CN1197884C - Polar monomer homopolymerizatino and copolymerization titanium-cobalt acetylacetonate composite catalyst and its preparing method - Google Patents

Abstract

The present invention relates to a titanium-co(acac)2(acetylacetonate) composite catalyst for preparing polyethyl pyridinium (P4-VP), polymethyl acrylate (PMA) and a copolymer of the polyethyl pyridinium, the polymethyl acrylate and ethylene by polar monomer 4-vinylpyridine and methyl acrylate homopolymerization and copolymerization, and a preparing method thereof. The components of the catalyst comprise a composite main catalyst and cocatalysts, wherein a titanium compound and acetylacetonate cobalt, or the titanium compound, the acetylacetonate cobalt and acetylacetone are loaded on a MgCl2-SiO2 composite carrier to be used as the composite main catalyst; AlEt2Cl or aluminum alkyl and AlEt2Cl are used as the cocatalysts. An impregnating reaction method is used for the preparing method. The obtained spherical composite catalyst system can prepare a homopolymer and a copolymer without catalyzing 4-vinylpyridine or acrylic methanoic acid homopolymerization and the 4-vinylpyridine, acrylic methanoic acid and ethene copolymerization by MAO.

Description

Polar monomer homopolymerization and copolymerization titanium-acetylacetone cobalt composite catalyst and preparation method thereof

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 4-7 thiazolinyl pyridine (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 for often 0.3 restraining Co (acac) ₂Add 15ml;

(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, filtered, 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 TiCl ₄: 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).

2.4-VP or the equal polymerization of 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 per 0.3 gram Co (acac) ₂Add 15ml;

(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: tetrahydrofuran (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 TiCl ₄: AlR ₃: Et ₂AlCl=1: (0～100): (50～150).