CN1470535A - Polar monomer homopolymerizatino and copolymerization titanium-cobalt acetylacetonate composite catalyst and its preparing method - Google Patents
Polar monomer homopolymerizatino and copolymerization titanium-cobalt acetylacetonate composite catalyst and its preparing method Download PDFInfo
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- CN1470535A CN1470535A CNA031269001A CN03126900A CN1470535A CN 1470535 A CN1470535 A CN 1470535A CN A031269001 A CNA031269001 A CN A031269001A CN 03126900 A CN03126900 A CN 03126900A CN 1470535 A CN1470535 A CN 1470535A
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- titanium
- acac
- alr
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- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 5
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 title 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001038 ethylene copolymer Polymers 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- YUICZVWBWNGNFK-UHFFFAOYSA-N [Co].C(C)(=O)CC(C)=O.[Ti] Chemical compound [Co].C(C)(=O)CC(C)=O.[Ti] YUICZVWBWNGNFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- -1 TiCl 4 Chemical compound 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 229920002319 Poly(methyl acrylate) Polymers 0.000 abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 229920002717 polyvinylpyridine Polymers 0.000 abstract description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 abstract 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a titanium-Co(acac)2 (cobalt acetylacetonate) compound catalyst for homopolymerization and copolymerization of polar monomer 4-vinylpyridine and methyl acrylate to prepare polyvinylpyridine (P4-VP), polymethyl acrylate (PMA) and copolymer of the above-mentioned materials and ethylene and its preparation method. The composition of said catalyst includes the compound main catalyst made up by loading titanium compound and cobalt acetylacetonate or titanium compound, cobalt acetylacetonate and acetylacetone on the MgCl2-SiO2 composite carrier and cocatalyst formed from AlEt2Cl or alkylaluminium and AlEt2Cl. Its preparation method adopts impregnation reaction process, and said invented product is a spherical compound catalytic system.
Description
Technical field
The present invention relates to a kind of titanium-acetylacetone cobalt Co (acac) that is used for polar monomer 4-vinylpridine, methyl acrylate homopolymerization and copolymerization polyvinylpyridine (P4-VP), polymethyl acrylate (PMA) and they and ethylene copolymer
2Composite catalyst and preparation method thereof.
Background technology
As everyone knows, adopt traditional Ziegler one Natta (Z-N) catalyzer to be difficult to make polar monomer polymerization and copolymerization to make homopolymer and multipolymer, reported in literature adopts diimine title complex and the copolymerization of methylaluminoxane (MAO) catalyzing propone acid methyl esters of rear transition metal Pd, has made random copolymers, causes extensive attention (JohnsomL.K., Mecking, S, Brookhart M., J.Am.Chem.Soc, 1996,118:267.).But this Preparation of Catalyst complexity also need adopt high MAO of valency or boron compound to make promotor, and the product ester that makes mainly is positioned at end group, and its performance and application are restricted.
Summary of the invention
The purpose of this invention is to provide a kind of titanium-Co (acac) that is used for polar monomer 4-vinylpridine, methyl acrylate homopolymerization and they and ethylene copolymer
2Composite catalyst and preparation method thereof; The AlEt that this catalyzer call for bids is honest and clean
2Cl or aluminum alkyls and AlEt
2Cl makes promotor, need not to use expensive MAO or boron compound, can catalysis 4-vinylpridine (4-VP), methyl acrylate (MA) makes the multiple multipolymer of homopolymer and they and ethene, have to produce and go up application prospect, thus solution existing in prior technology the problems referred to above.
Catalyzer of the present invention, its component comprises compound primary catalysts and promotor; With titanium compound and acetylacetone cobalt, perhaps titanium compound, methyl ethyl diketone and acetylacetone cobalt load on MgCl
2-SiO
2On the complex body, constitute compound primary catalysts; With AlEt
2Cl or aluminum alkyls and AlEt
2Cl is a promotor; Titanium compound is TiCl
4Aluminum alkyls is AlR
3, wherein R is C
2-C
8Alkyl.
The set of dispense of the invention described above catalyzer is than calculating MgCl by weight
2: SiO
2: TiCl
4=1: (2～15): (0.5～3.0), all the other each components are with TiCl
4Mole number calculate, its mol ratio is:
TiCl
4 1
Co(acac)
2 0.1～5
Methyl ethyl diketone (acac) 0～5
AlR
3 0～100
Et
2AlCl 50～150
When containing acac in the component, its proportioning is (with TiCl
4Mol ratio) be generally 0.1～5.In component, contain AlR
3The time, its proportioning is (with TiCl
4Mol ratio) be generally 10～100.
The invention described above catalyzer can adopt dipping-reaction method preparation, and concrete steps are as follows:
(1) with Co (acac)
2Be dissolved in the methylene dichloride, wherein the methylene dichloride consumption is every gram Co (acac)
2Add 15～30ml;
(2) with anhydrous MgCl
2Be dissolved in the pure and mild ether mixed solution at 60～75 ℃, stirring reaction 2～3 hours gets the homogeneous phase mother liquor; Wherein alcohol is ethanol, and ether is THF (tetrahydrofuran (THF)), and consumption is MgCl in molar ratio
2: alcohol=1: (3～5), MgCl
2: THF=1: (24～40);
(3) at N
2Protection is added 4～6 hours pretreated SiO of 400～600 ℃ of activation down in (2) are mother liquid obtained
2, stirring reaction 2～4 hours, liquid is drained in heating;
(4) in (3) products therefrom, add methylene dichloride, TiCl
4, methyl ethyl diketone and (1) gained Co (acac)
2Solution was warming up to 60～70 ℃ of stirring reactions 1～3 hour, filter, vacuum take out in, obtain the solid compound primary catalysts; The methylene dichloride consumption is every gram SiO
2Add 5～12ml;
(5) compound primary catalysts and AlEt
2Cl or AlEt
2Cl-AlR
3Promotor is formed the composite catalyst be used for polar monomer vinyl pyridine, methyl acrylate homopolymerization and they and ethylene copolymer, and its mol ratio is Ti: AlR
3: Et
2AlCl=1: (0～100): (50～150).
The present invention adopts titanium compound, acetylacetone cobalt and methyl ethyl diketone component, and above-mentioned specific dipping reaction method for preparing makes loaded catalyst, a general AlEt of need
2Cl or AlEt
2Cl-AlR
3Make promotor, need not MAO or boron compound; Can catalysis polar monomer 4-vinylpridine, methyl acrylate homopolymerization and they and ethylene copolymer, have the production application prospect.
Catalyst 4-vinylpridine homopolymerization product poly 4 vinyl pyridine of the present invention (P4-VP), catalytic efficiency are 4.8～35kgP4-VP/mol (Ti+Co); Catalysis MA polymerisate polymethyl acrylate (PMA), catalytic efficiency are 3.5～19kg PMA/mol (Ti+Co).Being used for catalyzed ethylene (E) and 4-VP copolymerization generation ethene-4 vinylpyridine copolymer [P (E-4-VP)] catalytic efficiency is 3.5～18kgP (E-4-VP)/mol (Ti+Co); Contain 0.5～30%4-VP in the multipolymer; [P (E-MA) catalytic efficiency is 4.0～12kg P (E-AM)/mol (Ti+Co), contains 0.3～18%MA in the multipolymer to be used for catalyzed ethylene and MA copolymerization generation ethylene-propylene manthanoate multipolymer.The catalyzer homopolymerization of invention is made solvent with heptane or toluene under 106.7kPa pressure, at the uniform velocity stir to add catalyzer and promotor in reaction flask, adds under 4-VP or the MA control certain temperature reaction 5h then; Termination reaction, washing, filtration, the dry product that gets.
The copolyreaction of catalyzer of the present invention under the anhydrous and oxygen-free condition, under ethylene pressure 106.7kPa, adds catalyzer, promotor reaction 0.5h; Add polar monomer 4-VP reaction 5h then, washing, filtration, the dry product that gets; Use dimethylbenzene, the methyl alcohol extracting 6h that refluxes respectively gets copolymerization product.Identical for ethene-MA copolyreaction operation, but use dimethylbenzene, THF (tetrahydrofuran (THF)) extracting 6h at last, the dry product that gets.
Embodiment
The invention will be further described below by embodiment
Embodiment one
1. Preparation of Catalyst:
1-1 is with 0.3g Co (acac)
2Be dissolved in the 15ml methylene dichloride, make uniform solution.
1-2 is with the anhydrous MgCl of 1g
2Place another reaction flask, add 15mlTHF and 2ml dehydrated alcohol, be heated to 60～75 ℃ of stirring reactions 2 hours to dissolving fully and make MgCl
2Mother liquor.
1-3 is at N
2Under the air-flow, with 3g SiO
2Heat up and dewater, be warming up to the cooling in 6 hours of 600 ℃ of constant temperature, get pretreated SiO
2, add 1-2 and make in the mother liquor, 65～70 ℃ of stirring reactions 2 hours, and under 65～80 ℃, drain wherein solvent.
1-4 adds methylene dichloride 15ml in the 1-3 product, stir to add 0.12ml TiCl down
4, at 60～70 ℃ of reaction 1-2h; Add 0.20ml methyl ethyl diketone and 1-1 and make Co (caca)
2Solution at 60～70 ℃ of reaction 1-2h, is drained solvent, obtains compound primary catalysts.
1-5 compound primary catalysts and AlEt
2Cl or AlEt
2Cl-AlR
3The complex catalyst system that promotor is formed is used for following polymerization process, makes polar monomer 4-VP or MA polymerization make homopolymer P4-VP and PMA; Make ethene and 4-VP or MA copolymerization make copolymer p (E-4-VP) or P (E-MA).
2. the equal polymerization of 4-VP or MA prepares homopolymer P4-VP or PMA:
Through 120 vacuum-dryings 1.5 hours, N
2Replace 3 times reaction flask, at N
2Add 50ml toluene and Al/Ti mol ratio under the protection and be 120/1 Et
2AlCl adds the compound primary catalysts that contains 3～5mg titanium again, adds 4-VP or MA then, and at 30 ℃ of stirring reaction 5h, with 10%HCl or 5%NaOH termination reaction, after the neutralization, filtration drying gets product P 4-VP or PMA.
3. ethene and 4-VP or MA copolymerization prepare copolymer p (E-4VP) or P (E-MA):
Through 120 ℃ of vacuum-dryings 1.5 hours, N
2Replace 3 secondary response bottles, at N
2Protection is down added 50ml toluene and Al/Ti mol ratio and is 120/1 Et
2AlCl adds the compound primary catalysts that contains 3～5mg titanium again.Take out N
2After, at first logical ethylene homo reaction 0.5h, pressure is 106.7kpa, 30 ℃ of temperature, and then add polar monomer 4-VP or MA copolyreaction 5h.For 4-VP 10%HCl termination reaction, add 30ml methyl alcohol then, filter, after the precipitation drying,, obtain insoluble copolymer p (E-4-VP) with dimethylbenzene, methyl alcohol difference extracting 6h.With containing ethanol 5%NaOH termination reaction, is acid with 10%HCl neutralization then for the MA copolymerization, filters, and after the precipitation drying, uses dimethylbenzene, and THF is extracting 6h respectively, drying products.
Under above-mentioned polymerizing condition, homopolymerization prepares P4-VP, and catalytic efficiency is 18.5kg P4-VP/mol (Ti+Co), and the 4-VP transformation efficiency is 78.5%; Preparation PMA, catalytic efficiency 7.5kg PMA/mol (Ti+Co), MA transformation efficiency are 45%.Copolyreaction prepares P (E-4-VP), and catalytic efficiency is 12.5kg P (E-4-VP)/mol (Ti+Co), contains 12%4-VP in the multipolymer; Preparation P (E-MA), catalytic efficiency is 8.5kgP (E-MA)/mol (Ti+Co), contains 8.5%MA in the multipolymer.
Embodiment two
With among the embodiment one step 1-1 " with 0.3g Co (acac)
2Be dissolved in the 15ml methylene dichloride " change into " with 0.15g Co (acac)
2Be dissolved in the 7.5ml methylene dichloride ", all the other conditions and operation are with embodiment one.The catalyzer that makes be used for embodiment one the same terms under polyreaction.
Under these conditions, homopolymerization prepares P4-VP, and catalytic efficiency is 20.9kg P4-VP/mol (Ti+Co), and the 4-VP transformation efficiency is 85.1%; Preparation PMA, catalytic efficiency is 12kg PMA/mol (Ti+Co), the MA transformation efficiency is 48%.It is 14kg P (E-4-VP)/mol (Ti+Co) that copolyreaction prepares P (E-4-VP) catalytic efficiency, contains 7.5%4-VP in the multipolymer; Preparation P (E-MA), catalytic efficiency is 10.3kg P (E-MA), contains 6.5%MA in the multipolymer.
Embodiment three
With " ... add 4-VP or MA then, " in embodiment one step 2 at 30 ℃ of stirring reaction 5h, change into " ... add 4-VP or MA then, behind 30 ℃ of stirring reaction 0.5h, add the Al/Ti mol ratio again and be 50/1 AlEt
3, continue reaction 5h ", all the other conditions and operation are with embodiment one.The catalyzer that makes be used for embodiment one the same terms under polyreaction.
Under these conditions, homopolymerization prepares P4-VP, and catalytic efficiency is 26kg P4-VP/mol (Ti+Co), 4-VP transformation efficiency 89%; Preparation PMA, catalytic efficiency 16kg PMA/mol (Ti+Co), MA transformation efficiency are 58%.Copolyreaction prepares P (E-4VP), and catalytic efficiency is 16kg P (E-4-VP)/mol (Ti+Co), contains 15%4-VP in the multipolymer; Preparation P (E-MA), catalytic efficiency is 12.5kg P (E-MA)/mol (Ti+Co), contains 12%MA in the multipolymer.
Embodiment four
With among the poly-1-4 of embodiment one step " ... add methyl ethyl diketone and 1-1 and make Co (acac)
2Solution, " change into and " add 1-1 and make Co (acac)
2Solution, " all the other conditions and the operation with embodiment one.The catalyzer that makes be used for embodiment one the same terms under polyreaction.
Under these conditions, homopolymerization prepares P4-VP, and catalytic efficiency is 16kg P4-VP/mol (Ti+Co), 4-VP transformation efficiency 56%; Preparation PMA, catalytic efficiency 6kg PMA/mol (Ti+Co), MA transformation efficiency are 18%.Copolyreaction prepares P (E-4VP), and catalytic efficiency is 10kg P (E-4-VP)/mol (Ti+Co), contains 5%4-VP in the multipolymer; Preparation P (E-MA), catalytic efficiency is 4.5kg P (E-MA)/mol (Ti+Co), contains 2.5%MA in the multipolymer.
Claims (5)
1. titanium-acetylacetone cobalt composite catalyst that is used for polar monomer homopolymerization and copolymerization, its component comprises compound primary catalysts and promotor; With titanium compound and acetylacetone cobalt, perhaps titanium compound, methyl ethyl diketone and acetylacetone cobalt load on MgCl
2-SiO
2On the complex body, constitute compound primary catalysts; With AlEt
2Cl or aluminum alkyls and AlEt
2Cl is a promotor; Titanium compound is TiCl
4, aluminum alkyls is AlR
3, wherein R is C
2-C
8Alkyl.
2. according to the described catalyzer of claim 1, it is characterized in that each set of dispense is than calculating MgCl by weight in the catalyzer
2: SiO
2: TiCl
4=1: (2～15): (0.5～3.0), all the other each components are with TiCl
4Mole number calculate, its mol ratio is:
TiCl
4 1
Co(acac)
2 0.1～5
Methyl ethyl diketone 0～5
AlR
3 0～100
Et
2AlCl 50～150
3. according to the described catalyzer of claim 2, it is characterized in that methyl ethyl diketone and TiCl in the catalyst component proportioning
4Mol ratio be 0.1～5.
4. according to claim 2 or 3 described catalyzer, it is characterized in that the AlR in the catalyst component proportioning
3With TiCl
4Mol ratio be 10～100.
5. claim 1 or 2 described Preparation of catalysts methods is characterized in that adopting the preparation of dipping-reaction method, and concrete steps are as follows:
(1) with Co (acac)
2Be dissolved in the methylene dichloride, wherein the methylene dichloride consumption is every gram Co (acac)
2Add 15～30ml;
(2) with anhydrous MgCl
2Be dissolved in the pure and mild ether mixed solution at 60～75 ℃, stirring reaction 2～3 hours gets the homogeneous phase mother liquor; Wherein alcohol is ethanol, and ether is tetrahydrofuran (THF), and consumption is MgCl in molar ratio
2: alcohol=1: (3～5), MgCl
2: THF=1: (24～40);
(3) at N
2Protection is added 4～6 hours pretreated SiO of 400～600 ℃ of activation down in (2) are mother liquid obtained
2, stirring reaction 2～4 hours, liquid is drained in heating;
(4) in (3) products therefrom, add methylene dichloride, TiCl
4, methyl ethyl diketone and (1) gained Co (acac)
2Solution, 60～70 ℃ of stirring reactions 1～3 hour of heating up filter, and vacuum is drained, and obtains the solid compound primary catalysts; The methylene dichloride consumption is every gram SiO
2Add 5～12ml;
(5) compound primary catalysts and AlEt
2Cl or AlEt
2Cl-AlR
3Promotor is formed the composite catalyst be used for polar monomer vinyl pyridine, methyl acrylate homopolymerization and they and ethylene copolymer, and its mol ratio is Ti: AlR
3: Et
2AlCl=1: (0～100): (50～150).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03126900 CN1197884C (en) | 2003-06-18 | 2003-06-18 | Polar monomer homopolymerizatino and copolymerization titanium-cobalt acetylacetonate composite catalyst and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03126900 CN1197884C (en) | 2003-06-18 | 2003-06-18 | Polar monomer homopolymerizatino and copolymerization titanium-cobalt acetylacetonate composite catalyst and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1470535A true CN1470535A (en) | 2004-01-28 |
| CN1197884C CN1197884C (en) | 2005-04-20 |
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ID=34153137
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313473C (en) * | 2005-05-19 | 2007-05-02 | 北京化工大学 | Preparation of acetylacetone cobalt |
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2003
- 2003-06-18 CN CN 03126900 patent/CN1197884C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313473C (en) * | 2005-05-19 | 2007-05-02 | 北京化工大学 | Preparation of acetylacetone cobalt |
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| Publication number | Publication date |
|---|---|
| CN1197884C (en) | 2005-04-20 |
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