CN105085739A - Alkene polymerization catalyst composition, preparation method and application - Google Patents
Alkene polymerization catalyst composition, preparation method and application Download PDFInfo
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- CN105085739A CN105085739A CN201410176216.3A CN201410176216A CN105085739A CN 105085739 A CN105085739 A CN 105085739A CN 201410176216 A CN201410176216 A CN 201410176216A CN 105085739 A CN105085739 A CN 105085739A
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Abstract
The invention relates to an alkene polymerization or copolymerization catalyst composition, a catalyst thereof, and a preparation method and application of the catalyst composition. The catalyst composition comprises at least one organic magnesium compound, at least one oxygen-containing titanium compound, at least one chlorhydrin-containing compound, and at least one chloride-containing organic aluminium compound. The prepared catalyst possesses relatively high ethylene polymerization activity, also possesses relatively high hydrogen regulating sensitivity, and thus the catalyst is beneficial for usage in a slurry polymerization serial process apparatus.
Description
Technical field
The present invention relates to a kind of component for olefinic polymerization or copolymerization catalyst and catalyzer thereof, and the preparation method of this catalyst component and purposes.
Background technology
Over nearly more than 20 years, with the development of olefin polymetiation process, the catalyzer matched with polymerization technique also achieves significant progress, and wherein effective catalyst relies on its excellent polymerization and ripe utilisation technology still to occupy an important position in polyolefin catalyst field.Through exploratory development for many years, the preparation method of Mg-Ti system effective catalyst at present more adopts chemical reaction method.
In chemical reaction method, many patents of invention relate to chemical feedstockss such as adopting organo-metallic magnesium compound, chlorizating agent and transition metal titanium compound, prepared the catalyzer of number of different types with this kind of reactant, they are disclosed in Chinese patent CN1158136, CN1299375, CN1795213 and US Patent No. 3787384, US4148754, US4173547, US4508843 and 5124296.In such Mg-Ti catalyzer, usually electron compound is added at catalyst composition preparatory phase, experiment proves, the introducing of electron donor compound can improve the polymerization activity of catalyzer, the oligomer etc. adjusted in the hydrogen regulation performance of catalyzer and reduction polymerisate.
In Chinese patent CN1129709A, by using electron donor compound in catalyst preparing, the tap density of the activity of catalyzer, hydrogen response and polymerisate can be improved.The electron donor compound used in this patent contains the organic compound of one or more pairs of unbound electron, mainly refers to acylate compounds, wherein except alcohols, phenols.In addition, people also improve the activity of olefin polymerization catalysis at the dissimilar additive of searching.
Summary of the invention
The invention provides a kind of catalyst component for olefinic polymerization, be provided in the preparation process of catalyzer and add suitable chloride alcohol compound, can improve the activity of catalyzer, gained catalyzer also has higher hydrogen response simultaneously.
Catalyst component for olefinic polymerization of the present invention, comprises at least one organo-magnesium compound, and at least one contains oxygen titanium compound, the reaction product of the chloride alcohol compound of at least one and the chloride organo-aluminium compound of at least one.
Described organo-magnesium compound is as logical formula I Mg (OR
1)
mcl
2-mshown in, R in formula
1c
2~ C
20alkyl, be preferably saturated or undersaturated straight chain, side chain or closed chain, 0 < m≤2, concrete compound is as at least one in diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and two octyloxy magnesium.
Described contains oxygen titanium compound as logical formula II Ti (OR
2)
ncl
4-nshown in, R in formula
2c
2~ C
20alkyl, be preferably saturated or undersaturated straight chain, side chain or closed chain, 0 < n≤4, be preferably tetravalent titanium compound, because it is in a liquid state at normal temperatures usually, and also fine with the consistency of multi-solvents under normal conditions.The compound of n=4 and the mixture of respective compound in the titanium compound preferred formula used in reaction are wherein conventional with tetrabutyl titanate.
Described chloride alcohol compound is as logical formula III HOR
3shown in, R in formula
3c
2~ C
20chloro alkyl, be preferably saturated or undersaturated straight chain, side chain or closed chain.Described chloride alcohol compound is fatty alcohol and/or aromatic alcohol, is preferably ethapon and/or trichloro-butyl alcohol.
Described chloride organo-aluminium compound is as logical formula IV AlR
4 acl
3-ashown in, R in its Chinese style
4c
2~ C
20alkyl, be preferably not higher than the alkyl of the straight or branched of 6 carbon atoms, 0≤a≤1.5 in general formula, preferably 0≤a≤1.0, concrete chloride organo-aluminium compound is selected from least one in ethyl aluminum dichloride, ethylaluminum sesquichloride and dichloro aluminium isobutyl, and wherein ethyl aluminum dichloride or dichloro aluminium isobutyl are preferred.
Present invention also offers the preparation method of above-mentioned catalyst component, the method comprises the following steps:
(1) formula I organo-magnesium compound and logical formula II will be led to and form clear solution containing the reaction of oxygen titanium compound.
(2) clear solution that step (1) obtains is mixed with the chloride alcohol compound of logical formula III, obtain mixed solution;
(3) mixed solution step (2) obtained and the chloride organo-aluminium compound contact reacts of logical formula IV are formed and precipitate, and obtain the suspension of catalyst component;
(4) quiet heavy, the washing of suspension step (3) obtained, drying obtain the powder of catalyst component.
In the preparation process of catalyst component of the present invention, ratio between each component is, in every general Formula (I) compound, logical formula II compound is 0.01 ~ 10 mole, preferably 0.05 ~ 5 mole, logical formula III compound is 0.01 ~ 20 mole, preferably 0.05 ~ 5 mole, logical formula IV compound is 0.5 ~ 50 mole, preferably 2 ~ 20 moles.
In the step (1) of Kaolinite Preparation of Catalyst, the temperature that organo-magnesium compound and titanium compound contact with each other depends on the character of reactant, carry out dissolving advantageously under being typically chosen in relatively high temperature, preferably below the decomposition temperature of reactant, temperature is usual not higher than 200 DEG C, generally not higher than 150 DEG C.The time of dissolving depends on character and the operational condition of reactant, general selection of time with till can obtaining completely transparent solution, required time generally at 10 minutes to 20 hours, preferably 2 to 10 hours.After organo-magnesium compound and titanium compound dissolve, the magnesium titanium complex solution formed can be used in combination with inert diluent, inert diluent is selected from aliphatic hydrocarbon usually, such as Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, general hexane is proper inert solvent.
In the step (2) of Kaolinite Preparation of Catalyst, the mixing temperature of magnesium titanium complex solution and chloride alcohol compound generally will, lower than the decomposition temperature of material, for simplicity, generally be selected between 0 ~ 150 DEG C, preferably between 15 ~ 65 DEG C.The mixing time of magnesium titanium complex solution and chloride alcohol compound generally selects 0.5 minute to 5 hours, preferably 30 minutes to 1 hour.
The step (3) of catalyst preparing also can be described as settling step, completes the chlorination reaction of magnesium titanium complex in this step, makes liquid title complex Precipitation from solution.The contact method of magnesium titanium complex solution and chloride organo-aluminium compound can adopt any known suitable method to carry out, the mode be progressively added drop-wise to by magnesium titanium complex solution in chloride organo-aluminium compound solution can be adopted, also can adopt the mode be progressively added drop-wise to by chloride organo-aluminium compound solution in magnesium titanium complex solution.The local superheating that rate of addition is selected not induce reaction usually is as the criterion, and usually carries out stirring being beneficial to steadily carrying out of reaction in dropping process.In this precipitin reaction step, temperature can control between 0 ~ 100 DEG C, preferably between 20 ~ 70 DEG C.The reaction times of settling step should be long enough to obtain to be precipitated completely, and the reaction times can last 1 minute to 10 hours, preferably 0.5 ~ 5 hour.
Experiment finds, after settling step, reacting for some time at a certain temperature, to carry out the particle shape of maturation process to catalyzer more favourable, also can improve the intensity of catalyst particle simultaneously, thus reduce the particle fragmentation phenomenon of catalyzer in catalyzed ethylene polymerization process.The temperature of maturation process is generally equal to or higher than the temperature of precipitin reaction, and the time of slaking reaction can control at 0.5 ~ 15 hour, preferably 1 ~ 10 hour.
After carrying out maturation process, generally to wash, to remove the by product formed in excessive reactant and preparation process, any inert solvent all can be used for this washing step, such as can select Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof etc., in experiment, usually select hexane to be the inert solvent washed.After washing, catalyst suspension can by carrying out drying with nitrogen purging under heating state, to obtain catalyst fines.
Present invention also offers a kind of catalyzer for olefinic polymerization or copolymerization, it contains catalyst component and the alkylaluminium cpd of the invention described above, and the general formula of described alkylaluminium cpd is AlR'''
3, R''' is identical or not identical C
1-8alkyl, wherein one or two alkyl can be replaced by chlorine, one or more aluminum alkyls can be selected used in combination, preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3, AlEt
2cl etc.
The catalyzer that the present invention relates to is applicable to the copolymerization of all polymerization or ethene and other alpha-olefins of various ethene, and wherein alpha-olefin adopts the one in propylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
Beneficial effect
The present invention employs chloride alcohol compound in olefin polymerization catalyst components, the polymerization activity of alkene is obviously significantly improved, the melting index of resulting polymers resin is higher, improve the hydrogen response of catalyzer, find in addition to use the tap density (BD) of chloride alcohol compound on polymer resin to affect not obvious.
Embodiment
Embodiment given below is in order to the present invention is described, instead of limits the invention.
Testing method:
Melt index (MI): measure according to ASTMD1238-99.
Tap density (BD): measure according to DIN-53194.
Embodiment 1
(1) take 45.3 grams of diethoxy magnesium, add 135 milliliters of tetrabutyl titanates, 140 DEG C of stirring and dissolving until form clear solution, solution temperature is down to room temperature, adds 1100 milliliters of dry hexane diluted for use.
(2) solution that 45 milliliter of (1) step obtains is got, mix with 0.6 milliliter of ethapon, the temperature of the mixed solution obtained is maintained 45 DEG C of half an hour, the hexane solution (concentration is 3M) of 30 milliliters of ethyl aluminum dichlorides is slowly dripped with drop-burette, after being added dropwise to complete, 65 DEG C of stirring reactions obtain catalyst suspension in 2 hours.
(3) catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 50 milliliters, after wash, when bathing temperature 65 DEG C, purging drying, obtain brown solid mobility powder with high pure nitrogen.
Evaluating catalyst: 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 90 DEG C, the disposable hydrogen adding 0.4MPa, then with ethene, the total pressure of system is maintained 1.0MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, the test tap density (BD) of polyethylene powder and the melting index under 2.16Kg load (MI), result is as shown in table 1.
Embodiment 2
0.6 milliliter of ethapon in catalyst preparation step (2) is replaced with 18 milliliters of trichloro-butyl alcohols room temperature saturated solution in hexane, and other conditions are with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Embodiment 3
0.6 milliliter of ethapon in catalyst preparation step (2) is replaced with 9 milliliters of trichloro-butyl alcohols room temperature saturated solution in hexane, and other conditions are with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Embodiment 4
0.6 milliliter of ethapon in catalyst preparation step (2) is replaced with 25 milliliters of trichloro-butyl alcohols room temperature saturated solution in hexane, and other conditions are with embodiment 1.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Comparative example 1
(1) take 45.3 grams of diethoxy magnesium, add 135 milliliters of tetrabutyl titanates, 140 DEG C of stirring and dissolving until form clear solution, solution temperature is down to room temperature, adds 400 milliliters of dry hexane diluted for use.
(2) get the solution that 45 milliliter of (1) step obtains, slowly drip the hexane solution (3M) of 30 milliliters of ethyl aluminum dichlorides at 45 DEG C with drop-burette, after being added dropwise to complete, 65 DEG C of stirring reactions obtain catalyst suspension in 2 hours.
(3) catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 50 milliliters, after wash, when bathing temperature 65 DEG C, purging drying, obtain brown solid mobility powder with high pure nitrogen.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Comparative example 2
(1) take 45.3 grams of diethoxy magnesium, add 135 milliliters of tetrabutyl titanates, 140 DEG C of stirring and dissolving until form clear solution, solution temperature is down to room temperature, adds 1100 milliliters of dry hexane diluted for use.
(2) solution that 45 milliliter of (1) step obtains is got, mix with 0.3 milliliter of ethyl benzoate, and its temperature is maintained 45 DEG C of half an hour, the hexane solution (3M) of 30 milliliters of ethyl aluminum dichlorides is slowly dripped with drop-burette, after being added dropwise to complete, 65 DEG C of stirring reactions obtain catalyst suspension in 2 hours.
(3) catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 50 milliliters, after wash, when bathing temperature 65 DEG C, purging drying, obtain brown solid mobility powder with high pure nitrogen.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Table 1
The experimental data of embodiment and comparative example as can be seen from table 1, chloride alcohol compound is used in the preparation process of catalyzer, catalyst ethylene polymerization activity obviously significantly improves, the melting index of resulting polymers resin is higher, improve the hydrogen response of catalyzer, find in addition to use the tap density (BD) of chloride alcohol compound on polymer resin to affect not obvious.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1., for a catalyst component for olefinic polymerization, comprise at least one organo-magnesium compound, at least one containing the reaction product of oxygen titanium compound, the chloride alcohol compound of at least one and the chloride organo-aluminium compound of at least one;
Described organo-magnesium compound is as logical formula I Mg (OR
1)
mcl
2-mshown in, R in formula
1c
2~ C
20alkyl, 0 < m≤2;
Described contains oxygen titanium compound as logical formula II Ti (OR
2)
ncl
4-nshown in, R in formula
2c
2~ C
20alkyl, 0 < n≤4;
Described chloride alcohol compound is as logical formula III HOR
3shown in, R in formula
3c
2~ C
20chloro alkyl;
Described chloride organo-aluminium compound is as logical formula IV AlR
4 acl
3-ashown in, R in formula
4c
2~ C
20alkyl, 0≤a≤1.5, preferably 0≤a≤1.0.
2. catalyst component according to claim 1, is characterized in that, the organo-magnesium compound in logical formula I is selected from least one in diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and two octyloxy magnesium.
3. catalyst component according to claim 1, is characterized in that, in logical formula II is tetravalent titanium compound containing oxygen titanium compound, is preferably tetrabutyl titanate.
4. catalyst component according to claim 1, is characterized in that, the chloride alcohol compound in logical formula III is fatty alcohol and/or aromatic alcohol, is preferably ethapon and/or trichloro-butyl alcohol.
5. catalyst component according to claim 1, is characterized in that, the R in the chloride organo-aluminium compound in logical formula IV
4for not higher than the alkyl of the straight or branched of 6 carbon atoms.
6. catalyst component according to claim 5, is characterized in that, described chloride organo-aluminium compound is selected from least one in ethyl aluminum dichloride, ethylaluminum sesquichloride and dichloro aluminium isobutyl, is preferably ethyl aluminum dichloride and/or dichloro aluminium isobutyl.
7. a preparation method for the catalyst component according to any one of claim 1 ~ 6, the method comprises the following steps:
1) formula I organo-magnesium compound and logical formula II will be led to and form clear solution containing the reaction of oxygen titanium compound;
2) by step 1) clear solution that obtains mixes with the chloride alcohol compound of logical formula III, obtains mixed solution;
3) by step 2) mixed solution that obtains and the chloride organo-aluminium compound contact reacts of logical formula IV form and precipitate, and obtains the suspension of catalyst component;
4) by step 3) quiet heavy, the washing of the suspension that obtains drying obtains described catalyst component.
8. the preparation method of catalyst component according to claim 7, it is characterized in that, the consumption of each material is in every general Formula (I) compound, logical formula II compound is 0.01 ~ 10 mole, preferably 0.05 ~ 5 mole, logical formula III compound is 0.01 ~ 20 mole, preferably 0.05 ~ 5 mole, logical formula IV compound is 0.5 ~ 50 mole, preferably 2 ~ 20 moles.
9., for a catalyzer for olefinic polymerization or copolymerization, it contains catalyst component according to any one of claim 1 ~ 8 and alkylaluminium cpd, and the general formula of described alkylaluminium cpd is AlR'''
3, R''' is identical or not identical C
1-8alkyl, wherein one or two alkyl is optionally replaced by chlorine.
10. a catalyzer as claimed in claim 9 application in olefin polymerization.
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|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299375A (en) * | 1998-04-06 | 2001-06-13 | 博里利斯技术有限公司 | Olfin polymerization catalyst componnet, its prepn. and use |
| CN1875037A (en) * | 2003-09-01 | 2006-12-06 | 英诺文尼制造比利时有限公司 | Process for the polymerization of olefins |
| CN102875706A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst component of ethylene polymerization reaction, and catalyst thereof |
| CN102875705A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst component and catalyst for ethylene polymerization |
-
2014
- 2014-04-29 CN CN201410176216.3A patent/CN105085739A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299375A (en) * | 1998-04-06 | 2001-06-13 | 博里利斯技术有限公司 | Olfin polymerization catalyst componnet, its prepn. and use |
| CN1875037A (en) * | 2003-09-01 | 2006-12-06 | 英诺文尼制造比利时有限公司 | Process for the polymerization of olefins |
| CN102875706A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst component of ethylene polymerization reaction, and catalyst thereof |
| CN102875705A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalyst component and catalyst for ethylene polymerization |
Non-Patent Citations (1)
| Title |
|---|
| 孔媛 汪红丽 义建军 张明革 黄启谷 杨万泰: "TiCl4／XROH／MgCl2／Et3Al催化剂合成宽分子量分布乙烯／1-己烯共聚物", 《应用化学》 * |
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