CN104987502B - Co-precipitation double metal cyanide catalyst, and preparation method and application thereof - Google Patents
Co-precipitation double metal cyanide catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a co-precipitation double metal cyanide catalyst and a preparation method thereof. According to the method, a ligand substance and a central molecule substance are subjected to a reaction in a water solution; and separation is carried out, such that the co-precipitation double metal cyanide catalyst is obtained. The ligand substance comprises a first ligand compound with a general formula M＜1＞iX＜1＞j, a second ligand compound with a general formula M＜2＞lX＜2＞m, and a water-soluble compound. The central molecule substance comprises a first central molecule compound with a general formula M＜3＞(CN)c(A＜1＞)d and a second central molecule compound with a general formula M＜4＞(CN)f(A＜2＞)f. The co-precipitation double metal cyanide catalyst has a general formula represented by a formula 1. The invention also provides a preparation method of a carbon dioxide-epoxide copolymer. The catalyst has high catalytic activity and better product selectivity. With the catalyst, the epoxide and carbon dioxide copolymerization product has high carbonate unit content and low cyclic carbonate content. The formula 1 is M＜1＞a[M＜3＞(CN)c(A＜1＞)d]r.q{M＜2＞b[M＜4＞(CN)e(A＜2＞)f]g}.hM＜1＞iX＜1＞j.kM＜2＞lX＜2＞m.nH＜2＞O.pL.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of co-precipitation type DMC catalysts, its system
Preparation Method and its application.
Background technology
Carbon dioxide is a kind of main greenhouse gases, while being used but also as carbon oxygen resource.Currently, it is how high
Effect has become the focus of research using CO_2 Resource.Wherein, the carbon dioxide based polyalcohol with carbon dioxide as raw material
With good development prospect.Carbon dioxide-epoxy propane copolymer is with carbon dioxide and expoxy propane as Material synthesis
Environmentally-friendly plastic, (Makromol.Chem., 1969,130,210), receive much concern always since its appearance.Such as, with regard to synthesis
Catalyst system and catalyzing used by carbon dioxide-epoxy propane copolymer, various countries scientist develop ZnEt in succession2- many proton compounds
System, rare-earth ternary system, phenol epoxide zinc system, beta diimine system, Salen systems etc., and achieve certain success.
The sixties in last century, AM General rubber for tire company find that double metal cyanide (DMC) efficiently can be urged first
Change epoxide homopolymerization, and the performance of gained polyethers such as low-unsaturation-degree and narrow molecular weight distribution etc., hence it is evident that better than traditional KOH
Catalyst.1985, Kuyper research groups used Zn first3[Fe(CN)6]2Catalysis carbon dioxide and epoxide combined polymerization, its
In, polymerization temperature is 35 DEG C, and polymerization time is more than 48 hours, catalytic efficiency only 44g polymer/g catalyst, cyclic carbonate
Content is 16% (US 4500704).Pass through to improve the catalysis activity of DMC catalysts itself, Coates etc.
In replacing, boundary and extraneous metal, develop two-dimentional DMC catalysts (CoNi (CN)4), the catalyst system and catalyzing catalytic polymerization
When generate without cyclic side products, but carbonate content relatively low (～25%) in gained copolymer, catalysis activity are～370g polymerizations
Thing/g catalyst (Dalton Trans., 2006,5390-5393).
Carbon dioxide-epoxide combined polymerization is carried out using above-described double metal cyanide, resulting copolymerization is produced
Thing can not take into account high carbon acid ester units content and low cyclic carbonate ester content and catalyst activity is not high.
The content of the invention
In view of this, the application provides a kind of co-precipitation type DMC catalysts, its preparation method and its application,
The catalyst that the application is provided has higher catalysis activity and more excellent selectivity of product, can make epoxide and carbon dioxide
The carbonate unit content of copolymerization product is high and cyclic carbonate ester content is low.
The present invention provides a kind of co-precipitation type DMC catalysts, with 1 formula of formula：
M1 a[M3(CN)c(A1)d]r·q{M2 b[M4(CN)e(A2)f]g}·hM1 iX1 j·kM2 lX2 m·nH2O·pL
Formula 1；
In formula 1, M1、M2、M3And M4Independently selected from the metal ion of bivalence, trivalent or multivalence；
A1For M3First in boundary's part, A2For M4Second in boundary's part；
X1For M1The first micromolecular water soluble ligand, X2For M2The second micromolecular water soluble ligand；
L is water soluble compound；
A, b, c, e, g and r are positive integer, and q is positive number, and d, f, h, i, j, k, l, m, n and p are independently selected from zero or just
Number, and whole catalyst molecule is in electric neutrality.
Preferably, M1、M2、M3And M4Independently selected from the first subgroup, the second subgroup, the 5th subgroup, the 6th subgroup, the 7th
Metal ion in subgroup, the 3rd main group and the 4th main group.
Preferably, A1And A2Independently selected from halogen ion, OH-、SO4 2-、SO3 2-、CO3 2-、CN-、NO3-、N3 -Or SCN-。
Preferably, X1And X2Independently selected from halogen ion, OH-、SO4 2-、SO3 2-、CO3 2-、CN-Or NO3-。
Preferably, L is water miscible alcohol, aldehyde, ether, carboxylic acid, amide, carboxylate, polyester, polyethers or Merlon.
Preferably, d and f is independently selected from 0,1 or 2；
a：R=(1～4)：1, b：G=(1～4)：1, i：J=(1～6)：1, l：M=(1～6)：1, a：H=(0.1～
4)：1, b：K=(0.1～4)：1, a：Q=(0.1～10)：1.
Preferably, the catalyst has any one formula in 2～5 formula of formula：
Zn3[Co(CN)6]2·0.85Co3[Co(CN)6]2·0.14ZnCl2·0.09CoCl2·1.68H2O·0.97t-
BuOH
Formula 2；
Zn3[Co(CN)6]2·4.52Zn3[Fe(CN)6]2·2.27ZnCl2·1.27H2O·0.85EGME
Formula 3；
ZnNi(CN)4·3.43CoNi(CN)4·0.15Zn(NO3)2·3.98CoSO4·1.36H2O·1.25PEG
Formula 4；
Cd3[Co(CN)5Br]2·0.15CdNi(CN)4·3.15CdSO4·1.83H2O·2.10DMF
Formula 5.
The present invention provides a kind of preparation method of co-precipitation type DMC catalysts, comprises the following steps：
Ligand substance is reacted in aqueous with central element material, it is separated, obtain co-precipitation type bimetallic
Cyanide catalyst；
The ligand substance includes that formula is M1 iX1 jThe first metal ligand compound, formula be M2 lX2 mThe second metal
Ligand compound and water soluble compound；
The central element material includes that formula is M3(CN)c(A1)dThe first metal center molecular compound and formula be
M4(CN)e(A2)fThe second metal center molecular compound；
The sedimentation type DMC catalysts have 1 formula of formula：
M1 a[M3(CN)c(A1)d]r·q{M2 b[M4(CN)e(A2)f]g}·hM1 iX1 j·kM2 lX2 m·nH2O·pL
Formula 1；
In formula 1, M1、M2、M3And M4Independently selected from the metal ion of bivalence, trivalent or multivalence；
A1For M3First in boundary's part, A2For M4Second in boundary's part；
X1For M1The first micromolecular water soluble ligand, X2For M2The second micromolecular water soluble ligand；
L is water soluble compound；
A, b, c, e, g and r are positive integer, and q is positive number, and d, f, h, i, j, k, l, m, n and p are independently selected from zero or just
Number, and whole catalyst molecule is in electric neutrality.
Preferably, after isolated crude product, also include：
The crude product is carried out into slurrying with the aqueous solution and the water soluble compound of the water soluble compound successively
Washing, is precipitated product；
The precipitated product is dried under vacuum to into constant weight, then inflatable body is processed under vacuum, the gas is selected from
Argon, nitrogen or carbon dioxide, obtain co-precipitation type DMC catalysts.
The present invention provides a kind of preparation method of carbon dioxide-epoxide co-polymer, comprises the following steps：
Under conditions of catalyst is present, carbon dioxide and epoxide are carried out into polyreaction, carbon dioxide-ring is obtained
Oxide block copolymer；
The catalyst is catalyst mentioned above.
The present invention adopts two kinds of metal center molecular compounds, with the ligand substance including metal ligand compound by altogether
The sedimentation method, prepare the co-precipitation type DMC catalysts with 1 formula of formula.Many metals in the catalyst it
Between synergism, break mutually lattice structure, the advantage of two kinds of metal center molecular compounds can be combined, with higher
Catalysis activity and more excellent selectivity of product.Using the catalyst carbon dioxide and epoxide combined polymerization, can carry
The carbonate unit content of high copolymerization product, and reduce cyclic carbonate ester content, so as to improve the performance of copolymerization product, beneficial to should
With.
Specific embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment
Only a part of embodiment of the invention, rather than the embodiment of whole.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment obtained under the premise of creative work is not made by art personnel, belongs to the model of present invention protection
Enclose.
The invention provides a kind of co-precipitation type DMC catalysts, with 1 formula of formula：
M1 a[M3(CN)c(A1)d]r·q{M2 b[M4(CN)e(A2)f]g}·hM1 iX1 j·kM2 lX2 m·nH2O·pL
Formula 1；
In formula 1, M1、M2、M3And M4Independently selected from the metal ion of bivalence, trivalent or multivalence；
A1For M3First in boundary's part, A2For M4Second in boundary's part；
X1For M1The first micromolecular water soluble ligand, X2For M2The second micromolecular water soluble ligand；
L is water soluble compound；
A, b, c, e, g and r are positive integer, and q is positive number, and d, f, h, i, j, k, l, m, n and p are independently selected from zero or just
Number, and whole catalyst molecule is in electric neutrality.
The co-precipitation type DMC catalysts that the present invention is provided have new performance, i.e. catalysis activity and product choosing
Selecting property etc. more preferably, can be preferably applied to carbon dioxide-epoxide combined polymerization.
In the present invention, the co-precipitation type DMC catalysts have 1 formula of formula.In formula 1, M1And M2For outer
Boundary's metal, M3And M4For interior boundary's metal；M1、M2、M3And M4Independently selected from the metal ion of bivalence, trivalent or multivalence, M1、M2、M3
And M4First subgroup, the second subgroup, the 5th subgroup, the 6th subgroup, the 7th subgroup, the 3rd main group and the 4th master preferably are selected from independently
Metal ion in race.In a preferred embodiment of the invention, M1、M2、M3And M4Such as Zn2+、Fe2+、Fe3+、Co2+、Co3+、Ni2+、
Sn2+、Sn4+、Pb2+、Mo4+、Mo6+、Al3+、V4+、V5+、Sr2+、W4+、W6+、Cr2+、Cr3+、Cd2+、Cu2+、Mn2+、Mn3+Deng.
In the present invention, M1、M2、M3And M4Can be with identical, it is also possible to different.In embodiments of the present invention, when only a kind of
During extraneous metal, interior boundary's metal will at least have two kinds；When a kind of only interior boundary's metal, extraneous metal will at least have two kinds；Or
Zhe Nei circle, extraneous metal have two kinds simultaneously.That is, at least while there are three kinds or four kinds of metals in this four metal ions
Ion.In one embodiment of the invention, M1For Zn2+, M2For Co2+, M3And M4It is Co3+.In an enforcement of the present invention
In example, M1And M2It is Zn2+, M3For Co3+, M4For Fe3+.In another embodiment of the present invention, M1For Zn2+, M2For Co2+, M3
And M4For Ni2+。
In formula 1, CN-For M3And M4Part, A1For M3First in boundary's part, A2For M4Second in boundary match somebody with somebody
Body.As with M3Or M4Interior boundary's part of metallic ion coordination, A1And A2Can be the monodentate or bidentate ligand of small molecule；A1And A2
Halogen ion, OH preferably are selected from independently-、SO4 2-、SO3 2-、CO3 2-、CN-、NO3-、N3 -Or SCN-.In the present invention, interior boundary's part A1
And A2Can be with identical, it is also possible to different.In one embodiment of the invention, A1And A2It is Br-。
In formula 1, X1For M1The first micromolecular water soluble ligand, X2For M2The second micromolecular water soluble ligand.At this
In invention, X1And X2For micromolecular water soluble ligand, can be with identical, it is also possible to different；X1And X2Independently preferably be selected from halogen ion,
OH-、SO4 2-、SO3 2-、CO3 2-、CN-Or NO3-.In one embodiment of the invention, X1And X2It is Cl-.The one of the present invention
In individual embodiment, X1For NO3-, X2For SO4 2-。
In formula 1, water (H2O it is) part.L is the water soluble compound of macromole or small molecule, preferably water miscible
Alcohol, aldehyde, ether, carboxylic acid, amide, carboxylate, polyester, polyethers or Merlon are more preferably rudimentary unitary saturated alcohols, methyl ether, low
Level amide, the polyethers that molecular weight is 200～600.In a preferred embodiment of the invention, water soluble compound L is selected from the tert-butyl alcohol
(t-BuOH), ethylene glycol monomethyl ether (EGME) or N,N-dimethylformamide (DMF).
In formula 1, a, b, c, e, g and r are positive integer, and q is positive number, d, f, h, i, j, k, l, m, n and p independence
Ground is selected from zero or positive number, and whole catalyst molecule is in electric neutrality.In a preferred embodiment of the invention, d and f independently selected from
0th, 1 or 2.In a preferred embodiment of the invention, a：R=(1～4)：1, b：G=(1～4)：1, i：J=(1～6)：1, l：M=
(1～6)：1, a：H=(0.1～4)：1, b：K=(0.1～4)：1, a：Q=(0.1～10)：1.
In embodiments of the present invention, corresponding extraneous metal ions M1、M2Mole summation and interior boundary's metal ions M3、M4
The ratio of mole summation is preferably 1：1～20：1, more preferably 5：1～10：1.In embodiments of the present invention, interior boundary's metal ions M3
With M4Between mol ratio can be 1：1～10：1；Extraneous metal ions M1With M2Between mol ratio can be 1：1～10：1.
In a preferred embodiment of the invention, the catalyst has any one formula in 2～5 formula of formula：
Zn3[Co(CN)6]2·0.85Co3[Co(CN)6]2·0.14ZnCl2·0.09CoCl2·1.68H2O·0.97t-
BuOH
Formula 2；
Zn3[Co(CN)6]2·4.52Zn3[Fe(CN)6]2·2.27ZnCl2·1.27H2O·0.85EGME
Formula 3；
ZnNi(CN)4·3.43CoNi(CN)4·0.15Zn(NO3)2·3.98CoSO4·1.36H2O·1.25PEG
Formula 4；
Cd3[Co(CN)5Br]2·0.15CdNi(CN)4·3.15CdSO4·1.83H2O·2.10DMF
Formula 5.
Accordingly, it is the invention provides a kind of preparation method of co-precipitation type DMC catalysts including following
Step：
Ligand substance is reacted in aqueous with central element material, it is separated, obtain co-precipitation type bimetallic
Cyanide catalyst；
The ligand substance includes that formula is M1 iX1 jThe first ligand compound, formula be M2 lX2 mLigands chemical combination
Thing and water soluble compound；
The central element material includes that formula is M3(CN)c(A1)dThe first central element compound and formula be M4
(CN)e(A2)fThe second central element compound；
The sedimentation type DMC catalysts have 1 formula of formula：
M1 a[M3(CN)c(A1)d]r·q{M2 b[M4(CN)e(A2)f]g}·hM1 iX1 j·kM2 lX2 m·nH2O·pL
Formula 1；
In formula 1, M1、M2、M3And M4Independently selected from the metal ion of bivalence, trivalent or multivalence；
A1For M3First in boundary's part, A2For M4Second in boundary's part；
X1For M1The first micromolecular water soluble ligand, X2For M2The second micromolecular water soluble ligand；
L is water soluble compound；
A, b, c, e, g and r are positive integer, and q is positive number, and d, f, h, i, j, k, l, m, n and p are independently selected from zero or just
Number, and whole catalyst molecule is in electric neutrality.
The metal cyanide catalyst of different activities is combined, advantage is combined together by coprecipitation by the present invention,
So as to prepare the co-precipitation type DMC catalysts with new capability.By urging that coprecipitation method of the present invention is obtained
Agent takes into account the advantage of multiple catalysts, such as has higher catalytic efficiency, higher CO2Fixed amount, using when make ring-type pair
Product assay is lower.
Ligand substance and water are preferably mixed by the embodiment of the present invention, obtain mixing salt solution, then molten to the salt-mixture
Liquid adds central element material aqueous solution, stirring to be reacted, then separates, is dried, and obtains co-precipitation type double metal cyanide and urges
Agent.
In the present invention, the ligand substance includes that formula is M1 iX1 jThe first ligand compound, formula be M2 lX2 m
Two ligand compounds and water soluble compound.For first, second ligand compound, M1And M2Independently selected from bivalence, trivalent or
The metal ion of multivalence, M1And M2Independently preferably be selected from the first subgroup, the second subgroup, the 5th subgroup, the 6th subgroup, the 7th subgroup,
Metal ion in 3rd main group and the 4th main group.In a preferred embodiment of the invention, M1And M2Such as Zn2+、Fe2+、Fe3+、Co2 +、Co3+、Ni2+、Sn2+、Sn4+、Pb2+、Mo4+、Mo6+、Al3+、V4+、V5+、Sr2+、W4+、W6+、Cr2+、Cr3+、Cd2+、Cu2+、Mn2+、
Mn3+Deng.M1And M2Can be with identical, it is also possible to different；In one embodiment of the invention, M1For Zn2+, M2For Co2+.At this
In bright one embodiment, M1And M2It is Zn2+.In one embodiment of the invention, M1For Zn2+, M2For Co2+。
For first, second ligand compound, X1For M1The first micromolecular water soluble ligand, X2For M2Second little point
Sub- water soluble ligand.In the present invention, X1And X2For micromolecular water soluble ligand, can be with identical, it is also possible to different；X1And X2Solely
Halogen ion, OH preferably are selected from the spot-、SO4 2-、SO3 2-、CO3 2-、CN-Or NO3-.In one embodiment of the invention, X1And X2It is
Cl-.In one embodiment of the invention, X1For NO3-, X2For SO4 2-。
Also, in the present invention, i, j, l and m be independently selected from zero or positive number, and whole ligand compound molecules are in electricity
Property.In a preferred embodiment of the invention, i：J=(1～6)：1, l：M=(1～6)：1.In one embodiment of the invention,
First ligand compound is ZnCl2, Ligands compound is CoCl2.In one embodiment of the invention, first and second
Ligand compound is ZnCl2.In another embodiment of the present invention, the first ligand compound is Zn (NO3)2, Ligands
Compound is CoSO4。
For the water soluble compound in ligand substance, which is represented with L, and L is the water solublity chemical combination of macromole or small molecule
Thing, preferably water miscible alcohol, aldehyde, ether, carboxylic acid, amide, carboxylate, polyester, polyethers or Merlon, more preferably rudimentary one
First saturated alcohols, methyl ether, rudimentary amide, the polyethers that molecular weight is 200～600.In a preferred embodiment of the invention, water solublity
Compound L is selected from the tert-butyl alcohol (t-BuOH), ethylene glycol monomethyl ether (EGME) or N,N-dimethylformamide (DMF).
With ligand substance and water as part, hybrid mode routinely is mixed (salt) solution to the present invention.The present invention is excellent
The mixing salt solution is warming up to 20 DEG C～80 DEG C and is incubated by choosing；In one embodiment of the invention, will preferably mix molten
Liquid constant temperature is 50 DEG C.
After obtaining the mixed solution of the first ligand compound, Ligands compound, water and water soluble compound, the present invention
Embodiment preferably Deca central element material aqueous solution thereto, is reacted, co-precipitation type bimetallic cyaniding is obtained after separation
Thing catalyst.
In the present invention, the central element material includes that formula is M3(CN)c(A1)dThe first central element compound
It is M with formula4(CN)e(A2)fThe second central element compound.For first, second central element compound, M3And M4It is independent
Metal ion of the ground selected from bivalence, trivalent or multivalence, M3And M4Independently preferably be selected from the first subgroup, the second subgroup, the 5th subgroup,
Metal ion in 6th subgroup, the 7th subgroup, the 3rd main group and the 4th main group.In a preferred embodiment of the invention, M3And M4
Such as Zn2+、Fe2+、Fe3+、Co2+、Co3+、Ni2+、Sn2+、Sn4+、Pb2+、Mo4+、Mo6+、Al3+、V4+、V5+、Sr2+、W4+、W6+、Cr2+、
Cr3+、Cd2+、Cu2+、Mn2+、Mn3+Deng.In the present invention, M3And M4Can be with identical, it is also possible to different.In a reality of the present invention
Apply in example, M3And M4It is Co3+.In one embodiment of the invention, M3For Co3+, M4For Fe3+.The present invention another
In embodiment, M3And M4For Ni2+。
For first, second central element compound, CN-For M3And M4Part, A1For M3First in boundary's part, A2For
M4Second in boundary's part.As with M3Or M4Interior boundary's part of metallic ion coordination, A1And A2Can be small molecule monodentate or
Bidentate ligand；A1And A2Halogen ion, OH preferably are selected from independently-、SO4 2-、SO3 2-、CO3 2-、CN-、NO3-、N3 -Or SCN-.In the present invention
In, interior boundary's part A1And A2Can be with identical, it is also possible to different.In one embodiment of the invention, A1And A2It is Br-。
Also, in the present invention, c and e are positive integer, d and f is independently selected from zero or positive number, and whole central element
Compound molecule is in electric neutrality.In a preferred embodiment of the invention, d and f is independently selected from 0,1 or 2.In the enforcement of the present invention
In example, the central element material is used generally in the form of water soluble salt, such as potassium salt, sodium salt etc..In a reality of the present invention
Apply in example, the first and second central element compounds are K3[Co(CN)6].In one embodiment of the invention, the first center
Molecular compound is K3[Co(CN)6], the second central element compound is K3[Fe(CN)6].In an alternative embodiment of the invention
In, the first and second central element compounds are K2[Ni(CN)4].In another embodiment of the present invention, the first center point
Sub- compound is K3[Co(CN)5Br], the second central element compound is K2[Pt(CN)4]。
In the present invention, first, second ligand compound can provide extraneous metal, first, second center point
Sub- compound can provide interior boundary's metal；That is, M1And M2For extraneous metal, M3And M4For interior boundary's metal.In embodiments of the present invention,
When a kind of only extraneous metal, interior boundary's metal will at least have two kinds；When a kind of only interior boundary's metal, extraneous metal at least will
There are two kinds；Or interior boundary, extraneous metal have two kinds simultaneously.For the ligand compound in the embodiment of the present invention, central element
Compound, M1、M2Mole summation and M3、M4The ratio of mole summation is preferably 1：1～20：1, more preferably 5：1～10：1.At this
In inventive embodiments, M3With M4Between mol ratio can be 1：1～10：1；M1With M2Between mol ratio can be 1：1～10：1.
Embodiment of the present invention Deca is reacted by the mixed liquor that central element material and water are constituted, and rate of addition can be
0.2mL/min～0.5mL/min；The process usual used time of whole Deca is 1.5 hours～2.5 hours.The each original of present invention mixing
Material is carried out preferably under conditions of stirring, and the speed of stirring can be 500rpm.Also, water used by of the invention is preferably deionization
Water.The temperature reacted by the present invention is preferably 20 DEG C～80 DEG C, more preferably 30 DEG C～60 DEG C.The embodiment of the present invention is dripped
Cheng Hou, can continue to stir under the rotating speed of 500rpm, react 2 hours～3 hours.
The reactant that reaction is obtained is separated by the embodiment of the present invention, obtains co-precipitation type double metal cyanide-catalyzed
Agent.In the present invention, described separation is preferably centrifugation；The embodiment of the present invention can separate 30 points under the rotating speed of 5000rpm
Clock～40 minute, are precipitated thing.
Gained sediment is crude product, after the isolated crude product of the embodiment of the present invention, is preferably also included：Will be described thick
Product carries out slurrying with the aqueous solution and the water soluble compound of the water soluble compound successively and washs, then separates, is dried,
It is precipitated product.
In the present invention, it is preferably 3～10 times with the number of times of the solution washing of the water soluble compound.In the present invention
One embodiment in, the volume ratio of the water soluble compound and water is followed successively by 30/30,36/24,42/18,48/12,54/
6.The slurrying washing is carried out preferably under conditions of stirring, and the speed of the stirring can be 60rpm～100rpm, preferably
70rpm～90rpm；The time that slurrying is washed every time is preferably 0.5 hour～1 hour.In embodiments of the present invention, each slurrying
After washing, can Jing 5000rpm centrifugation 30 minutes～40 minutes, remove cleaning mixture, be precipitated product.
After being precipitated product, the present invention preferably also includes：The precipitated product is dried under vacuum to into constant weight, then true
Under empty condition, inflatable body is processed, and the gas is selected from argon, nitrogen or carbon dioxide, obtains co-precipitation type double metal cyanide and urges
Agent.
In the present invention, the vacuum drying temperature is preferably 50 DEG C～60 DEG C.The embodiment of the present invention can be by after constant weight
Product be sub-packed in ampere bottle again, applying argon gas (Ar), nitrogen (N under vacuum2) or carbon dioxide (CO2) process, obtain
Co-precipitation type DMC catalysts.In one embodiment of the invention, the vacuum condition includes：It is true at 50 DEG C
It is empty to 20Pa～40Pa.In the present invention, the purity of the gas is 99.99%.It is little that the time of inflatable body process is preferably 48
When～60 hours, more preferably 50 hours～55 hours.Also, in embodiment of the present invention processing procedure, fill Ar, N2Or CO2It is more than
24 times, gained final product can above-mentioned gas protection under sealing preserve.
After obtaining final product, the embodiment of the present invention carries out atomic absorption spectroscopy to which.The final product is common
Sedimentation type DMC catalysts, which has 1 formula of formula：
M1 a[M3(CN)c(A1)d]r·q{M2 b[M4(CN)e(A2)f]g}·hM1 iX1 j·kM2 lX2 m·nH2O·pL
Formula 1；
In formula 1, M1、M2、M3And M4Independently selected from the metal ion of bivalence, trivalent or multivalence；
A1For M3First in boundary's part, A2For M4Second in boundary's part；
X1For M1The first micromolecular water soluble ligand, X2For M2The second micromolecular water soluble ligand；
L is water soluble compound；
A, b, c, e, g and r are positive integer, and q is positive number, and d, f, h, i, j, k, l, m, n and p are independently selected from zero or just
Number, and whole catalyst molecule is in electric neutrality.
In formula 1, a, b, c, e, g and r are positive integer, and q is positive number, d, f, h, i, j, k, l, m, n and p independence
Ground is selected from zero or positive number, and whole catalyst molecule is in electric neutrality.In a preferred embodiment of the invention, d and f independently selected from
0th, 1 or 2.In a preferred embodiment of the invention, a：R=(1～4)：1, b：G=(1～4)：1, i：J=(1～6)：1, l：M=
(1～6)：1, a：H=(0.1～4)：1, b：K=(0.1～4)：1, a：Q=(0.1～10)：1.
Co-precipitation type DMC catalysts prepared by the present invention can be used to be catalyzed CO2With epoxide copolymerization, system
It is standby to obtain Merlon.Thus, present invention also offers a kind of preparation method of carbon dioxide-epoxide co-polymer, including
Following steps：
Under conditions of catalyst is present, carbon dioxide and epoxide are carried out into polyreaction, carbon dioxide-ring is obtained
Oxide block copolymer；The catalyst is catalyst mentioned above.
In polymerization autoclave, the embodiment of the present invention is preferably in CO2Under protection, inject a certain amount of by co-precipitation type bimetallic
The catalyst suspension of cyanide catalyst and epoxide composition, reinjects thereafter the epoxide, rapidly under agitation,
CO is filled with by the supply line with pressure adjusting function into kettle2, polyreaction is carried out, carbon dioxide-epoxide is obtained
Copolymer.
In an embodiment of the present invention, the polymerization autoclave preferably carries out pretreatment, and the pretreatment includes：First take out true
Empty is 20Pa～40Pa, then fills CO2Process 4 hours～8 hours, fill CO altogether210～15 times.Also, the temperature of the pretreatment is excellent
Elect 85 DEG C～95 DEG C as.After the polymerization autoclave is cooled to room temperature, in CO2Protection is lower to add each material.In the present invention, institute
Use CO2Purity it is general all 99.99%.
In the present invention, the epoxide is compound well-known in the art, and preferably epoxyalkane, epoxy take
For alkane, shrink ether compound, one or more aoxidized in cycloolefins and styrene oxide, more preferably epoxy C2～8
Alkane, epoxy halo C2～8 alkane, glycidyl ether, cyclopentene oxide, cyclohexene oxide (7-oxa-bicyclo[4.1.0) and Oxybenzene second
One or more in alkene.In an embodiment of the present invention, the epoxide is expoxy propane, 7-oxa-bicyclo[4.1.0,1,2- rings
Oxygen butane or epoxychloropropane.
In the present invention, the catalyst is co-precipitation type DMC catalysts, itself and content mentioned above
Unanimously, will not be described here.The consumption of the catalyst is typically catalyzed in every milliliter of epoxide of 0.05 gram of catalyst to 0.2 gram
Between every milliliter of epoxide of agent.Catalyst and epoxide can be formed catalyst suspension by the embodiment of the present invention, reinject
In polymeric kettle.In one embodiment of the invention, in the catalyst suspension, the consumption of catalyst and epoxide is
0.1 gram of catalyst is dissolved in 50 milliliters of epoxide.
The embodiment of the present invention can be filled with CO into polymerization reaction kettle under stirring of the speed for 500rpm2, make pressure in kettle
Reach 3.5MPa～5MPa, be preferably 4MPa～4.5MPa, polyreaction is carried out with the epoxide of 50mL～200mL.It is described
, preferably under constant pressure and continuous stirring, such as speed is to carry out under the stirring of 500rpm for polyreaction.The temperature of the polyreaction
Preferably 50 DEG C～120 DEG C, more preferably 70 DEG C～100 DEG C；The time that reaction is carried out continuously is preferably 3 hours～20 hours,
More preferably 5 hours～15 hours.
After polyreaction terminates, polymeric kettle can be cooled to room temperature by the embodiment of the present invention, discharge residual carbon dioxide, and will be poly-
The polymer with water that conjunction reaction is obtained settles out, then scrubbed, dry, obtains crude product carbon dioxide-epoxide co-polymer.
In the present invention, it is technological means commonly used in the art to go out polymer with water precipitating；The water used by polymer that settles out is preferred
For distilled water.Obtained polymer can carry out washing by soaking with distilled water, in one embodiment of the invention, washing by soaking time
Number is 3 times, and the time of each washing by soaking is 24 hours.Polymer after washing by soaking can be placed in 30 DEG C by the embodiment of the present invention
Vacuum drying oven in, be dried to constant weight, obtain carbon dioxide-epoxide co-polymer crude product.
The embodiment of the present invention takes out polymer crude product, using nuclear magnetic resonance, NMR1H NMR and gel permeation chromatography (GPC) are surveyed
Examination.As a result show, in gained copolymer, the weight content of cyclic carbonate is relatively low, carbonate unit content is higher.It is indicated above that
The catalyst that the application is provided has higher catalysis activity and more excellent selectivity of product, catalysis carbon dioxide and epoxide
Combined polymerization, can improve the performance of product, beneficial to application.
For a further understanding of the application, the co-precipitation type double metal cyanide provided to the application with reference to embodiment
Catalyst, its preparation method and its application are specifically described.
Embodiment 1
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 2.17g ZnCl2With 1.9g CoCl2·6H2O、
In the mixed solution of 60mL deionized waters and 30mL tert-butyl alcohols composition, Deca is by 1.33g K3[Co(CN)6] and 20mL deionized waters
The mixed solution of composition, whole Deca process used time are 1.5 hours, after being added dropwise to complete, continue the stirring for 500rpm in speed
Lower reaction 2 hours.
The reactant Jing 5000rpm centrifugations that reaction is obtained 30 minutes, gained sediment is crude product；In speed it is
Under the stirring of 60rpm, the crude product continuously with the tert-butyl alcohol/deionized water (V/V)=30/30,36/24,42/18,48/12,
54/6 mixed solution and the pure tert-butyl alcohol carry out slurrying washing, after each slurrying washing, 30 points of equal Jing 5000rpm centrifugations
Clock, removes cleaning mixture, and each slurrying is washed 0.5 hour, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the N that purity is 99.99% to 20Pa2Process 48 hours, in processing procedure, inflatable body is more than 24 times, and gained is urged
Agent final product is in N2The lower sealing preserve of protection, is designated as：DMC-1.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
2 formula of formula：
Zn3[Co(CN)6]2·0.85Co3[Co(CN)6]2·0.14ZnCl2·0.09CoCl2·1.68H2O·0.97t-
BuOH
Formula 2.
Embodiment 2
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 5.44g ZnCl2, 60mL deionized waters and 30mL
In the mixed solution of EGME compositions, Deca is by 0.3g K3[Co(CN)6]、1g K3[Fe(CN)6] and 20mL deionized waters composition
Mixed solution, whole Deca process used time are 2.5 hours, after being added dropwise to complete, continue to react 2 under stirring of the speed for 500rpm
Hour.
The reactant Jing 5000rpm centrifugations that reaction is obtained 40 minutes, gained sediment is crude product；In speed it is
Under the stirring of 100rpm, the continuous spent glycol monomethyl ether/deionized water (V/V)=30/30 of the crude product, 36/24,42/18,
48/12nd, 54/6 mixed solution and pure glycol monoethyl ether carry out slurrying washing, after each slurrying washing, equal Jing 5000rpm from
The heart is separated 40 minutes, removes cleaning mixture, and each slurrying is washed 1.0 hours, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the CO that purity is 99.99% to 40Pa2Process 60 hours, in processing procedure, inflatable body is more than 24 times, and gained is urged
Agent final product is in CO2The lower sealing preserve of protection, is designated as：DMC-2.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
3 formula of formula：
Zn3[Co(CN)6]2·4.52Zn3[Fe(CN)6]2·2.27ZnCl2·1.27H2O·0.85EGME
Formula 3.
Embodiment 3
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 0.07g Zn (NO3)2、0.56g CoSO4, 60mL goes
In the mixed solution of ionized water and 30mL PEG-400 compositions, Deca is by 1g K2Ni(CN)4It is mixed with 20mL deionized waters composition
Solution is closed, the whole Deca process used time is 2 hours, after being added dropwise to complete, continue the reaction 2 under stirring of the speed for 500rpm little
When.
The reactant Jing 5000rpm centrifugations that reaction is obtained 35 minutes, gained sediment is crude product；In speed it is
Under the stirring of 80rpm, the crude product continuously with PEG-400/ deionized waters (V/V)=30/30,36/24,42/18,48/12,
54/6 mixed solution and pure PEG-400 carry out slurrying washing, after each slurrying washing, 35 points of equal Jing 5000rpm centrifugations
Clock, removes cleaning mixture, and each slurrying is washed 0.5 hour, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum is filled the Ar that purity is 99.99% and is processed 50 hours to 40Pa, and in processing procedure, inflatable body is more than 24 times, and gained is urged
Agent final product sealing preserve under Ar protections, is designated as：DMC-3.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
4 formula of formula：
ZnNi(CN)4·3.43CoNi(CN)4·0.15Zn(NO3)2·3.98CoSO4·1.36H2O·1.25PEG
Formula 4.
Embodiment 4
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 27.4g CdSO4·6H2O, 60mL deionized water and
In the mixed solution of 30mL DMF compositions, Deca is by 1.4g K3[Co(CN)5Br]、0.14g K2Pt(CN)4With 20mL deionizations
The mixed solution of water composition, the whole Deca process used time is 2.5 hours, after being added dropwise to complete, continues the stirring for 500rpm in speed
Mix lower reaction 2 hours.
The reactant Jing 5000rpm centrifugations that reaction is obtained 30 minutes, gained sediment is crude product；In speed it is
Under the stirring of 90rpm, the crude product continuously with DMF/deionized water (V/V)=30/30,36/24,42/
18th, 48/12,54/6 mixed solution and pure DMF carry out slurrying washing, after each slurrying washing, equal Jing
5000rpm centrifugations 40 minutes, remove cleaning mixture, and each slurrying is washed 1.0 hours, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the N that purity is 99.99% to 30Pa2Process 48 hours, in processing procedure, inflatable body is more than 24 times, and gained is urged
Agent final product is in N2The lower sealing preserve of protection, is designated as：DMC-4.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
5 formula of formula：
Cd3[Co(CN)5Br]2·0.15CdNi(CN)4·3.15CdSO4·1.83H2O·2.10DMF
Formula 5.
Embodiment 5
Under conditions of temperature is 90 DEG C, it is 20Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 8 hours, fill CO altogether210 times, after the polymerization autoclave is cooled to room temperature, in CO2(purity is 99.99%) is protected
Under, the catalyst suspension being made up of 10mg catalyst DMC-1 and 50mL expoxy propane is injected, 50mL epoxies third are reinjected thereafter
Alkane, rapidly under agitation (speed is 500rpm), is filled with CO by the supply line with pressure adjusting function into kettle2, make kettle
Interior pressure reaches 4.0MPa, and polyreaction is carried out 4 hours under the continuous stirring in 4.0MPa constant pressures and speed for 500rpm, is polymerized
Temperature is 80 DEG C.
After polyreaction terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and it is poly- to be settled out with 1000mL distilled water
Compound, obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion is put
In 30 DEG C of vacuum drying ovens, it is dried to constant weight, obtains 32g carbon dioxide-epoxide co-polymer crude product.
The present invention takes out crude product to be used for1H NMR and GPC are tested, and are as a result shown, the cyclic carbonate produced by copolymer
Weight content be 5%, in copolymer carbonate unit content be 38%；Catalytic efficiency is 3.2kg polymer/g.DMC-1；Mn
=120000g/mol, PDI=3.7.Referring also to table 1, table 1 is prepared by the embodiment of the present invention and comparative example to partial test result
The performance of carbon dioxide-epoxide co-polymer.
Embodiment 6
Under conditions of temperature is 90 DEG C, it is 30Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 4 hours, fill CO altogether215 times, after the polymerization autoclave is cooled to room temperature, in CO2(purity is 99.99%) is protected
Under, the catalyst suspension being made up of 10mg catalyst DMC-2 and 50mL 7-oxa-bicyclo[4.1.0s is injected, 50mL epoxies are reinjected thereafter
Hexamethylene, rapidly under agitation (speed is 500rpm), is filled with CO by the supply line with pressure adjusting function into kettle2,
Pressure in kettle is made to reach 3.0MPa, polyreaction is carried out 8 hours under the continuous stirring in 3.0MPa constant pressures and speed for 500rpm,
Polymerization temperature is 90 DEG C.
After polyreaction terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and it is poly- to be settled out with 1000mL distilled water
Compound, obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion is put
In 30 DEG C of vacuum drying ovens, it is dried to constant weight, obtains 11g carbon dioxide -7-oxa-bicyclo[4.1.0 copolymer crude product.
The present invention takes out crude product to be used for1H NMR and GPC are tested, and are as a result shown, the cyclic carbonate produced by copolymer
Weight content be 0.5%, in copolymer carbonate unit content be 88%；Catalytic efficiency is 1.1kg polymer/g.DMC-2；
Mn=54000g/mol, PDI=4.3.Partial test result is referring also to table 1.
Embodiment 7
Under conditions of temperature is 90 DEG C, it is 40Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 6 hours, fill CO altogether212 times, after polymerization autoclave is cooled to room temperature, in CO2Under (purity is 99.99%) protection, note
Enter by 10mg catalyst DMC-3 and 50mL 1, the catalyst suspension of 2- epoxy butanes composition, reinject thereafter 50mL 1,2-
Epoxy butane, rapidly under agitation (speed is 500rpm), is filled with into kettle by the supply line with pressure adjusting function
CO2, make pressure in kettle reach 2.0MPa, polyreaction carries out 14 under the continuous stirring in 2.0MPa constant pressures and speed for 500rpm
Hour, polymerization temperature is 110 DEG C.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and is settled out polymerization with 1000mL distilled water
Thing, obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion is in 30 DEG C
Under, be dried to constant weight in vacuum drying oven, obtain 6g carbon dioxide-epoxy butane copolymer crude product.
The present invention takes out crude product to be used for1H NMR and GPC are tested, and are as a result shown, the cyclic carbonate produced by copolymer
Weight content be 0, in copolymer carbonate unit content be 69%, catalytic efficiency be 0.6kg polymer/g.DMC-3, Mn=
4000g/mol, PDI=5.3.Partial test result is referring also to table 1.
Embodiment 8
Under conditions of temperature is 90 DEG C, it is 30Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 6 hours, fill CO altogether210 times, after polymerization autoclave is cooled to room temperature, in CO2Under (purity is 99.99%) protection, note
Enter the catalyst suspension being made up of 10mg catalyst DMC-3 and 50mL epoxychloropropane, reinject thereafter 50mL epoxy chloropropionates
Alkane, rapidly under agitation (speed is 500rpm), is filled with CO by the supply line with pressure adjusting function into kettle2, make kettle
Interior pressure reaches 5.0MPa, and polyreaction is carried out 20 hours under the continuous stirring in 5.0MPa constant pressures and speed for 500rpm, gathered
It is 90 DEG C to close temperature.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 25g carbon dioxide-epihalohydrin copolymer crude product.
The present invention takes out crude product to be used for1H NMR and GPC are tested, and are as a result shown, the cyclic carbonate produced by copolymer
Weight content be 5.3%, in copolymer carbonate unit content be 28%, catalytic efficiency be 2.5kg polymer/g.DMC-4,
Mn=13000g/mol, PDI=3.3.Partial test result is referring also to table 1.
Comparative example 1
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 3.26g ZnCl2, 60mL deionized waters and uncle 30mL
In the mixed solution of butanol composition, Deca is by 1.33g K3[Co(CN)6] with 20mL deionized waters composition mixed solution, entirely
The Deca process used time is 1.5 hours, after being added dropwise to complete, continues to react 2 hours under stirring of the speed for 500rpm.
The reactant Jing 5000rpm centrifugations that reaction is obtained 30 minutes, gained sediment is crude product；In speed it is
Under the stirring of 60rpm, the crude product continuously with the tert-butyl alcohol/deionized water (V/V)=30/30,36/24,42/18,48/12,
54/6 mixed solution and the pure tert-butyl alcohol carry out slurrying washing, after each slurrying washing, equal Jing 5000rpm centrifugations 30 minutes
Cleaning mixture is removed, each slurrying is washed 0.5 hour, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the N that purity is 99.99% to 20Pa2Process 48 hours, in processing procedure, inflatable body is more than 24 times, and gained is urged
Agent final product is in N2The lower sealing preserve of protection, is designated as：DMC-1’.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
2 ' formula of formula：
Zn3[Co(CN)6]2·0.17ZnCl2·1.87H2O1.24t-BuOH formulas 2 '.
Comparative example 2
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 5.71g CoCl2, 60mL deionized waters and uncle 30mL
In the mixed solution of butanol composition, Deca is by 1.33g K3[Co(CN)6] with 20mL deionized waters composition mixed solution, entirely
The Deca process used time is 1.5 hours, after being added dropwise to complete, continues to react 2 hours under stirring of the speed for 500rpm.
The reactant Jing 5000rpm centrifugations that reaction is obtained 30 minutes, gained sediment is crude product；In speed it is
Under the stirring of 60rpm, the crude product continuously with the tert-butyl alcohol/deionized water (V/V)=30/30,36/24,42/18,48/12,
54/6 mixed solution and the pure tert-butyl alcohol carry out slurrying washing, after each slurrying washing, 30 points of equal Jing 5000rpm centrifugations
Clock, removes cleaning mixture, and each slurrying is washed 0.5 hour, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the N that purity is 99.99% to 20Pa2Process 48 hours, in processing procedure, fill N2More than 24 times, gained catalyst
Final product is in N2The lower sealing preserve of protection.It is designated as：DMC-2’.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
Formula 2 " formula：
Co3[Co(CN)6]2·0.37CoCl2·2.08H2O1.02t-BuOH formulas 2 ".
Comparative example 3
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 5.44g ZnCl2, 60mL deionized waters and 30mL second
In the mixed solution of glycol monomethyl ether composition, Deca is by 1.32g K3[Fe(CN)6] molten with the mixing of 20mL deionized waters composition
Liquid, whole Deca process used time are 2.5 hours, after being added dropwise to complete, continue to react 2 hours under stirring of the speed for 500rpm.
The reactant Jing 5000rpm centrifugations that reaction is obtained 40 minutes, gained sediment is crude product；In speed it is
Under the stirring of 100rpm, the continuous spent glycol monomethyl ether/deionized water (V/V)=30/30 of the crude product, 36/24,42/18,
48/12nd, 54/6 mixed solution and pure glycol monoethyl ether carry out slurrying washing, after each slurrying washing, equal Jing 5000rpm from
The heart is separated 40 minutes, removes cleaning mixture, and each slurrying is washed 1.0 hours, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the CO that purity is 99.99% to 40Pa2Process 60 hours, in processing procedure, fill CO2More than 24 times, gained catalysis
Agent final product is in CO2The lower sealing preserve of protection, is designated as：DMC-3’.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
3 ' formula of formula：
Zn3[Fe(CN)6]2·0.19ZnCl2·1.68H2O1.31EGME formulas 3 '.
Comparative example 4
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 0.73g Zn (NO3)2, 60mL deionized waters and 30mL
In the mixed solution of PEG-400 compositions, Deca is by 1g K2Ni(CN)4With the mixed solution of 20mL deionized waters composition, whole drop
Plus the process used time is 2 hours, after being added dropwise to complete, continue to react 2 hours under stirring of the speed for 500rpm.
The reactant Jing 5000rpm centrifugations that reaction is obtained 35 minutes, gained sediment is crude product；In speed it is
Under the stirring of 80rpm, the crude product continuously with PEG-400/ deionized waters (V/V)=30/30,36/24,42/18,48/12,
54/6 mixed solution and pure PEG-400 carry out slurrying washing, after each slurrying washing, 35 points of equal Jing 5000rpm centrifugations
Clock, removes cleaning mixture, and each slurrying is washed 0.5 hour, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum is filled the Ar that purity is 99.99% and is processed 50 hours, fill Ar more than 24 times in processing procedure to 40Pa, gained catalysis
Agent final product sealing preserve under Ar protections, is designated as：DMC-4’.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
4 ' formula of formula：
ZnNi(CN)4·0.28Zn(NO3)2·1.28H2O1.07PEG formulas 4 '.
Comparative example 5
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 0.62g CoSO4, 60mL deionized waters and 30mL
In the mixed solution of PEG-400 compositions, Deca is by 1g K2Ni(CN)4With the mixed solution of 20mL deionized waters composition, whole drop
Plus the process used time is 2 hours, after being added dropwise to complete, continue to react 2 hours under stirring of the speed for 500rpm.
The reactant Jing 5000rpm centrifugations that reaction is obtained 35 minutes, gained sediment is crude product；In speed it is
Under the stirring of 80rpm, the crude product continuously with PEG-400/ deionized waters (V/V)=30/30,36/24,42/18,48/12,
54/6 mixed solution and pure PEG-400 carry out slurrying washing, after each slurrying washing, 35 points of equal Jing 5000rpm centrifugations
Clock, removes cleaning mixture, and each slurrying is washed 0.5 hour, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum is filled the Ar that purity is 99.99% and is processed 50 hours, fill Ar more than 24 times in processing procedure to 40Pa, gained catalysis
Agent final product sealing preserve under Ar protections, is designated as：DMC-5’.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
Formula 4 " formula：
CoNi(CN)4·0.78CoSO4·1.04H2O1.57PEG formulas 4 ".
Comparative example 6
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 30g CdSO4·6H2O, 60mL deionized water and
In the mixed solution of 30mL DMFs composition, Deca is by 1.54gK3[Co(CN)5Br] and 20mL deionized water groups
Into mixed solution, the whole Deca process used time be 2.5 hours, after being added dropwise to complete, continue speed for 500rpm stirring under
Reaction 2 hours.
The reactant Jing 5000rpm centrifugations that reaction is obtained 30 minutes, gained sediment is crude product；In speed it is
Under the stirring of 90rpm, the crude product continuously with DMF/deionized water (V/V)=30/30,36/24,42/
18th, 48/12,54/6 mixed solution and pure DMF carry out slurrying washing, after each slurrying washing, equal Jing
5000rpm centrifugations 40 minutes, remove cleaning mixture, and each slurrying is washed 1.0 hours, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the N that purity is 99.99% to 30Pa2Process 48 hours, in processing procedure, inflatable body is more than 24 times, and gained is urged
Agent final product is in N2The lower sealing preserve of protection, is designated as：DMC-6’.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
5 ' formula of formula：
Cd3[Co(CN)5Br]2·1.42CdSO4·1.57H2O1.35DMF formulas 5 '.
Comparative example 7
Under stirring of the speed for 500rpm, to 50 DEG C of constant temperature by 30g CdSO4·6H2O, 60mL deionized water and
In the mixed solution of 30mL DMFs composition, Deca is by 1.51g K2[Pt(CN)4] and 20mL deionized water groups
Into mixed solution, the whole Deca process used time be 2.5 hours, after being added dropwise to complete, continue speed for 500rpm stirring under
Reaction 2 hours.
The reactant Jing 5000rpm centrifugations that reaction is obtained 30 minutes, gained sediment is crude product；In speed it is
Under the stirring of 90rpm, the crude product continuously with DMF/deionized water (V/V)=30/30,36/24,42/
18th, 48/12,54/6 mixed solution and pure DMF carry out slurrying washing, after each slurrying washing, equal Jing
5000rpm centrifugations 40 minutes, remove cleaning mixture, and each slurrying is washed 1.0 hours, is precipitated product.
Gained precipitated product is dried under vacuum to constant weight at 50 DEG C, and the product after constant weight is sub-packed in ampere bottle again, 50
At DEG C, vacuum fills the N that purity is 99.99% to 30Pa2Process 48 hours, in processing procedure, inflatable body is more than 24 times, and gained is urged
Agent final product is in N2The lower sealing preserve of protection, is designated as：DMC-7’.
Atomic absorption spectroscopy is carried out to gained catalyst final product, analysis result is as follows, the catalyst has
Formula 5 " formula：
CoPt(CN)4·3.18CdSO4.·1.56H2O1.24DMF formulas 5 ".
Comparative example 8
Under conditions of temperature is 90 DEG C, it is 20Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 8 hours, fill CO altogether210 times, after the polymerization autoclave is cooled to room temperature, in CO2(purity is 99.99%) is protected
Under, the catalyst suspension being made up of 3mg catalyst DMC-1 ' and 50mL expoxy propane is injected, 50mL epoxies third are reinjected thereafter
Alkane, rapidly under agitation (speed is 500rpm), is filled with CO by the supply line with pressure adjusting function into kettle2, make kettle
Interior pressure reaches 4.0MPa, and polyreaction is carried out 4 hours under the continuous stirring in 4.0MPa constant pressures and speed for 500rpm, is polymerized
Temperature is 80 DEG C.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 144g carbon dioxide-epoxy propane copolymer crude products.
Taking out crude product is used for1H NMR and GPC are tested, and are as a result shown, the weight of the cyclic carbonate produced by copolymer
Content is 1.3%, and in copolymer, carbonate unit content is 40%, and catalytic efficiency is 48kg polymer/g.DMC-1 ', Mn=
121000g/mol, PDI=3.9.Partial test result is referring also to table 1.
Comparative example 9
Under conditions of temperature is 90 DEG C, it is 20Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 8 hours, fill CO altogether210 times, after the polymerization autoclave is cooled to room temperature, in CO2(purity is 99.99%) is protected
Under, the catalyst suspension being made up of 10mg catalyst DMC-2 ' and 50mL expoxy propane is injected, 50mL epoxies are reinjected thereafter
Propane, rapidly under agitation (speed is 500rpm), is filled with CO by the supply line with pressure adjusting function into kettle2, make
In kettle, pressure reaches 4.0MPa, and polyreaction is carried out 4 hours under the continuous stirring in 4.0MPa constant pressures and speed for 500rpm, gathered
It is 80 DEG C to close temperature.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 5g carbon dioxide-epoxy propane copolymer crude products.
Taking out crude product is used for1H NMR and GPC are tested, and are as a result shown, the weight of the cyclic carbonate produced by copolymer
Content is 7%, and in copolymer, carbonate unit content is 32%, and catalytic efficiency is 0.5kg polymer/g.DMC-2 ', Mn=
79000g/mol, PDI=3.1.Partial test result is referring also to table 1.
Comparative example 10
Under conditions of temperature is 90 DEG C, it is 30Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 4 hours, fill CO altogether215 times, after the polymerization autoclave is cooled to room temperature, in CO2(purity is 99.99%) is protected
Under, the catalyst suspension being made up of 50mg catalyst DMC-3 ' and 50mL 7-oxa-bicyclo[4.1.0s is injected, 50mL rings are reinjected thereafter
Oxygen hexamethylene, rapidly under agitation (speed is 500rpm), is filled with into kettle by the supply line with pressure adjusting function
CO2, make pressure in kettle reach 3.0MPa, polyreaction carries out 8 under the continuous stirring in 3.0MPa constant pressures and speed for 500rpm
Hour, polymerization temperature is 90 DEG C.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 3.5g carbon dioxide -7-oxa-bicyclo[4.1.0 copolymer crude product.
Taking out crude product is used for1H NMR and GPC are tested, and are as a result shown, the weight of the cyclic carbonate produced by copolymer
Content is 0.3%, and in copolymer, carbonate unit content is 90%, and catalytic efficiency is 0.07kg polymer/g.DMC-3 ', Mn=
41000g/mol, PDI=4.9.Partial test result is referring to table 1.
Comparative example 11
Under conditions of temperature is 90 DEG C, it is 40Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 6 hours, fill CO altogether212 times, after polymerization autoclave is cooled to room temperature, in CO2Under (purity is 99.99%) protection, note
Enter by 50mg catalyst DMC-4 ' and 50mL 1, the catalyst suspension of 2- epoxy butanes composition, reinject thereafter 50mL 1,2-
Epoxy butane, rapidly under agitation (speed is 500rpm), is filled with into kettle by the supply line with pressure adjusting function
CO2, make pressure in kettle reach 2.0MPa, polyreaction carries out 14 under the continuous stirring in 2.0MPa constant pressures and speed for 500rpm
Hour, polymerization temperature is 110 DEG C.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 2.7g carbon dioxide-epoxy butane copolymer crude product.
Taking out crude product is used for1H NMR and GPC are tested, and are as a result shown, the weight of the cyclic carbonate produced by copolymer
Content is 20.3%, and in copolymer, carbonate unit content is 70%, and catalytic efficiency is 0.05kg polymer/g.DMC-4 ', Mn
=2400g/mol, PDI=5.7.Partial test result is referring to table 1.
Comparative example 12
Under conditions of temperature is 90 DEG C, it is 40Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 6 hours, fill CO altogether212 times, after polymerization autoclave is cooled to room temperature, in CO2Under (purity is 99.99%) protection, note
Enter the catalyst suspension being made up of 10mg catalyst DMC-5 ' and 50mlL1,2- epoxy butane, reinject thereafter 50mL 1,2-
Epoxy butane, rapidly under agitation (speed is 500rpm), is filled with into kettle by the supply line with pressure adjusting function
CO2, make pressure in kettle reach 2.0MPa, polyreaction carries out 14 under the continuous stirring in 2.0MPa constant pressures and speed for 500rpm
Hour, polymerization temperature is 110 DEG C.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 8g carbon dioxide-epoxy butane copolymer crude product.
Taking out crude product is used for1H NMR and GPC are tested, and are as a result shown, the weight of the cyclic carbonate produced by copolymer
Content is 0%, and in copolymer, carbonate unit content is 25%, and catalytic efficiency is 0.8kg polymer/g.DMC-5 ', Mn=
84000g/mol, PDI=4.7.Partial test result is referring also to table 1.
Comparative example 13
Under conditions of temperature is 90 DEG C, it is 30Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 6 hours, fill CO altogether210 times, after polymerization autoclave is cooled to room temperature, in CO2Under (purity is 99.99%) protection, note
Enter the catalyst suspension being made up of 5mg catalyst DMC-6 ' and 50mL epoxychloropropane, reinject thereafter 50mL epoxy chloropropionates
Alkane, rapidly under agitation (speed is 500rpm), is filled with CO by the supply line with pressure adjusting function into kettle2, make kettle
Interior pressure reaches 5.0MPa, and polyreaction is carried out 14 hours under the continuous stirring in 5.0MPa constant pressures and speed for 500rpm, gathered
It is 80 DEG C to close temperature.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 16g carbon dioxide-epihalohydrin copolymer crude product.
Taking out crude product is used for1H NMR and GPC are tested, and are as a result shown, the weight of the cyclic carbonate produced by copolymer
Content is 30.7%, and in copolymer, carbonate unit content is 17%, and catalytic efficiency is 3.2kg polymer/g.DMC-6 ', Mn=
15000g/mol, PDI=3.7.Partial test result is referring to table 1.
Comparative example 14
Under conditions of temperature is 90 DEG C, it is 30Pa by polymerization autoclave elder generation evacuation, then to fill purity is 99.99%
CO2Process 6 hours, fill CO altogether210 times, after polymerization autoclave is cooled to room temperature, in CO2Under (purity is 99.99%) protection, note
Enter the catalyst suspension of 10mg catalyst DMC-7 ' and 50mL epoxychloropropane composition, reinject thereafter 50mL epoxy chloropropionates
Alkane, rapidly under agitation (speed is 500rpm), is filled with CO by the supply line with pressure adjusting function into kettle2, make kettle
Interior pressure reaches 5.0MPa, and polyreaction is carried out 14 hours under the continuous stirring in 5.0MPa constant pressures and speed for 500rpm, gathered
It is 80 DEG C to close temperature.
After polymerization terminates, polymeric kettle is cooled to room temperature, discharges residual carbon dioxide, and polymer is settled out with 1000mL distilled water,
Obtained polymer 500mL distilled water immersions are washed 3 times, each washing by soaking 24 hours.Polymer after immersion at 30 DEG C,
It is dried in vacuum drying oven to constant weight, obtains 8.4g carbon dioxide-epihalohydrin copolymer crude product.
Taking out crude product is used for1H NMR and GPC are tested, and are as a result shown, the weight of the cyclic carbonate produced by copolymer
Content is 4.3%, and in copolymer, carbonate unit content is 62%, and catalytic efficiency is 0.84kg polymer/g.DMC-7 ', Mn=
2400g/mol, PDI=5.7.Partial test result is referring to table 1.
The performance of carbon dioxide-epoxide co-polymer prepared by 1 embodiment of the present invention of table and comparative example
Note：Carbonate unit mass content in CU representation polymer chains；Wpc represents the quality point of cyclic carbonate in product
Number.
As it can be seen from table 1 the co-precipitation type DMC catalysts that the present invention is provided have higher carbonic ester
Unit content (CU), higher selectivity of product (Wpc) and higher catalysis activity.
Claims (2)
1. a kind of co-precipitation type DMC catalysts, with any one formula in 3～4 formula of formula：
Zn3[Co(CN)6]2·4.52Zn3[Fe(CN)6]2·2.27ZnCl2·1.27H2O·0.85EGME
Formula 3；
ZnNi(CN)4·3.43CoNi(CN)4·0.15Zn(NO3)2·3.98CoSO4·1.36H2O·1.25PEG
Formula 4.
2. a kind of preparation method of carbon dioxide-epoxide co-polymer, comprises the following steps：
Under conditions of catalyst is present, carbon dioxide and epoxide are carried out into polyreaction, carbon dioxide-epoxidation is obtained
Composition copolymer；
The catalyst is the catalyst described in claim 1.
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| CN102059134A (en) * | 2010-12-09 | 2011-05-18 | 海南大学 | Method for preparing double metal cyanide catalyst |
| CN102617844A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparing method of poly (carbonic ester-ether) polyalcohol |
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| CN101623656A (en) * | 2009-07-31 | 2010-01-13 | 广州市达志化工科技有限公司 | Double metal cyanide catalyst, preparation method and usage thereof |
| CN102059134A (en) * | 2010-12-09 | 2011-05-18 | 海南大学 | Method for preparing double metal cyanide catalyst |
| CN102617844A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院长春应用化学研究所 | Preparing method of poly (carbonic ester-ether) polyalcohol |
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