CN104250322B - A kind of catalytic component and its catalyst for ethylene polymerization - Google Patents
A kind of catalytic component and its catalyst for ethylene polymerization Download PDFInfo
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- CN104250322B CN104250322B CN201310269111.8A CN201310269111A CN104250322B CN 104250322 B CN104250322 B CN 104250322B CN 201310269111 A CN201310269111 A CN 201310269111A CN 104250322 B CN104250322 B CN 104250322B
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Abstract
The present invention relates to the purposes of a kind of catalytic component and its catalyst for ethylene polymerization, and the catalyst.The catalytic component includes a kind of ultra-fine inorganic oxide carrier, the reaction product of a kind of magnesium halide, halohydrin, at least one halogenated titanium and at least one electron donor compound is loaded on this carrier, it is obtained by the reaction comprised the steps of：（1）It is prepared by mother liquor：In electron donor compound by magnesium halide, halogenated titanium and formula be XnROH halohydrin carries out reaction and prepares mother liquor；（2）Carrier is blended：By step（1）The mother liquor of middle preparation with ultra-fine inorganic oxide carrier blend obtaining slurry liquid；（3）Spray shaping：By step（2）In obtained slurry liquid be spray-dried, obtain ingredient of solid catalyst.There is higher catalyst activity during the combined polymerization of homopolymerization or ethene and other alhpa olefins of the obtained catalyst for ethene, the hexane extract of resulting polymers is low, and the oligomer of polymer is low.
Description
Technical field
The present invention relates to the use of a kind of catalytic component and its catalyst for ethylene polymerization, and the catalyst
On the way.
Background technology
In the polymerisation or ethene of ethene and the copolymerization of alpha-olefin, the performance impact of catalyst polymer
Performance.Some oligomer can be produced while catalyst vinyl polymerization, oligomer makes the stress shape between polyethylene molecule
Condition changes, and influences the performance and processing characteristics of product, and its yield strength to product, elongation and rigidity etc. have
Influence.The number of oligomer is general to be weighed with the number of hexane extract, therefore, and the number of hexane extract is also that measurement is urged
One important indicator of agent performance.
CN100368440 discloses a kind of polymerization catalyst of spray drying and the polymerization side using the polymerization catalyst
Method, the catalyst includes the spray-dried compositions of inertia porous aggregate and following substance reaction product：Magnesium halide, solvent, give
Electron compound, the mixture of transistion metal compound or reaction product.Filler is substantially spherical and particle mean size is 1 μm
~12 μm.But the catalyst is active not high enough, and the oligomer in polymer is more.
CN1493599 discloses a kind of improved catalyst for vinyl polymerization, by catalyst activity component
Mother liquor adds alkyl silicic acids fat in preparing, and to improve catalyst activity, and reduces the oligomer in polymer.But should
Catalyst it is active not high enough.
For above the deficiencies in the prior art, the invention provides a kind of catalytic component for ethylene polymerization and
Its catalyst, not only activity is high for the catalyst, and the oligomer of resulting polymers is low.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of catalytic component for ethylene polymerization and its urge
Agent, the catalyst activity is high, and the hexane extract of resulting polymers is low, and the oligomer of resulting polymers is low.
A kind of catalytic component for ethylene polymerization, it includes a kind of ultra-fine inorganic oxide carrier, in the load
The reaction product of a kind of magnesium halide, halohydrin, at least one halogenated titanium and at least one electron donor compound is loaded on body, its
Obtained by the reaction comprised the steps of：
（1）It is prepared by mother liquor：In electron donor compound by magnesium halide, halogenated titanium and formula be XnROH halohydrin enters
Row reaction prepares mother liquor, wherein R be straight chain, the alkyl of side chain, cycloalkyl or the carbon number that carbon number is 1~10 be 6~
20 aryl, X is halogen, and n is 1~3 integer, and described electron donor compound is selected from ether, ester or ketone；
（2）Carrier is blended：By step（1）The mother liquor of middle preparation with ultra-fine inorganic oxide carrier blend obtaining slurry
Liquid, the wherein particle diameter of ultra-fine inorganic oxide carrier are 0.01~10 micron；
（3）Spray shaping：By step（2）In obtained slurry liquid be spray-dried, obtain ingredient of solid catalyst, its
Middle spray condition is 80~240 DEG C of inlet temperature, 60~130 DEG C of outlet temperature.
The formula of described halohydrin is XnROH, R be carbon number be 1-10 straight chain, the alkyl of side chain, cycloalkyl or
Carbon number is 6~20 aryl；X is halogen, and n is 1~3 integer.Particular compound is selected from 2,2,2- ethapons, 2,2-
Dichlroroethanol, ethylene chlorhydrin, trimethylene chlorohydrin, the chloro- 1- hexanols of 6-, the bromo- 1- propyl alcohol of 3-, the chloro- 1- amylalcohols of 5-, the chloro- 1- fourths of 4-
At least one of alcohol, 6- amino -1- hexanols, 2- chloro cyclohexanols.It is preferred that 2,2,2- ethapons.
Described electron donor compound is selected from ether, ester or ketone, specifically such as：C1~C4Arrcostab, the C of aliphatic saturated monocarboxylic acid7
~C8Aromatic carboxylic acids Arrcostab, C2~C6Aliphatic ether, C3~C4Cyclic ethers, C3~C6One kind or their mixing in saturated fat ketone
Thing, preferably methyl formate, ethyl acetate, butyl acetate, ether, hexyl ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK) etc.,
Most preferably tetrahydrofuran.These electron donors can be used alone, and can also be used in mixed way.
Described halogenated titanium is titanium chloride or titanium bromide, preferably TiCl3Or TiCl4。
Described magnesium halide is magnesium dichloride, dibrominated magnesium or magnesium diiodide, preferably magnesium dichloride.
Oxide of the described ultra-fine inorganic oxide carrier typically from silicon and/or aluminium, its particle diameter is usually 0.01~
10 microns, preferable particle size is less than 5 microns, more preferably 0.1~2 micron, most preferably 0.1~1 micron of silica supports.
The catalyst particle shape of so thin silica gel generation is good, and intensity is high, not fragile essence.
The mol ratio of the halogenated titanium and halohydrin is 1：0.5~20；It is preferred that 1：1~10.
The ratio of the halogenated titanium and magnesium dihalide is：0.1 ＜ magnesium titaniums ＜ 10；Mole of titanium and electron donor compound
Than general control at 1 mole to 600 moles, preferably 20 moles to 200 moles.
The above-mentioned catalytic component for ethylene polymerization can be prepared using following methods：
（1）It is prepared by mother liquor：In electron donor compound by magnesium halide, halogenated titanium and formula be XnROH halohydrin enters
Row reaction prepares mother liquor, wherein R be straight chain, the alkyl of side chain, cycloalkyl or the carbon number that carbon number is 1~10 be 6~
20 aryl, X is halogen, and n is 1~3 integer, and described electron donor compound is selected from ether, ester or ketone；
（2）Carrier is blended:By step（1）The mother liquor of middle preparation with ultra-fine inorganic oxide carrier blend obtaining slurry
Liquid；
Oxide of the described ultra-fine inorganic oxide carrier typically from silicon and/or aluminium, its particle diameter is usually 0.01~
10 microns, preferable particle size is less than 5 microns, more selects 0.1~2 micron, most preferably 0.1~1 micron of silica supports.
This carrier should be water that is dry, i.e., not adsorbing when in use.Sufficient amount of carrier and mother liquor should be mixed,
The slurry liquid for being suitable for being spray-dried is formed, i.e., the content of the carrier is 5wt%~50wt% in slurry liquid, preferably
10wt%~30wt%.
（3）Spray shaping：By step（2）In obtained slurry liquid be spray-dried, obtain ingredient of solid catalyst.Spray
Mist condition：80-240 DEG C of inlet temperature, 60-130 DEG C of outlet temperature.120-180 DEG C of preferred inlet temperatures, outlet temperature 90-110
℃。
In order that the ingredient of solid catalyst obtained after spray drying is applied to production ethene polymers, it is necessary to using activation
Titanium atom in the catalytic component is reduced into the state that ethene can be made effectively to polymerize by agent component organo-aluminum compound.Typically
Ground, in varsol, by step（3）Obtained ingredient of solid catalyst is reacted with activator component, obtains catalyst；
Can also be in the course of the polymerization process by step（3）Obtained ingredient of solid catalyst is reacted with activator component, so as to trigger
Olefinic polyreaction.
Described activator component is formula AlR 'nX3-nOrgano-aluminum compound, R ' is hydrogen in formula or carbon number is 1
~20 alkyl, X is halogen, and n is the number of 1 ＜ n≤3, specifically such as：Triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three are just
One kind or their mixture in octyl group aluminium or aluminium diethyl monochloride.Wherein in activator component in aluminium and titaniferous active component
The mol ratio of titanium is 5~500, preferably 10~200.
Described varsol such as isopentane, hexane, heptane, toluene, dimethylbenzene, naphtha and mineral oil etc..
Catalyst of the present invention is applied to the homopolymerization of various ethene or the combined polymerization of ethene and other alpha-olefins, its
In alpha-olefin select propylene, butylene, amylene, hexene, octene, 4- methylpentenes -1 in one kind.Its polymerization technique uses gas
Xiang Fa, slurry process and solwution method, more suitable for gas fluidised bed polymerisation.
Compared with the prior art the present invention, there is following obvious advantage：
The present invention's is used for the catalyst of vinyl polymerization or combined polymerization, and it does carrier using ultra-fine inorganic oxide, with to
Electron compound solvent dissolves to magnesium halide, and adds a certain proportion of halohydrin, is produced with the mode of spray shaping
The catalyst of high activity, the hexane extract of resulting polymers is low, oligomer in the polymer of the catalyst preparation
It is low.
Embodiment
Method of testing：
1st, it is active：Represented with the weight of resin obtained by every gram of catalyst
2nd, the percentage composition of hexane extract used the hexane polymer in boiling temperature after 4 hours, by polymer
Evaporate and weighed after hexane, and calculate reduction weight, obtain the percentage composition of hexane extract.
Example given below is in order to illustrate the present invention, rather than to limit the invention.
Embodiment 1
（1）The preparation of catalyst
Blown to one by nitrogen and 1.5 grams of TiCl are successively added in the 250ml there-necked flasks of row4, 4.4 grams of anhydrous MgCl2、6.1
Gram ethapon and 100ml tetrahydrofurans, are warming up to 65 DEG C, at this temperature isothermal reaction 3 hours under stirring.It is cooled to 35
℃。
6 grams of silica gel are added into a 250ml there-necked flask that row is blown by nitrogen（Cabot Corporation TS-
610, particle diameter is 0.02~0.1 micron）, the mother liquor after cooling is added, 35 DEG C of keeping temperature, after stirring 1 hour, silica gel mixed
Mother liquor after mixed is spray-dried with spray dryer, spray condition：180 DEG C of inlet temperature, 110 DEG C of outlet temperature, is obtained
Ingredient of solid catalyst, wherein Ti content are 2.2Wt%.
（2）Ethene slurry polymerization
To be blown by nitrogen and 1 liter of hexane is added in 2 liters of polymeric kettles of row, at the same add 1 milliliter of 1mmol triethyl aluminum and
0.03 gram of catalyst, is warming up to 75 DEG C of addition hydrogen 0.18Mpa, and hydrogenation adds ethene 0.75Mpa after finishing, is warming up to 85 DEG C,
After reaction 2 hours, cooling discharge.Polymerization result is shown in Table 1.
Embodiment 2
（1）The preparation be the same as Example 1 of catalyst.Simply the amount of ethapon is 12.2 grams, gained ingredient of solid catalyst
Ti content be 2.2Wt%.
（2）Ethene slurry polymerization be the same as Example 1.Polymerization result is shown in Table 1.
Embodiment 3
（1）The preparation be the same as Example 1 of catalyst.Simply the amount of ethapon is 15.3 grams, gained ingredient of solid catalyst
Ti content be 2.3Wt%.
（2）Ethene slurry polymerization be the same as Example 1.Polymerization result is shown in Table 1.
Comparative example 1
（1）The preparation of catalyst
Blown to one by nitrogen and 1.5 grams of TiCl are successively added in the 250ml there-necked flasks of row4, 4.0 grams of anhydrous MgCl2With
65 DEG C are warming up under 100ml tetrahydrofurans, stirring, at this temperature isothermal reaction 3 hours.It is cooled to 35 DEG C.
6 grams of silica gel are added into a 250ml there-necked flask that row is blown by nitrogen（Cabot Corporation TS-
610, particle diameter is 0.02~0.1 micron）, the mother liquor after cooling is added, 35 DEG C of keeping temperature, after stirring 1 hour, silica gel mixed
Mother liquor after mixed is spray-dried with spray dryer, spray condition：195 DEG C of inlet temperature, 110 DEG C of outlet temperature, is obtained
Ingredient of solid catalyst, wherein Ti content are 2.4Wt%.
（2）Ethene slurry polymerization be the same as Example 1.Polymerization result is shown in Table 1.
Table 1
It is can be seen that from the aggregated data of table 1 under same polymerizing condition, catalyst activity of the invention is higher, institute
The hexane extract for obtaining polymer is low, and oligomer is low.
Claims (3)
1. a kind of catalytic component for ethylene polymerization, it is obtained one of by the following method：
Method one：
Blown to one by nitrogen and 1.5 grams of TiCl are successively added in the 250ml there-necked flasks of row4, 4.4 grams of anhydrous MgCl2, 6.1 gram three
Chlorethanol and 100ml tetrahydrofurans, are warming up to 65 DEG C under stirring, at this temperature isothermal reaction 3 hours, are cooled to 35 DEG C；
6 grams of silica gel are added into a 250ml there-necked flask that row is blown by nitrogen, the mother liquor after cooling are added, keeping temperature
35 DEG C, after stirring 1 hour, the mother liquor after silica gel is blended is spray-dried with spray dryer, spray condition：Inlet temperature
180 DEG C, 110 DEG C of outlet temperature obtains ingredient of solid catalyst, wherein Ti content is 2.2Wt%；
Method two：
Prepare with method one, simply the amount of ethapon is 12.2 grams, the Ti content of gained catalytic component is 2.2Wt%；
Method three：
Prepare with method one, simply the amount of ethapon is 15.3 grams, the Ti content of gained catalytic component is 2.3Wt%.
2. a kind of catalyst for ethylene polymerization, it includes the reaction product of following components：
(1) catalytic component for ethylene polymerization described in claim 1；
(2) formula is AlR 'nX3-nOrgano-aluminum compound, the alkyl that R ' is hydrogen or carbon number is 1~20 in formula, X is halogen,
1 ＜ n≤3.
3. the application for the catalyst of ethylene polymerization in ethylene polymerization described in claim 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102266927B1 (en) * | 2017-03-14 | 2021-06-21 | 사우디 아라비안 오일 컴퍼니 | Ethylene Oligomerization Process for Making Alpha-Olefins |
| CN106928380B (en) * | 2017-04-19 | 2019-10-11 | 大连理工大学 | A kind of Ziegler-Natta catalyst of the component containing furans and preparation method thereof |
| CN110862473A (en) * | 2018-08-28 | 2020-03-06 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization reaction, preparation method and composite catalyst |
| EP3872100A4 (en) * | 2018-10-26 | 2022-08-17 | China Petroleum & Chemical Corporation | Polyolefin catalyst component containing mesoporous material, preparation method therefor and use thereof |
| CN112625153B (en) * | 2019-10-09 | 2023-03-17 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method, catalyst and application thereof |
| CN112812205B (en) * | 2019-11-18 | 2023-05-09 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization reaction, catalyst and preparation method and application thereof |
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| CN1493599A (en) * | 2002-10-31 | 2004-05-05 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
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| CN1958623A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst in use for polymerization or combined polymerization of ethylene, preparation and application |
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| CN1405191A (en) * | 2001-09-19 | 2003-03-26 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization or copolymerization, and catalyst and use thereof |
| CN1493599A (en) * | 2002-10-31 | 2004-05-05 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization |
| CN1769308A (en) * | 2004-10-27 | 2006-05-10 | 中国石油化工股份有限公司 | Ethene polymerization catalyst ingredient and its preparation method and catalyst |
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