CN1759934A - Catalyst of complexes of polymetal and multiple ligand, and preparation method - Google Patents
Catalyst of complexes of polymetal and multiple ligand, and preparation method Download PDFInfo
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- CN1759934A CN1759934A CN 200510019361 CN200510019361A CN1759934A CN 1759934 A CN1759934 A CN 1759934A CN 200510019361 CN200510019361 CN 200510019361 CN 200510019361 A CN200510019361 A CN 200510019361A CN 1759934 A CN1759934 A CN 1759934A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000003446 ligand Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000013110 organic ligand Substances 0.000 claims abstract description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 150000001450 anions Chemical group 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyoxypropylene Polymers 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- VJQKUDKYRCLZST-UHFFFAOYSA-N [K+].[K+].[K+].[K+].[K+].[K+].[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N.[O-][Mn](=O)(=O)C#N VJQKUDKYRCLZST-UHFFFAOYSA-N 0.000 claims 8
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims 8
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 claims 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims 2
- 150000001913 cyanates Chemical class 0.000 claims 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims 1
- 229960001826 dimethylphthalate Drugs 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229920000570 polyether Polymers 0.000 abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 11
- 125000002947 alkylene group Chemical group 0.000 abstract description 9
- 230000006698 induction Effects 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 3
- 230000003078 antioxidant effect Effects 0.000 abstract description 3
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 22
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 238000003828 vacuum filtration Methods 0.000 description 15
- 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 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000001294 propane Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- AGZFLONEGJYOST-UHFFFAOYSA-N dipotassium dioxido(dioxo)manganese oxalonitrile Chemical class [Mn](=O)(=O)([O-])[O-].[K+].N#CC#N.[K+] AGZFLONEGJYOST-UHFFFAOYSA-N 0.000 description 8
- 150000002334 glycols Chemical class 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 7
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 7
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000005711 Benzoic acid Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 241001550224 Apha Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
本发明公开了一种用作催化环氧烷聚合的多金属多配体配合物及其合成方法。其特征在于：1.这种催化剂包括两种以上的金属和两种以上的有机配体；2.应用于催化环氧烷聚合反应，诱导期可以缩短到13～16min；3.其催化活性远远高于KOH和双金属氰化物催化剂，而且用量低，应用于环氧烷聚合反应，用量只要25ppm；4.催化活性在105℃，25ppm条件下，活性可达到1339 gPO/g，min；5.制备的聚醚不饱和度低于0.005mmol/g；6、制备的聚醚多元醇稳定性好，无需加抗氧化剂；7.可以省去催化剂的后处理而不影响聚氨酯的性能。The invention discloses a multi-metal multi-ligand complex used for catalyzing the polymerization of alkylene oxide and a synthesis method thereof. It is characterized in that: 1. This catalyst includes more than two kinds of metals and more than two kinds of organic ligands; 2. It is applied to catalyze the polymerization of alkylene oxide, and the induction period can be shortened to 13-16 minutes; 3. Its catalytic activity is far It is much higher than KOH and double metal cyanide catalysts, and the dosage is low. It is only 25ppm when used in the polymerization of alkylene oxide; 4. The catalytic activity can reach 1339 gPO/g, min at 105°C and 25ppm; 5 .The unsaturation degree of the prepared polyether is lower than 0.005mmol/g; 6. The prepared polyether polyol has good stability without adding antioxidant; 7. The aftertreatment of the catalyst can be omitted without affecting the performance of the polyurethane.
Description
Technical field
The present invention relates to a kind of many metals multiple ligand composition catalyst and preparation method thereof, particularly relate to a kind of synthetic many metals multiple ligand composition catalyst of polyethers and preparation method thereof that is used for, this catalyst can be used for preparing polyethers, polyester and PPG.
Background technology
At present, the traditional catalyst that is used as alkylene oxide polymerization is KOH, but KOH exists significantly limitation and defective as this type of catalyst for reaction: the PPG degree of unsaturation height of production, can not satisfy the requirement of high performance polyurethane; The PPG molecular weight of producing is restricted, and generally all be low-molecular-weight, and small molecular weight impurity is more, can not satisfy the high performance requirements of polyurethane; Production cycle is long, and technology is loaded down with trivial details, and investment in fixed assets is big, the integrated cost height of production; The KOH consumption is generally 0.1wt%～1.0wt% (in oxyalkylene) greatly, and being present in can heavy damage properties of product, thoroughly removal in the product.And, in order to remove KOH, needing to increase operation and equipment such as neutralization, dehydration, the degassing, filtration in the production process, fixed investment cost and production cost all improve greatly; And can increase the small molecular weight impurity and the degree of unsaturation of product, also can reduce productive rate, cause environmental pollution.
Make the limitation of alkylene oxide polymerization catalyst at KOH, the someone has tested DMC catalysts, and Comparatively speaking, the DMC catalysts activity is obviously than KOH height, and the polyethers degree of unsaturation of preparation is low, therefore is expected to substitute KOH on producing.
Typical DMC catalysts (DMC) is by the reactant aqueous solution generation zinc hexacyanocobaltate precipitation of zinc chloride and Cobalt Potassium Cyanide, again with the glyme effect, generates DMC catalysts.The result shows that although compare with KOH, its activity is quite high, but still not ideal enough, is difficult to drop into commercial Application.Because, active under the condition of catalyst amount 100ppm (based on the weight of final PPG) at 105 ℃ less than 2gPO/min (PO is an expoxy propane), and be difficult to separation (US, Pat No, 5,158,922).
Have the people that the preparation method of DMC catalysts is improved recently, substitute glyme with the tert-butyl alcohol, catalytic activity has had raising, and at 105 ℃, under the catalyst amount 100ppm condition, activity has reached 3gPO/min.Its activity is still not high enough, and catalyst amount is up to 100ppm.Also need catalyst is separated from product, otherwise can influence the performance of polyurethane.Therefore,, must further improve activity, reduce consumption as ideal catalyst of alkylene oxide polymer.
Summary of the invention
The present invention seeks to limitation and defective in order to overcome KOH and DMC catalysts, a kind of many metals multiple ligand composition catalyst and preparation method thereof is provided, this catalyst has the advantages that activity is high, consumption is low, and guarantee that catalyst is incorporated into concentration of metal ions in the product less than 20ppm, thereby simplify the polyethers production technology, reduce production costs.
Technical scheme of the present invention is: change the traditional double metal cyanides and form, introduce the collaborative part of two or more organic compounds as cyanic acid ion, change metal ion charge distribution density and stereochemical structure on every side, thereby improve activity of such catalysts.
Many metals of kind multiple ligand composition catalyst of the present invention, its composition expression formula is:
M
a′[M″(CN)
b]
c·dMX
n·eH
2O·fL′·gL″·hL
In the formula,
M ' is a metal ion species, is selected from following metal ion: Zn
2+, Fe
2+, Co
3+, Mn
2+, Co
2+, Sn
2+Or Fe
3+
M " is a metal ion species, is selected from following metal ion: Fe
2+, Fe
3+, Co
3+, Mn
2+, Mn
3+Or Co
2+M ' and M are " identical or different;
M is a metal ion species, is selected from following metal ion: Fe
2+, Fe
3+, Co
3+, Mn
2+, Mn
3+Or Co
2+M ' is identical or different with M ; M is " identical or different with M ;
X is a kind of anion, is the anion in the following compounds: halide, cyanide and cyanate;
L ' is the tert-butyl alcohol or tert-pentyl alcohol;
" be a kind of organic ligand, be 200～500 PPOX ether for dibutyl phthalate, repefral, tert-butylamine or molecular weight to L
L is BF
3Or tributyltin chloride;
A, b, c, d, e, f, g, h, n are coefficients, its numerical value is mark or the integer greater than zero, but whole composition is electroneutral.
The preferred Zn of wherein said M '
2+, Fe
2+, Mn
2+Or Co
2+
Described M " preferred Co
2+, Co
3+Or Fe
3+
The preferred Fe of described M
2+, Zn
2+Or Mn
2+
The preferred F of described X
1-, CI
1-Or Br
1-
The preparation method of many metals multiple ligand composition catalyst of the present invention prepares by following step:
The 1st takes by weighing Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganates, puts in the reactor, and the water that adds 8～10 times of its quality dissolves it, again with M X
n25wt%～40wt% aqueous solution under agitation splash in the reactor, splash into M X
nQuality be Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganates 10～13 times, stirred again after dripping off 30～60 minutes, the aqueous solution that adds L ' 40wt%～60wt% then, add its L ' aqueous solution quality and be Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganates 20～30 times, stirred 1～2 hour, the concentration that adds L again is the methanol solution of 0.2wt%～1wt%, add its L methanol solution quality and be Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganates 1～2 times, stirred 0.5～3 hour, filter filter cake;
The 2nd changes the resulting filter cake of step 1 in the aqueous solution that L ' concentration is 60wt%～80wt% over to, L ' concentration is that the consumption of 60wt%～80wt% aqueous solution is Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganate quality 20～30 times, put in the reactor then, stirred 1～2 hour, " and the mixed solution of pure water; mixed solution is in 10g L ' and 15g L " and prepare by the ratio of 160g pure water to add L ' and L again, the mixed solution consumption is Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganate quality 1～3 times, stirred 0.5～2 hour, filter filter cake;
The 3rd changes the resulting filter cake of step 2 among the pure L ' over to, pure L ' consumption is Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganate quality 20～30 times, put in the reactor, stirred 1～2 hour, adding pure L at last, "; pure L " consumption is Cobalt Potassium Cyanide or potassium hexacynoferrate or six cyanogen potassium manganate quality 2～3 times, stirs after 1.5～4 hours, filter filter cake;
The 4th with the resulting filter cake of step 3 in 50～70 ℃ of following vacuum drying to constant weight, promptly get catalyst prod.
Technology predicate among the present invention, catalyst amount: mean weight based on final PPG product; PO is an expoxy propane.
The present invention is based on double metal cyanide has catalytic action to the preparation of polyethers, but activity is still not high enough, is difficult to use in industrial practice.Be surprised to find in the present invention, behind the introducing L , catalyst has following characteristics:
1, activity of such catalysts is about 10 times of double metal cyanide raw catalyst, can reach at 105 ℃, and under the catalyst amount 25ppm condition, activity is 1370gPO/g, min.The every gram catalyst of per minute transforms the 1370g alkylene oxide.
2, catalyst consumption is low especially, and catalyst amount can make reaction carry out smoothly under the 25ppm condition, and fast when being 100ppm than known DMC catalysts (DMC) consumption.
3, lack the induction period of catalyst, can reach below 30 minutes, even 13 minutes.Be generally the induction period of known dmc catalyst (EP 0 755 716 A1) about 240 minutes.
4, adopt the polyethers of this Preparation of Catalyst, have the low advantage of degree of unsaturation.
5, adopt the polyethers of this Preparation of Catalyst, its molecular weight is unrestricted substantially.
6, adopt the polyethers of this Preparation of Catalyst, good stability need not to add antioxidant.
7, this catalyst is used for alkylene oxide polymerization and prepares PPG, and consumption is low, and alkali metal ion content measured post processing such as does not need to filter below 3ppm, can reduce production costs greatly.
8, Preparation of catalysts condition of the present invention is simple, and the adding of organic ligand can be before precipitation generates, also can be after precipitation generates.
The catalytic activity that catalyst of the present invention is applied to the alkylene oxide polymerization reaction is high especially.Its preparation polyethers of industrial application, consumption is low especially, can remove the step of separating catalyst from product from, and do not influence properties of product, the reaction speed height, generated time reduces 80%～90% than traditional KOH catalysis, especially Zhi Bei pfpe molecule amount height, and there is not small molecular weight impurity, degree of unsaturation is low, relative molecular mass height and narrowly distributing, single functionality impurity is few, number-average's height, good stability need not to add characteristics such as antioxidant, for the upgrading of polyether product provides possibility, can be widely used in the production polyurethane elastomer, the soft bubble of high resilience, fluid sealants etc. make goods have elasticity preferably, elongation at break and tear resistance are for preparation high-quality polyurethane goods provide necessary raw material sources.
The specific embodiment
Embodiment 1
The preparation of catalyst 1, its preparation process is:
1st, get Cobalt Potassium Cyanide 13g, be dissolved in the 130 gram pure water, get solution 1
1Get zinc chloride 40g, be dissolved in the 120g pure water, get solution 2
1Get the 234g tert-butyl alcohol and 156g pure water and mix, get solution 3
1Compound concentration is 0.2wt% tributyltin chloride (C
4H
9)
3The methanol solution of SnCl gets solution 4
1In the 10g tert-butyl alcohol and 15g molecular weight is the ratio obtain solution 5 of 400 PPOX ether (being called for short PPG-204) and 160g pure water
1
2nd, in the reactor of 2000ml, add solution 1
1, under agitation drip solution 2 then
1, homogenizing 30 minutes again after adding adds solution 3 again
1, and stirred 1 hour, add 24g solution 4 at last
1, and stirred 3 hours.Vacuum filtration gets solid A
1
3rd, with solid A
1Put into reaction vessel, adding concentration is 60wt% tert-butyl alcohol aqueous solution 390g, stirs 2 hours, and then adds 13g solution 5
1, stirred vacuum filtration 2 hours.Get solid B
1
4th, with solid B
1Add in the reaction vessel, add the 260g tert-butyl alcohol and stirred 1 hour, add 18g o-benzoic acid dibutyl ester and 8g molecular weight again and be 400 PPOX ether, stirred 4 hours, vacuum filtration then, filter cake to constant weight, get catalyst 1 product through after grinding 70 ℃ of following vacuum drying.
Embodiment 2:
The preparation of catalyst 2, its preparation process is:
1st, get potassium hexacynoferrate 11g, be dissolved in the 88g pure water, get solution 1
2Get manganese chloride 43g, be dissolved in the 65g pure water, get solution 2
2Get 88g tert-pentyl alcohol and 132g pure water and mix, get solution 3
2Compound concentration is 1.0wt% tributyltin chloride (C
4H
9)
3The methanol solution of SnCl gets solution 4
2In the 10g tert-butyl alcohol: 15g tert-butylamine: the ratio obtain solution 5 of 160g pure water
2
2nd, in the reactor of 2000ml, add solution 1
2, under agitation drip solution 2 then
2, homogenizing 60 minutes again after adding adds solution 3 again
2, and stirred 2 hours, add 11g solution 4 at last
2, and stirred 0.5 hour.Vacuum filtration gets solid A
2
3rd, with solid A
2Put into reaction vessel, adding concentration is 80wt% tert-butyl alcohol aqueous solution 220g, stirs 1 hour, and then adds 33g solution 4
2, to stir 1.5 hours, vacuum filtration gets solid B
2
4th, with solid B
2Add in the reaction vessel, adding 330g tert-pentyl alcohol stirred 2 hours, added 8g o-benzoic acid dimethyl ester and 3g tert-butylamine, stirred 3 hours, and vacuum filtration then, filter cake to constant weight, gets catalyst 2 products through after grinding 50 ℃ of following vacuum drying.
Embodiment 3
Comparative example, with reference to United States Patent 5,627,120 preparation DMC catalysts, preparation process is:
1st, get zinc chloride 252g and tert-butyl alcohol 168g, be dissolved in the 924g pure water, get solution 1
3Get Cobalt Potassium Cyanide 25.2g, be dissolved in the 336 gram pure water, get solution 2
3Get the 6.7g tert-butyl alcohol and 26.9g molecular weight and be 400 PPOX ether and mix with the 160g pure water, mixed solution 3
3
2nd, be equipped with in the reactor of 4000ml of stirring, logical nitrogen, thermometric, dropping liquid and heater in adding, at first add solution 1
3, be warming up to 50 ℃ then, under the mixing speed of 450rpm, drip solution 2
3, add the back and feed nitrogen, and improve mixing speed to 900rpm stirring 1 hour, reduce mixing speed again to 200rpm, drip mixed solution 3
3, under the mixing speed of 200rpm, mixed 3 minutes again after adding, stop to stir and logical nitrogen, carry out vacuum filtration, get solid A
3
3rd, with solid A
3Change in the reactor, add the 437g tert-butyl alcohol and 186g pure water solution, mixing speed with 900rpm was mixed 1 hour, reduce mixing speed then to 200rpm, adding 6.7g molecular weight is 400 PPOX ether, mixes 3 minutes under the mixing speed of 200rpm after adding again, and stops to stir, carry out vacuum filtration, get solid B
3
4th, with solid B
3Change in the reactor, add the 622g tert-butyl alcohol, mixing speed with 900rpm was mixed 1 hour, reduce mixing speed then to 200rpm, adding 3.4g molecular weight is 400 PPOX ether, mixes 3 minutes under the mixing speed of 200rpm after adding again, and stops to stir, carry out vacuum filtration, get solid C;
5th, solid C is placed vacuum drying chamber, to constant weight, get catalyst 3 products through after grinding 60 ℃ of following vacuum drying.
Embodiment 4
The preparation of catalyst 4, its preparation process is:
1st, get Cobalt Potassium Cyanide 12g, be dissolved in the 100 gram pure water, get solution 1
4Get zinc bromide 42g, be dissolved in the 90g pure water, get solution 2
4Get the 150g tert-butyl alcohol and 150g pure water and mix, get solution 3
4Compound concentration is 0.5wt% tributyltin chloride (C
4H
9)
3The methanol solution of SnCl gets solution 4
4Ratio obtain solution 5 in the 10g tert-butyl alcohol and 15g o-benzoic acid dibutyl ester and 160g pure water
4
2nd, in the reactor of 2000ml, add solution 1
4, under agitation drip solution 2 then
4, homogenizing 40 minutes again after adding adds solution 3 again
4, and stirred 1.5 hours, add 18g solution 4 at last
4, and stirred 2 hours, vacuum filtration gets solid A
4
3rd, with solid A
4Put into reaction vessel, adding concentration is 70wt% tert-butyl alcohol aqueous solution 250g, stirs 2 hours, and then adds 15g solution 5
4, to stir 0.5 hour, vacuum filtration gets solid B
4
4th, with solid B
4Add in the reaction vessel, add the 300g tert-butyl alcohol and stirred 1.8 hours, adding 24g o-benzoic acid dibutyl ester and 12g molecular weight are 400 PPOX ether, stirred 3 hours, vacuum filtration then, filter cake to constant weight, get catalyst 4 products through after grinding 60 ℃ of following vacuum drying.
Embodiment 5
The preparation of catalyst 5, its preparation process is:
1st, get Cobalt Potassium Cyanide 12g, be dissolved in the 100g pure water, get solution 1
5Get zinc chloride 40g, be dissolved in the 90g pure water, get solution 2
5Get the 150g tert-butyl alcohol and 150g pure water and mix, get solution 3
5Compound concentration is 0.3wt% tributyltin chloride (C
4H
9)
3The methanol solution of SnCl gets solution 4
5Ratio preparation mixed solution 5 in the 10g tert-butyl alcohol and 15g o-benzoic acid dimethyl ester and 160g pure water
5
2nd, in the reactor of 2000ml, add solution 1
5, under agitation drip solution 2 then
5, homogenizing 30 minutes again after adding adds solution 3 again
5, and stirred 2 hours, add 18g solution 4 at last
5, and stirred 2 hours, vacuum filtration gets solid A
5
3rd, with solid A
5Put into reaction vessel, add 80wt% concentration tert-butyl alcohol aqueous solution 250g, stirred 2 hours, and then add 15g mixed solution 5
5, to stir 0.5 hour, vacuum filtration gets solid B
5
With solid B
5Add in the reaction vessel, add 280g tert-butyl alcohol stirring 2 hours, add 36g o-benzoic acid dibutyl ester and stirred 1.5 hours, vacuum filtration then, filter cake to constant weight, gets catalyst 5 products through after grinding 70 ℃ of following vacuum drying.Applicating example:
Embodiment 6
One be equipped with stir and the 2L reactor of heat exchanger in, add mean molecule quantity and be 700 the polyether Glycols 70g and the catalyst 0.02g (catalyst amount is 25ppm) of embodiment 1 preparation, stir miscible, and vacuumize and slough trace water and small molecular weight impurity in the initial reagent, then for several times with nitrogen replacement; Be heated to 140 ± 10 ℃, feed the 35g expoxy propane, observing response still pressure, temperature variation; Reactor temperature sharply rises when observing, press in the reactor when obviously descending, and indicates that catalyst is activated, and catalytic reaction begins, and record is induction period from adding the time period of expoxy propane to the reaction beginning; Can feed remaining 715g expoxy propane this moment continuously, and adding speed and rate of heat exchange by the adjustable ring Ethylene Oxide, and the control reaction temperature is that 130 ± 10 ℃, pressure are 0.07 ± 0.02MPa; Until adding expoxy propane, and press in the reactor and keep constant; At last, by vacuumizing unreacted small molecule monomer is reclaimed; Be cooled to room temperature, bottling; Get water white polyether Glycols.
Embodiment 7 presses the method for embodiment 6, only uses the catalyst of catalyst equivalent replacement embodiment 1 preparation of embodiment 2 preparations, prepares polyether Glycols equally.
Embodiment 8 presses the method for embodiment 6, only uses the catalyst of catalyst equivalent replacement embodiment 1 preparation of embodiment 3 preparations, prepares polyether Glycols equally.
Embodiment 9 presses the method for embodiment 6, only uses the catalyst of catalyst equivalent replacement embodiment 1 preparation of embodiment 4 preparations, prepares polyether Glycols equally.
Embodiment 10 presses the method for embodiment 6, only uses the catalyst of catalyst equivalent replacement embodiment 1 preparation of embodiment 5 preparations, prepares polyether Glycols equally.
Embodiment 11 is at a 2M that stirring and heat exchanger are housed
3In the reactor, add mean molecule quantity and be 700 the polyether Glycols 140Kg and the catalyst 40g (catalyst amount is 25ppm) of embodiment 1 preparation, stir misciblely, and vacuumize and slough trace water and small molecular weight impurity in the initial reagent, then for several times with nitrogen replacement; Be heated to 140 ± 10 ℃, feed the 45Kg expoxy propane, observing response still pressure, temperature variation; Reactor temperature sharply rises when observing, press in the reactor when obviously descending, and indicates that catalyst is activated, and catalytic reaction begins, and record is induction period from adding the time period of expoxy propane to the reaction beginning; Can feed remaining 1415Kg expoxy propane this moment continuously, and adding speed and rate of heat exchange by the adjustable ring Ethylene Oxide, and the control reaction temperature is that 130 ± 10 ℃, pressure are 0.12 ± 0.04MPa; Until adding expoxy propane, and press in the reactor and keep constant; At last, by vacuumizing unreacted small molecule monomer is reclaimed; Be cooled to 80 ℃, barrelling; Get water white polyether Glycols.
The response parameter of embodiment 6～embodiment 11 is listed in the table 1.
Table 1
| Embodiment | Catalyst amount ppm | Induction period min | Polymerization time min | Polymerization speed/degree gPO/min | Catalyst activity/property gPO/g, min | Hydroxyl value mgKOH/g | Molecular weight | Degree of unsaturation mmol/g | Colourity (APHA) |
| 6 7 8 9 10 11 | 25 25 25 25 25 25 | 13 17 216 15 18 23 | 28 31 357 29 30 55 | 27 24 2.1 26 25 26545 | 1339 1210 105 1293 1250 664 | 14.0 13.8 14.2 14.1 14.3 13.9 | 8015 8130 7903 7958 7846 8073 | 0.0045 0.0077 0.0057 0.0051 0.0069 0.0067 | ＜50 ＜50 ＜50 ＜50 ＜50 ＜50 |
It is about 94% to find out that from table 1 catalyst activity height, particularly induction period that the activity of such catalysts of embodiment 1, embodiment 2, embodiment 4 and embodiment 5 preparations obviously makes than embodiment 3 (comparative example) have shortened, and has improved the production capacity of reactor greatly.Catalyst is used for industrial amplification test, also shortened about 90% induction period, the reactivity of catalyst has reached 664gPO/g, min, difference between itself and the embodiment 4 is the restricted artificial limit reaction rates of heat-sinking capability of equipment during because of industrial production, and the result makes the catalyst activity value energy of calculating on the low side.
Claims (6)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302286B (en) * | 2008-05-09 | 2010-10-27 | 中国石油化工股份有限公司 | Multi-metal cyanide complex catalyst |
| CN107118341A (en) * | 2017-06-19 | 2017-09-01 | 于天荣 | A kind of bimetallic catalyst and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU552988B2 (en) * | 1982-03-31 | 1986-06-26 | Shell Internationale Research Maatschappij B.V. | Polymerizing epoxides and catalyst suspensions for this |
| US5391722A (en) * | 1990-03-30 | 1995-02-21 | Olin Corporation | Acid-catalyzed fabrication of precursors for use in making polyols using double metal cyanide catalysts |
| US6077978A (en) * | 1997-09-17 | 2000-06-20 | Arco Chemical Technology L.P. | Direct polyoxyalkylation of glycerine with double metal cyanide catalysis |
| US6063897A (en) * | 1998-05-05 | 2000-05-16 | Arco Chemical Technology, L.P. | Acid-treated double metal cyanide complex catalysts |
| US6028230A (en) * | 1998-06-05 | 2000-02-22 | Arco Chemical Technology, L.P. | Epoxide polymerization process |
| DE10001779A1 (en) * | 2000-01-18 | 2001-07-19 | Basf Ag | Production of polyether-alcohol, used as starting material for polyurethane production, involves alkoxylation of H-functional starter with alkylene oxide in the presence of multi-metal cyanide catalyst and acid compound |
| CN1459332A (en) * | 2002-05-24 | 2003-12-03 | 中国石化集团金陵石油化工有限责任公司 | Complex catalyst contg. two or more than two kinds of bimetal cyanide, prepn. method and application thereof |
| CN100430136C (en) * | 2002-11-13 | 2008-11-05 | 中国石油化工股份有限公司 | Double metal cyanide catalysts |
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| CN101302286B (en) * | 2008-05-09 | 2010-10-27 | 中国石油化工股份有限公司 | Multi-metal cyanide complex catalyst |
| CN107118341A (en) * | 2017-06-19 | 2017-09-01 | 于天荣 | A kind of bimetallic catalyst and preparation method and application |
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