CN102443160A - Composite catalyst for carbon dioxide/epoxy compound copolymerization, preparation method and application thereof - Google Patents
Composite catalyst for carbon dioxide/epoxy compound copolymerization, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method and an application of a double metal cyanide (DMC) and functional SalenCoX complex composite catalyst. The catalyst contains the double metal cyanide and the functional SalenCoX complex, wherein the mole ratio of metal Y in metal cyanide Y(CN)b of the double metal cyanide to metal Co in the functional SalenCoX complex catalyst is Y: Co=1:0.01-1:100. The preparation method of the composite catalyst has advantages of simple preparation steps, low cost, convenient operation and no addition of a cocatalyst and a solvent. The composite catalyst can be used to catalyze carbon dioxide/epoxy compound copolymerization at the reaction temperature of 80 DEG C at reaction pressure of 8.0 MPa and with the reaction time of 6 hours. The content of the obtained product cyclic carbonate unit is 91%; average molecular weight is 247900; molecular weight distribution is 1.39; and catalytic efficiency is 30 Kg polymer/g composite DMC catalyst.
Description
Technical field:
The present invention relates to the copolyreaction of carbonic acid gas and epoxy compounds, be specially the preparation method and the application of a kind of double metal cyanide (DMC) and functional type SalenCoX compound composite catalyst.
Background technology:
Carbonic acid gas (CO
2) be the main gas that causes " Greenhouse effect ", but also be one of carbon resource of reserves maximum on the earth, it is more than the summation of reserves Sweet natural gas, oil and the coal of the earth.In view of the harm of dioxide gas to environment, the human approach that always all utilizes carbonic acid gas at Scientific exploration.Utilize CO
2With the synthetic aliphatic polycarbonate of epoxide copolymerization, be CO
2Utilize in the research one of direction of tool researching value and application prospect, aliphatic polycarbonate has been applied to bio-medical material, gas barrier material, hard brittle material toughner, elastomeric material strengthening agent, novel liquid crystal material, unsaturated polyester, sizing agent, photoresist material, solid electrolyte and a plurality of fields such as electron device, matrix material.
Be used for epoxy alkane and the carbon dioxide copolymerization reported close catalyst for reaction and comprise zinc ethyl-many reactive hydrogens proton compound catalystsystem, catalysis of metalloporphyrin system, the complex-catalyzed system of three-element catalytic system, bimetallic cyaniding that contains rare earth metal salt and SalenMX catalystsystem etc.Patent US3385168 adopts metal Organoalkyl zinc and the catalyzer that contains many reactive hydrogens compositions to obtain the alternating copolymer of carbonic acid gas and epoxy compounds; The activation that has realized carbonic acid gas is with fixing, but its catalytic efficiency (is generally 3 kg of polymer/kg catalyst.Patent JP2575199 adopts porphyrin metal complex catalystsystem catalysis carbonic acid gas and propylene oxide copolymerization; This catalyzer has the characteristics of living polymerization, but speed of reaction is slow, long reaction time (generally greater than 7 days); The price of catalyzer is also somewhat expensive, and the resulting polymers molecular weight is on the low side.Patent CN1257753A with reported a kind of rare-earth ternary catalystsystem; This catalystsystem has good catalytic activity to catalysis carbonic acid gas and propylene oxide copolymerization; Catalytic efficiency (can reach 50g polymkeric substance/g catalyzer, but the catalytic activity of carbonic acid gas and epoxy cyclohexane copolymerization is needed to improve.Patent US4500704 has reported that at first double metal cyanide (DMC) is used for catalysis CO
2With epoxide copolymerization aliphatic polycarbonate, catalysis PO and CO
2Activity is merely 44g polymkeric substance/g catalyzer during copolymerization; Document (Polymer, 2004,45:6519-6524) reported a kind of highly active dmc catalyst, catalysis PO and CO
2During copolymerization, react that activity reaches as high as 2Kg polymkeric substance/g catalyzer after 10 hours, but the carbonate unit content in the polymkeric substance is merely 30%; Though dmc catalyst has a high catalytic activity, the problem that patent of delivering and document dmc catalyst exist is that the content of carbonate unit is low in the polymerisate, the highlyest is merely 64%.Patent CN101020747A has reported a kind of functional type Salen MnX catalyzer, catalysis PO and CO
2During copolymerization; The content that reacts carbonate unit in 6 hours products reaches more than 99%; Catalytic activity can reach 1Kg polymkeric substance/g catalyzer; Compare functional type Salen MnX catalyzer advantage with dmc catalyst and be that the content of carbonate unit in the polymerisate is very high, but its catalytic activity to be lower than dmc catalyst.
Summary of the invention:
The purpose of this invention is to provide a kind of catalyzer that is used for carbonic acid gas and epoxy compounds copolymerization, be double metal cyanide (DMC) and functional type SalenCoX title complex compound catalyzer.Use double metal cyanide (DMC) catalysis carbonic acid gas and epoxide copolymerization separately, activity reaches 15-35kg polymkeric substance/g catalyzer, and the content of carbonate unit is 34-79% in the gained multipolymer, molecular weight 5000-500,000, MWD 1.29-5.11; Independent complex-catalyzed carbonic acid gas of functions of use type SalenCoX and synthesis of epoxy compounds, catalytic efficiency (is 0.5-3.0Kg polycarbonate/g catalyzer, carbonate unit content 92-99% in the product; Molecular weight 11; 000-350,000, MWD 1.21-2.41; Use composite catalyst catalysis carbonic acid gas and epoxy compounds copolymerization, obtain carbonate unit content 50-93% in the copolymerization product, the compound dmc catalyst of catalytic efficiency (2-30Kg polymkeric substance/g of catalyzer; Molecular weight 11; 900-470,000, MWD 1.32-3.98.DMC catalystsystem catalytic activity is high, and carbonate unit content is lower in the product; The complex-catalyzed system catalytic activity of SalenCoX is lower, and carbonate unit content is high in the product; Composite catalyst system does not significantly reduce with respect to DMC catalystsystem activity, and carbonate unit content but has a more substantial increase in the product; Composite catalyst has comprised the advantage of two kinds of catalystsystem, and has remedied deficiency separately.
Technical scheme of the present invention is:
A kind of composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization, this catalyzer comprise double metal cyanide and functional type SalenCoX title complex, metal cyanides Y (CN) in the double metal cyanide
bThe molar ratio of metal Co is Y: Co=1: 0.01-1 in containing metal Y of institute and the functional type SalenCoX composition catalyst: 100;
Wherein, described double metal cyanide structural formula is: B
a[Y (CN)
b] cDG
dETfAgH
2O
In the described double metal cyanide structural formula:
Formula B
a[Y (CN)
b] in, Y is metals ion: Zn (II), Fe (II), Fe (III), Co (II), Co (III), Ni (II), Cr (III), Mn (II) or Mn (III) in the compound of representative; B is metals ion: Zn (II), Fe (II), Fe (III), Co (II), Co (III), Ni (II), Cr (III) or Mn (II), and b is 4,6 or 8, and the valence state value of a value and metals ion B is long-pending, adds that the valence number sum of metals ion Y equals b;
Formula DG
dD is metals ion: Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Al (III), V (IV), V (V), Sr (II), W (IV), W (VI), Cu (II), Cr (II), Cd (II), Hg (II), Pd (II), Pt (II), Mg (II), Ca (II) or Ba (II) in the compound of representative, and G is identical or different negatively charged ion; The value of d is 1 to 3.
The organic ligand of formula T representative is alcohol, aldehyde, ketone, ether, the urea of C1～C10,
The macromole assistant ligand of formula A representative is a molecular weight greater than 150 polyethers, polyester or other macromolecular cpd,
C, e, f, g are respectively a numerical value between 0-9.0 in the structural formula;
The following compound of its structural formula of described functional type SalenCoX title complex (I):
In the formula: R
1It is 1,2 dibasic diamines; R
2Be formula
Or the substituted heterogeneous ring compound of nitrogen, R
3Be hydrogen, alkyl or alkoxyl group, wherein M is halogen, acid group, phenol oxygen base, nitrine or tetrafluoride boron, and Z is nitrogen or phosphorus, Y
1, Y
2, Y
3Be respectively the alkyl of C1～C16, n is 0-10, and X is halogen, acid group, phenol oxygen base, tetrafluoride boron, nitrine.
Described G is preferably halogen ion, hydroxide radical, sulfate radical, carbonate, cyanate radical, thiocyanate ion, isocyano, isosulfocyanate radical, carboxylate radical, oxalate or nitrate radical; The value of d is 1 to 3.
Described organic ligand is preferably Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, dme, dioxane, propylene glycol monomethyl ether, glycerine, THF.
Described macromole assistant ligand is preferably PTMEG600, PTMEG2000, PEG200, PEG400, PEG600, PPG600, PPG1000.
Said 1,2 dibasic diamines is preferably cyclohexanediamine, O-Phenylene Diamine, quadrol or 1,2-diphenyl ethylene diamine;
The substituted heterogeneous ring compound of said nitrogen is preferably the substituted imidazolyl of nitrogen, the substituted hexahydropyridine base of nitrogen, the substituted morpholinyl of nitrogen or the substituted Pyrrolidine base of nitrogen;
The alkyl of said C1～C16 is preferably methyl, ethyl, propyl group, normal-butyl, n-pentyl, phenyl or iso-octyl;
Said halogen, acid group or phenol oxygen base are preferably chlorine, bromine, nitrate radical, acetate moiety, trichoroacetic acid(TCA) root, trifluoroacetic acid root, p-methyl benzenesulfonic acid root, p-NP oxygen base or 2,4 dinitrophenol oxygen bases.
The preparation method of double metal cyanide and functional type SalenCoX compound composite catalyst who is used for carbonic acid gas/epoxy compounds copolymerization is following:
Under argon shield, functional type SalenCoX title complex is put into configurator, add the propylene oxide dissolving, be mixed with the solution of concentration range at 0.1-5.0g title complex/L; 20 ℃ were stirred 1 hour, added DMC catalysts subsequently, and wherein the molar ratio of double metal cyanide and functional type SalenCoX title complex is Y: Co=1: 0.01-1: 100; 20 ℃ were stirred 1 hour; Vacuum rotary steam removes away solvent, obtains composite catalyst, preserves under the argon gas condition.
The method of use of double metal cyanide and functional type SalenCoX compound composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization is following:
90 ℃ take out the moisture and oxygen that still removed wherein trace in 1 hour with vacuum pump after; Be cooled to 25 ℃; Under carbon-dioxide protecting, add composite catalyst and epoxy compounds in reaction kettle, make the concentration of bimetallic catalyst in the composite catalyst (DMC) remain on 0.01-0.3g/L and charge into CO
2Gas is opened and is stirred and heating, and temperature is controlled at 30-140 ℃; Pressure-controlling is at 2-12Mpa; Reaction times is controlled at 2-14h; Reaction finishes below the fast cooling to 25 ℃, emits gas and obtains solid polymer, and sampling is carried out nuclear-magnetism and characterized.
Beneficial effect of the present invention is that this composite catalyst preparation process is simple, with low cost, easy to operate; Do not need to add again promotor and solvent; Just can obtain product cyclic carbonate ester units content 91% in 80 ℃ of temperature of reaction, reaction pressure 8.0MPa, reaction times 6h catalysis carbonic acid gas and epoxy compounds copolymerization, molecular-weight average is 247900; MWD 1.39, catalytic efficiency (are the compound dmc catalyst of 30Kg polymkeric substance/g.
Embodiment
Double metal cyanide is with reference to number of patent application 201110074990.X (the synthetic preparation method with DMC catalysts of a kind of polycarbonate, method preparation CN102179262A);
Functional type SalenCoX title complex with reference to number of patent application 201110087465.1 (its structural formula is following for a kind of preparation method of Salen-metal complex, the preparation of CN102212085A) method:
Be used for the preparation of the functional type SalenCoX title complex and double metal cyanide (DMC) composite catalyst of carbonic acid gas and epoxy compounds copolymerization:
Embodiment 1:
Get 100ml single armed bottle under the argon gas condition, add the SalenCoX title complex (I of 40mg such as top structural formula
1), wherein: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, R
2Be formula
M is a nitrate radical, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is a nitrate radical.Add the dissolving of 50ml propylene oxide, 20 ℃ are stirred half a hour, and the structural formula of the DMC catalysts DMC-1 that adding 3mg obtains is: Zn
3[Co (CN)
6]
21.3ZnCl
22.0t-BuOH0.5H
2O (wherein the molar ratio of metal Co and double metal cyanide metal Co is 6.4: 1 in the functional type SalenCoX composition catalyst); 20 ℃ were stirred 1 hour under the 150rmp rotating speed; Vacuum rotary steam removes away solvent under the vacuum tightness 0.1MPa, preserves under the argon gas condition, obtains composite catalyst C-1.
Embodiment 2:
Use DMC catalysts DMC-2:Zn
3[Co (CN)
6]
21.4ZnCl
22.1DME0.6H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-2.
Embodiment 3:
Use DMC catalysts DMC-3:Zn
3[Co (CN)
6]
21.2ZnCl
22.0MPP0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-3.
Embodiment 4:
Use DMC catalysts DMC-4:Zn
3[Co (CN)
6]
21.2ZnCl
22.1Ethanol0.7H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-4.
Embodiment 5:
Use DMC catalysts DMC-5:Zn
3[Co (CN)
6]
21.2ZnCl
22.1THF0.7H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-5.
Embodiment 6:
Use DMC catalysts DMC-6:Zn
3[Co (CN)
6]
21.2ZnBr
22.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-6.
Embodiment 7:
Use DMC catalysts DMC-7:Zn
3[Co (CN)
6]
21.0ZnI2.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-7.
Embodiment 8:
Use DMC catalysts DMC-8:Zn
3[Co (CN)
6]
21.0ZnSO
42.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-8.
Embodiment 9:
Use DMC catalysts DMC-9:Fe
3[Co (CN)
6]
21.1FeSO
42.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-9.
Embodiment 10:
Use DMC catalysts DMC-10:Co
3[Co (CN)
6]
21.3CoCl
22.0t-BuOH0.7H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-10.
Embodiment 11:
Use DMC catalysts DMC-11:Ni
3[Co (CN)
6]
21.3Ni (NO
3)
22.0t-BuOH0.6H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-11.
Embodiment 12:
Use DMC catalysts DMC-12:Zn
3[Mn (CN)
6]
21.2ZnBr
22.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-12.
Embodiment 13:
Use DMC catalysts DMC-13:Zn
3[Mo (CN)
8]
21.2ZnBr
22.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-13.
Embodiment 14:
Use DMC catalysts DMC-14:Zn
3[Cr (CN)
6]
21.2ZnBr
22.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-14.
Embodiment 15:
Use DMC catalysts DMC-15:Zn
3[Cr (CN)
6]
21.2ZnI
22.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-15.
Embodiment 16:
Use DMC catalysts DMC-16:Zn
3[Ni (CN)
6]
21.4ZnCl
22.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-16.
Embodiment 17:
Use DMC catalysts DMC-17:Zn
2[Ni (CN)
4] 1.2ZnBr
22.0t-BuOH0.5H
2O replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-17.
Embodiment 18:
Use DMC catalysts DMC-18:Zn
3[Co (CN)
6]
21.4ZnCl
22.0t-BuOH0.4H
2O2.0PEG200 replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-18.
Embodiment 19:
Use DMC catalysts DMC-19:Zn
3[Co (CN)
6]
21.4ZnCl
22.1t-BuOH0.4H
2O0.9PEG400 replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-19.
Embodiment 20:
Use DMC catalysts DMC-20:Zn
3[Co (CN)
6]
21.3ZnCl
22.1t-BuOH0.5H
2O0.8PEG600 replaces DMC catalysts DMC-1 (wherein the molar ratio of metal Co and double metal cyanide metal Co is 9.7: 1 in the functional type SalenCoX composition catalyst) among the embodiment 1; Other operations obtain composite catalyst C-20 with embodiment 1.
Embodiment 21:
Use DMC catalysts DMC-21:Zn
3[Co (CN)
6]
21.3ZnCl
22.1t-BuOH0.5H
2O0.9PTMEG600 replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-21.
Embodiment 22:
Use DMC catalysts DMC-22:Zn
3[Co (CN)
6]
21.4ZnCl
22.1t-BuOH0.5H
2O0.7PPG600 replaces DMC catalysts DMC-1 among the embodiment 1, and other are operated with embodiment 1, obtain composite catalyst C-22.
Embodiment 23:
With SalenCoX title complex (I
2) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
2) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a nitrate radical, and Z is a phosphine, Y
1, Y
2, Y
3Be respectively phenyl, n is 3, and X is a nitrate radical, and other are operated with embodiment 20, obtain composite catalyst C-23.
Embodiment 24:
With SalenCoX title complex (I
3) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
3) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a nitrate radical, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 4, and X is a nitrate radical, and other are operated with embodiment 20, obtain composite catalyst C-24.
Embodiment 25:
With SalenCoX title complex (I
4) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
4) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a nitrate radical, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 2, and X is a nitrate radical, and other are operated with embodiment 20, obtain composite catalyst C-25.
Embodiment 26:
With SalenCoX title complex (I
5) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
5) in: R
1Be diphenyl ethylene diamine, R
3Be the tertiary butyl, M is a nitrate radical, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is a nitrate radical, and other are operated with embodiment 20, obtain composite catalyst C-26.
Embodiment 27:
With SalenCoX title complex (I
6) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
6) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a chlorine, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is a chlorine, and other are operated with embodiment 20, obtain composite catalyst C-27.
Embodiment 28:
With SalenCoX title complex (I
7) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
7) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is 2,4 dinitrophenol(DNP), and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is 2,4 dinitrophenol(DNP), and other are operated with embodiment 20, obtain composite catalyst C-28.
Embodiment 29:
With SalenCoX title complex (I
8) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
8) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a trichoroacetic acid(TCA), and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is a trichoroacetic acid(TCA), and other are operated with embodiment 20, obtain composite catalyst C-29.
Embodiment 30:
With SalenCoX title complex (I
9) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
9) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a nitrine, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is a nitrine, and other are operated with embodiment 20, obtain composite catalyst C-30.
Embodiment 31:
With SalenCoX title complex (I
10) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
10) in: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a trifluoroacetic acid, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is a trifluoroacetic acid, and other are operated with embodiment 20, obtain composite catalyst C-31.
Embodiment 32:
With SalenCoX title complex (I
11) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
11) in:: R
1Be cyclohexanediamine, R
3Be the tertiary butyl, M is a nitrate radical, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively iso-octyl, n is 3, and X is a nitrate radical, and other are operated with embodiment 20, obtain composite catalyst C-32.
Embodiment 33:
With SalenCoX title complex (I
12) replace the SalenCoX title complex (I among the embodiment 20
1), SalenCoX title complex (I
12) in: R
1Be cyclohexanediamine, R
3Be methoxyl group, M is a nitrate radical, and Z is a nitrogen, Y
1, Y
2, Y
3Be respectively normal-butyl, n is 3, and X is a nitrate radical, and other are operated with embodiment 20, obtain composite catalyst C-33.
Embodiment 34:
The SalenCoX title complex (I among the embodiment 20
1) being increased to 60mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 14.6: 1 in the functional type SalenCoX composition catalyst), other are operated with embodiment 20, obtain composite catalyst C-34.
Embodiment 35:
The SalenCoX title complex (I among the embodiment 20
1) being increased to 80mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 19.4: 1 in the functional type SalenCoX composition catalyst), other are operated with embodiment 20, obtain composite catalyst C-35.
Embodiment 36:
The SalenCoX title complex (I among the embodiment 20
1) reducing to 20mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 4.9: 1 in the functional type SalenCoX composition catalyst), other are operated with embodiment 20, obtain composite catalyst C-36.
Embodiment 37:
The SalenCoX title complex (I among the embodiment 20
1) reducing to 5mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 1.3: 1 in the functional type SalenCoX composition catalyst), other are operated with embodiment 20, obtain composite catalyst C-37.
Embodiment 38:
The SalenCoX title complex (I among the embodiment 20
1) reducing to 1mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 0.25: 1 in the functional type SalenCoX composition catalyst), other are operated with embodiment 20, obtain composite catalyst C-38.
Embodiment 39:
Reduce to 1mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 59: 1 in the functional type SalenCoX composition catalyst) to the DMC catalysts among the embodiment 35, other are operated with embodiment 35, obtain composite catalyst C-39.
Embodiment 40:
Be increased to 6mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 0.1: 1 in the functional type SalenCoX composition catalyst) to the DMC catalysts among the embodiment 38, other are operated with embodiment 38, obtain composite catalyst C-40.
Embodiment 41:
Be increased to 12mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 0.05: 1 in the functional type SalenCoX composition catalyst) to the DMC catalysts among the embodiment 38; Other operations obtain composite catalyst C-41 with embodiment 38.
Embodiment 42:
Be increased to 24mg (wherein the molar ratio of metal Co and double metal cyanide metal Co is 0.02: 1 in the functional type SalenCoX composition catalyst) to the DMC catalysts among the embodiment 38; Other operations obtain composite catalyst C-42 with embodiment 38.
Be used for the use of the double metal cyanide and the functional type SalenCoX compound composite catalyst of carbonic acid gas/epoxy compounds copolymerization:
Embodiment 43:
90 ℃ take out the moisture and oxygen that still removed wherein trace in 1 hour with vacuum pump after; Be cooled to 25 ℃; 43mg composite catalyst C-1 (wherein the molar ratio of metal Co and double metal cyanide metal Co is 6.4: 1 in the functional type SalenCoX composition catalyst) and 130ml propylene oxide join in the reaction kettle of 250ml under carbon-dioxide protecting in the lump, charge into C0
2Gas is opened and is stirred and heating, keeps still internal pressure 6.0MPa constant, and 80 ℃, react pressure release after 6 hours, get the 89g multipolymer, it is 158800 that gel permeation chromatography records molecular-weight average, MWD 1.61, carbonate unit content 82%.
Embodiment 44:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-2, other are operated with embodiment 43, get the 35g multipolymer, and it is 81400 that GPC records molecular-weight average, MWD 1.52, carbonate unit content 59%.
Embodiment 45:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-3, other are operated with embodiment 43, get the 24g multipolymer, and it is 55400 that GPC records molecular-weight average, MWD 1.68, carbonate unit content 54%.
Embodiment 46:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-4, other are operated with embodiment 43, get the 54g multipolymer, and it is 75600 that GPC records molecular-weight average, MWD 1.93, carbonate unit content 60%.
Embodiment 47:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-5, other are operated with embodiment 43, get the 13g multipolymer, and it is 21500 that GPC records molecular-weight average, MWD 1.68, carbonate unit content 51%.
Embodiment 48:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-6, other are operated with embodiment 43, get the 71g multipolymer, and it is 131500 that GPC records molecular-weight average, MWD 1.44, carbonate unit content 71%.
Embodiment 49:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-7, other are operated with embodiment 43, get the 59g multipolymer, and it is 81900 that GPC records molecular-weight average, MWD 3.75, carbonate unit content 75%.
Embodiment 50:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-8, other are operated with embodiment 43, get the 16g multipolymer, and it is 14300 that GPC records molecular-weight average, MWD 2.81, carbonate unit content 51%.
Embodiment 51:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-9, other are operated with embodiment 43, get the 63g multipolymer, and it is 128600 that GPC records molecular-weight average, MWD 1.56, carbonate unit content 73%.
Embodiment 52:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-10, other are operated with embodiment 43, get the 57g multipolymer, and it is 72100 that GPC records molecular-weight average, MWD 1.51, carbonate unit content 64%.
Embodiment 53:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-11, other are operated with embodiment 43, get the 20g multipolymer, and it is 41200 that GPC records molecular-weight average, MWD 1.82, carbonate unit content 56%.
Embodiment 54:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-12, other are operated with embodiment 43, get the 19g multipolymer, and it is 15900 that GPC records molecular-weight average, MWD 3.59, carbonate unit content 50%.
Embodiment 55:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-13, other are operated with embodiment 43, get the 48g multipolymer, and it is 78700 that GPC records molecular-weight average, MWD 1.48, carbonate unit content 64%.
Embodiment 56:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-14, other are operated with embodiment 43, get the 57g multipolymer, and it is 62100 that GPC records molecular-weight average, MWD 1.37, carbonate unit content 57%.
Embodiment 57:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-15, other are operated with embodiment 43, get the 54g multipolymer, and it is 58300 that GPC records molecular-weight average, MWD 1.45, carbonate unit content 53%.
Embodiment 58:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-16, other are operated with embodiment 43, get the 69g multipolymer, and it is 89300 that GPC records molecular-weight average, MWD 1.33, carbonate unit content 74%.
Embodiment 59:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-17, other are operated with embodiment 43, get the 61g multipolymer, and it is 62100 that GPC records molecular-weight average, MWD 1.43, carbonate unit content 68%.
Embodiment 60:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-18, other are operated with embodiment 43, get the 91g multipolymer, and it is 162500 that GPC records molecular-weight average, MWD 1.63, carbonate unit content 84%.
Embodiment 61:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-19, other are operated with embodiment 43, get the 95g multipolymer, and it is 184100 that GPC records molecular-weight average, MWD 1.51, carbonate unit content 85%.
Embodiment 62:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-20, other are operated with embodiment 43, get the 96g multipolymer, and it is 209800 that GPC records molecular-weight average, MWD 1.32, carbonate unit content 87%.
Embodiment 63:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-21, other are operated with embodiment 43, get the 78g multipolymer, and it is 115700 that GPC records molecular-weight average, MWD 1.74, carbonate unit content 76%.
Embodiment 64:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-22, other are operated with embodiment 43, get the 75g multipolymer, and it is 148600 that GPC records molecular-weight average, MWD 1.55, carbonate unit content 83%.
Embodiment 65:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-23, other are operated with embodiment 43, get the 44g multipolymer, and it is 74400 that GPC records molecular-weight average, MWD 1.25, carbonate unit content 70%.
Embodiment 66:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-24, other are operated with embodiment 43, get the 86g multipolymer, and it is 155900 that GPC records molecular-weight average, MWD 1.29, carbonate unit content 84%.
Embodiment 67:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-25, other are operated with embodiment 43, get the 75g multipolymer, and it is 114100 that GPC records molecular-weight average, MWD 1.65, carbonate unit content 81%.
Embodiment 68:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-26, other are operated with embodiment 43, get the 82g multipolymer, and it is 149800 that GPC records molecular-weight average, MWD 2.28, carbonate unit content 85%.
Embodiment 69:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-27, other are operated with embodiment 43, get the 20g multipolymer, and it is 18100 that GPC records molecular-weight average, MWD 4.75, carbonate unit content 57%.
Embodiment 70:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-28, other are operated with embodiment 43, get the 83g multipolymer, and it is 163200 that GPC records molecular-weight average, MWD 1.91, carbonate unit content 86%.
Embodiment 71:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-29, other are operated with embodiment 43, get the 61g multipolymer, and it is 87700 that GPC records molecular-weight average, MWD 1.79, carbonate unit content 70%.
Embodiment 72:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-30, other are operated with embodiment 43, get the 17g multipolymer, and it is 35800 that GPC records molecular-weight average, MWD 4.43, carbonate unit content 59%.
Embodiment 73:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-31, other are operated with embodiment 43, get the 23g multipolymer, and it is 24900 that GPC records molecular-weight average, MWD 2.16, carbonate unit content 76%.
Embodiment 74:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-32, other are operated with embodiment 43, get the 73g multipolymer, and it is 95600 that GPC records molecular-weight average, MWD 2.45, carbonate unit content 72%.
Embodiment 75:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-33, other are operated with embodiment 43, get the 59g multipolymer, and it is 114800 that GPC records molecular-weight average, MWD 1.99, carbonate unit content 78%.
Embodiment 76:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-34, other are operated with embodiment 43, get the 64g multipolymer, and it is 151400 that GPC records molecular-weight average, MWD 1.65, carbonate unit content 89%.
Embodiment 77:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-35, other are operated with embodiment 43, get the 35g multipolymer, and it is 121400 that GPC records molecular-weight average, MWD 1.96, carbonate unit content 93%.
Embodiment 78:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-36, other are operated with embodiment 43, get the 59g multipolymer, and it is 188600 that GPC records molecular-weight average, MWD 1.38, carbonate unit content 74%.
Embodiment 79:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-37, other are operated with embodiment 43, get the 76g multipolymer, and it is 222500 that GPC records molecular-weight average, MWD 1.65, carbonate unit content 70%.
Embodiment 80:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-38, other are operated with embodiment 43, get the 85g multipolymer, and it is 242800 that GPC records molecular-weight average, MWD 2.78, carbonate unit content 58%.
Embodiment 81:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-39, other are operated with embodiment 43, get the 32g multipolymer, and it is 32300 that GPC records molecular-weight average, MWD 2.55, carbonate unit content 97%.
Embodiment 82:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-40, other are operated with embodiment 43, get the 124g multipolymer, and it is 259600 that GPC records molecular-weight average, MWD 2.11, carbonate unit content 53%.
Embodiment 83:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-41, other are operated with embodiment 43, get the 39g multipolymer, and it is 45300 that GPC records molecular-weight average, MWD 3.94, carbonate unit content 54%.
Embodiment 84:
Replace the composite catalyst C-1 among the embodiment 43 with composite catalyst C-42, other are operated with embodiment 43, get the 11g multipolymer, and it is 22500 that GPC records molecular-weight average, MWD 4.02, carbonate unit content 51%.
Embodiment 85:
Bring up to 90 ℃ to the temperature among the embodiment 62, other are operated with embodiment 62, get the 98g multipolymer, and it is 242300 that GPC records molecular-weight average, MWD 1.36, carbonate unit content 80%.
Embodiment 86:
Bring up to 100 ℃ to the temperature among the embodiment 62, other are operated with embodiment 62, get the 104g multipolymer, and it is 274800 that GPC records molecular-weight average, MWD 1.45, carbonate unit content 74%.
Embodiment 87:
Bring up to 70 ℃ to the temperature among the embodiment 62, other are operated with embodiment 62, get the 64g multipolymer, and it is 122100 that GPC records molecular-weight average, MWD 1.76, carbonate unit content 88%.
Embodiment 88:
Bring up to 60 ℃ to the temperature among the embodiment 62, other are operated with embodiment 62, get the 52g multipolymer, and it is 110900 that GPC records molecular-weight average, MWD 2.33, carbonate unit content 81%.
Embodiment 89:
To 7MPa, other are operated with embodiment 62 the boost in pressure among the embodiment 62, get the 98g multipolymer, and it is 221900 that GPC records molecular-weight average, MWD 1.32, carbonate unit content 86%.
Embodiment 90:
To 8MPa, other are operated with embodiment 62 the boost in pressure among the embodiment 62, get the 105g multipolymer, and it is 247900 that GPC records molecular-weight average, MWD 1.39, carbonate unit content 91%.
Embodiment 91:
Drop to 5MPa to the pressure among the embodiment 62, other are operated with embodiment 62, get the 57g multipolymer, and it is 143000 that GPC records molecular-weight average, MWD 1.39, carbonate unit content 73%.
Embodiment 92:
Be increased to 8h to the time among the embodiment 62, other are operated with embodiment 62, get the 98g multipolymer, and it is 224300 that GPC records molecular-weight average, MWD 1.36, carbonate unit content 83%.
Embodiment 93:
Be increased to 10h to the time among the embodiment 62, other are operated with embodiment 62, get the 106g multipolymer, and it is 247900 that GPC records molecular-weight average, MWD 1.42, carbonate unit content 83%.
Embodiment 94:
Be reduced to 4h to the time among the embodiment 62, other are operated with embodiment 62, get the 42g multipolymer, and it is 64300 that GPC records molecular-weight average, MWD 2.56, carbonate unit content 76%.
Embodiment 95:
Be increased to 150ml to the propylene oxide amount that adds among the embodiment 62, other are operated with embodiment 62, get the 81g multipolymer, and it is 134700 that GPC records molecular-weight average, MWD 1.56, carbonate unit content 81%.
Embodiment 89:
Reduce to 110ml to the propylene oxide amount that adds among the embodiment 62, other are operated with embodiment 62, get the 89g multipolymer, and it is 119200 that GPC records molecular-weight average, MWD 2.46, carbonate unit content 75%.
Embodiment 96:
Reduce to 90ml to the propylene oxide amount that adds among the embodiment 62, other are operated with embodiment 62, get the 75g multipolymer, and it is 85300 that GPC records molecular-weight average, MWD 3.26, carbonate unit content 71%.
Embodiment 97:
Reduce to 70ml to the propylene oxide amount that adds among the embodiment 62, other are operated with embodiment 62, get the 75g multipolymer, and it is 66700 that GPC records molecular-weight average, MWD 3.88, carbonate unit content 68%.
Annex 1
Polymerizing condition: pressure 6.0Mpa, 80 ℃ of temperature, time 6h
Propylene oxide: 130ml
Annex 2
Polymerizing condition: pressure 6.0Mpa, 80 ℃ of temperature, time 6h
Propylene oxide: 130ml
Can find out from top embodiment; The composite catalyst C-20 (wherein the molar ratio of metal Co is 1: 9.7 in double metal cyanide metal Co and the functional type SalenCoX composition catalyst) that is made up of double metal cyanide (DMC) and SalenCoX title complex of the present invention is in 80 ℃ of temperature of reaction, reaction pressure 8.0MPa, reaction times 6h catalysis carbonic acid gas and epoxy compounds copolymerization; Obtain product cyclic carbonate ester units content 91%; Molecular-weight average is 247900; MWD 1.39, catalytic efficiency (are the compound dmc catalyst of 30Kg polymkeric substance/g, and product carbonate unit content is better than independent use DMC catalysts far away.
Claims (10)
1. a composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization is characterized by this catalyzer and comprises double metal cyanide and functional type SalenCoX title complex, metal cyanides Y (CN) in the double metal cyanide
bThe molar ratio of metal Co is Y: Co=1: 0.01-1 in containing metal Y of institute and the functional type SalenCoX composition catalyst: 100;
Wherein, described double metal cyanide structural formula is: B
a[Y (CN)
b] cDG
dETfAgH
2O
In the described double metal cyanide structural formula:
Formula B
a[Y (CN)
b] in, Y is metals ion: Zn (II), Fe (II), Fe (III), Co (II), Co (III), Ni (II), Cr (III), Mn (II) or Mn (III) in the compound of representative; B is metals ion: Zn (II), Fe (II), Fe (III), Co (II), Co (III), Ni (II), Cr (III) or Mn (II), and b is 4,6 or 8, and the valence state value of a value and metals ion B is long-pending, adds that the valence number sum of metals ion Y equals b;
Formula DG
dD is metals ion: Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Al (III), V (IV), V (V), Sr (II), W (IV), W (VI), Cu (II), Cr (II), Cd (II), Hg (II), Pd (II), Pt (II), Mg (II), Ca (II) or Ba (II) in the compound of representative, and G is identical or different negatively charged ion; The value of d is 1 to 3.
The organic ligand of formula T representative is alcohol, aldehyde, ketone, ether, the urea of C1～C10,
The macromole assistant ligand of formula A representative is a molecular weight greater than 150 polyethers, polyester or other macromolecular cpd,
C, e, f, g are respectively a numerical value between 0-9.0 in the structural formula;
The following compound of its structural formula of described functional type SalenCoX title complex (I):
In the formula: R
1It is 1,2 dibasic diamines; R
2Be formula
Or the substituted heterogeneous ring compound of nitrogen, R
3Be hydrogen, alkyl or alkoxyl group, wherein M is halogen, acid group, phenol oxygen base, nitrine or tetrafluoride boron, and Z is nitrogen or phosphorus, Y
1, Y
2, Y
3Be respectively the alkyl of C1～C16, n is 0-10, and X is halogen, acid group, phenol oxygen base, tetrafluoride boron, nitrine.
2. the composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1 is characterized by described G and is preferably halogen ion, hydroxide radical, sulfate radical, carbonate, cyanate radical, thiocyanate ion, isocyano, isosulfocyanate radical, carboxylate radical, oxalate or nitrate radical; The value of d is 1 to 3.
3. the composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1 is characterized by described organic ligand and is preferably Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, dme, dioxane, propylene glycol monomethyl ether, glycerine, THF.
4. the composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1 is characterized by described macromole assistant ligand and is preferably PTMEG600, PTMEG2000, PEG200, PEG400, PEG600, PPG600, PPG1000.
5. the composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1 is characterized by said 1,2 dibasic diamines and is preferably cyclohexanediamine, O-Phenylene Diamine, quadrol or 1,2-diphenyl ethylene diamine;
6. the composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1 is characterized by the substituted heterogeneous ring compound of said nitrogen and is preferably the substituted imidazolyl of nitrogen, the substituted hexahydropyridine base of nitrogen, the substituted morpholinyl of nitrogen or the substituted Pyrrolidine base of nitrogen;
7. the composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1, the alkyl that it is characterized by said C1～C16 is preferably methyl, ethyl, propyl group, normal-butyl, n-pentyl, phenyl or iso-octyl;
8. the composite catalyst that is used for carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1; It is characterized by said halogen, acid group or phenol oxygen base and be preferably chlorine, bromine, nitrate radical, acetate moiety, trichoroacetic acid(TCA) root, trifluoroacetic acid root, p-methyl benzenesulfonic acid root, p-NP oxygen base or 2,4 dinitrophenol oxygen bases.
9. the preparation method who is used for the composite catalyst of carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1 is characterized by and comprises the steps:
Under argon shield, functional type SalenCoX title complex is put into configurator, add the propylene oxide dissolving, be mixed with the solution of concentration range at 0.1-5.0g title complex/L; 20 ℃ were stirred 1 hour, added DMC catalysts subsequently, and wherein the molar ratio of double metal cyanide and functional type SalenCoX title complex is Y: Co=1: 0.01-1: 100; 20 ℃ were stirred 1 hour; Vacuum rotary steam removes away solvent, obtains composite catalyst, preserves under the argon gas condition.
10. the method for use that is used for the composite catalyst of carbonic acid gas/epoxy compounds copolymerization as claimed in claim 1 is characterized by and comprises the steps:
90 ℃ take out the moisture and oxygen that still removed wherein trace in 1 hour with vacuum pump after; Be cooled to 25 ℃; Under carbon-dioxide protecting, add composite catalyst and epoxy compounds in reaction kettle, make the concentration of bimetallic catalyst in the composite catalyst (DMC) remain on 0.01-0.3g/L and charge into CO
2Gas is opened and is stirred and heating, and temperature is controlled at 30-140 ℃; Pressure-controlling is at 2-12Mpa; Reaction times is controlled at 2-14h; Reaction finishes below the fast cooling to 25 ℃, emits gas and obtains solid polymer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242375A (en) * | 2013-05-08 | 2013-08-14 | 沈阳金久奇科技有限公司 | High-activity bifunctional catalyst for preparing chiral epoxy alkane and diol and application thereof |
| CN103351464A (en) * | 2013-07-22 | 2013-10-16 | 吉林金源北方科技发展有限公司 | Novel process for carbon dioxide copolymer, and novel product |
| CN105218820A (en) * | 2015-10-19 | 2016-01-06 | 昆明理工大学 | The preparation method of a kind of sulfurous gas, carbonic acid gas and epoxy compound composition copolymer |
| WO2018158389A1 (en) * | 2017-03-01 | 2018-09-07 | Econic Technologies | Method for preparing polycarbonate ether polyols |
| CN113801314A (en) * | 2021-11-03 | 2021-12-17 | 中国科学院过程工程研究所 | Preparation method of polycarbonate |
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| CN102212085A (en) * | 2011-04-08 | 2011-10-12 | 河北工业大学 | Method for preparing Salen-metal complex |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242375A (en) * | 2013-05-08 | 2013-08-14 | 沈阳金久奇科技有限公司 | High-activity bifunctional catalyst for preparing chiral epoxy alkane and diol and application thereof |
| CN103242375B (en) * | 2013-05-08 | 2015-08-26 | 沈阳金久奇科技有限公司 | A kind of High-activity bifunctional catalyst and application thereof preparing chiral epoxy alkane and glycol |
| CN103351464A (en) * | 2013-07-22 | 2013-10-16 | 吉林金源北方科技发展有限公司 | Novel process for carbon dioxide copolymer, and novel product |
| CN105218820A (en) * | 2015-10-19 | 2016-01-06 | 昆明理工大学 | The preparation method of a kind of sulfurous gas, carbonic acid gas and epoxy compound composition copolymer |
| CN105218820B (en) * | 2015-10-19 | 2017-09-22 | 昆明理工大学 | A kind of preparation method of sulfur dioxide, carbon dioxide and epoxy compound composition copolymer |
| WO2018158389A1 (en) * | 2017-03-01 | 2018-09-07 | Econic Technologies | Method for preparing polycarbonate ether polyols |
| CN113801314A (en) * | 2021-11-03 | 2021-12-17 | 中国科学院过程工程研究所 | Preparation method of polycarbonate |
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