Polor monomer homopolymerization and copolymerization titanium-substituted beta-dione-cobalt acetylacetonate composite catalyst and its preparing method
A polar monomer and catalyst technology, applied in the field of titanium-substituted β-diketone-cobalt acetylacetonate Co2 composite catalyst and its preparation, can solve the problems of complex catalyst preparation, performance and application limitations, etc.
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Embodiment 1
[0022] 1. Catalyst preparation:
[0023] 1-1 mix 0.3g Co(acac) 2 Dissolve in 15ml of dichloromethane to make a homogeneous solution.
[0024] 1-2 Add 1g of anhydrous MgCl 2 Place in another reaction flask, add 15ml THF and 2ml absolute ethanol, heat to 60-75°C and stir for 2 hours until completely dissolved to obtain MgCl 2 mother liquor.
[0025] 1-3 in N 2 Under air flow, 3g SiO 2 Heating and dehydration, heating to 600°C and cooling for 6 hours to obtain pretreated SiO 2 , add 1-2 to the prepared mother liquor, stir and react at 65-70°C for 2 hours, and drain the solvent at 65-80°C.
[0026] 1-4 Add 15ml of dichloromethane to the product of 1-3, and add 0.12ml of TiCl under stirring 4 , react at 60~70°C for 1-2h; add 0.24ml benzoylacetone (bzac) and 1-1 to prepare Co(caca) 2 The solution is reacted at 60-70° C. for 1-2 hours, and the solvent is drained to obtain a composite main catalyst.
[0027] 1-5 composite main catalyst and AlEt 2 Cl or AlEt 2 Cl-AlR 3 The ...
Embodiment 2
[0034] In embodiment 1 step 1-1 " will 0.3g Co(acac) 2 Dissolved in 15ml of dichloromethane" was changed to "0.15g Co(acac) 2 Dissolved in 7.5ml of dichloromethane", all the other conditions and operations are the same as in Example 1. The prepared catalyst is used for the polymerization reaction under the same conditions as in Example 1.
[0035] Under the above conditions, the homopolymerization reaction prepares P4-VP, and the catalytic efficiency is 43kg. PMA / mol(Ti+Co), MA conversion 52%. Copolymerization reaction prepares P (E-4-VP) catalytic efficiency is 24kg P (E-4-VP) mol (Ti+Co), contains 17.5% 4-VP in the copolymer; Prepares P (E-MA), catalytic efficiency It is 18.3kg P(E-MA), and the copolymer contains 6.5% MA.
Embodiment 3
[0037] In Step 2 of Example 1, "...then add 4-VP or MA, stir and react at 30°C for 5h" to "...then add 4-VP or MA, stir and react at 30°C for 0.5h, then add AlEt with Al / Ti molar ratio 50 / 1 3 , Continue to react for 5h ", and all the other conditions and operations are the same as in Example One. The prepared catalyst is used for the polymerization reaction under the same conditions as in Example One.
[0038] Under the above conditions, the homopolymerization reaction prepares P4-VP, the catalytic efficiency is 65kg P4-VP / mol (Ti+Co), and the 4-VP conversion rate is 95%; the preparation of PMA, the catalytic efficiency is 59kg PMA / mol (Ti+Co) , MA conversion was 53%. Copolymerization prepared P(E-4VP), the catalytic efficiency was 32kg P(E-4-VP) / mol(Ti+Co), containing 22% 4-VP in the copolymer; prepared P(E-MA), the catalytic efficiency It is 20.5kg P(E-MA) / mol(Ti+Co), and the copolymer contains 12% MA.
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