less, can reduce the trouble that polymkeric substance runs into like this in the device aftertreatment, increase the device traveling comfort.
In the art, using the reactant that comprises titan-alkoxide, magnesium compound and liquid titanium compound to prepare the catalyzer that is used for olefinic polyreaction has been known.Prepared the catalyzer of number of different types with this class reactant.Philips Petroleum Co. discloses a kind of technology for preparing catalyzer at US5275992, with titan-alkoxide and magnesium halide reaction, add aikyl aluminum halide then as precipitation additive, the precipitation that generates is through after washing, add alkylaluminium cpd and carry out pre-polymerization by ethene, the time and the speed of control pre-polymerization, the solid that obtains contacts with a kind of halogenated titanium again; The influence of pre-polymerization to catalyst performance disclosed in US5244990, compared the not slow and very fast three kinds of catalyzer that mode prepares of pre-polymerization speed through pre-polymerization, pre-polymerization speed, fine powder content is minimum in the polymkeric substance of finding to obtain according to the catalyst vinyl polymerization that the slow mode of pre-polymerization speed prepares; In EP0580102, find to prepare catalyzer copolymerization of ethylene and hexene well according to the disclosed technology of US5275992.CN 1086223A discloses a kind of Preparation of catalysts technology, in the dissolution process of titan-alkoxide and magnesium halide, add an amount of water, add aikyl aluminum halide then as precipitation additive, the precipitation that generates is through after washing, add alkylaluminium cpd and carry out pre-polymerization by ethene, the time and the speed of control pre-polymerization, the solid that obtains contacts with a kind of halogenated titanium again, and the catalyzer that obtains has improved the effect of ethene and high alpha-olefin copolymerization.
Though these catalyzer have very high activity, and the fine powder content in the polymkeric substance is less, be very suitable for slurry loop technology, also will be but will introduce precipitation agent in the Preparation of catalysts process through the prepolymerization reaction of ethene, complicated process of preparation and cycle are longer.
Summary of the invention
The objective of the invention is at the problems referred to above, the preparation method of a kind of technology catalyst component simple, with short production cycle is provided, when being used for vinyl polymerization, activity of such catalysts is very high by the catalyst component of this preparation method preparation, and the ethene polymers fine powder content that obtains simultaneously is less.
For achieving the above object, the invention provides a kind of preparation method who is used for the catalyst component of ethylene polymerization, it comprises following steps:
(1) alkoxy titanium compound and magnesium compound are reacted, wherein the mol ratio of Ti in the alkoxy titanium compound and the Mg in the magnesium compound is 1～50, is preferably 1.2～15; Temperature of reaction is 0 ℃～350 ℃, is preferably 30 ℃～200 ℃; Reaction times is 20 minutes～6 hours, is preferably 1 hour～4 hours, obtains reaction soln;
(2) directly and the liquid titanium compound contact reacts with the above-mentioned reaction soln that obtains, wherein in the liquid titanium compound in Ti and the magnesium compound mol ratio of Mg be 4～500, be preferably 10～200; Catalytic temperature is-60 ℃～40 ℃, is preferably-40 ℃～10 ℃; Reacted 20 minutes～4 hours, and be preferably 40 minutes～2 hours; Improve temperature of reaction to 100 ℃～140 ℃ then, be preferably 110 ℃～130 ℃, continue reaction 1 hour～5 hours, better reaction is 1.5 hours～3.5 hours; With hexane or heptane thorough washing, obtain ingredient of solid catalyst;
Wherein the general formula of the alkoxy titanium compound described in the step (1) is Ti (OR)
mX
4-m, m is integer 0＜m≤4, and wherein R is identical or different, and R is selected from C
1-C
20Straight chain or C
3-C
20The alkyl of side chain, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20A kind of in the aralkyl, X is identical or different, be halogen atom or hydrocarbyl group; The general formula of described magnesium compound is MgX
nR
2-n, wherein n is integer 0≤n≤2, and X is a halogen atom, and substituent R is identical or different, and R is selected from C
1-C
20Straight chain or C
3-C
20The alkyl of side chain, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20Aralkyl and alkoxyl group wherein a kind of;
Wherein the liquid titanium compound general formula described in the step (2) is TiX
4, X is a halogen.
Specifically, the reaction of alkoxy titanium compound and magnesium compound forms solution in the step (1), and reaction is preferably in alkane or the aromatic hydrocarbons to be carried out.
Alkoxy titanium compound described in the step (1) comprises:
Four titan-alkoxides, Ti (OR
1) (OR
2) (OR
3) (OR
4) substituent R wherein
1, R
2, R
3And R
4Can be the same or different, be selected from C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl.As purity titanium tetraethoxide, tetramethoxy titanium, four positive propoxy titaniums, tetraisopropoxy titanium, four titanium butoxide, four isobutoxy titaniums, diethyl di-isopropyl titanium, diethyl diisobutyl titanium, ethyl triisopropyl titanium etc.;
The tri-alkoxy titanium, Ti (OR
1) (OR
2) (OR
3) X substituent R wherein
1, R
2, R
3Can be the same or different, be selected from C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; X can be that halogen atom also can be a hydrocarbyl group.As: trimethoxy titanium chloride, triethoxy titanium chloride, three isobutoxy titanium bromides, diethoxy methoxyl group chlorination titanium, oxyethyl group methoxy base butoxy titanium chloride, methyl triethoxy titanium etc.;
The dialkoxy titanium, Ti (OR
1) (OR
2) X
1X
2Substituent R wherein
1, R
2Can be the same or different, be selected from C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; X
1, X
2Can be that halogen atom can be a hydrocarbyl group also, can be the same or different.As: dimethoxy titanium dichloride, diethoxy titanium dichloride, oxyethyl group methoxy base titanium dichloride, dimethyl diethoxy titanium, isopropyl methyl diethoxy titanium etc.;
One titan-alkoxide, Ti (OR
1) X
1X
2X
3Substituent R wherein
1Can be the same or different, be selected from C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl; X
1, X
2, X
3Can be that halogen atom can be a hydrocarbyl group also, can be the same or different.As: methoxyl group titanous chloride, oxyethyl group titanous chloride, oxyethyl group di-isopropyl titanium chloride, isobutyl-triethyl titanium etc.
Wherein be preferably four titan-alkoxides, best is purity titanium tetraethoxide, four titanium butoxide and tetraisopropoxy titanium, can be used in combination two or more above-mentioned alkoxy titanium compounds.
Wherein the magnesium compound in the step (1) comprises:
Mg R
1R
2Two substituent R wherein
1, R
2Can be the same or different, be selected from C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, or its corresponding alkoxyl group.Be specially: dimethyl magnesium, magnesium ethide, dibutylmagnesium, ethyl-butyl magnesium, diethoxy magnesium, dibutoxy magnesium, oxyethyl group butoxy magnesium, ethyl magnesium ethylate, butyl magnesium ethylate etc.;
MgXR
1Wherein X is fluorine, chlorine, bromine or iodine, R
1Be selected from C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl, C
7-C
20A kind of in the aralkyl, or its corresponding alkoxyl group.Be specially: methoxyl group chlorination magnesium, oxyethyl group magnesium chloride, benzylmagnesium chloride, phenoxy group magnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide etc.;
MgX
2Wherein X can be fluorine, chlorine, bromine or iodine.Be specially: magnesium chloride, magnesium bromide, magnesium fluoride, magnesium iodide etc.
Magnesium compound among the present invention is magnesium halide preferably, is more preferably magnesium chloride, can be used in combination two or more above-mentioned magnesium compounds.
Wherein the liquid titanium compound described in the step (2) comprises titanium tetrachloride, titanium tetrafluoride, titanium tetrabromide, titanium tetra iodide, and best is titanium tetrachloride, can be used in combination two or more above-mentioned titanium compounds.
The present invention also provides a kind of catalyst component that is made by above-mentioned preparation method.
In addition, the invention still further relates to a kind of catalyzer that is used for ethylene polymerization, it comprises the reaction product of following component:
(1) a kind of catalyst component of making of above-mentioned preparation method;
(2) general formula is AlR
nX
3-nOrgano-aluminium compound, R is that hydrogen or carbonatoms are 1～20 alkyl, aralkyl in the formula, aryl, X are halogen, n is the integer of 0≤n≤3.
Component in vinyl polymerization (1) is a Primary Catalysts, and component (2) is a promotor.
Wherein component (2) formula of is AlR
nX
3-nOrgano-aluminium compound as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride etc., preferred triethyl aluminum, triisobutyl aluminium.
The mol ratio of the aluminium in titanium in the main catalyst component (1) and the cocatalyst component (2) 1: 1～1: 2000 is preferably 1: 1～1: 500.
In the ethene polymerization process of the present invention, this catalyst system can the catalyzed ethylene homopolymerization under the effect of the catalyzer that contains solid titanium catalyst and alkyl metal cpd, also can catalyzed ethylene and other olefin-copolymerization.
Other alkene among the present invention can be to contain C
3-C
20Alpha-olefin, aromatic vinyl compound, alicyclic ring vinyl compound, one or more in the cycloolefin.As propylene, butylene, hexene, 3-methyl-1-butene, 3-ethyl-1-amylene, vinylbenzene, allyl benzene, vinyl cyclohexane, vinyl pentamethylene, tetrahydrobenzene, norbornylene, 5-methyl-2-norbornylene etc.
Catalyzer of the present invention can be used for intermittently or continuous mode production, can be used for solution, gas phase and slurry phase polymerisation technology, is specially adapted to slurry phase polymerisation technology.When using slurry polymerization processes, generally select a kind of inert alkane as thinner, polymer beads can be dispersed in thinner with slurry form, reaction end back is by flash distillation or remove by filter thinner.Common thinner has propane, Trimethylmethane, pentane, hexane, heptane.Typical polymerizing condition be polymerization temperature at 20 ℃～250 ℃, be preferably in 50 ℃～160 ℃; Polymeric pressure is at 1kg/cm
2～80kg/cm
2, be preferably in 5kg/cm
2～60kg/cm
2Can use the melting index and the molecular weight of hydrogen telomerized polymer in the polymerization technique.
The polyvinyl tap density that the present invention obtains is at 0.20g/cm
3～0.60g/cm
3, the melting index of polymkeric substance (ASTM D 1238E, 190 ℃) is at 0.01g/10min～4000g/10min.
The preparation method of the catalyst component that is used for ethylene polymerization of the present invention is simple, cycle is short, the gained catalyzer can be with very high active catalytic vinyl polymerization, and makes the ethene polymers that makes have good particle performance, and the gained catalyzer is particularly suitable for slurry polymerization processes.
Embodiment
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
The preparation of solid titanium catalyst:
In 80ml toluene, add the magnesium chloride of 2g (21mmol) and the purity titanium tetraethoxide of 13.7g (60mmol), at room temperature mix half an hour after, be heated to 110 ℃ the reaction three hours, cool to room temperature.After an exsiccant reactor is replaced three times with high purity nitrogen, the titanium tetrachloride that adds 80ml, the temperature that reduces titanium tetrachloride is to-5 ℃, slowly drip above-mentioned toluene solution, the temperature fluctuation range of control reaction solution is at ± 0.2 ℃, the dropping time was about two hours, drip and finish the back-5 ℃ of continuation reactions one hour, the temperature to 110 ℃ of reaction solution then gradually raises, reaction is two hours under this temperature, remove the upper strata mother liquor after the sedimentation, the solid of lower floor washs fully with hexane, and is dried to catalyst fines.
Polymerization:
After one 2 liters autoclave is fully replaced with high purity nitrogen, use hydrogen exchange, under a little more than atmospheric condition, the purifying hexane that adds 1 liter, add the triethyl aluminium solution of 1ml (mmol/ml) and the solid catalyst of 8mg then, the temperature of system is raised to 80 ℃, adds hydrogen and make the pressure in the still reach 0.28kg/cm
3, then feed ethene and make the stagnation pressure in the still reach 0.73kg/cm
3, keeping the constant reaction of stagnation pressure two hours, polymerization is separated polyethylene after finishing from hexane, carry out drying at last.Polymeric the results are shown in table 1.
Embodiment 2
Prepare solid titanium catalyst with the method identical with embodiment 1, but in the process of preparation, the starting temperature of titanium tetrachloride becomes-20 ℃ by-5 ℃, other condition is constant.With the identical method polymerization of embodiment 1, it the results are shown in table 1 with this catalyzer.
Embodiment 3
Prepare solid titanium catalyst with the method identical with embodiment 1, but in the process of preparation, the add-on of purity titanium tetraethoxide becomes 18.3g (80mmmol) by 13.7g (60mmmol), other condition is constant.With the identical method polymerization of embodiment 1, it the results are shown in table 1 with this catalyzer.
Embodiment 4
Prepare solid titanium catalyst with the method identical with embodiment 1, but in the process of preparation, the add-on of purity titanium tetraethoxide becomes 10.3g (45mmmol) by 13.7g (60mmmol), other condition is constant.With the identical method polymerization of embodiment 1, it the results are shown in table 1 with this catalyzer.
Embodiment 5
Prepare solid titanium catalyst with the method identical with embodiment 1, with the identical method polymerization of embodiment 1, but in polymerization process, after adding hexane, add the hexene of 5ml purifying with this catalyzer, other condition is constant.It the results are shown in table 1.
Comparative Examples 1
Method for preparing catalyst carries out according to embodiment in the European patent EP 0,594,190 1, adopts ethene and hervene copolymer described in the embodiment of the invention 5 to close evaluation method evaluation, and it the results are shown in table 1.
Comparative Examples 2
Method for preparing catalyst carries out according to embodiment 4 among the Chinese patent CN 1086223A, adopts the vinyl polymerization evaluation method described in the embodiment of the invention 1 to estimate, and it the results are shown in table 1.
Table 1 polymer performance
Data by embodiment and Comparative Examples more as can be seen, when the catalyzer that is made by preparation method of the present invention was used for vinyl polymerization, catalyst activity was higher, the fine polymer powder that obtains is less.
Claims (8)
1. preparation method who is used for the catalyst component of ethylene polymerization, it comprises following steps:
(1) alkoxy titanium compound and magnesium compound are reacted, wherein the mol ratio of Ti in the alkoxy titanium compound and the Mg in the magnesium compound is 1～50, and temperature of reaction is 0 ℃～350 ℃, and the reaction times is 20 minutes～6 hours, obtains reaction soln;
(2) the direct and liquid titanium compound contact reacts with the above-mentioned reaction soln that obtains, wherein in the liquid titanium compound in Ti and the magnesium compound mol ratio of Mg be 4～500, catalytic temperature is-60 ℃～40 ℃, reacted 20 minutes～4 hours, improve temperature of reaction to 100 ℃～140 ℃ then, continue reaction 1 hour～5 hours,, obtain ingredient of solid catalyst with hexane or heptane thorough washing;
Wherein the general formula of the alkoxy titanium compound described in the step (1) is Ti (OR)
mX
4-m, m is integer 0＜m≤4, and wherein R is identical or different, and R is selected from C
1-C
20Straight chain or C
3-C
20The alkyl of side chain, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20A kind of in the aralkyl, X is identical or different, be halogen atom or hydrocarbyl group; The general formula of described magnesium compound is MgX
nR
2-n, wherein n is integer 0≤n≤2, and X is a halogen atom, and substituent R is identical or different, and R is selected from C
1-C
20Straight chain or C
3-C
20The alkyl of side chain, C
3-C
20Cycloalkyl, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20Aralkyl and alkoxyl group wherein a kind of;
Wherein the liquid titanium compound general formula described in the step (2) is TiX
4, X is a halogen.
2. the preparation method who is used for the catalyst component of ethylene polymerization according to claim 1 is characterized in that, in step (2), the reaction soln that obtains in the described step (1) and the contact reacts temperature of liquid titanium compound are-40 ℃～10 ℃.
3. the preparation method who is used for the catalyst component of ethylene polymerization according to claim 1 is characterized in that Ti in the alkoxy titanium compound and the mol ratio of the Mg in the magnesium compound are 1.2～15; Ti in the liquid titanium compound and the mol ratio of the Mg in the magnesium compound are 10～200.
4. the preparation method who is used for the catalyst component of ethylene polymerization according to claim 1 is characterized in that the alkoxy titanium compound described in the step (1) is four alkoxy titanium compounds.
5. the preparation method who is used for the catalyst component of ethylene polymerization according to claim 4 is characterized in that described alkoxy titanium compound is at least a in purity titanium tetraethoxide, four titanium butoxide and the tetraisopropoxy titanium.
6. the preparation method who is used for the catalyst component of ethylene polymerization according to claim 1 is characterized in that described magnesium compound is a magnesium dichloride.
7. the preparation method who is used for the catalyst component of ethylene polymerization according to claim 1 is characterized in that the liquid titanium compound described in the step (2) is a titanium tetrachloride.
8. a kind of catalyst component that makes according to the described preparation method of arbitrary claim in the claim 1～7.
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|---|---|---|---|
| CN200810224880A CN101724103A (en) | 2008-10-24 | 2008-10-24 | Preparation method of catalyst component for ethylene polymerization |
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|---|---|---|---|
| CN200810224880A CN101724103A (en) | 2008-10-24 | 2008-10-24 | Preparation method of catalyst component for ethylene polymerization |
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ID=42445712
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321206A (en) * | 2011-06-23 | 2012-01-18 | 中国石油天然气股份有限公司 | Ethylene polymerization catalyst, preparation and application thereof |
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2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321206A (en) * | 2011-06-23 | 2012-01-18 | 中国石油天然气股份有限公司 | Ethylene polymerization catalyst, preparation and application thereof |
| WO2012174691A1 (en) * | 2011-06-23 | 2012-12-27 | 中国石油天然气股份有限公司 | Ethylene polymerization catalyst, preparation therefor and application thereof |
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Application publication date: 20100609 |