Bimetallic cyanide catalyst for epoxide ring-opening polymerization

Abstract

The present invention discloses one kind of bimetallic cyanide catalyst for the ring-opening polymerization of epoxide. The catalyst has the chemical general expression of Ma1[M2(CN)b]d.xM3(X)c.wH2O.yT.jL1.zL2, where, L1 is polytetrahydrofuran oxyprpopyl olefin blocked polyether and L2 is polyether ester sulfate in the structure as shown. The present invention is used for the ring-opening polymerization of alkylene oxide and has high activity and other excellent performance.

Description

Technical field:

[0001] The invention relates to a double metal cyanide (DMC) complex catalyst. Background technique:

[0002] Double metal cyanide (DMC) complex catalysts are used for ring-opening polymerization of epoxides. The polyether polyols produced by this catalyst have lower unsaturation than those produced by basic catalysts (usually KOH), and can produce A higher molecular weight is obtained, and the resulting polyether is usually exempted from post-processing. The composition of DMC catalyst is generally:

[0003] m a 1 [M 2 (EN) b (A) c ] d ·xM 3 (X) e ·wH 2 O·yT·zL Formula I

[0004] m 1 is selected from: Zn (II) , Fe (II) , Fe (III) 、Co (II) 、Ni (II) 、Mo (IV) , Sn (II) 、Cu (II) , Pb (II) 、Mo (VI) 、Al (III) , V (IV) , V (V) 、Sr (II) , W (IV) , W (VI) , Mn (II) and Cr (III) at least one metal ion in

[0005] m 2 is selected from: Fe (II) , Fe (III) 、Co (II) 、Co (III) 、Cr (II) 、Cr (III) , Mn (II) , Mn (III) 、Ni (III) , V ...

Examples

Embodiment 1

[0048] System cat: Zn 3 [Co(CN) 6 ] 2 ·ZnCl 2 0.4H 2 O 0.18TBA 0.055L 1 0.055L 2

[0049] 120g ZnCl in a container 2 Dissolve in 250ml TBA / 450ml deionized water, in another container, 30g K 3 [Co(CN) 6 ] dissolved in 450ml of deionized water, fully mixed for solid-liquid separation to obtain DMC paste, washed with about 50% TBA aqueous solution 1000ml, that is, the process of solid-liquid separation after fully mixing to form a slurry, this washing process is carried out Three times, and finally washed once with 1000ml pure TBA to replace the water in DMC. The separated paste was added with 6g polytetrahydrofuran propylene oxide block polyether (M n =2500, by molecular weight is 1000 polytetrahydrofuran propoxylated to the target molecular weight) and 6g polyether sulfate (M n =2000, the structure is: dodecyl alcohol is initially propoxylated to a molecular weight of about 1000, and sulfuric acid is used to diesterize), then add 500-1000ml and mix well, press filter...

Embodiment 2

[0088] Catalyst performance comparison when the polytetrahydrofuran propoxyethylene block polyether used in the present invention has different molecular weights (the sulfuric acid polyether ester used remains unchanged).

[0089] With embodiment 1 processing step, used L 1 Structure is similar, molecular weight is different, with prepared catalyst by example A system polyoxypropylene glycol (M n =4000) the result is as follows:

Embodiment 3

[0091] Catalyst performance comparison during different structures of polyethersulfate polyether ester in the present invention (used polytetrahydrofuran propoxypropylene block polyether is the same as embodiment 1)

[0092] With embodiment 1 processing step, used L 2 The polyether part has different structures, and the polyoxypropylene dibasic alcohol (M n =4000) the result is as follows:

Technical field:

[0001] The invention relates to a double metal cyanide (DMC) complex catalyst. Background technique:

[0002] Double metal cyanide (DMC) complex catalysts are used for ring-opening polymerization of epoxides. The polyether polyols produced by this catalyst have lower unsaturation than those produced by basic catalysts (usually KOH), and can produce A higher molecular weight is obtained, and the resulting polyether is usually exempted from post-processing. The composition of DMC catalyst is generally:

[0003] m a 1 [M 2 (EN) b (A) c ] d ·xM 3 (X) e ·wH 2 O·yT·zL Formula I

[0004] m 1 is selected from: Zn (II) , Fe (II) , Fe (III) 、Co (II) 、Ni (II) 、Mo (IV) , Sn (II) 、Cu (II) , Pb (II) 、Mo (VI) 、Al (III) , V (IV) , V (V) 、Sr (II) , W (IV) , W (VI) , Mn (II) and Cr (III) at least one metal ion in

[0005] m 2 is selected from: Fe (II) , Fe (III) 、Co (II) 、Co (III) 、Cr (II) 、Cr (III) , Mn (II) , Mn (III) 、Ni (III) , V ...

Examples

Embodiment 1

[0048] System cat: Zn 3 [Co(CN) 6 ] 2 ·ZnCl 2 0.4H 2 O 0.18TBA 0.055L 1 0.055L 2

[0049] 120g ZnCl in a container 2 Dissolve in 250ml TBA / 450ml deionized water, in another container, 30g K 3 [Co(CN) 6 ] dissolved in 450ml of deionized water, fully mixed for solid-liquid separation to obtain DMC paste, washed with about 50% TBA aqueous solution 1000ml, that is, the process of solid-liquid separation after fully mixing to form a slurry, this washing process is carried out Three times, and finally washed once with 1000ml pure TBA to replace the water in DMC. The separated paste was added with 6g polytetrahydrofuran propylene oxide block polyether (M n =2500, by molecular weight is 1000 polytetrahydrofuran propoxylated to the target molecular weight) and 6g polyether sulfate (M n =2000, the structure is: dodecyl alcohol is initially propoxylated to a molecular weight of about 1000, and sulfuric acid is used to diesterize), then add 500-1000ml and mix well, press filter...

Embodiment 2

[0088] Catalyst performance comparison when the polytetrahydrofuran propoxyethylene block polyether used in the present invention has different molecular weights (the sulfuric acid polyether ester used remains unchanged).

[0089] With embodiment 1 processing step, used L 1 Structure is similar, molecular weight is different, with prepared catalyst by example A system polyoxypropylene glycol (M n =4000) the result is as follows:

Embodiment 3

[0091] Catalyst performance comparison during different structures of polyethersulfate polyether ester in the present invention (used polytetrahydrofuran propoxypropylene block polyether is the same as embodiment 1)

[0092] With embodiment 1 processing step, used L 2 The polyether part has different structures, and the polyoxypropylene dibasic alcohol (M n =4000) the result is as follows:

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