CN101029130A - Bimetal catalyst, its production and use - Google Patents
Bimetal catalyst, its production and use Download PDFInfo
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- CN101029130A CN101029130A CN 200710020313 CN200710020313A CN101029130A CN 101029130 A CN101029130 A CN 101029130A CN 200710020313 CN200710020313 CN 200710020313 CN 200710020313 A CN200710020313 A CN 200710020313A CN 101029130 A CN101029130 A CN 101029130A
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- mixture
- epoxide
- metal
- bimetallic catalyst
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 150000004820 halides Chemical class 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 150000002924 oxiranes Chemical class 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229920000570 polyether Polymers 0.000 claims description 14
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 12
- -1 oxyethane Chemical compound 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000003352 sequestering agent Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920005668 polycarbonate resin Polymers 0.000 claims description 8
- 239000004431 polycarbonate resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 5
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims description 2
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000007037 hydroformylation reaction Methods 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002738 chelating agent Substances 0.000 abstract 2
- 150000002118 epoxides Chemical class 0.000 abstract 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 description 1
- HKUXNVWRYJXDLV-UHFFFAOYSA-N zinc;iron(2+);tetracyanide Chemical compound [Fe+2].[Zn+2].N#[C-].N#[C-].N#[C-].N#[C-] HKUXNVWRYJXDLV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Polyethers (AREA)
Abstract
A bimetal catalyst is cheap and efficient and has high activity. The structural formula is MM1aLbXc(H2O)dPeRf, M is two-valence metal, M1 is triple or valence-variable metal, L is ligand which forms into complex anion with metal M1, X is halogen, P is organic chelating agent containing at least two ligand atoms, and R is epoxide. The process is carried out by adding organic chelating agent P or its solution into halide solution containing metal M, dripping into L complex anion ligand solution containing valence-variable metal M1, collecting reactive deposits, removing by products, drying, adding into epoxide, reacting and removing non-reacted epoxide to obtain the final product.
Description
Technical field
The present invention relates to bimetallic catalyst, relate in particular to a kind of DMC catalysts and preparation method who is used for the carbon dioxide/epoxide copolymerization, this catalyzer is used for the copolymerization of catalysis carbon dioxide/epoxide synthetic aliphatic polycarbonate resin, polyethers and segmented copolymer thereof.
Background technology
Carbonic acid gas and epoxide be the copolymerization aliphatic polycarbonate resin directly, the reduction reaction of carbon is not experienced in this reaction, and resulting aliphatic polycarbonate resin can be used as uses such as the pottery, metallic substance of engineering plastics, low-temperature thermal cracking material, biodegradable plastic master batch, oil resisting rubber starting material, urethane starting material, special construction purposes.The research of relevant carbon dioxide/epoxide copolymerization, the exploitation of particularly novel carbon dioxide/epoxide catalyst for copolymerization is subjected to extensive concern.At present, developed multiple catalyst system, wherein be typically water reactant (Inoue S. the most with equivalent, Koinuna H., Tsuruta T., Macromol Chem., 1969,130-210), with 1 kilogram of polycarbonate resin of the every production of this system need consume 0.3 kilogram to water and oxygen sensitivity and the higher zinc ethyl of price, product cost is higher.Rare-earth system has advantages of high catalytic activity, and (CN 1257753, CN00136189), also need a large amount of zinc ethyls to water and oxygen sensitivity during its preparation, and price is higher.(US 478344, and EP 358326, and US 4943677, and US 4960862 for the zinc carboxylate catalyst system, JP 9128227, and US 4789727) have advantages of high catalytic activity, however its preparation technology is comparatively complicated, and cost is higher, simultaneously, it is longer that it is used for the polymerization the reaction time, generally more than 48h.The complex compound of iron zinc cyanide and diglyme is a kind of catalyzer of epoxide homopolymerization, when being used for this reaction, it can obtain 44 gram polycarbonate from every gram catalyzer, the while conversion rate of epoxide can reach 71%, and (US 4500704, US 1747983A), but this catalyzer of every preparation 1 gram need consume the more expensive diglyme of 13 grams, the cost that makes multipolymer is higher, in addition, in the prepared polycarbonate of this catalyzer, the carbonate group mass contg is lower, generally about 7%, approach polyethers and be not polycarbonate.
People such as Chen Liban adopt the high molecular organic complexing agent, as polyoxyethylene glycol, polyethers, polyvinyl alkyl oxide, polyoxymethylene, polyester etc., prepare the carbon dioxide/epoxide catalyst for copolymerization (CN 1044663A) with greater activity, the carbonate group mass contg is 40～50% in the resulting polycarbonate resin; It is longer that yet this catalyzer is used for the polymerization the reaction time, and generally at 24～60 hours, when being used for industrial production, the polymerization cost is also higher.
Summary of the invention
Purpose of the present invention provides a kind of bimetallic catalyst and preparation method thereof, prepare a class bimetal complex catalyst with cheap cost, when being used for epoxide and carbon dioxide copolymerization, this catalyzer can obtain higher catalytic efficiency, on the homopolymerization of epoxide, demonstrate high catalytic activity.
Purpose of the present invention is achieved through the following technical solutions:
Bimetallic catalyst is characterized in that: this catalyzer is the complex compound of at least two kinds of metals and several different ligands, and structural formula is MM
1 aL
bX
c(H
2O)
dP
eR
f, wherein---
M is one or more the mixture in two valency metallic zinc, cadmium, cobalt, nickel, copper, the iron;
M
1Be one or more the mixture in trivalent or variable valency metal iron, cobalt, chromium, aluminium, the tin;
L is easy and metal M
1The mixture of one or more in the part alkoxyl group of formation complex anion, halogen, cyano group, thiocyanogen, the oxalate;
X is one or more the mixture in halogen atom fluorine, chlorine, bromine, iodine, the astatine;
P is the organic sequestering agent that contains n ligand atomic oxygen, sulphur, nitrogen, phosphorus, or contains the oligopolymer or the polymkeric substance of n ligand atom, n 〉=2;
R is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide;
The value of a, b, c, d, e, f is 1～10.
Further, above-mentioned bimetallic catalyst, P is polyethers, polyvinyl alkyl oxide, polyoxymethylene, polyester, polymeric amide, polyvinyl alcohol, polythioether in the wherein said structural formula, or the etherificate of these polymkeric substance, hydroformylation or esterified derivative; Or one or more the mixture in the polynary ether, thioether, acetal, ketone, ester, amine.
Aforesaid bimetallic catalyst, be prepared in accordance with the following methods: the mixture or its aqueous solution that in the halide solution that contains a kind of two valency metal M or several two valency metal M mixtures, add a kind of organic sequestering agent P or its aqueous solution or several organic sequestering agent P earlier, wherein the contained ligating atom and the mol ratio of two valency metals are 0.01～500 in the organic sequestering agent, progressively drip after fully stirring and contain a kind of variable valency metal M
1Or several variable valency metal M
1The L complex anion part aqueous solution of mixture, wherein variable valency metal M
1Or the mol ratio of its mixture and two valency metal M is 0.01～50, collect the throw out that reaction forms with centrifugal or filter method, after washing removes by product, under 0～120 ℃, vacuum or non-vacuum condition, dry 0.1～100h, after treating the product drying, the mixture that adds one or several epoxide, wherein the mol ratio of epoxide and metal M is 0.001～10, at 0～120 ℃ of thorough mixing, reaction 0.1～50hr, reaction finishes to dry and removes unreacted epoxide, obtains bimetallic catalyst.
Aforesaid bimetallic catalyst, be used for the copolyreaction of catalysis carbon dioxide/epoxide, epoxide homopolymerization, the perhaps building-up reactions of polycarbonate resin, polyether resin, wherein the consumption of bimetallic catalyst is 0.002～50% of a reaction monomers gross weight; Described epoxide is the mixture of one or more in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide especially.
The outstanding substantive distinguishing features and the obvious improvement of technical solution of the present invention is mainly reflected in:
1. preparing a class bimetal complex catalyst with cheap cost, when this catalyzer is used for epoxide and carbon dioxide copolymerization, can obtain higher catalytic efficiency, is 40～100g resin/g catalyzer; Especially adopt this catalyzer, copolymerization time to shorten significantly, foreshorten to about 2 hours, use this catalyzer can increase substantially plant factor, reduce production costs;
2. this catalyzer demonstrates high catalytic activity on the homopolymerization of epoxide;
3. bimetallic catalyst provided by the present invention is light yellow or white soft powder, and water insoluble, organic solvent does not have obvious water absorbability, under room temperature and lucifuge condition, and stable storing in air.
Embodiment
The invention provides a kind of bimetal complex catalyst and preparation method thereof, prepare a class bimetal complex catalyst with cheap cost; The structure of this catalyzer is: MM
1 aL
bX
c(H
2O)
dP
eR
f, wherein M is two valency metals, M
1Be 3 valencys or variable valency metal, L is easy and metal M
1Form the part of complex anion, X is a halogen, and P is the organic sequestering agent (n 〉=2) that contains n ligand atom, and R is an epoxide, and a, b, c, d, e, f are 1～10 numerical value.
Embodiment 1
Under agitation condition, be the polyether glycol (molecular weight is 2000) that adds 0.5 gram, 2 functionality in 5% the solder(ing)acid to 100ml concentration, dropping 40ml concentration is 20% the potassium cobalticyanide aqueous solution under the agitation condition, filter and collect the white precipitate that generates, after washing 5 times with water, be dried to constant weight and obtain the 6.1g white powder, in this white powder, add the 1g propylene oxide, stirring reaction 10h under 20 ℃ of conditions, vacuum-drying is to constant weight.
Embodiment 2
Under agitation condition, be the polyether glycol (molecular weight is 2000) that adds 0.5 gram, 2 functionality in 5% the solder(ing)acid to 100ml concentration, dropping 40ml concentration is 20% potassium ferricyanide aqueous solution under the agitation condition, filter and collect the yellow mercury oxide that generates, after washing 5 times with water, be dried to constant weight under 100 ℃, obtain the 6.3g yellow powder, in this yellow powder, add the 2g cyclohexene oxide, under 80 ℃ of agitation conditions, the reaction 10h, again 80 ℃ of following vacuum-dryings to constant weight.
Embodiment 3
To in the 1000ml of thorough drying autoclave, adding the prepared catalyzer of 5g embodiment 1, the polyether glycol that adds (moisture content 300ppm, molecular weight are 300) 3 functionality of 500ml propylene oxide, 10ml process thorough drying, under agitation condition, add the 250g carbonic acid gas, be warming up to 60 ℃, react discharging after 2 hours, adopt vacuum removal unreacted propylene oxide completely, obtain 247g thickness resin, carbonate content is 32% in the resin, and weight-average molecular weight is 8100.
Embodiment 4
To in the autoclave of the 1000ml of thorough drying, adding the prepared catalyzer of 2g embodiment 2, add the 500ml propylene oxide, under agitation condition, add the 250g carbonic acid gas, be warming up to 60 ℃, react discharging after 2 hours, adopt the not propylene oxide of complete reaction of vacuum removal, obtain the 147g high viscosity resins, carbonate content is 34% in the resin, and weight-average molecular weight is 51000.
Embodiment 5
To the bimetallic catalyst that in the 1000ml of thorough drying autoclave, adds 0.025g embodiment 1 preparation, add polyether glycol, the 24ml propylene oxide of 1g through (moisture content 300ppm, molecular weight are 300) 3 functionality of thorough drying, be warming up to 110 ℃, progressively drip and contain the 420ml propylene oxide solution of 20g through the polyethers of (molecular weight is 300) 3 functionality of thorough drying, rate of addition 1g/min, drip and finish back continuation reaction 20 minutes, adopt vacuum removal unreacted propylene oxide completely, obtain polyethers 345g, weight-average molecular weight is 4400.
This catalyzer is used for the carbon dioxide/epoxide copolymerization or the epoxide homopolymerization prepares aliphatic polycarbonate resin, polyethers or their segmented copolymer, when being used for the copolymerization of carbonic acid gas epoxide, obtained higher catalytic efficiency, it is 40～100g resin/g catalyzer, especially after adopting this catalyzer, the copolymerization time shortens significantly, foreshortens to 0.1～2.5 hour, plant factor significantly improves, and production cost obviously reduces.In addition, this catalyzer is comparatively stable in air, and component is single, preserves easily and operates; Have very high activity and selectivity, and cheap, be widely used in industrial application.
More than by specific embodiment technical solution of the present invention has been done to further specify, the example that provides only is an exemplary applications, can not be interpreted as limiting the scope of the invention.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the claim scope of the present invention.
Claims (5)
1. bimetallic catalyst is characterized in that: this catalyzer is the complex compound of at least two kinds of metals and several different ligands, and structural formula is MM
1 aL
bX
c(H
2O)
dP
eR
f, wherein---
M is one or more the mixture in two valency metallic zinc, cadmium, cobalt, nickel, copper, the iron;
M
1Be one or more the mixture in trivalent or variable valency metal iron, cobalt, chromium, aluminium, the tin;
L is easy and metal M
1The mixture of one or more in the part alkoxyl group of formation complex anion, halogen, cyano group, thiocyanogen, the oxalate;
X is one or more the mixture in halogen atom fluorine, chlorine, bromine, iodine, the astatine;
P is the organic sequestering agent that contains n ligand atomic oxygen, sulphur, nitrogen, phosphorus, or contains the oligopolymer or the polymkeric substance of n ligand atom, n 〉=2;
R is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide;
The value of a, b, c, d, e, f is 1～10.
2. bimetallic catalyst according to claim 1, it is characterized in that: P is polyethers, polyvinyl alkyl oxide, polyoxymethylene, polyester, polymeric amide, polyvinyl alcohol, polythioether in the described structural formula, or the etherificate of these polymkeric substance, hydroformylation or esterified derivative; Or one or more the mixture in the polynary ether, thioether, acetal, ketone, ester, amine.
3. the preparation method of the described bimetallic catalyst of claim 1, it is characterized in that: the mixture or its aqueous solution that in the halide solution that contains a kind of two valency metal M or several two valency metal M mixtures, add a kind of organic sequestering agent P or its aqueous solution or several organic sequestering agent P earlier, wherein the contained ligating atom and the mol ratio of two valency metals are 0.01～500 in the organic sequestering agent, progressively drip after fully stirring and contain a kind of variable valency metal M1 or several variable valency metal M
1The L complex anion part aqueous solution of mixture, wherein variable valency metal M
1Or the mol ratio of its mixture and two valency metal M is 0.01～50, collect the throw out that reaction forms with centrifugal or filter method, after washing removes by product, under 0～120 ℃, vacuum or non-vacuum condition, dry 0.1～100h, after treating the product drying, the mixture that adds one or several epoxide, wherein the mol ratio of epoxide and metal M is 0.001～10, at 0～120 ℃ of thorough mixing, reaction 0.1～50hr, reaction finishes to dry and removes unreacted epoxide, obtains bimetallic catalyst.
4. the described bimetallic catalyst of claim 1 is used for the copolyreaction of catalysis carbon dioxide/epoxide, epoxide homopolymerization, the perhaps building-up reactions of polycarbonate resin, polyether resin, wherein the consumption of bimetallic catalyst is 0.002～50% of a reaction monomers gross weight.
5. the application of the described bimetallic catalyst of claim 4 is characterized in that: described epoxide is one or more the mixture in propylene oxide, oxyethane, cyclohexene oxide, butylene oxide ring, oxidation iso-butylene, the cyclopentene oxide.
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| CN102206333A (en) * | 2011-04-18 | 2011-10-05 | 中科院广州化学有限公司 | Low molecular weight polycarbonate polyatomic alcohol and preparation method and application thereof |
| CN102351417A (en) * | 2011-09-07 | 2012-02-15 | 四川明晶光电科技有限公司 | Binary chelation separation process |
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| US5714428A (en) * | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
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| US10214614B2 (en) | 2008-05-09 | 2019-02-26 | Cornell University | Copolymerization of ethylene oxide and carbon dioxide |
| CN102206333A (en) * | 2011-04-18 | 2011-10-05 | 中科院广州化学有限公司 | Low molecular weight polycarbonate polyatomic alcohol and preparation method and application thereof |
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