CN100999573A - Bimetallic cyanide catalyst for epoxide ring-opening polymerization - Google Patents
Bimetallic cyanide catalyst for epoxide ring-opening polymerization Download PDFInfo
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- CN100999573A CN100999573A CN 200710019506 CN200710019506A CN100999573A CN 100999573 A CN100999573 A CN 100999573A CN 200710019506 CN200710019506 CN 200710019506 CN 200710019506 A CN200710019506 A CN 200710019506A CN 100999573 A CN100999573 A CN 100999573A
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- China
- Prior art keywords
- iii
- opening polymerization
- epoxide ring
- cyanide catalyst
- bimetallic cyanide
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims abstract description 21
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 150000002118 epoxides Chemical group 0.000 title claims abstract 12
- -1 ester sulfate Chemical class 0.000 claims abstract description 37
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 9
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 241000282326 Felis catus Species 0.000 description 12
- 229920001002 functional polymer Polymers 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 150000002924 oxiranes Chemical group 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 230000001939 inductive effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 206010019133 Hangover Diseases 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FYCFRLZSMPWEPP-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enamide Chemical compound NC(=O)C=C.OC(=O)\C=C/C(O)=O FYCFRLZSMPWEPP-ODZAUARKSA-N 0.000 description 1
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The present invention discloses one kind of bimetallic cyanide catalyst for the ring-opening polymerization of epoxide. The catalyst has the chemical general expression of Ma1[M2(CN)b]d.xM3(X)c.wH2O.yT.jL1.zL2, where, L1 is polytetrahydrofuran oxyprpopyl olefin blocked polyether and L2 is polyether ester sulfate in the structure as shown. The present invention is used for the ring-opening polymerization of alkylene oxide and has high activity and other excellent performance.
Description
Technical field:
The present invention relates to a kind of double metal cyanide (DMC) complex catalyst.
Background technology:
Double metal cyanide (DMC) complex catalyst is used for epoxide ring-opening polymerization, the polyether glycol that this kind catalyzer makes is lower than making the product degree of unsaturation with basic catalyst (being generally KOH), and can make higher molecular weight, generally the gained polyethers avoids aftertreatment.The dmc catalyst composition is generally:
M
a 1[M
2(CN)
b(A)
c]
dXM
3(X)
eWH
2OyTzL formula I
M
1Be to be selected from: Zn
(II), Fe
(II), Fe
(III), Co
(II), Ni
(II), Mo
(IV), Sn
(II), Cu
(II), Pb
(II), Mo
(VI), Al
(III), V
(IV), V
(V), Sr
(II), W
(IV), W
(VI), Mn
(II)And Cr
(III)In at least a metal ion;
M
2Be to be selected from: Fe
(II), Fe
(III), Co
(II), Co
(III), Cr
(II), Cr
(III), Mn
(II), Mn
(III), Ni
(III), V
(IV), V
(V), Ir
(III), Rh
(III), Ru
(II)In at least a transition metal ion;
M
3Represent M
1And/or M
2
A, X are CN
-, F
-, Cl
-, Br
-, I
-, OH
-, NO
2 -, CO
3 2-, NO
3 -, SO
4 2-, CNO
-, C
2O
4 2-, CNS
-, NCO
-, NCS
-And carboxylate radical RCOO
-, A, X can be identical or different
A, b, c, d, e are integer, satisfy the positive and negative charge balance, even the bimetallic cyaniding compounds keeps electric neutrality;
T represents the small molecules organic complexing agent as alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture, and wherein trimethyl carbinol TBA has been a known technology as complexing agent.
L represents the functional polymer
At present the dmc catalyst molecular structure or at least its host molecule structure meet following formula substantially:
Zn
3[Co (CN)
6]
2XZnCl
2WH
2OyTzL formula II
Wherein T is organic alcohol substantially, and L is the functional polymer
Zn wherein
3[Co (CN)
6]
2Be by ZnCl
2With alkali metal cyanide, be generally K
3[Co (CN)
6] reaction.
Dmc catalyst does not have the functional polymer in the nineteen nineties early stage patent, promptly there is not L, T is glycol dimethyl ether or diethylene glycol dimethyl ether (using TBA although the existing patent of the eighties is mentioned) substantially, active low, afterwards Arco (usp5482908) TBA as the T among the formula I simultaneously with polyethers (M＞500) as formula I in L. from then on begin further to improve the dmc catalyst performance with the functional polymer in the dmc catalyst: it preferentially uses M
n=2000～4000 polyoxytrimethylene two or trivalent alcohol for example contain polyoxytrimethylene dibasic alcohol (M in the catalyzer
n=4000) 45.8%wt, activity: 105 ℃, catalyzer 100pm, reaction pressure 0.07Mpa, when making polyoxytrimethylene triol 6k-3, speed of reaction 6.69kgPo/gCo/min, degree of unsaturation 0.0042mol/kg.The used afterwards functional polymer of Arco company (open CN1145373A) is M
n=200～10000 with 1, the end capped polyoxypropylene polyol of 1-dimethyl ethylene oxide, the functional polymer measures 5～80%wt in the gained solid catalyst, for example it contains 23%wt 1, the catalyst activity of 1-dimethyl ethylene oxide end-blocking polyoxytrimethylene dibasic alcohol (M=4000): polyoxytrimethylene triol (M
n=700) 70g makes initiator, pressure 0.07Mpa, and 105 ℃, catalyzer 100pm, maximum speed of reaction 29.4gPO/min makes the 6K-T polyethers, degree of unsaturation 0.0043mol/kg, M
w/ M
n1.15 these catalyzer characteristics think that gained polyethers degree of unsaturation is still lower under comparatively high temps, it is given in the example and makes 8K-D 150 ℃ of reactions, degree of unsaturation 0.0074mol/kg.
The functional polymer selects range extension for use in Arco company (usp5714428) catalyzer, make the ultralow degree of unsaturation of polyether glycol, viscosity is low, the polymer hangover reduces, available functional polymer comprises: polyacrylamide, acrylamide-maleic acid, polyacrylic acid, poly-(2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid), vinylformic acid-maleic acid, polyacrylonitrile, polyalkyl acrylate, polymethacrylate, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate (PVA), polyvinyl alcohol, poly-(N-vinyl pyrrolidone), N-vinyl pyrrolidone-acrylic copolymer, poly-(N, the N-DMAA), polyvinyl methyl ketone, poly-(4-vinylphenol), poly-(4-vinylpridine), polyvinyl chloride, vinylformic acid-styrol copolymer, polyvinyl sulfuric acid ester, polyvinyl sulfuric acid ester sodium salt etc., and other is as polyester (polyethyleneglycol adipate, poly-dipropylene glycol adipic acid ester), polycarbonate [poly-(1,6-hexylene glycol carbonic ether) oxazoline polymkeric substance (poly-2-ethyl-2-oxazoline), poly-alkane enamine, toxilic acid and copolymer-maleic anhydride, Natvosol, starch and polyacetal, vinyl butyral-vinyl alcohol-acetate ethylene copolymer etc.For example it makes organic complexing agent with TBA, the catalyzer that contains polyvinyl methyl ethermaleic anhydride (cooperating polyoxytrimethylene triol Mn=1000) is characterized in easy preparation, easily separated, high reactivity, the ultralow degree of unsaturation of gained polyethers, low viscosity, the polymer hangover reduces activity: 70g polyoxytrimethylene triol (Mn=700), 130 ℃, catalyzer 25ppm,, speed of reaction (pressure 0.07Mpa) 21.7gPO/min makes 6K-3 viscosity (25 ℃) 3450mpas.
The made DMC cat of Bayer company (usp6204357) makes coordination agent with TBA, contain functional polymer's cyclodextrin, its cyclodextrin that is suitable for has: unsubstituted ring dextrin or their ester, alkyl oxide, hydroxyalkyl ether, alkoxycarbonyl alkyl ether and carbonylic alkyl ether derivant.For example contain 13.8%wt2,6-DM-, its activity: with 50g polyoxytrimethylene dibasic alcohol (M
n=1000) make initiator, catalyzer 20pm, under 105 ℃, induce in the still and when reacting pressure keep 0.25MPa, induction time 197min, total reaction time 478min makes hydroxyl value 27.9mgKOH/g (M
n=3500), degree of unsaturation 0.008mol/kg, viscosity (25 ℃) is the poly-polyoxypropyleneglycol of 1022mpas.
Bayer company (usp6291388) is a coordination agent with TBA again, contains the ethoxy alkene polyethers (M of 5～80%wt among the cat
n＞500) as the functional polymer, activity increases.Dmc catalyst contains ethoxy alkene polyethers 41.1%wt in the example preferably, its activity: with the poly-polyoxytrimethylene dibasic alcohol (M of 50g
n=1000) make initiator, catalyzer 15pm, under 105 ℃, induce in the still and when reacting pressure keep 0.25MPa, total reaction time 395min makes hydroxyl value 29.8mgKOH/g (M
n=3810), degree of unsaturation 0.011mol/kg, viscosity (25 ℃) is the poly-third oxygen enediol of 935mpas.
The dmc catalyst performance shows that mainly on the catalytic activity, other requirement has: the following storage time of normal temperature is long, made polyether glycol narrow molecular weight distribution, and the polyethers degree of unsaturation is low etc.Comprehensive these factors, the dmc catalyst performance still remains to be improved in the above patent.
Summary of the invention
The object of the present invention is to provide a kind of ring-opening polymerization of alkylene oxide excellent property, highly active bimetallic cyanide catalyst for epoxide ring-opening polymerization of being used for.
Technical solution of the present invention is:
A kind of bimetallic cyanide catalyst for epoxide ring-opening polymerization, chemical general formula is:
M
a 1[M
2(CN)
b]
d·xM
3(X)
c·wH
2O·yT·j?L
1·z?L
2
Wherein: M
1Be to be selected from: Zn
(II), Fe
(II), Fe
(III), Co
(II), Ni
(II), Mo
(IV), Sn
(II), Cu
(II), Pb
(II), Mo
(VI), Al
(III), V
(IV), V
(V), Sr
(II), W
(IV), W
(VI), Mn
(II)And Cr
(III)In at least a metal ion;
M
2Be to be selected from: Fe
(II), Fe
(III), Co
(II), Co
(III), Cr
(II), Cr
(III), Mn
(II), Mn
(III), V
(IV), V
(V), Ir
(III), Rh
(III), Ru
(II), Ni
(II)In at least a transition metal ion; M
3Represent M
1And/or M
2
X is for being selected from CN
-, F
-, Cl
-, Br
-, I
-, OH
-, NO
2 2-, CO
3 2-, NO
3 -, SO
4 2-, CNO
-, C
2O
4 2-, CNS
-, NCO
-, NCS
-And carboxylate radical RCOO
-In at least a;
The selection of a, b, c, d is satisfied with positive and negative charge and is equated, even the bimetallic cyaniding compounds keeps electric neutrality;
T is selected from low molecule organic complexing agent: alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture; It is characterized in that: L
1The polytetrahydrofuran third oxygen alkene block polyether for following structural formula:
N, m are integer, n value 1～30; M value 1～85;
L
2Sulfated polyoxyalkylene ester for following structural formula:
N is an integer, value 4～85;
R be 1～18 C alkyl or
X=0.1 in the catalyzer general formula～5, w=0.1～1, y=0.1～1, j=0.01～1.33, z=0.01～1.33.L
1, L
2Total amount contains 2～70%wt in catalyzer.L
1, L
2Total amount contains 10～30%wt in catalyzer.L
1, L
2Part by weight be 1: 4～4: 1 scopes.M
1Be Zn
(II)M
2Be Co
(III)M
3Be Zn
(II)X is Cl
-T is the trimethyl carbinol (TBA).
Catalyst preparation process process: typically with Zn
(II)Be M
1, M
3, Co
(III)Be M
2, Cl
-For X institute controlling catalyst is an example:
A. join about 10～20%wt ZnCl
2Solution contains 5%～70%wt concentration range trimethyl carbinol in the solution, and can contain the polytetrahydrofuran third oxygen alkene block polyether and the sulfated polyoxyalkylene ester respectively is 0.05～3%.
B. join K
3[Co (CN)
6] solution, concentration range 5%～20%wt.
C. above ZnCl
2And K
3[Co (CN)
6], selecting mass ratio is 1: 1～6: 1, the material thorough mixing generates Zn during two kinds of reactions
3[Co (CN)
6]
2And by product KCl.
D. after reaction is finished, filter to isolate especially an alkali metal salt of various water-soluble salts, obtain the DMC mashed prod, wash with the trimethyl carbinol aqueous solution, so-called washing is to add the organic complexing agent aqueous solution in the mashed prod to form the isolating again several repetitive process of slurry.Used trimethyl carbinol concentration range 10%～80%wt in the washing process can contain polytetrahydrofuran third oxygen alkene block polyether and the sulfated polyoxyalkylene ester of 0.1%～1%wt in the washings.
E. after washing finishes, replace moisture content in the slurries (to moisture content＜15%wt), add polytetrahydrofuran third oxygen alkene block polyether and sulfated polyoxyalkylene ester then, thorough mixing 0.5～5h greater than theoretical aequum with the pure trimethyl carbinol.
F. obtain the DMC mashed prod of solid content 12～35% by press filtration with spreading mass.
G. mashed prod is epoxide ring-opening polymerization dmc catalyst of the present invention through 30～80 ℃ of vacuum dryings.
The present invention is used for ring-opening polymerization of alkylene oxide excellent property, high reactivity.70g polyoxytrimethylene dibasic alcohol (M for example
n=400) make initiator, temperature is under 105 ℃, and cat 12.5ppm reaches pressure maintenance 0.07MPa when reacting before inducing, system polyoxytrimethylene dibasic alcohol (M
n=4000) test-results: inductive phase 40min, total reaction time 240min, maximum speed of reaction 15g PO/min.Gained polyether glycol degree of unsaturation can reach 0.002～0.005mol/kg, belongs to ultralow degree of unsaturation scope.The dmc catalyst storage time of the present invention is long, and for example above experiment uses 25 ℃ of air-tight states of catalyzer to preserve similarity condition test after 60 days down, and the result does not have notable difference.
Use polytetrahydrofuran third oxygen alkene block polyether and sulfated polyoxyalkylene ester to do the functional polymer in the catalyzer of the present invention, they can use separately, but common the use has fiting effect, these two kinds of functional polymers have bigger promoter action to activity of such catalysts, the catalyst stores time is long, obtained polyethers viscosity low (even molecular weight distribution).
The invention will be further described below in conjunction with embodiment:
Embodiment
Embodiment 1:
System cat:Zn
3[Co (CN)
6]
2ZnCl
20.4H
2O0.18TBA0.055 L
10.055L
2
In a container with 120g ZnCl
2Be dissolved in the 250ml TBA/450ml deionized water, in another container, 30g K
3[Co (CN)
6] be dissolved in the 450ml deionized water, carry out solid-liquid separation behind the thorough mixing, obtain the DMC mashed prod, wash with about 50%TBA aqueous solution 1000ml, promptly thorough mixing forms process of solid-liquid separation behind the slurry again, this washing process carries out three times, washs once to displace moisture content among the DMC with the pure TBA of 1000ml at last.Separate mashed prod and add the 6g polytetrahydrofuran third oxygen alkene block polyether (M
n=2500, by molecular weight be 1000 polytetrahydrofuran again propoxylation to target molecular weight) and 6g sulfated polyoxyalkylene ester (M
n=2000, on the structure be: the initial propoxylation of lauryl alcohol is about 1000 to molecular weight, with the sulfuric acid double esterification), add 500～1000ml thorough mixing again, with the slurry press filtration till the solid content 15%～25%, 40～60 ℃ of vacuum-dryings, pulverize cat A 42g.
By analysis: Zn=27.0%, Co=12.5%, H
2O=0.90%, TBA=1.2%, L
1=9.5%, L
2=9.5%.
Comparative example 1: system cat Zn
3[Co (CN)
6]
2ZnCl
20.4H
2O0.18TBA0.11L
1
With embodiment 1 operation, do not add L
2, only add the 12g polytetrahydrofuran third oxygen alkene block polyether (M
n=2500) get cat B 42g.
By analysis: Zn=27.1%, Co=12.2%, H
2O=0.86%, TBA=1.2%, L
1=19.0%.
Comparative example 2: system cat Zn
3[Co (CN)
6]
2ZnCl
20.4H
2O0.18TBA0.11L
2
With embodiment 1, but only add 12g L
2, get cat C 43kg.
By analysis: Zn=27.2%, Co=12.4%, H
2O=0.85%, TBA=1.2%, L
2=19.2%.
The system polyether glycol:
70g polyoxypropyleneglycol (M
n=400) make initiator, cat 8～30ppm (polyvalent alcohol of made relatively theoretical molecular), place the 2L autoclave pressure, stir down, temperature vacuumizes 30min under 105 ℃, remove micro-moisture, adds propylene oxide 20g, pressure 0.05MPa, after pressure sharply descends, under the residual epoxide propane certain pressure, remain under certain temperature of reaction and add, the process afterreaction phase is to consume all propylene oxide in the still, take out volatile matter for 90 ℃, obtain polyvalent alcohol, carry out hydroxyl value, double bond content, mensuration such as viscosity.
Example A
With cat A (15ppm) system polyoxytrimethylene dibasic alcohol (M
n=4000)
With above-mentioned steps, 105 ℃, make polyvalent alcohol under the 0.07MPa, the result is as follows:
Inductive phase (min): 45
Total reaction time (min): 280
Maximum speed of reaction (g PO/min): 13
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 28.4
Double bond content (mol/Kg): 0.0040
Viscosity (25 ℃, mpas): 900
Comparative examples A
With cat B (15ppm) system polyoxytrimethylene dibasic alcohol (M
n=4000), condition is the same, and the result is as follows:
Inductive phase (min): 55
Total reaction time (min): 320
Maximum speed of reaction (g PO/min): 10.0g/min
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 29.2
Double bond content (mol/Kg): 0.0045
Viscosity (25 ℃, mpas): 1500
Comparative example B
With Cat C, condition is the same, and the result is as follows:
Inductive phase (min): 70min
Total reaction time (min): 410
Maximum speed of reaction (g PO/min): 8g/min
Polyvalent alcohol:
Hydroxyl value (mg KOH/g): 29.9
Double bond content (mol/Kg): 0.0060
Viscosity (25 ℃, mpas): 2000
Embodiment 2:
Catalyst performance relatively (used sulfated polyoxyalkylene ester is constant) during the used polytetrahydrofuran third oxygen alkene block polyether different molecular weight among the present invention.
With embodiment 1 processing step, used L
1Similar, the molecular weight difference is made polyoxytrimethylene dibasic alcohol (M with institute's controlling catalyst by routine A
n=4000) result is as follows:
Embodiment 3:
Catalyst performance relatively (the used polytetrahydrofuran third oxygen alkene block polyether is constant with embodiment 1) during polyether thiourea polyether acid ester different structure among the present invention
With embodiment 1 processing step, used L
2Polyether moiety structure difference is made polyoxytrimethylene dibasic alcohol (M with institute's controlling catalyst by routine A
n=4000) result is as follows:
Embodiment 4:
A kind of bimetallic cyanide catalyst for epoxide ring-opening polymerization is used the step identical with embodiment 1, and select for use the raw material that meets following general formula needs to make: gained catalyst chemical general formula is:
M
a 1[M
2(CN)
b]
d·xM
3(X)
c·wH
2O·yT·j?L
1·z?L
2
Wherein: M
1Be to be selected from: Zn
(II), Fe
(II), Fe
(III), Co
(II), Ni
(II), Mo
(IV), Sn
(II), Cu
(II), Pb
(II), Mo
(VI), Al
(II), V
(IV), V
(V), Sr
(II), W
(IV), W
(VI), Mn
(II)And Cr
(III)In at least a metal ion;
M
2Be to be selected from: Fe
(II), Fe
(III), Co
(II), Co
(III), Cr
(II), Cr
(III), Mn
(II), Mn
(III), V
(IV), V
(V), Ir
(III), Rh
(III), Ru
(II), Ni
(II)In at least a transition metal ion; M
3Represent M
1And/or M
2
X is for being selected from CN
-, F
-, Cl
-, Br
-, I
-, OH
-, NO
2 2-, CO
3 2-, NO
3 -, SO
4 2-, CNO
-, C
2O
4 2-, CNS
-, NCO
-, NCS
-And carboxylate radical RCOO
-In at least a;
The selection of a, b, c, d is satisfied with positive and negative charge and is equated, even the bimetallic cyaniding compounds keeps electric neutrality;
T is selected from low molecule organic complexing agent: alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture; L
1The polytetrahydrofuran third oxygen alkene block polyether for following structural formula:
N, m are integer, n value 1～30 (example 1,5,15,, 20,30); M value 1～85 (example 1,9,45,85);
L
2Sulfated polyoxyalkylene ester for following structural formula:
N is an integer, value 4～85 (example 4,8,50,85);
R be 1～18 (example 1,9,18) C alkyl or
X=0.1 in the catalyzer general formula～5 (example 0.1,3,5), w=0.1～1 (example 0.1,0.5,1), y=0.1～1 (example 0.1,0.5,1), j=0.01～1.33 (example 0.01,0.8,1.33), z=0.01～1.33 (example 0.01,0.8,1.33).L
1, L
2Total amount contains 2～70%wt (example 2%, 10%, 30%, 70%) in catalyzer.L
1, L
2Part by weight be 1: 4～4: 1 scopes (example 1: 1,1: 4,4: 1).
Claims (10)
1, a kind of bimetallic cyanide catalyst for epoxide ring-opening polymerization, chemical general formula is:
M
a 1[M
2(CN)
b]
d·xM
3(X)
c·wH
2O·yT·jL
1·zL
2
Wherein: M
1Be to be selected from: Zn
(II), Fe
(II), Fe
(III), Co
(II), Ni
(II), Mo
(IV), Sn
(II), Cu
(II), Pb
(II), Mo
(VI), Al
(III), V
(IV), V
(V), Sr
(II), W
(IV), W
(VI), Mn
(II)And Cr
(III)In at least a metal ion;
M
2Be to be selected from: Fe
(II), Fe
(III), Co
(II), Co
(III), Cr
(II), Cr
(III), Mn
(II), Mn
(III), V
(IV), V
(V), Ir
(III), Rh
(III), Ru
(II), Ni
(II)In at least a transition metal ion;
M
3Represent M
1And/or M
2
X is for being selected from CN
-, F
-, Cl
-, Br
-, I
-, OH
-, NO
2 2-, CO
3 2-, NO
3 -, SO
4 2-, CNO
-, C
2O
4 2-, CNS
-, NCO
-, NCS
-And carboxylate radical RCOO
-In at least a;
The selection of a, b, c, d is satisfied with positive and negative charge and is equated;
T is selected from low molecule organic complexing agent: alcohol, aldehyde, ketone, ether, ester, acid amides, nitrile, sulfide or its mixture; It is characterized in that: L
1The polytetrahydrofuran third oxygen alkene block polyether for following structural formula:
N, m are integer, n value 1～30; M value 1～85;
L
2Sulfated polyoxyalkylene ester for following structural formula:
N is an integer, value 4～85;
R be 1～18C alkyl or
2, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 1 is characterized in that: x=0.1 in the catalyzer general formula～5, w=0.1～1, y=0.1～1, j=0.01～1.33, z=0.01～1.33.
3, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 1 and 2 is characterized in that: L
1, L
2Total amount contains 2～70%wt in catalyzer.
4, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 3 is characterized in that: L
1, L
2Total amount contains 10～30%wt in catalyzer.
5, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 3 is characterized in that: L
1, L
2Part by weight be 1: 4～4: 1 scopes.
6, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 1 and 2 is characterized in that: M
1Be Zn
(II)
7, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 1 and 2 is characterized in that: M
2Be Co
(III)
8, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 1 and 2 is characterized in that: M
3Be Zn
(II)
9, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 1 and 2 is characterized in that: X is Cl
-
10, bimetallic cyanide catalyst for epoxide ring-opening polymerization according to claim 1 and 2 is characterized in that: T is the trimethyl carbinol.
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|---|---|---|---|
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| CN102516554A (en) * | 2011-11-23 | 2012-06-27 | 中北大学 | Method for preparing hydroxyl-terminated polytetrahydrofuran polypropylene oxide block copolyether |
| EP2546278A3 (en) * | 2010-02-02 | 2013-03-27 | Henkel AG & Co. KGaA | Polyether block copolymers and the compositions resulting from these |
| CN111303401A (en) * | 2020-04-07 | 2020-06-19 | 淮安巴德聚氨酯科技有限公司 | Double metal cyanide complex catalyst and preparation method thereof |
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Family Cites Families (4)
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|---|---|---|---|---|
| US5482908A (en) * | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
| US5545601A (en) * | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
| CN1080589C (en) * | 1998-04-29 | 2002-03-13 | 中国科学院山西煤炭化学研究所 | Double metal cyanide catalyst and its prepn. method |
| CN100349956C (en) * | 2005-09-07 | 2007-11-21 | 黎明化工研究院 | Bimetallic cyanide complex catalyst and its prepn process |
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2007
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| US20130085239A1 (en) * | 2010-02-02 | 2013-04-04 | Henkel Ag & Co. Kgaa | Polyether block copolymers and compositions that can be obtained therefrom |
| JP2013518954A (en) * | 2010-02-02 | 2013-05-23 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Polyether block copolymer and composition obtained therefrom |
| US8969511B2 (en) * | 2010-02-02 | 2015-03-03 | Henkel Ag & Co. Kgaa | Polyether block copolymers and compositions that can be obtained therefrom |
| CN102516554A (en) * | 2011-11-23 | 2012-06-27 | 中北大学 | Method for preparing hydroxyl-terminated polytetrahydrofuran polypropylene oxide block copolyether |
| CN111303401A (en) * | 2020-04-07 | 2020-06-19 | 淮安巴德聚氨酯科技有限公司 | Double metal cyanide complex catalyst and preparation method thereof |
| CN111303401B (en) * | 2020-04-07 | 2022-06-14 | 淮安巴德聚氨酯科技有限公司 | Double metal cyanide complex catalyst and preparation method thereof |
| CN114213645A (en) * | 2021-12-23 | 2022-03-22 | 淮安巴德聚氨酯科技有限公司 | Bimetallic catalyst for synthesizing pure ethylene oxide polyether and preparation method thereof |
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| WO2023214891A1 (en) | 2022-05-04 | 2023-11-09 | Pcc Rokita Sa | Method for the manufacture of a polyether diol product |
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