CN101928390A - Metal cyanide coordination catalyst and preparation method and application thereof - Google Patents
Metal cyanide coordination catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN101928390A CN101928390A CN 201010253936 CN201010253936A CN101928390A CN 101928390 A CN101928390 A CN 101928390A CN 201010253936 CN201010253936 CN 201010253936 CN 201010253936 A CN201010253936 A CN 201010253936A CN 101928390 A CN101928390 A CN 101928390A
- Authority
- CN
- China
- Prior art keywords
- formula
- metal cyanide
- catalyst
- catalyzer
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a metal cyanide coordination catalyst and a preparation method and application thereof. The catalyst has the structural formula of M1a[M2(CN)bL1c]d(X)m(L2)n.xSu.yL3.zH2O. The method for preparing the metal cyanide coordination catalyst comprises the following steps of: regulating mixed solution I' which consists of L3, M3e[M2(CN)bL1c]f, deionized water I, alcohol and/or an ether solvent to have a pH value of less than 7; and adding the solution I' into mixed solution II' which consists of M1(X)g salt, Su or a Su precursor, and deionized water II, and stirring for reaction at the temperature of between 20 and 120 DEG C for 0.5 to 200 hours; and separating, drying, the repeatedly dispersing to form slurry in an anhydrous organic solvent in which L2 is dissolved, distilling, separating and drying to prepare the metal cyanide coordination catalyst. The catalyst has the advantages of porous structure of less than 100nm, presence of coordination of M1 and L2 on a chemical structure, and obvious alternative selectivity in the process of catalyzing the copolymerization of epoxide and carbon dioxide.
Description
Technical field
The invention belongs to the Polymer Synthesizing catalyst field, be specifically related to a kind of metal cyanide coordination catalyst and its production and application.
Background technology
The sixties in last century, AM General rubber for tire company found that first double metal cyanide (DMC) is the effective catalyst that the homopolymerization of catalysis epoxidation thing prepares polyether glycol, catalysis gained polyether glycol have low-unsaturation-degree (0.005～0.008mol/kg), narrow molecular weight distributions (M
w/ M
nAdvantage such as＜1.2), its quality obviously is better than using the polyethers of KOH catalytic preparation.The preparation research of dmc catalyst mainly concentrates on the problem that research can be eliminated high molecular in the polyether glycol building-up process " hangover " in recent years, and the Application Areas of developing dmc catalyst, as is applied to catalysis carbonic acid gas (CO
2) and reactions such as epoxide copolymerization polycarbonate, epoxide and acid anhydrides copolymerization polyester.Contriver place research group has reported dmc catalyst catalysis epoxidation thing/CO
2Copolymerization polycarbonate (Polymer, 2004,45,6519; J.Polym.Sci.Part A:Polym.Chem., 2004,42,5284; 2008,46,3128; The catalysis journal, 2006,27 (4), 355; The patent No. is the Chinese patent of ZL200710066763.6), dmc catalyst catalysis epoxidation thing/CS
2Copolymerization polythiocarbonates (Macromolecules, 2008,41 (5), 1587; The polymer journal, 2009,6,546), dmc catalyst catalysis epoxidation thing/acid anhydrides copolymerization polyester (J.Appl.Polym.Sci., 2004,93 (4), 1788), dmc catalyst catalysis epoxidation thing/CO
2The systematic study work of poly-(ester-carbonic ether) aspects such as (application number are 200910098650.3 Chinese patent application) of/acid anhydrides terpolymer preparation, and the various dmc catalyst that is used for the above-mentioned reaction of catalysis is disclosed.
The disclosed dmc catalyst of prior art is mainly used in the polyethers of synthetic lower molecular weight, and part relates to the synthetic of polycarbonate polyol, extends to the study on the synthesis of polyester polyol at present gradually.At dmc catalyst catalysis epoxidation thing and CO
2Or in the acid anhydrides copolyreaction, develop more high polymerization activity and optionally dmc catalyst be key problem.As to DMC catalysis propylene oxide (PO) and CO
2There is the low shortcoming of polycarbonate (or polyester) chain link content in (or acid anhydrides) copolymerization polycarbonate (or polyester).And activity of such catalysts is generally lower.For the homopolymerization of dmc catalyst catalysis epoxidation thing, because the high reactivity of dmc catalyst often causes the inductive phase of rapid polymerization (implode) afterwards, a large amount of heat releases both may cause the generation of high molecular weight product, also can bring serious potential safety hazard.Therefore catalytic process steadily carries out and eliminates the key issue that high molecular " hangover " is the high-quality polyether glycol of acquisition.
In theory, for the heterogeneous catalyst as DMC, its catalysis behavior and effect are decided by its active centre structure, and its active centre structure comprises the coordination structure of surface metal ion, part and metal ion and part.For the improvement of dmc catalyst, prior art is mainly by changing extraneous coordination agent, add salt, partly replacing interior boundary's metal and methods such as cyano group and loadization.Above-mentioned improvement technology is still carried out at aqueous phase, and prepared catalyzer also is mainly used in the homopolymerization of epoxide.
Sum up DMC technology of preparing in the prior art, following common ground is arranged: 1) catalyst precursor mainly is preferably the precipitin reaction of zinc salt and cobalt, iron metallocyanide salt (or corresponding acid), and zinc salt is excessive often; 2) mixing solutions with water/extraneous organic complexing agent is the primitive reaction medium, and extraneous organic complexing agent is water miscible macromole (generally being polyether glycol) or micromolecular compound (trimethyl carbinol, glycol dimethyl ether) substantially.Yet since water molecules less and with the strong characteristics of catalyst metal active centre avidity, thereby than general organic complexing agent such as closeer catalyzer such as the trimethyl carbinol, tetrahydrofuran (THF), these water both had been difficult to remove from catalyzer, also cause simultaneously extraneous part to be difficult to form coordination structure, thereby in aqueous phase system, be difficult to implement the change of catalyst active center's coordination environment with the active centre metal.Especially the extraneous coordination agent of the insoluble or indissoluble of some water more difficultly in aqueous systems forms coordination structure with catalyst active center.Thereby the catalyst epoxide of existing technology of preparing preparation and with acid anhydrides or CO
2Can not improve the alternately degree of multipolymer during (especially PO) copolymerization.
Summary of the invention
The invention provides a kind of metal cyanide coordination catalyst and its production and application, described catalyzer is a nano-sheet or spherical, and has nano-pore structure, thereby has high-specific surface area; In catalyzer, introduced simultaneously can with active centre coordinate part, thereby at homopolymerization of catalysis epoxidation thing and and CO thereof
2, show catalytic performance preferably during copolymerization such as acid anhydrides.
A kind of metal cyanide coordination catalyst is characterized in that, it forms structural formula as the formula (1):
M
1 a[M
2(CN)
bL1
c]
d(X)
m(L2)
n·xSu·yL3·zH
2O (1)
In the formula (1),
M
1Be divalent-metal ion, be preferably selected from Zn
2+, Co
2+, Ni
2+Or Fe
2+In a kind of;
M
2For not comprising Fe
2+And Fe
3+Divalence or trivalent metal ion, be preferably selected from Co
3+, Ni
2+, Cd
2+, Cr
3+Or Mn
3+In a kind of;
L1 is and M
2Boundary's part can adopt part known in the art in the coordinate, be preferably selected from O, S, P or N be ligating atom unidentate ligand, with O, S, P or N be the bitooth ligand of ligating atom, in the halogen negatively charged ion one or both, be preferably Cl
-, Br
-, I
-, CN
-, N
3 -, OCN
-, SCN
-, OH
-, NH
3, pyridine or dipyridyl;
X is a negatively charged ion, is preferably selected from F
-, Cl
-, Br
-, I
-, OAc
-, 8O
4 2-, NO
3 -, in aryloxy negative ion and the organic carboxyl acid radical ion one or more; Further be preferably selected from Cl
-, Br
-, OAc
-, SO
4 2-, NO
3 -, a kind of in aryloxy negative ion or the organic carboxyl acid radical ion;
L2 is and M
1The known sub-property of power supply neutral ligand in coordinate this area is preferably selected from the neutral ligand that ligating atom is N, O, P and S; Further be preferably selected from N-alkyl imidazole, N-Aryimidazole, dipyridyl, pyridine, aliphatics nitrile, aromatic series nitrile, N, N '-dialkyl amide, N, N '-diaryl acid amides, N-substituted ring acid amides, sulfoxide or sulfone compound, organic carboxylic ester, ketone, cyclic ketones class, phosphoric acid ester, all alkyl replace tripolyphosphazene, full aryl replaces tripolyphosphazene, carbonic ether, lactone, thioether, cyclic carbonate ester or cyclic ethers class.
What emphasize is that L2 should be the neutral ligand with the sub-property of power supply, not can be the organic ligand that contains proton, as alcohols, carboxylic-acid and phenolic compound and corresponding macromolecular cpd etc.
Su is one or more in the nitrate, halogenation lithium salts, silicon-dioxide, titanium dioxide of vitriol, IIA family and IIIA family metallic element of halogenide, IIA family and IIIA family metallic element of IIA family and IIIA family metallic element; When containing silicon-dioxide or titanium dioxide among the Su, be in generating the process of catalyzer, to generate synchronously, this moment, Su can be considered as the inert support of catalyzer, and methods involving is existing disclosure the in the Chinese patent of ZL200710066763.6 in the inventor's the patent No.;
L3 is water miscible polymkeric substance, the polymkeric substance of self-assembly in the mixing solutions of water and alcohol, the polymkeric substance of self-assembly in the mixing solutions of water and ether, the perhaps polymkeric substance of self-assembly in the mixing solutions that water and pure and mild ether are formed, be preferably the polyoxyethylene polyvalent alcohol, water miscible or can be at water/alcohol, two blocks or the triblock copolymer of the oxyethane of self-assembly and propylene oxide in water/ether or water/alcohol/ethereal solution, polyester, polyether ester, polyether-modified polysiloxane, poly-(methyl) Hydroxyethyl acrylate, poly-N, N '-diethyl acrylamide, the N-N-isopropylacrylamide, polyethylene oxide-poly-N, N '-diethyl acrylamide segmented copolymer, polyethylene oxide-poly N-isopropyl acrylamide segmented copolymer, polyethylene oxide-polyacrylic acid segmented copolymer, in the segmented copolymer of polyethylene oxide-polyacrylic acid (ester) one or more; In the catalyzer building-up process, the existence of L3 is again to regulate the microtexture form of catalyzer and the template of pore structure both as extraneous coordination agent.Thereby this base polymer should form the nanometer aggregate by self-assembly in the solution that water or water and alcohol, ether equal solvent are formed, and this is to make the catalyzer state of aggregation physically have nano-sheet, spherical and contain the key point of vesicular structure.These constructional features are that catalyzer provided by the invention is distinguished in one of morphological specificity of other dmc catalyst.
A and d are positive number, and b is a positive integer, and c is 0,1 or 2, and m and n are positive number, and x, y and z are zero or positive number, wherein, and a: d=1～4, a: n=0.001～5.
From chemical terms, M
1 a[M
2(CN)
bL1
c]
d(X)
m(L2)
nAs a whole, metal ions M wherein
1Both with cyanide complex negatively charged ion [M
2(CN)
bL1
c] strong coordination takes place, also with the L2 coordination.Adopt the intensive vacuum drying method can not remove L2, show that the bonding force in L2 and active centre is adsorbed greater than general physical.And, can remove the trimethyl carbinol by the intensive vacuum drying method for being coordination agent synthetic catalyzer at the trimethyl carbinol.Alcohols, the ethers that adopts the sub-ability of power supply to be weaker than L2 in addition is difficult to the L2 in the flush away catalyzer.Characterization results such as infrared spectra information, wide-angle x-ray diffraction, laser Raman spectroscopy show L2 and M
1Between coordination takes place.The existence that this just new active centre coordination concerns is the most critical reason that catalyzer of the present invention can be obtained unprecedented catalytic effect.
The preparation of above-mentioned metal cyanide coordination catalyst may further comprise the steps:
Step 1: the mixed solution I that will be made up of metallocyanide complex compound, deionized water I, alcohols and/or ether solvent shown in L3, the formula (2) ' transfer to the pH value less than 7 adds to by M again
1(X)
gAmong the mixed solution I I ' that the presoma of salt, Su or Su, deionized water II form, 0～120 ℃ of stirring reaction 0.5～200 hour, preferable reaction temperature was 20～100 ℃, and the preferred reaction time is 1～60 hour, can adopt machinery or magnetic agitation method, stirring velocity 100～2000 is changeed; Reaction finishes after obtain the solid state product after centrifugal, filtration, washing and the seasoning;
M
3 e[M
2(CN)
bL1
c]
f (2)
In the formula (2), M
3Be alkalimetal ion, alkaline-earth metal ions or hydrogen ion, e and f are positive integer, M
2, L1, b, c be with the definition in the described formula (1);
Wherein, L3, M
1, X, Su be with the definition in the described formula (1), g is 1 or 2;
Described mixed solution I ' in, the stoichiometric ratio of metallocyanide complex compound shown in the formula (2) and deionized water I is 0.005～2 gram: 1 milliliter, be preferably 0.1～1 gram: 1 milliliter;
Described mixed solution I ' in, described L3 is 0～40% of a deionized water I weight;
Described mixed solution I ' in, described alcohols and/or ether solvent are 0～2 times of deionized water I volume, are preferably 0～0.8 times; Having of these solvents helps L3 energy good distribution or self-assembly in solution, and this is the physical basis that forms pore structure.
Described alcoholic solvent is an alcohols known in this area, is preferably carbonatoms less than 6 the tertiary alcohol and secondary alcohol; Described ether solvent is an ethers known in this area, is preferably at least a in tetrahydrofuran (THF), dioxane, glycol dimethyl ether, Propylene Glycol Dimethyl Ether or the crown ether; It also can be the mixture of at least two kinds of solvents in the above-mentioned solvent;
The acidity of regulator solution, can adopt mineral acid or water miscible organic acid, be preferably hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or carbonic acid, the consumption of acid transfers to below 7 with the pH value with solution and is as the criterion, be preferably less than 4, so both can eliminate the alkali formula structure (Zn-OH structure) of existence possible in the catalyzer, the while can obtain suitable pH scope again and help dispersion and the assembling of L3 in system.
Among the described mixed solution I I ', M
1(X)
gThe stoichiometric ratio of salt and deionized water II is 0.05～1 gram: 1 milliliter, be preferably 0.1～0.5 gram: 1 milliliter;
Metallocyanide complex compound and M shown in the formula (2)
1(X)
gThe reaction mol ratio of salt is 1: 1～50, be preferably 1: 1～and 30;
The weight ratio of the presoma of the metallocyanide complex compound shown in the formula (2) and described Su or Su is 1: 0～20;
When Su is metal-salt, be preferably the nitrate or the halogenation lithium salts of vitriol, IIA family and IIIA family metallic element of halogenide, IIA family and the IIIA family metallic element of IIA family and IIIA family metallic element, the weight fraction of Su this moment in final catalyzer is 0～10%.Adopt the effect of this type of metal-salt to be to form more defects, thereby improve the concentration at catalyst surface active center at catalyst surface;
When Su is SiO
2Or TiO
2The time, be to utilize silicon ester, titanic acid ester etc. to be presoma, in the process that generates catalyzer, generate synchronously, this moment, Su can be considered as the inert support of catalyzer, methods involving is existing disclosure the in the Chinese patent of ZL200710066763.6 in the inventor's the patent No., but significantly different is that the L3 that introduces among the present invention makes final catalyzer have vesicular structure physically, and Su shared weight fraction in final catalyzer is 5～90% in the case.
Step 2: with solid repeating dispersion slurry in being dissolved with the anhydrous organic solvent of L2 of a rapid gained, the mol ratio of the metallocyanide complex compound shown in L2 and the formula (2) is 0.1～10; Changing the slurry temperature is 20～120 ℃, is preferably 40 ℃～100 ℃, also can be at the reflux temperature slurry of system; Changing the slurry time is 0.5～200 hour, is preferably 1～48 hour; Change slurry under inert atmosphere or in the airtight reaction vessel, again through distillation, centrifugal or filtration step, final drying to constant weight obtains metal cyanide coordination catalyst behind the dispersion-change slurry;
In the optimized technical scheme, in being dissolved with the anhydrous organic solvent of L2, contain M
1(X)
gSalt, M
1(X)
gThe mol ratio of the metallocyanide complex compound shown in salt and the formula (2) is 0～2, when using M
1(X)
gDuring salt, can effectively increase M
1The content of metal ion in catalyzer guarantees M at least
1Metal ion does not lose in step 2, thereby plays the effect that increases the active centre.
In the step 2, described organic solvent is alcohols known in the field or ether solvent, described alcoholic solvent is a carbonatoms less than 6 the tertiary alcohol and secondary alcohol, and described ether solvent is at least a in tetrahydrofuran (THF), dioxane, glycol dimethyl ether, Propylene Glycol Dimethyl Ether or the crown ether.Described organic solvent is the small molecules coordination agent in traditional DMC preparation process, is again the solvent of flush away L3 simultaneously.Residual L3 is unfavorable for that too much the dispersion of catalyzer in the polymerization process and monomer to the diffusion in active centre, increase decomposition induction time sometimes.Often contain a certain amount of L3 in the catalyzer.In addition, because described organic solvent, promptly residual being proved to be of lower boiling such as alcohols and ethers coordination agent do not have promoter action to catalytic activity, although these solvents can influence the grain size and the form of catalyzer.Simultaneously residual solvent is alcoholic solvent especially, will cause chain transfer in polymerization process, thereby cause the reduction of molecular weight of product, and it is necessary therefore the catalyzer for preparing gained being carried out thorough drying.The catalyzer of the present invention's preparation does not contain above-mentioned low boiling point solvent, and this also is the remarkable composition characteristic that catalyzer provided by the invention is different from traditional dmc catalyst.
Dmc catalyst is at catalysis epoxidation thing and acid anhydrides, CO in the prior art
2Though each is variant for the activity during Deng copolymerization, the polymeric selectivity is basic identical.This phenomenon shows chemical structure and the microenvironment of not improving catalyst active center among the existing preparation method.The preparation method that the present invention adopts and select the sub-property coordination agent L2 of power supply for use, and with the metal center M of short of electricity
1Ion forms coordination, and forming thus can be by formula M
1 a[M
2(CN)
bL1
c]
d(X)
m(L2)
nThe active ingredient of expression.New catalyzer is at catalysis epoxidation thing and acid anhydrides, CO
2Shown significant polymerization during Deng copolymerization and optionally improved, i.e. the raising of alternate degree, this is also just from the successful part of the angular adjustment DMC active centre structure strategy of chemistry.
Among the preparation method provided by the invention, the change slurry process of step 2 because content of water in system is very low, is equivalent to the solvent thermal process.Experimental result shows the M that can promote in coordination agent L2 and the catalyzer
1Coordination is as selected coordination agent L2 and M
1Coordination ability is greater than the alcohols or ether solvent and the M that dissolve it
1Solvation the time, have better effect.Often can be by the washing process in the step 2 with most of L3 flush away, the size of L3 reservation amount is little to polymerization activity and selectivity influence, but influences the pore size of gained catalyzer, and this often influences induction period in polymerization; The drying process of step 2 is completely, so small molecules coordination agent such as tetrahydrofuran (THF), the trimethyl carbinol etc. can be removed.
Method synthetic catalyzer of the present invention, wherein M
1With M
2Mol ratio (being the ratio of a/d) be 1～4; M
1With the mol ratio (being the ratio of a/n) of L2 be 0.001～5.Scanning electron microscope result shows that it is the spherical or sheet structure (as Fig. 1) of nanometer; Wide-angle x-ray diffraction result shows that this catalyzer is a polycrystalline structure, and the diffracted ray of broadening shows its poly grains size below 100nm (as Fig. 2); Adopt nitrogen adsorption-desorption experimental result to measure the catalyst pores structure, before test, need with the organic constituent in the catalyzer comprise L3 and L2 thoroughly remove be necessary also be the treatment step of using always.Usually adopt method for calcinating to remove organism, be generally less than to calcine under 400 ℃ of conditions and can not destroy the catalyst backbone structure, and can remove organism again; Adopt in addition intensive polar solvent under less than 200 ℃ of conditions repeatedly extracting also can remove organic constituent in the catalyzer.Could more accurately measure the pore structure of catalyzer after treatment.The result shows that it contains irregular nano-pore structure, and average pore size is 3～100nm, and specific surface area is 50～800m
2/ g is 100～600m generally speaking
2/ g.
The metal cyanide coordination catalyst of the present invention preparation, but high reactivity, the thing homopolymerization of highly selective catalysis epoxidation and and carbonic acid gas, acid anhydrides alternating copolymerization prepare polycarbonate, polyester etc.Wherein, described epoxide is a well-known compound in this area, be preferably and be selected from oxyethane, propylene oxide, butylene oxide ring, 1,1-dimethyl ethylene oxide, epoxy chloropropane, epoxy bromopropane, Styrene oxide 98min., cyclohexene oxide, 4-vinyl cyclohexene oxide, cyclopentene oxide or C
5-C
20Alpha-oxidation alkene at least a, described acid anhydrides is a well-known compound in this area, is preferably to be selected from maleic anhydride, Pyroglutaric acid, Succinic anhydried, anhydride diethylene glycol, Tetra hydro Phthalic anhydride or several mixture arbitrarily in them.
When described metal cyanide coordination catalyst is used for the ring-opening polymerization of catalysis epoxidation thing, embody high catalytic efficiency, catalyzed polymerization process is comparatively steady simultaneously, eliminated the very exothermic process, thereby reaction system pressure held stationary, catalyzer can inactivation in the longer reaction times, has significantly reduced high-molecular weight " hangover " simultaneously.
Described metal cyanide coordination catalyst is used for catalysis epoxidation thing and CO
2Or during the acid anhydrides copolymerization, embody high catalytic efficiency, especially the alternately degree of copolymerization product obtains greatly to improve.As to epoxide and/CO
2Copolymerization, at first with autoclave through dewatering and CO
2After the displacement, add catalyzer, epoxide and/or initiator at ambient temperature, in the sealed high pressure reactor, be pressed into CO again
2Gas, CO in the maintenance system
2Pressure is 0.5-10MPa, and temperature is 0-150 ℃, reacts 2-24 hour, can add polyether glycol, polyester polyol, polyester ether polylol, small molecular alcohol or the water of initiator such as different molecular weight.The catalytic activity of catalyzer＞1kg polycarbonate/g active ingredient (is M
1 a[M
2(CN)
bL1
c]
d(X)
m), replacing degree＞90%, number-average molecular weight reaches as high as 150,000.
Described metal cyanide coordination catalyst is used for catalysis epoxidation thing and acid anhydrides copolymerization, or epoxide, acid anhydrides and CO
2Terpolymer embodies high catalytic efficiency and high copolymerization replaces rate.Autoclave is through dewatering and N
2After the displacement, add at ambient temperature catalyzer, epoxide and (or) initiator, in the sealed high pressure reactor, (to epoxide and acid anhydrides copolymerization) or 0.5-10MPa are (to epoxide, acid anhydrides and CO under system self pressure
2Terpolymer) carries out under.Temperature of reaction is 0-180 ℃, is preferably 20-150 ℃; Reaction times is 0.5-100 hour, is preferably 2-24 hour; Wherein initiator can be the materials such as polyether glycol, polyester polyol, polyester ether polylol and small molecule alcohol of different molecular weight, also can not add initiator, when not adding initiator, can think that initiator is the water in the system.Catalysis epoxidation thing and acid anhydrides binary copolymerization, catalytic efficiency can replace degree＞95%, number-average molecular weight＞10,000 greater than 2kg polymkeric substance/g active ingredient; Catalysis epoxidation thing, acid anhydrides and CO
2Terpolymer, catalytic efficiency can reach 1.5kg polymkeric substance/g active ingredient, replace degree＞95%, number-average molecular weight＞20,000.
With respect to prior art, the present invention has following useful technique effect:
1) sub-ligand L 2 of power supply and M have been realized in the method for preparing catalyst provided by the invention
1Coordination, thereby obtained the novel metal cyanide complex catalyst of active centre different in kind in traditional DMC.This catalyzer has shown surprising catalytic effect, and especially to copolyreaction, under the highly active catalytic prerequisite, the polymerization selectivity significantly improves;
2) introduce L3 to the preparation system, except the effect that shows the extraneous coordination agent of macromole, the more important thing is the template as catalyzer (or containing carrier), obtain nano-sheet or spherical and contain the porous catalyst of nano-pore structure, effectively improved the specific surface area of catalyzer from physical angle;
3) in the Preparation of Catalyst scheme of the present invention, by directly controlling the pH value less than 7, under acidic conditions, eliminate " Zn-OH " structure, avoided the disadvantageous effect of the existence of " Zn-OH ", especially can effectively eliminate high molecular " hangover " part polymerization activity and molecular weight;
4) with respect to traditional preparation process technology, two-step approach provided by the invention prepares technology, thereby do not need a large amount of mixing solutionss that use as traditional extraneous organic complexing agent such as the trimethyl carbinol, glycol dimethyl ether and tetrahydrofuran (THF) and water, thereby avoided the waste of organic ligand and to the pollution of environment.
Description of drawings
Fig. 1 is the scanning electron microscope result of catalyzer of the present invention, and wherein A is the catalyzer of embodiment 2 preparations, and B is the catalyzer of embodiment 3 preparations;
Fig. 2 is the wide-angle x-ray diffraction result of catalyzer of the present invention, and wherein A is the catalyzer of embodiment 2 preparations, and B is the catalyzer of embodiment 3 preparations;
Fig. 3 is the infrared spectrogram of catalyzer of the present invention, and wherein A is the catalyzer of embodiment 2 preparations, and B ' is the catalyzer of embodiment 5 preparations.
Embodiment
Describe the present invention in detail below in conjunction with drawings and Examples, but the present invention is not limited to this.
The preparation of embodiment 1 metal cyanide coordination catalyst
Step 1: with 0.80g K
3Co (CN)
6(0.0024mol) be dissolved among the 50mL deionized water I, add trimethyl carbinol 2mL (1.57g), obtain mixed solution I ', adding aqueous hydrochloric acid adjusting mixed solution I ' to pH＜7, the dissolving homogeneous transparent, be added under agitation condition then by 4.0g (0.029mol) zinc chloride in 20mL deionized water II in the lysigenous solder(ing)acid (mixed solution I I '), in 40 ℃ of stirring reactions 24 hours, suction filtration obtained half-dried solid filter cake;
Step 2: the mixture of rapid gained filter cake of previous step and 0.5g zinc chloride (0.0037mol) is scattered in to have dissolved 2.0g 1-phenylimidazole (be the N-phenylimidazole, 0.0139mol) anhydrous tertiary butanol (20mL) in, in 60 ℃ of stirrings 10 hours, suction filtration obtained white solid.The white solid redispersion of gained in the 40mL anhydrous tertiary butanol, is stirred 10 hours postcooling in 60 ℃ and filters, and same step repeats 3 times.Collect the trimethyl carbinol distillation reuse that at every turn filters out, solid obtains solid metal cyanide complex catalyst 1.3g 80 ℃ of following vacuum-dryings 2 days.
Results of elemental analyses: Zn:26.4wt%; Co:11.4wt%; Cl:2.4wt%; C:28.7wt%; H:2.10wt%; N:21.1wt%
SEM is viewed as nano-sheet, sheet thickness: 20～40nm;
XRD result is ° interval broad peak that shows in 2 θ=13～25.
It is 4nm that the nitrogen adsorption method records mean pore size.
The preparation of embodiment 2 metal cyanide coordination catalysts
With embodiment 1, just mixed solution I ' middle the adding in step 1 has 2.1g EO
20PO
70EO
20(Pluronic P123 Aldrich), is the 4.2wt% of deionized water I weight (50g).Finally obtain solid metal cyanide complex catalyst 1.5g.
Results of elemental analyses: Zn:19.4wt%; Co:9.6wt%; Cl:6.3wt%; C:28.84wt%; H:3.27wt%; N:16.35wt%
SEM observes (seeing Figure 1A): spherical, median size is less than 100nm;
XRD result's (seeing Fig. 2 A) is ° interval broad peak that shows in 2 θ=13～25;
It is 8nm that the nitrogen adsorption method records mean pore size.
The peak that infrared spectrogram (seeing Fig. 3 A) is located 2294 and 472 wave numbers is the characteristic infrared absorption peak of CN and Co-C key in the catalyzer; The absorption peak of 1500 and 1200 wave numbers shows being present in the catalyzer of organic ligand.
The preparation of embodiment 3 metal cyanide coordination catalysts
With embodiment 1, just in step 2, change the 1-phenylimidazole into equimolar diphenyl sulfoxide, anhydrous tertiary butanol changes isopyknic anhydrous tetrahydro furan into, decentralized slurry in anhydrous tetrahydro furan, changing the slurry temperature is the reflux temperature of tetrahydrofuran (THF).Obtain solid metal cyanide complex catalyst 1.8g.
Results of elemental analyses: Zn:19.2wt%; Co:9.2wt%; Cl:2.8wt%; C:26.04wt%; H:1.03wt%; N:15.78wt%.
It is sheet that SEM observes (seeing Figure 1B), sheet thickness: 20～40nm;
XRD result is ° interval broad peak that shows in 2 θ=13～25;
It is 45nm that the nitrogen adsorption method records mean pore size.
The preparation of embodiment 4 metal cyanide coordination catalysts
With embodiment 1, just change the 4.0g zinc chloride in the step 1 into the 15.0g zinc acetate, change 1-phenylimidazole in the step 2 into equimolar diphenatril, and do not use zinc acetate in step 2.Finally obtain solid metal cyanide complex catalyst 1.5g.
Results of elemental analyses: Zn:26.6wt%; Co:12.5wt%; C:31.45wt%; H:1.49wt%; N:17.32wt%.
SEM is viewed as spherical, and median size is～50nm.
The preparation of embodiment 5 metal cyanide coordination catalysts
Step 1:
With 8.0g EO
20PO
70EO
20Be dissolved in 60mL deionized water and the 2mL tetrahydrofuran (THF), dissolve and add 1.0g K again after transparent
3Co (CN)
6(0.003mol) dissolving is transparent, obtain mixed solution I ', under agitation condition, add concentrated hydrochloric acid solution and regulate mixed solution I ' to pH=4, dissolving homogeneous transparent (EO
20PO
70EO
20With the weight fraction of deionized water be 13.3%);
4.g tetraethoxy (TEOS) is added to stirring fast in the solder(ing)acid, forms mixed solution I I ', solder(ing)acid is to be dissolved in the 20mL water by 2.5g (0.018mol) zinc chloride to obtain, vigorous stirring, and rotating speed is 800 commentaries on classics;
Then with mixed solution I ' drop among the mixed solution I I ', in 40 ℃ of stirring reactions 24 hours, suction filtration obtained half-dried white solid filter cake;
Step 2:
Rapid gained filter cake of previous step and 0.5g zinc chloride are scattered in the anhydrous tertiary butanol (50mL) that has dissolved 4.5g dipyridyl (0.0288mol), left standstill 10 hours for following 95 ℃ in the system autogenous pressure in the autoclave that is lined with tetrafluoroethylene, suction filtration obtains white solid; And then wash and starch with the trimethyl carbinolization and to wash 3 times, vacuum-drying obtains solid 2.3g to constant weight.
Results of elemental analyses: Zn:23.4wt%; Co:7.8wt%; Cl:4.2wt%; C:36.19wt%; H:2.18wt%; N:16.63wt%.
SEM is viewed as irregular sheet, and sheet thickness is 80nm;
XRD result is ° interval broad peak that shows in 2 θ=13～25.
It is 32nm that the nitrogen adsorption method records mean pore size.
The peak that infrared spectrogram (seeing Fig. 3 B ') is located 2294 and 472 wave numbers is the characteristic infrared absorption peak of CN and Co-C key in the catalyzer; 1500 wave numbers are the infrared absorption peak of the part of introducing, contain the silica supports of TEOS hydrolysis generation and the polyethers of small amount of residual during the broad peak at 1000～1300 wave number places shows in the catalyzer.
The preparation of embodiment 6 metal cyanide coordination catalysts
In embodiment 5, with K
2Ni (CN)
4(0.0033mol) replace K
3[Co (CN)
6], prepare SiO
2The Ni-Zn catalyzer 1.6g of load.
Results of elemental analyses: SiO
2: 22.3%; Zn:16.5wt%; Ni:3.8wt%; Cl:3.5wt%; C:25.73wt%; H:1.39wt%; N:16.86wt%.
The SEM observations is irregular sheet, and the mean thickness of sheet is less than 100nm.
The preparation of embodiment 7 metal cyanide coordination catalysts
According to embodiment 6 methods, with the K of equimolar amount
3[Co (CN)
5Br] replacement K
3Co (CN)
6, (1.7g 0.0024mol), is prepared into SiO according to embodiment 6 methods to change dipyridyl into the hexaphenyl tripolyphosphazene
2The catalyzer 2.5g that contains different interior boundaries part of load.
Results of elemental analyses: Zn:20.4wt%; Co:7.6wt%; Cl:4.3wt%; Br:4.5wt%; C:32.68wt%; H:2.09wt%; N:16.25wt%.
SEM observes spherical, and median size is less than 100nm;
It is 60nm that the nitrogen adsorption method records mean pore size.
In the above-mentioned analytical procedure, x ray fluorescence spectrometry, atomic spectroscopy and CHN elemental microanalysis method are mainly adopted in ultimate analysis; When adopting nitrogen adsorption desorption method gaging hole footpath, need remove the organic constituent in the catalyzer in advance, adopt method for calcinating under less than 350 ℃ of conditions, to calcine (most of organism decomposition this moment, and the catalyst backbone structure can not be destroyed, such catalyzer is just decomposing more than 400 ℃), perhaps adopt intensive polar solvent extracting repeatedly under less than 200 ℃ of conditions.Nitrogen adsorption desorption curve and transmission electron microscope observing result show that the hole that catalyzer forms is mainly the irregular hole that nano particle is piled up generation.
The application of embodiment 8 metal cyanide coordination catalysts
Weight-average molecular weight and molecular weight distribution in following examples are by gel permeation chromatography; Cyclic products content, copolymerization component ratio by
1H NMR method is measured; Activity of such catalysts is determined by weighting method; Second-order transition temperature is measured by thermal analysis system, heats up by 10 ℃/min, and getting for the second time, the heating curve heat deflection is the second-order transition temperature value.Activity of such catalysts is according to active ingredient M in the catalyzer
1 a[M
2(CN)
bL1
c]
d(X)
mAmount be that benchmark calculates.
Adopt the catalyst epoxide homopolymerization (substep feed way) of embodiment 1 preparation
In 500 milliliters of stainless steel autoclaves, add 20 gram initiator (PPG-400) and 7.0 milligrams of catalyzer earlier, heating rises to certain temperature (110 ℃) then, with nitrogen replacement for several times, vacuum hydro-extraction 0.5h continues to be warming up to after 120 ℃, squeeze into 10 milliliters of PO with volume pump, when waiting abrupt pressure reduction to occur (18 minutes), in about 5 hours, add the PO monomer, about each 10ml (totally 100 milliliters) in batches.React the back decompression and removed residual monomer, must be with the thickness liquid product.
Number-average molecular weight 3.83kg/mol, molecular weight distribution 1.08, wherein number-average molecular weight is lower than 500ppm greater than product content in gross product of 100,000, and in traditional dmc catalyst catalysis PO homopolymerization product number-average molecular weight greater than 100,000 product in gross product content generally greater than 1000ppm;
Activity of such catalysts is 30kg polymkeric substance/gM
1 a[M
2(CN)
bL1
c]
d(X)
m
Adopt the catalyst epoxide and the carbon dioxide copolymerization of embodiment 5 preparations
Add the 15.0g catalyzer to the autoclave of cleaning,, be cooled to room temperature then at 80 ℃ of following vacuum-drying 24h.Under condition of negative pressure 100mL exsiccant propylene oxide ring is injected in the still, agitation condition is pushed down into 6.0MPa CO
2, being heated to 60 ℃ then, reaction 10h postcooling is emitted unnecessary gas in the reactor earlier, and methanol wash is adopted in discharging again, obtains solid product in drying.Crude product is used
1HNMR and GPC test, the characterize polymers structure, weighting method is calculated productive rate.
Polymkeric substance number-average molecular weight 12.0 ten thousand, molecular weight distribution 1.9;
Multipolymer alternate degree 98.7%, cyclic carbonate ester content 2.0wt% in the crude product;
Activity of such catalysts is 2.3kg polymkeric substance/g M
1 a[M
2(CN)
bL1
c]
d(X)
m
The second-order transition temperature measured value is 38 ℃.
Adopt the catalyst epoxide/acid anhydrides copolymerization of embodiment 4 preparations
Before the polyreaction with capacity be earlier 60ml autoclave in 110 ℃ removed moisture in following about 2 hours and in drying tower under be cooled to room temperature.Add 3.0mg catalyzer, maleic anhydride 2.0g, cyclohexene oxide 4.0mL and tetrahydrofuran (THF) 4.0mL in reactor, the good seal reactor joins in the oil bath that is preheated to 90 ℃, the magnetic agitation reaction is after 5 hours, fast cooling, relief pressure takes out crude product.Elder generation's removal of solvent under reduced pressure, dissolve crude product with THF again, be settled out polymkeric substance in methyl alcohol, obtain yellow product after the vacuum-drying, weighting method is calculated transformation efficiency, calculates polyester chain link and polyethers chain link content by nucleus magnetic hydrogen spectrum.
Polymkeric substance number-average molecular weight 2.4 ten thousand, molecular weight distribution 1.6;
Multipolymer alternate degree 96%;
Activity of such catalysts is 2.0kg polymkeric substance/g M
1 a[M
2(CN)
bL1
c]
d(X)
m
82 ℃ of second-order transition temperatures.
Adopt the catalyst epoxide/acid anhydrides/CO of embodiment 4 preparations
2Terpolymer
The autoclave that before the polyreaction with capacity is 100ml was earlier removed moisture in following about 2 hours in 110 ℃.In reactor, add catalyzer 10.0mg catalyzer, cyclohexene oxide 40.0mL, maleic anhydride 4.0g and tetrahydrofuran (THF) 40mL successively, the good seal reactor.Add CO
2To CO
2Pressure is 4.0MPa, and stirring reaction is after 5 hours, fast cooling, and relief pressure takes out crude product.Crude product is through CH
2Cl
2Obtain yellow product after/methanol wash, the vacuum-drying, weighting method is calculated transformation efficiency, calculates the content of polyester chain link and polyethers chain link by nucleus magnetic hydrogen spectrum.
Polymkeric substance number-average molecular weight 3.0 ten thousand, molecular weight distribution 1.8;
Multipolymer alternate degree 98%;
Activity of such catalysts 3.5kg polymkeric substance/g M
1 a[M
2(CN)
bL1
c]
d(X)
m
108 ℃ of second-order transition temperatures.
Claims (9)
1. a metal cyanide coordination catalyst is characterized in that, it forms structural formula as the formula (1):
M
1 a[M
2(CN)
bL1
c]
d(X)
m(L2)
n·xSu·yL3·zH
2O (1)
In the formula (1),
M
1Be divalent-metal ion, be selected from Zn
2+, Co
2+, Ni
2+Or Fe
2+In a kind of;
M
2For not comprising Fe
2+And Fe
3+Divalence or trivalent metal ion, be selected from Co
3+, Ni
2+, Cd
2+, Cr
3+Or Mn
3+In a kind of;
L1 is and M
2Boundary's part in the coordinate is selected from N, O, P and S and is the unidentate ligand of ligating atom, is the bitooth ligand of ligating atom or in the halogen negatively charged ion one or both with O, S, P or N;
X is a negatively charged ion, is selected from F
-, Cl
-, Br
-, I
-, OAc
-, SO
4 2-, NO
3 -, in aryloxy negative ion and the organic carboxyl acid radical ion one or more;
L2 is and M
1Coordinate contains the neutral ligand with power supply sub-property ligating atom N, O, P and S;
Su is one or more in the nitrate, halogenation lithium salts, silicon-dioxide, titanium dioxide of vitriol, IIA family and IIIA family metallic element of halogenide, IIA family and IIIA family metallic element of IIA family and IIIA family metallic element;
L3 is the polymkeric substance of self-assembly in the mixing solutions of polymkeric substance, water and ether of water miscible polymkeric substance, self-assembly in the mixing solutions of water and alcohol or the polymkeric substance of self-assembly in the mixing solutions of water and pure and mild ether composition;
A and d are positive number, and b is a positive integer, and c is 0,1 or 2, and m and n are positive number, and x, y and z are zero or positive number, wherein, and a: d=1～4, a: n=0.001～5.
2. metal cyanide coordination catalyst as claimed in claim 1, it is characterized in that, described L2 is N-alkyl imidazole, N-Aryimidazole, dipyridyl, pyridine, aliphatics nitrile, aromatic series nitrile, N, N '-dialkyl amide, N, N '-diaryl acid amides, N-substituted ring acid amides, sulfoxide or sulfone compound, organic carboxylic ester, ketone, cyclic ketones class, phosphoric acid ester, all alkyl replace tripolyphosphazene, full aryl replaces tripolyphosphazene, carbonic ether, cyclic lactone, thioether, cyclic carbonate ester or cyclic ethers class.
3. metal cyanide coordination catalyst as claimed in claim 1 is characterized in that it is a nano-sheet or spherical, and has the pore structure of mean pore size less than 100 nanometers.
4. as the preparation method of the arbitrary described metal cyanide coordination catalyst of claim 1～3, it is characterized in that, may further comprise the steps:
Step 1: the mixed solution I that will be made up of metallocyanide complex compound, deionized water I, alcohols and/or ether solvent shown in L3, the formula (2) ' transfer to the pH value less than 7 adds to by M again
1(X)
gAmong the mixed solution I I ' that the presoma of salt, Su or Su, deionized water II are formed, 0～120 ℃ of stirring reaction 0.5～200 hour, reaction finished after separate, obtain solid after the drying;
M
3 e[M
2(CN)
bL1
c]
f (2)
In the formula (2), M
3Be alkalimetal ion, alkaline-earth metal ions or hydrogen ion, e and f are positive integer, M
2, L1, b, c be with the definition in the described formula (1);
Wherein, L3, M
1, X, Su be with the definition in the described formula (1), g is 1 or 2;
Described mixed solution I ' in, the stoichiometric ratio of metallocyanide complex compound shown in the formula (2) and deionized water I is 0.005～2 gram: 1 milliliter; Described L3 is 0～40% of a deionized water I weight, and described alcohols and/or ether solvent are 0～2 times of deionized water I volume;
Among the described mixed solution I I ', M
1(X)
gThe stoichiometric ratio of salt and deionized water II is 0.05～1 gram: 1 milliliter;
Metallocyanide complex compound and M shown in the formula (2)
1(X)
gThe reaction mol ratio of salt is 1: 1～50; The weight ratio of the presoma of the metallocyanide complex compound shown in the formula (2) and described Su or Su is 1: 0～20;
Step 2: with solid repeating dispersion slurry in being dissolved with the anhydrous organic solvent of L2 of step 1 gained, the mol ratio of the metallocyanide complex compound shown in L2 and the formula (2) is 0.1～10, changing the slurry temperature is 20～120 ℃, changing the slurry time is 0.5～200 hour, under inert atmosphere or in the airtight reaction vessel, change slurry, again through distillation, separation, drying, obtain metal cyanide coordination catalyst behind the dispersion-change slurry.
5. preparation method as claimed in claim 4 is characterized in that, in the described step 1, and metallocyanide complex compound and the M shown in the formula (2)
1(X)
gThe reaction mol ratio of salt is 1: 1～30.
6. preparation method as claimed in claim 4 is characterized in that, the mixed solution I of described step 1 ' in, described alcohols and/or ether solvent are 0～0.8 times of deionized water I volume.
7. preparation method as claimed in claim 4 is characterized in that, in the described step 2, changing the slurry temperature is 40 ℃～100 ℃.
8. preparation method as claimed in claim 4 is characterized in that, in the described step 2, contains M in the anhydrous organic solvent of the described L2 of being dissolved with
1(X)
gSalt, M
1(X)
gMetallocyanide complex compound mol ratio shown in salt and the formula (2) is 0～2.
9. preparing polyethers, catalysis epoxidation thing and acid anhydrides alternating copolymerization as the arbitrary described metal cyanide coordination catalyst of claim 1～3 in the homopolymerization of catalysis epoxidation thing prepares polyester, catalysis epoxidation thing, acid anhydrides and carbon dioxide copolymerization and prepares application in the polyester-polycarbonate multipolymer.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102539367A CN101928390B (en) | 2010-08-13 | 2010-08-13 | Metal cyanide coordination catalyst and preparation method and application thereof |
| PCT/CN2010/079735 WO2012019405A1 (en) | 2010-08-13 | 2010-12-13 | Metal cyanide complex catalyst, preparation method and uses thereof |
| US13/394,267 US8859452B2 (en) | 2010-08-13 | 2010-12-13 | Metal cyanide complex catalyst and its preparation and application |
| US14/484,490 US9469722B2 (en) | 2010-08-13 | 2014-09-12 | Metal cyanide complex catalyst and its preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102539367A CN101928390B (en) | 2010-08-13 | 2010-08-13 | Metal cyanide coordination catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101928390A true CN101928390A (en) | 2010-12-29 |
| CN101928390B CN101928390B (en) | 2012-05-23 |
Family
ID=43367852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102539367A Active CN101928390B (en) | 2010-08-13 | 2010-08-13 | Metal cyanide coordination catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101928390B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580780A (en) * | 2011-12-19 | 2012-07-18 | 浙江大学 | Synthesizing method and application for bi-component bi-metallic catalyst |
| CN105555400A (en) * | 2013-07-18 | 2016-05-04 | Sk新技术株式会社 | Double metal cyanide catalyst and epoxide/carbon dioxide copolymer prepared using the same |
| CN107556489A (en) * | 2017-10-16 | 2018-01-09 | 山东理工大学 | A kind of spin crossover molecular magnetic materialses of Stress control and preparation method thereof |
| CN108179278A (en) * | 2017-12-21 | 2018-06-19 | 浙江理工大学 | A kind of noble metal extracting solution, preparation method and applications |
| CN110669489A (en) * | 2019-10-14 | 2020-01-10 | 中国石油化工股份有限公司 | Low-power depolymerization emulsification viscosity reducer for cold production of thick oil and preparation method thereof |
| WO2020062816A1 (en) | 2018-09-29 | 2020-04-02 | 杭州普力材料科技有限公司 | Mixed acid-modified zinc-cobalt two-metal cyanide catalyst and preparation method thereof |
| CN110964192A (en) * | 2018-09-29 | 2020-04-07 | 杭州普力材料科技有限公司 | Mixed acid modified double metal cyanide catalyst for preparing carbon dioxide-based polycarbonate and preparation method thereof |
| CN110964191A (en) * | 2018-09-29 | 2020-04-07 | 杭州普力材料科技有限公司 | Mixed acid modified zinc-cobalt double metal cyanide catalyst and preparation method thereof |
| CN111944134A (en) * | 2020-08-24 | 2020-11-17 | 浙江大学 | Preparation method of high molecular weight unsaturated polyester and product thereof |
| CN112126053A (en) * | 2020-09-22 | 2020-12-25 | 河北工业大学 | Preparation method and application of double metal cyanide catalyst |
| CN114230783A (en) * | 2022-01-12 | 2022-03-25 | 万华化学集团股份有限公司 | Composite catalyst for epoxy ring opening and preparation method and application thereof |
| CN115286781A (en) * | 2022-08-01 | 2022-11-04 | 中国科学院长春应用化学研究所 | Electron-withdrawing group polycarbonate ether polyol and efficient preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6362126B1 (en) * | 1998-03-05 | 2002-03-26 | Basf Aktiengesellschaft | Supported double metal cyanide catalysts, method for producing them, and their use for producing polyether alcohols |
| CN101003622A (en) * | 2007-01-18 | 2007-07-25 | 浙江大学 | Catalyst of load type bimetallic cyaniding complex, preparation method and application |
-
2010
- 2010-08-13 CN CN2010102539367A patent/CN101928390B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6362126B1 (en) * | 1998-03-05 | 2002-03-26 | Basf Aktiengesellschaft | Supported double metal cyanide catalysts, method for producing them, and their use for producing polyether alcohols |
| CN101003622A (en) * | 2007-01-18 | 2007-07-25 | 浙江大学 | Catalyst of load type bimetallic cyaniding complex, preparation method and application |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580780A (en) * | 2011-12-19 | 2012-07-18 | 浙江大学 | Synthesizing method and application for bi-component bi-metallic catalyst |
| CN102580780B (en) * | 2011-12-19 | 2015-04-15 | 浙江大学 | Synthesizing method and application for bi-component bi-metallic catalyst |
| CN105555400A (en) * | 2013-07-18 | 2016-05-04 | Sk新技术株式会社 | Double metal cyanide catalyst and epoxide/carbon dioxide copolymer prepared using the same |
| CN105555400B (en) * | 2013-07-18 | 2019-01-04 | Sk新技术株式会社 | DMC catalysts and the epoxides/carbon dioxide copolymer prepared using it |
| CN107556489A (en) * | 2017-10-16 | 2018-01-09 | 山东理工大学 | A kind of spin crossover molecular magnetic materialses of Stress control and preparation method thereof |
| CN107556489B (en) * | 2017-10-16 | 2020-06-19 | 山东理工大学 | Pressure-controlled spin cross molecular magnetic material and preparation method thereof |
| CN108179278A (en) * | 2017-12-21 | 2018-06-19 | 浙江理工大学 | A kind of noble metal extracting solution, preparation method and applications |
| CN108179278B (en) * | 2017-12-21 | 2019-09-20 | 浙江理工大学 | A kind of noble metal extracting solution, preparation method and applications |
| CN110964191A (en) * | 2018-09-29 | 2020-04-07 | 杭州普力材料科技有限公司 | Mixed acid modified zinc-cobalt double metal cyanide catalyst and preparation method thereof |
| CN110964192A (en) * | 2018-09-29 | 2020-04-07 | 杭州普力材料科技有限公司 | Mixed acid modified double metal cyanide catalyst for preparing carbon dioxide-based polycarbonate and preparation method thereof |
| WO2020062816A1 (en) | 2018-09-29 | 2020-04-02 | 杭州普力材料科技有限公司 | Mixed acid-modified zinc-cobalt two-metal cyanide catalyst and preparation method thereof |
| CN110964192B (en) * | 2018-09-29 | 2022-05-17 | 杭州普力材料科技有限公司 | Mixed acid modified double metal cyanide catalyst for preparing carbon dioxide-based polycarbonate and preparation method thereof |
| CN110669489A (en) * | 2019-10-14 | 2020-01-10 | 中国石油化工股份有限公司 | Low-power depolymerization emulsification viscosity reducer for cold production of thick oil and preparation method thereof |
| CN110669489B (en) * | 2019-10-14 | 2021-10-22 | 中国石油化工股份有限公司 | Low-power depolymerization emulsification viscosity reducer for cold production of thick oil and preparation method thereof |
| CN111944134A (en) * | 2020-08-24 | 2020-11-17 | 浙江大学 | Preparation method of high molecular weight unsaturated polyester and product thereof |
| CN111944134B (en) * | 2020-08-24 | 2021-08-03 | 浙江大学 | Preparation method of high molecular weight unsaturated polyester and product thereof |
| CN112126053A (en) * | 2020-09-22 | 2020-12-25 | 河北工业大学 | Preparation method and application of double metal cyanide catalyst |
| CN112126053B (en) * | 2020-09-22 | 2022-06-21 | 河北工业大学 | Preparation method and application of double metal cyanide catalyst |
| CN114230783A (en) * | 2022-01-12 | 2022-03-25 | 万华化学集团股份有限公司 | Composite catalyst for epoxy ring opening and preparation method and application thereof |
| CN114230783B (en) * | 2022-01-12 | 2023-05-26 | 万华化学集团股份有限公司 | Composite catalyst for epoxy ring opening and preparation method and application thereof |
| CN115286781A (en) * | 2022-08-01 | 2022-11-04 | 中国科学院长春应用化学研究所 | Electron-withdrawing group polycarbonate ether polyol and efficient preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101928390B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101928390B (en) | Metal cyanide coordination catalyst and preparation method and application thereof | |
| CN101942081B (en) | Method for preparing aliphatic polycarbonates by catalyzing by metal cyanide coordination catalyst | |
| US9469722B2 (en) | Metal cyanide complex catalyst and its preparation and application | |
| Hu et al. | Bifunctional metal-doped ZIF-8: A highly efficient catalyst for the synthesis of cyclic carbonates from CO2 cycloaddition | |
| Zhang et al. | Carbon dioxide/epoxide copolymerization via a nanosized zinc–cobalt (III) double metal cyanide complex: substituent effects of epoxides on polycarbonate selectivity, regioselectivity and glass transition temperatures | |
| Jayakumar et al. | Cationic Zn-porphyrin immobilized in mesoporous silicas as bifunctional catalyst for CO2 cycloaddition reaction under cocatalyst free conditions | |
| CN101003622B (en) | Catalyst of load type bimetallic cyaniding complex, preparation method and application | |
| CN111393630B (en) | Polymer polyol and preparation method thereof | |
| Sun et al. | Alternating copolymerization of carbon dioxide and cyclohexene oxide catalyzed by silicon dioxide/Zn CoIII double metal cyanide complex hybrid catalysts with a nanolamellar structure | |
| Ayed et al. | Conjugated microporous polymers with immobilized TiO2 nanoparticles for enhanced visible light photocatalysis | |
| Wei et al. | Highly regioselective and alternating copolymerization of racemic styrene oxide and carbon dioxide via heterogeneous double metal cyanide complex catalyst | |
| Huang et al. | Ring‐opening polymerization of propylene oxide catalyzed by a calcium‐chloride‐modified zinc‐cobalt double metal‐cyanide complex | |
| Baghbamidi et al. | The reduction of 4‐nitrophenol and 2‐nitroaniline by palladium catalyst based on a KCC‐1/IL in aqueous solution | |
| CN108409954B (en) | Synthesis method of carbon dioxide-based polycarbonate block copolymer | |
| CN107619466B (en) | Polymerization method for preparing fluorine-containing alternating polymer through photocatalyst | |
| Sebastian et al. | Factors influencing catalytic activity of Co–Zn double-metal cyanide complexes for alternating polymerization of epoxides and CO2 | |
| Nourmohammadi et al. | Magnetic nanocomposite of crosslinked chitosan with 4, 6-diacetylresorcinol for gold immobilization (Fe3O4@ CS/DAR-Au) as a catalyst for an efficient one-pot synthesis of propargylamine | |
| Huang et al. | Controlled ring‐opening polymerization of propylene oxide catalyzed by double metal‐cyanide complex | |
| CN101440159B (en) | Process for synthesizing aliphatic polycarbonate | |
| An et al. | Effects of addition mode on Zn–Co double metal cyanide catalyst for synthesis of oligo (propylene‐carbonate) diols | |
| CN111085267A (en) | Polymer-loaded Cu/TEMPO catalyst and preparation method and application thereof | |
| Duan et al. | Propylene oxide cycloaddition with carbon dioxide and homopolymerization: Application of commercial beta zeolites | |
| Howard et al. | Polymer-supported metal catalysts for the heterogeneous polymerisation of lactones | |
| Sandaroos et al. | Efficient synthesis of sulfones and sulfoxides from sulfides by cobalt-based Schiff complex supported on nanocellulose as catalyst and Oxone as the terminal oxidant | |
| Shi et al. | Ag nanoparticles encapsulated in carboxyl-functionalized hollow microporous organic nanospheres for highly efficient catalysis applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20101229 Assignee: Nanyang Tianguan New Material Technology Co., Ltd Assignor: ZHEJIANG University Contract record no.: X2020330000026 Denomination of invention: Metal cyanide coordination catalyst and preparation method and application thereof Granted publication date: 20120523 License type: Exclusive License Record date: 20200430 |
|
| EE01 | Entry into force of recordation of patent licensing contract |