CN1264873C - Preparation method of composite carrier catalyst used for olefine polymerized lamellar silicate - Google Patents
Preparation method of composite carrier catalyst used for olefine polymerized lamellar silicate Download PDFInfo
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- CN1264873C CN1264873C CN 200410015747 CN200410015747A CN1264873C CN 1264873 C CN1264873 C CN 1264873C CN 200410015747 CN200410015747 CN 200410015747 CN 200410015747 A CN200410015747 A CN 200410015747A CN 1264873 C CN1264873 C CN 1264873C
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- magnesium
- layered silicate
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- silicate
- olefinic polymerization
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000969 carrier Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- 239000011777 magnesium Substances 0.000 claims description 22
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- -1 alkoxyl magnesium Chemical compound 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000004760 silicates Chemical class 0.000 abstract 3
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 150000002681 magnesium compounds Chemical class 0.000 abstract 1
- 239000004711 α-olefin Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 5
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 3
- 101150019148 Slc7a3 gene Proteins 0.000 description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention discloses a preparation method for a compound supported catalyst containing layer silicates for olefinic polymerization. The catalysts prepared by the method has the characteristics of adjustable activity and small consumption of a required catalyst promoter of triethyl aluminium; furthermore, the catalyst comprises the components of the layer silicates, magnesium compounds, inner electron donors and titanium tetrachloride, and the contents of the layer silicates in carriers varies from 5% to 95% by mass. Besides changing the carrying capacity of the titanium tetrachloride and the ratio of the catalyst promoter of aluminum alkyl to the inner and outer electron donors, the activity of catalytic polymerization, the molecular weight of polymerisates and the distribution thereof can be adjusted by changing the compounding ratio of the catalyst compounded with the carriers. The catalysts can be used for the homopolymerization or the copolymerization of the alpha olefin of ethylene, propene, etc., and can also be used for the preparation of polyolefin layer silicate nanometer composite materials.
Description
Technical field
The present invention relates to a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization.
Background technology
Supported catalyst preparation method about olefinic polymerization was a lot of in the past, their used carriers are generally magnesium chloride, silicon-dioxide, aluminum oxide or its mixture, Preparation of catalysts technology is different, the particle form that purpose is to improve activity of such catalysts and improves polymerisate.Chinese patent (CN1330101A) discloses the preparation method of a kind of montmorillonite-TiCl 4 catalyst and polyolefin/montmorillonite composite thereof.But what adopted in this patent is without pretreated common polynite, and sodium ion that it had or calcium ion especially have material impact to propylene polymerization activity and polymericular weight to catalytic activity.
Summary of the invention
The object of the present invention is to provide simple and easy to do a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization, the catalyzer that makes with this method has active adjustable, the few characteristics of required promotor triethyl aluminum usage quantity; Both can be used for ethene, propylene and alhpa olefin homopolymerization or copolymerization, also can be used for the synthesis of polyolefins laminated nm-silicate composite material.
In order to achieve the above object, the technical solution used in the present invention comprises following several steps:
A. the preparation of magnesium-base layer-shaped silicate
With cation exchange capacity is 50～200meq/100g, and particle diameter is that the layered silicate of 40～100um is scattered in 80～1000ml deionized water for 0.5～40 part, adds 0.5～15 part of magnesium salts, stirs 30 minutes～8 hours, filters the final vacuum drying;
B. the preparation of layered silicate complex carrier
With the magnesium-base layer-shaped silicate for preparing among the step a 80～150 ℃ of dryings or vacuum-drying 8～16 hours, 10 parts of dry magnesium-base layer-shaped silicate of crossing are scattered in the 1000ml dispersion liquid, add 0.5～190 part of magnesium-containing compound, are heated to 60～150 ℃, stir, till the evaporate to dryness dispersion liquid;
C. contain the preparation of the complex carrier olefin polymerization catalysis of layered silicate component
Get 100 parts of complex carriers and under nitrogen atmosphere, add electron donor(ED) in 3～30 parts, 300～700 parts of titanium tetrachlorides reacted 1～3 hour down in 80～110 ℃, after inert solvent washing 3～6 times, adding 300～700 parts of titanium tetrachlorides reacted 1～3 hour down for 80～110 ℃, with inert solvent washing 3～6 times, vacuum-drying is preserved.
Described layered silicate is polynite, bentonite or mica etc., and the laminar silicic acid salts contg accounts for the mass percent of complex carrier from 5%～95%.
Layered silicate is earlier through magnesium ion exchange and drying treatment during Preparation of Catalyst, and the solubility magnesium salts that is used for the exchange of magnesium ion salt is magnesium chloride, sal epsom or magnesium bromide etc.
Described magnesium-containing compound is magnesium chloride, alkoxyl magnesium, alkyl magnesium or Ge Shi magnesium; Be preferably alkoxyl magnesium etc.
Described dispersion liquid is deionized water, ethanol, propyl alcohol, hexane or toluene organic solvent etc.
Electron donor(ED) is ethyl benzoate or phenylformic acid dibutylester aromatic ester etc. in described.
Described inert solvent is tetracol phenixin, hexane, heptane, sherwood oil or toluene organic solvent etc.
The advantage that the present invention has is: use the carrier of layered silicate as catalyst for olefines polymerizing, the preparation method is easy, and it is adjustable that the catalyzer that makes with this method has activity, the few characteristics of required promotor triethyl aluminum usage quantity; This catalyzer contains layered silicate, magnesium-containing compound, interior electron donor(ED), titanium tetrachloride component, and carrier laminate silicate content changes from 5%～95% (mass percent); Except that the ratio that changes titanium tetrachloride charge capacity, promotor aluminum alkyls and interior external electronic donor, the proportioning that changes the catalyzer complex carrier also can be regulated the activity of catalyzed polymerization and the molecular weight and the distribution thereof of polymerisate; This catalyzer can be used for the homopolymerization or the copolymerization of alhpa olefins such as ethene, propylene, also can be used for preparing polyolefine stratiform silicate nanometer composite material.
Description of drawings
Accompanying drawing is single carrier of Mg-MMT and Mg-MMT/Mg (OEt)
2The DSC spectrum of composite carried catalyst catalyzing propone polymerisate.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
A. the preparation of magnesium base montmorillonite (Mg-MMT): 20g calcium-base montmorillonite (Ca-MMT) and 10gMgCl
66H
2O puts into the 250ml flask, adds the 200ml deionized water.80 ℃ were stirred 6 hours down, behind the suction filtration in baking oven 105 ℃ dry 12 hours down.Putting into moisture eliminator after the grinding refinement preserves.
B. the preparation of complex carrier: 10g magnesium base montmorillonite (Mg-MMT) and 2gMg (OEt)
2Put into the 250ml flask, add the 100ml dehydrated alcohol, 70 ℃ of lower magnetic forces stirred 2 hours.Use immediately or moisture eliminator are preserved standby after the solvent evaporated.
C.5g exsiccant Mg-MMT places the core reactor, and 100 ℃ of following vacuum 2 hours add 50ml toluene, mix, and slowly add by 5mlTiCl by constant pressure funnel
4, the mixed solution formed of 0.22ml ethyl benzoate and 45ml toluene, dropwise back 100 ℃ and continue reaction 2 hours down, cooling leaches product, it is inferior to give a baby a bath on the third day after its birth with 50ml toluene, vacuum is drained under the room temperature.Whole process guarantees anhydrous and oxygen-free in the reactor.The gained catalyzer is called Cat1 (Ti 0.73mmol/g).
Embodiment 2
Step a.b. is identical with embodiment 1.
C.5g exsiccant Mg-MMT/Mg (OEt)
2Complex carrier places the core reactor, and 100 times ℃ of vacuum 2 hours add 50ml toluene, mix, and slowly add by 5mlTiCl by constant pressure funnel
4, the mixed solution formed of 0.22ml ethyl benzoate and 45ml toluene, dropwise back 100 ℃ and continue reaction 2 hours down, cooling leaches product, it is inferior to give a baby a bath on the third day after its birth with 50ml toluene, vacuum is drained under the room temperature.Whole process guarantees anhydrous and oxygen-free in the reactor.The gained catalyzer is called Cat4 (Ti 1.41mmol/g).
Also Cat4 can be inserted in the reaction flask, add 5mlTiCl
4With 20ml toluene, 115 ℃ were reacted 2 hours down, behind cooling, the standing demix, removed supernatant liquid, and it is inferior to give a baby a bath on the third day after its birth with 30ml toluene, and vacuum is drained under the room temperature.Whole process guarantees anhydrous and oxygen-free in the reactor.The gained catalyzer is called Cat5 (Ti 1.22mmol/g).
Embodiment 3
A. the preparation of magnesium basis soap soil (Mg-BEN): 20g calcium basis soap soil (Ca-BEN) and 10gMgClc6HcO put into the 250ml flask, add the 200ml deionized water.80 ℃ were stirred 6 hours down, behind the suction filtration in baking oven 105 ℃ dry 12 hours down.Putting into moisture eliminator after the grinding refinement preserves.
B. the preparation of complex carrier: 10g magnesium basis soap soil (Mg-BEN) and 4gMg (OEt)
2Put into the 250ml flask, add the anhydrous propyl alcohol of 100ml, 80 ℃ of lower magnetic forces stirred 2 hours.Use immediately or moisture eliminator are preserved standby after the solvent evaporated.
C.5g exsiccant Mg-BEN/Mg (OEt)
2Complex carrier places the core reactor, and 100 times ℃ of vacuum 2 hours add 50ml toluene, mix, and slowly add by 5mlTiCl by constant pressure funnel
4, the mixed solution formed of 0.22ml ethyl benzoate and 45ml toluene, dropwise back 100 ℃ and continue reaction 2 hours down, cooling leaches product, it is inferior to give a baby a bath on the third day after its birth with 50ml toluene, vacuum is drained under the room temperature.Whole process guarantees anhydrous and oxygen-free in the reactor.Add 5mlTiCl
4With 20ml toluene, 115 ℃ were reacted 2 hours down, behind cooling, the standing demix, removed supernatant liquid, and it is inferior to give a baby a bath on the third day after its birth with the 30ml hexane, and vacuum is drained under the room temperature.Whole process guarantees anhydrous and oxygen-free in the reactor.The gained catalyzer is called Cat6 (Ti 3.38mmol/g)
Comparative example
10g exsiccant Mg (OEt)
2In inserting the core reactor, 100 ℃ of following vacuum 2 hours add 75mlTiCl
4With the 1.87ml ethyl benzoate, 50 ℃ were reacted 2 hours down, and it is inferior to give a baby a bath on the third day after its birth with 50ml toluene after product leaches, and vacuum is drained under the room temperature.Whole process guarantees anhydrous and oxygen-free in the reactor.The gained catalyzer is called Cat2 (Ti 1.54mmol/g).
Cat2 is placed reaction flask, add 5mlTiCl
4With 20ml toluene, 115 ℃ were reacted 2 hours down, removed supernatant liquid behind the standing demix, and it is inferior to give a baby a bath on the third day after its birth with 30ml toluene, and vacuum is drained under the room temperature.The gained catalyzer is called Cat3 (Ti 1.35mmol/g).
Polymerization example 1
The 250ml reaction flask is after propylene pump drainage displacement three times, and design temperature is 50 ℃, and magnetic agitation adds the 100ml dry toluene successively, an amount of promotor AlEt
3With external electron donor DDS (dimethoxydiphenylsilane), logical propylene adds catalyzer and carries out slurry polymerization to saturation solubility.To certain hour, with acidifying ethanol termination reaction, product after washing with alcohol is filtered, 70 ℃ of following vacuum-dryings.Product is polypropylene or polypropylene stratiform silicate nanometer composite material.
Polymerization example 2
The 2L autoclave is warming up to 50 ℃ after vacuum-drying in 12 hours, advance nitrogen replacement, adds 1g promotor AlEt successively
3, 0.02g external electron donor DDS and 10g catalyzer are pressed into the 1.4L propylene monomer then, and pressure rises to 2Mpa, carries out the liquid-phase bulk polymerization reaction, and the control mixing speed is 120rpm.After the polymerization 1 hour, the emptying propylene monomer stops polyreaction.Product is the polypropylene Nano composite material of montmorillonite, and wherein polynite content is 5%.
Adopt each catalyzer to carry out propylene low pressure slurry polymerization or high-pressure liquid phase mass polymerization, example sees Table 1 as a result.As seen, adopt the activity of single Mg-MMT carried catalyst and molecular weight lower; When adopting Mg (OEt)
2During single carried catalyst, polymerization activity and molecular weight are all higher; Carry out the compound of two kinds of carriers, can carry out the adjusting of polymerization activity and polymericular weight and distribution thereof.
Accompanying drawing is single carrier of Mg-MMT and Mg-MMT/Mg (OEt)
2The DSC spectrum of composite carried catalyst catalyzing propone polymerisate.Show that the employing of complex carrier does not influence the fusing point of polymerisate.
The polymerization yield rate of table 1 different catalysts and molecular weight
| Catalyst type | The polymerization implementation method | Al/Cat. (mmol/g) | Polymerization yield rate (g/gCat) | M η×10 -4 |
| Cat1 a Cat2 a Cat3 a Cat3 a Cat4 a Cat4 a Cat5 b Cat6 b Cat5 c | Polymerization example 1 polymerization example 1 polymerization example 1 polymerization example 1 polymerization example 1 polymerization example 1 polymerization example 1 polymerization example 1 polymerization example 2 | 12.5 12.5 12.5 25 25 12.5 12.5 2.5 2.5 | 1 9 11 21 0.6 1.3 8.7 12.4 200 | 7.0 18.4 24.0 15.1 15.4 16.3 20.7 17.7 36 |
Polymerizing condition: 50 ℃, Al/Si=10; Polymerization time:
a2 hours,
b4 hours,
c1 hour.
Claims (7)
1, a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization is characterized in that it comprises following several steps:
A. the preparation of magnesium-base layer-shaped silicate is 50～200meq/100g with cation exchange capacity, particle diameter is that the layered silicate of 40～100um is scattered in 80～1000ml deionized water for 0.5～40 part, add 0.5～15 part of magnesium salts, stirred 30 minutes～8 hours, filter the final vacuum drying;
B. the preparation of layered silicate complex carrier
With the magnesium-base layer-shaped silicate for preparing among the step a 80～150 ℃ of dryings or vacuum-drying 8～16 hours, 10 parts of dry magnesium-base layer-shaped silicate of crossing are scattered in the 1000ml dispersion liquid, add 0.5～190 part of magnesium-containing compound, are heated to 60～150 ℃, stir, till the evaporate to dryness dispersion liquid;
C. contain the preparation of the complex carrier olefin polymerization catalysis of layered silicate component
Get 100 parts of complex carriers and under nitrogen atmosphere, add electron donor(ED) in 3～30 parts, 300～700 parts of titanium tetrachlorides reacted 1～3 hour down in 80～110 ℃, after inert solvent washing 3～6 times, adding 300～700 parts of titanium tetrachlorides reacted 1～3 hour down for 80～110 ℃, with inert solvent washing 3～6 times, vacuum-drying is preserved.
2, a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization according to claim 1, it is characterized in that: described layered silicate is polynite, bentonite or mica, and the mass percent that the laminar silicic acid salts contg accounts for complex carrier is 5%～95%.
3, a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization according to claim 1, it is characterized in that: described magnesium salts is magnesium chloride, sal epsom or magnesium bromide.
4, a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization according to claim 1, it is characterized in that: described magnesium-containing compound is magnesium chloride, alkoxyl magnesium, alkyl magnesium or Ge Shi magnesium.
5, a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization according to claim 1, it is characterized in that: described dispersion liquid is deionized water, ethanol, propyl alcohol, hexane or toluene.
6, a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization according to claim 1 is characterized in that: electron donor(ED) is ethyl benzoate or phenylformic acid dibutylester in described.
7, a kind of composite carried catalyst preparation method who contains layered silicate who is used for olefinic polymerization according to claim 1, it is characterized in that: described inert solvent is tetracol phenixin, hexane, heptane, sherwood oil or toluene.
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| CN 200410015747 CN1264873C (en) | 2004-01-07 | 2004-01-07 | Preparation method of composite carrier catalyst used for olefine polymerized lamellar silicate |
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| CN1264873C true CN1264873C (en) | 2006-07-19 |
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|---|---|---|---|---|
| CN105985462B (en) * | 2015-02-02 | 2018-12-25 | 中国石油天然气股份有限公司 | Clay modified silica gel composite carrier and preparation method thereof |
| CN106317266B (en) * | 2016-08-19 | 2018-11-16 | 常爱荣 | A kind of complex carrier catalyst for olefinic polymerization and preparation method thereof |
| CN109535290B (en) * | 2018-11-26 | 2020-06-16 | 上海化工研究院有限公司 | Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method and application thereof |
| CN115785308B (en) * | 2022-11-30 | 2024-05-28 | 上海化工研究院有限公司 | Catalyst for producing reinforced polyolefin, and preparation and application thereof |
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2004
- 2004-01-07 CN CN 200410015747 patent/CN1264873C/en not_active Expired - Fee Related
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