CN106543316A - For the catalytic component of olefinic polymerization, catalyst and preparation method thereof - Google Patents
For the catalytic component of olefinic polymerization, catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of catalytic component for olefinic polyreaction, catalyst and preparation method thereof.The catalytic component is included：1) ultra-fine inorganic oxide carrier, and the 2) product of magnesium halide, halogenated silanes, halogenated titanium and electron donor compound.Product of the catalyst comprising following components：(A) catalytic component of the present invention；(B) formula is AlR 'nX3-nOrgano-aluminum compound, in formula R ' for hydrogen or carbon number for 1-20 alkyl, X is halogen, preferably chlorine, bromine, iodine, the organo-aluminum compound of 0 ＜ n≤3.The catalyst activity of the present invention is very high, and resulting polymers have very high melt index, and hexane extract is very low.
Description
Technical field
The invention belongs to catalyst field, and in particular to a kind of catalytic component for olefinic polymerization, catalyst
And preparation method thereof.
Background technology
In the polyreaction or ethylene of ethylene with the copolymerization of α-alkene, the performance impact of catalyst
The performance of polymer.Some oligomer can be produced while catalyst vinyl polymerization, oligomer makes polyethylene
Intermolecular force-bearing situation changes, and affects the performance and processing characteristics of product, its surrender to product
Intensity, percentage elongation and rigidity etc. all have an impact.The general number with hexane extract of number of oligomer weighing,
Therefore, hexane extract number be also weigh catalyst performance an important indicator.
CN100368440 discloses a kind of polymerization catalyst of spray drying and using the poly- of the polymerization catalyst
Conjunction method, the catalyst include the spray-dried compositions of inertia porous aggregate and following substance reaction product：Halogen
Change magnesium, solvent, electron donor compound, the mixture of transistion metal compound or product.Filler is basic
Spherical and particle mean size be 1um-12um.But the catalyst is active not high enough, oligomeric in polymer
Thing is more.
CN1493599 discloses a kind of improved catalyst for vinyl polymerization, by catalyst activity group
The mother solution for dividing adds alkyl silicic acids fat in preparing, and to improve catalyst activity, and reduces oligomeric in polymer
Thing content.But the catalyst is active not high enough.
The content of the invention
For above the deficiencies in the prior art, the invention provides one kind is particularly ethylene polymerization for alkene
Catalytic component and its catalyst.Not only activity is high for the catalyst, and the oligomer of resulting polymers
It is low.
Present invention firstly provides a kind of catalytic component for olefinic polymerization.The catalytic component is included：
1) ultra-fine inorganic oxide carrier, and
2) product of magnesium halide, halogenated silanes, halogenated titanium and electron donor compound.
Catalyst according to the invention component, the magnesium halide, halogenated silanes, halogenated titanium and electron donor chemical combination
The product of thing is carried on the ultra-fine inorganic oxide carrier.
The preferred implementation of catalyst according to the invention component, in the catalytic component, the quality of titanium
Content is 0.1-5%, preferably 0.5-3%.
The mol ratio of the preferred implementation of catalyst according to the invention component, halogenated titanium and halogenated silanes is 1:
(0.5-20), preferably 1:(1-10), more preferably 1:(2-8).
The mol ratio of the preferred implementation of catalyst according to the invention component, halogenated titanium and magnesium halide is 0.1<
Magnesium titanium<10, preferably 1<Magnesium titanium<10, more preferably 2<Magnesium titanium<7.
The preferred implementation of catalyst according to the invention component, halogenated titanium and electron donor compound mole
Than for 1:(1-600), preferably 1:(20-200), more preferably 1:(50-150).
The preferred implementation of catalyst according to the invention component, ultra-fine inorganic oxide carrier is in the catalysis
In agent component, shared percentage by weight is 5-50wt%, preferably 10-30wt%, more preferably 15-25wt%.
Described ultra-fine inorganic oxide carrier typically selects the oxide of silicon and/or aluminum.Its particle diameter is usually
0.01-10 microns, more preferably preferably smaller than 5 microns of particle diameter, most preferably 0.1-2 microns, 0.1-1 microns.
The silica supports of 0.1-1 microns are most preferred.The catalyst particle shape that so thin silica gel is generated is good, intensity
Height, not fragile essence.
The preferred implementation of catalyst according to the invention component, the magnesium halide are selected from magnesium dichloride, dibromo
Change magnesium or magnesium diiodide.
The preferred implementation of catalyst according to the invention component, the halogenated titanium are titanium bromide or titanium chloride,
It is preferred that at least one in titanium tribromide, titanium tetrabromide, titanous chloride. and titanium tetrachloride, more preferably titanous chloride.
And/or titanium tetrachloride.
The preferred implementation of catalyst according to the invention component, the formula of the halogenated silanes is SiXaRb,
Wherein X is halogen, and such as fluorine, chlorine, bromine, iodine, R are alkyl, and a is more than 0, and a+b=4.Preferably,
In the formula of the halogenated silanes, R is C1-C10Alkyl, C3-C10Cycloalkyl or C6-C10Aryl.
The C1-C10Examples of alkyl groups include methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, uncle
Butyl, isobutyl group, n-pentyl, n-hexyl, n-heptyl etc..C3-C10Cycloalkyl example include cyclopropyl,
Cyclobutyl, cyclopenta, cyclohexyl, suberyl etc..C6-C10Aryl example include phenyl, ethylphenyl,
Aminomethyl phenyl, benzyl etc..According to some embodiments, the halogenated silanes selected from Silicon chloride., Silicon bromide.,
Silicon tetraiodide, phenyl trichlorosilicane, phenyl tribromo SiClx, phenyl triiodo SiClx, benzyl trichlorosilicane, benzene
Methyl tribromo SiClx, benzyl triiodo SiClx, methyl trichlorosilicane, methyl tribromo SiClx, methyl triiodo SiClx,
Ethyl trichlorosilicane, ethyl tribromo SiClx, ethyl triiodo SiClx, propyl group trichlorosilicane, propyl group tribromo SiClx,
Propyl group triiodo SiClx, butyl trichlorosilicane, butyl tribromo SiClx, butyl triiodo SiClx, cyclohexyl trichlorosilicane,
At least one in cyclohexyl tribromo SiClx, cyclohexyl triiodo SiClx；More preferably phenyl trichlorosilicane.
The preferred implementation of catalyst according to the invention component, the electron donor compound be ester, ether or
Ketone, preferred C1-C4The Arrcostab of aliphatic saturated monocarboxylic acid, C7-C8Aromatic carboxylic acids Arrcostab, C2-C6Aliphatic ether,
C3-C4Cyclic ethers, C3-C6At least one of saturated fat ketone.
According to some embodiments, the electron donor compound is selected from methyl formate, Ethyl formate, formic acid isopropyl
Ester, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate,
At least one in isobutyl acetate, ether, propyl ether, hexyl ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK).
It is preferred that methyl formate, ethyl acetate, butyl acetate, ether, hexyl ether, tetrahydrofuran, acetone and methyl are different
Butyl ketone etc., most preferably tetrahydrofuran.These electron donors can be used alone, it is also possible to be used in mixed way.
The preferred implementation of catalyst according to the invention component, the preparation process bag of the catalytic component
Include：
It is prepared by step S1, mother solution：Magnesium halide, halogenated titanium and halogenated silanes are carried out in electron donor compound
Reaction prepares mother solution；
Step S3, carrier blending：The mother solution prepared in step step S1 is entered with ultra-fine inorganic oxide carrier
Row blending obtains slurry liquid material；
Step S3, spray shaping：The slurry liquid obtained in step step S1 is spray-dried, institute is obtained
State catalytic component.
Preferably, spray drying is inlet temperature 80-240 DEG C, outlet temperature 60-130 DEG C.
Therefore, present invention also offers the preparation method of the catalytic component, including：
It is prepared by step S1, mother solution：Magnesium halide, halogenated titanium and halogenated silanes are carried out in electron donor compound
Reaction prepares mother solution；
Step S2, carrier blending：Mother solution prepared by step S1 is blended with ultra-fine inorganic oxide carrier
Obtain slurry liquid material；
Step S3, spray shaping：The slurry liquid that step S2 is obtained is spray-dried, and obtains the catalysis
Agent component.
The preferred implementation of preparation in accordance with the present invention, the spray condition in step S3 is：Enter
Mouth temperature is 80-240 DEG C, preferred 120-180 DEG C；Outlet temperature is 60-130 DEG C, preferably 90-110 DEG C.
In above-mentioned preparation method, the ultra-fine inorganic oxide carrier should be dry when in use, that is, do not have
There is the water of absorption.Sufficient amount of carrier and mother solution should be mixed, formation is suitable for what is be spray-dried
Slurry liquid, i.e., in slurry liquid, the content of the carrier is 5wt%-50wt%, preferred 10wt%-30wt%.
In order that the ingredient of solid catalyst obtained after being spray-dried is applied to production ethene polymerss, it is necessary to adopt
Titanium atom in the catalytic component is reduced into by activator component organo-aluminum compound can be such that ethylene effectively gathers
The state of conjunction.Usually, in varsol, the ingredient of solid catalyst that step S3 is obtained and activator
Component is reacted, and obtains catalyst；The catalytic component that in the course of the polymerization process step S3 can also be obtained
Reacted with activator component, so as to cause olefinic polyreaction.
Present invention also offers a kind of catalyst for olefinic polyreaction, which includes reaction product of following components
Thing：
(A) catalytic component of the present invention；
(B) formula is A1R 'nX3-nOrgano-aluminum compound, in formula, R ' is that hydrogen or carbon number are 1-20's
Alkyl, X are halogen, preferably chlorine, bromine, iodine, the organo-aluminum compound of 0 ＜ n≤3.
According to specific embodiment, in formula A1R 'nX3-nIn, 1 ＜ n≤3.In certain embodiments, it is described
Formula is A1R 'nX3-nOrgano-aluminum compound selected from triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three
One kind or their mixture in octyl aluminum or aluminium diethyl monochloride.Preferably, in the catalyst,
In component (B), contained aluminum and the mol ratio of titanium contained in component (A) are 5:1-500:1, preferably 10:1-200:1.
The varsol such as isopentane, hexane, heptane, toluene, dimethylbenzene, Petroleum and mineral oil etc..
The catalyst of the present invention can be used for homopolymerization and the copolymerization of alkene.
The catalyst of the present invention is applied to the combined polymerization of the homopolymerization of various ethylene or ethylene and other alkene, its
In alpha-olefin from propylene, butylene, amylene, hexene, octene, the one kind in 4- methylpentenes -1.Which gathers
Close technique and adopt vapor phase method, slurry process and solwution method, more suitable for gas fluidised bed polymerisation.
Compared with the prior art the present invention, has following obvious advantage：
The catalyst for olefinic polymerization or combined polymerization of the present invention does carrier using ultra-fine inorganic oxide, with giving
Electron compound solvent is dissolved to magnesium halide, and adds a certain proportion of halogenated silanes, with mist molding of disputing
Mode generate highly active catalyst, resulting polymers bulk density is higher, and refers to higher melting
Number.The catalyst activity is high in addition, and the hexane extract of resulting polymers is low, and the oligomer of resulting polymers contains
Amount is low.
Specific embodiment
Method of testing：
1st, activity：Represented with the weight of resin obtained by every gram of catalyst；
2nd, melt index (MI)：6932 type melt indexers, Italian CEAST companies；
3rd, hexane polymer of the hexane extract percentage composition in boiling temperature, will be poly- after 4 hours
Compound is weighed after evaporating hexane, and calculates the quality of reduction, obtains hexane extract percentage composition.
Example given below is, in order to illustrate the present invention, rather than to limit the invention.
Embodiment 1
(1) preparation of catalyst
Blow through nitrogen to one and successively add in the 250ml there-necked flasks of row 1.5 grams of TiCl4, 4.4 grams anhydrous
MgCl2, 1.28ml phenyl trichlorosilicane and 100ml tetrahydrofurans are warming up to 65 DEG C, in this temperature under stirring
Lower isothermal reaction 3 hours.It is cooled to 35 DEG C.
In the 250ml there-necked flask of row addition 6 gram silica gel (Cabot Corporations are blown through nitrogen to one
TS-610, particle diameter are 0.02～0.1 micron), the mother solution after cooling is added, 35 DEG C of keeping temperature, stirring 1
After hour, the mother solution 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, and wherein Ti content is 1.91wt%.
(2) ethylene slurry polymerization
1 liter of hexane is added during 2 liters of polymeric kettles of row will be blown through nitrogen, while adding the three of 1 milliliter of 1mmol
Aluminium ethide and 0.03 gram of catalyst, are warming up to 75 DEG C of addition hydrogen 0.18Mpa, and hydrogenation adds ethylene after finishing
0.75Mpa, is warmed up to 85 DEG C, after reacting 2 hours, cooling discharge.Polymerization result is shown in Table 1.
Embodiment 2
(1) preparation of catalyst is with embodiment 1.Simply the amount of phenyl trichlorosilicane is 0.64ml, and gained solid urges
The Ti content of agent component is 2.12wt%.
(2) with embodiment 1, polymerization result is shown in Table 1 to ethylene slurry polymerization.
Embodiment 3
(1) preparation of catalyst is with embodiment 1.Simply the amount of phenyl trichlorosilicane is 2.56ml, and gained solid urges
The Ti content of agent component is 2.24wt%.
(2) with embodiment 1, polymerization result is shown in Table 1 to ethylene slurry polymerization.
Comparative example 1
(1) preparation of catalyst
Blow through nitrogen to one and successively add in the 250ml there-necked flasks of row 1.5 grams of TiC14, 4.0 grams anhydrous
65 DEG C are warming up under MgCl2 and 100ml tetrahydrofurans, stirring, at this temperature isothermal reaction 3 hours.
It is cooled to 35 DEG C.
In the 250ml there-necked flask of row addition 6 gram silica gel (Cabot Corporations are blown through nitrogen to one
TS-610, particle diameter are 0.02～0.1 micron), the mother solution after cooling is added, 35 DEG C of keeping temperature, stirring 1
After hour, the mother solution after silica gel is blended is spray-dried with spray dryer, spray condition：Inlet temperature
195 DEG C, 110 DEG C of outlet temperature obtains ingredient of solid catalyst, and wherein Ti content is 2.2wt%.
(2) with embodiment 1, polymerization result is shown in Table 1 to ethylene slurry polymerization.
Table 1
Can be seen that under same polymerizing condition from the aggregated data of table 1, the catalyst activity of the present invention is very
Height, resulting polymers have very high melt index, and hexane extract is very low.
Claims (10)
1. a kind of catalytic component for olefinic polyreaction, which includes：
1) ultra-fine inorganic oxide carrier, and
2) product of magnesium halide, halogenated silanes, halogenated titanium and electron donor compound.
2. catalytic component according to claim 1, it is characterised in that halogenated titanium and halogenated silanes
Mol ratio is 1:(0.5-20), preferably 1:(1-10), more preferably 1:(2-8)；Halogenated titanium and halogenation
The mol ratio of magnesium is 0.1<Magnesium titanium<10, preferably 1<Magnesium titanium<10, more preferably 2<Magnesium titanium<7；Halogenated titanium
Mol ratio with electron donor compound is 1:(1-600), preferably 1:(20-200), more preferably 1:
(50-150)；Ultra-fine inorganic oxide carrier shared percentage by weight in the catalytic component is
5-50wt%, preferably 10-30wt%, more preferably 15-25wt%.
3. catalytic component according to claim 1 and 2, it is characterised in that the ultra-fine inorganic oxygen
Compound carrier is that particle diameter is 0.1-10 microns, the titanium dioxide for being preferably 0.5-5 microns, being more preferably 0.1-1 microns
Silicon.
4. the catalytic component according to any one of claim 1-3, it is characterised in that the magnesium halide
Selected from magnesium dichloride, dibrominated magnesium or magnesium diiodide；The halogenated titanium selected from titanium tribromide, titanium tetrabromide, three
At least one in titanium chloride and titanium tetrachloride, preferred titanous chloride. and/or titanium tetrachloride.
5. the catalytic component according to any one of claim 1-4, it is characterised in that described halo
The formula of silane is SiXaRb, wherein X is halogen, and R is alkyl, and a is more than 0, and a+b=4；Preferably,
The halogenated silanes is selected from Silicon chloride., Silicon bromide., silicon tetraiodide, phenyl trichlorosilicane, phenyl tribromide
Silicon, phenyl triiodo SiClx, benzyl trichlorosilicane, benzyl tribromo SiClx, benzyl triiodo SiClx, methyl
Trichlorosilicane, methyl tribromo SiClx, methyl triiodo SiClx, ethyl trichlorosilicane, ethyl tribromo SiClx, ethyl
Triiodo SiClx, propyl group trichlorosilicane, propyl group tribromo SiClx, propyl group triiodo SiClx, butyl trichlorosilicane, butyl
Tribromo SiClx, butyl triiodo SiClx, cyclohexyl trichlorosilicane, cyclohexyl tribromo SiClx, cyclohexyl triiodo SiClx
In at least one.
6. the catalytic component according to any one of claim 1-5, it is characterised in that the electron
Body compound is selected from C1-C4The Arrcostab of aliphatic saturated monocarboxylic acid, C7-C8Aromatic carboxylic acids Arrcostab, C2-C6Fat
Ether, C3-C4Cyclic ethers, C3-C6At least one of saturated fat ketone；Preferably, the electron donor compound choosing
From methyl formate, Ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, acetic acid
N-propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, ether, propyl ether, hexyl ether, tetrahydrofuran,
At least one in acetone and methyl iso-butyl ketone (MIBK).
7. the preparation method of the catalytic component according to any one of claim 1-6, including：
It is prepared by step S1, mother solution：Magnesium halide, halogenated titanium and halogenated silanes are carried out in electron donor compound
Reaction prepares mother solution；
Step S2, carrier blending：Mother solution prepared by step S1 is blended with ultra-fine inorganic oxide carrier
Obtain slurry liquid material；
Step S3, spray shaping：The slurry liquid that step S2 is obtained is spray-dried, and obtains the catalysis
Agent component.
8. preparation method according to claim 7, it is characterised in that the spray strip in step S3
Part is：Inlet temperature is 80-240 DEG C, preferred 120-180 DEG C；Outlet temperature is 60-130 DEG C, preferably 90-110
℃。
9. a kind of catalyst for olefinic polyreaction, which includes the product of following components：
(A) catalytic component any one of claim 1-6 and/or pass through 7 or 8 institute of claim
The catalytic component that the preparation method stated is obtained；
(B) formula is A1R 'nX3-nOrgano-aluminum compound, in formula, R ' is that hydrogen or carbon number are 1-20's
Alkyl, X are halogen, preferably chlorine, bromine, iodine, the organo-aluminum compound of 0 ＜ n≤3.
10. application of the catalyst described in claim 9 in alkene homopolymerization or copolymerization.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563496A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method and application thereof |
| CN114437259A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Application of olefin polymer in olefin polymerization, olefin polymerization catalyst and olefin polymerization method |
| CN116041572A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and application |
| CN116041571A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst system for loading siloxane compounds and preparation method and application thereof |
| CN116063590A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Cyclosiloxane-containing catalyst component for olefin polymerization, and preparation method and application thereof |
| CN116063591A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Metal organic compound catalyst for olefin polymerization and preparation method and application thereof |
| CN116063593A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst containing catalyst component, preparation method and application of catalyst component |
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| CN101575386A (en) * | 2008-05-09 | 2009-11-11 | 中国石油天然气股份有限公司 | Preparation method of silica gel supported titanium magnesium catalyst |
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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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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563496A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization or copolymerization and preparation method and application thereof |
| CN114437259A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Application of olefin polymer in olefin polymerization, olefin polymerization catalyst and olefin polymerization method |
| CN116041572A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and application |
| CN116041571A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst system for loading siloxane compounds and preparation method and application thereof |
| CN116041572B (en) * | 2021-10-28 | 2024-07-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and application |
| CN116041571B (en) * | 2021-10-28 | 2024-07-02 | 中国石油化工股份有限公司 | Catalyst system for loading siloxane compounds and preparation method and application thereof |
| CN116063590A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Cyclosiloxane-containing catalyst component for olefin polymerization, and preparation method and application thereof |
| CN116063591A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Metal organic compound catalyst for olefin polymerization and preparation method and application thereof |
| CN116063591B (en) * | 2021-10-29 | 2024-06-04 | 中国石油化工股份有限公司 | Metal organic compound catalyst for olefin polymerization and preparation method and application thereof |
| CN116063590B (en) * | 2021-10-29 | 2024-06-04 | 中国石油化工股份有限公司 | Cyclosiloxane-containing catalyst component for olefin polymerization, and preparation method and application thereof |
| CN116063593A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst containing catalyst component, preparation method and application of catalyst component |
| CN116063593B (en) * | 2021-10-30 | 2024-07-02 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, catalyst containing catalyst component, preparation method and application of catalyst component |
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