CN103910865B - Bimetallic cyanide catalyst containing micro-molecular polyether polyol and preparation method of bimetallic cyanide catalyst - Google Patents
Bimetallic cyanide catalyst containing micro-molecular polyether polyol and preparation method of bimetallic cyanide catalyst Download PDFInfo
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Abstract
The invention discloses a bimetallic cyanide catalyst containing micro-molecular polyether polyol and a preparation method of the bimetallic cyanide catalyst. The structural general formula of the bimetallic cyanide catalyst is Aa[Bb(CN)c]d.r(EmYn).wD.xZ, wherein A is Zn or Fe and the like; E is Zn or Fe and the like; B is Fe or Co and the like; Y is Cl- or Br- and the like; D is a ligand; Z is glycerol. The preparation method of the bimetallic cyanide catalyst comprises the steps of adding a metallic cyanide saline solution into a saturated metallic saline solution, stirring and reacting for 30 minutes, adding tert-butyl alcohol into a prepared reaction solution until forming precipitations, mixing and filtering by using a solution consisting of the ligand and glycerol, controlling the temperature of a prepared filter cake at 80-150 DEG C, and drying until keeping constant weight to obtain the bimetallic cyanide catalyst containing micro-molecular polyether polyol with higher activity. By applying the bimetallic cyanide catalyst containing micro-molecular polyether polyol to the production of polyether, the induction time is greatly shortened, and an initiator is not needed, so that the production cost is reduced, and the production efficiency is improved.
Description
Technical field
The present invention relates to a kind of DMC catalysts containing small molecule polyether polyol and preparation method thereof.Little
Molecule polyether polyol plays the effect of similar initiator in catalyst polyethers.Mass fraction is 1% in the catalyst
10%.The catalyst that catalyst of the present invention and preparation method thereof makes with traditional method is compared has higher activity；Mainly solve
In conventional polyethers produces, it is long to there is catalyst induction period, the problems such as need initiator to induce.Greatly shorten induction time, and
And do not need to add initiator, save cost, improve efficiency.
Background technology
It is known that Narrow Molecular Weight Distribution and high molecular weight polyether have the characteristics that capability and performance is stable, in the poly- ammonia of soft bubble
Ester, high-rebound polyurethane, polyurethane elastomer, sapecial coating, specific rubber, hydraulic oil, metalworking fluid and aircraft materials are quenched
The fields such as fiery agent have a extensive future.At present, the polyether product on domestic market is substantially with traditional base catalysiss technique productions
, in product, unitary alcohol content is high, and average functionality is low, and double bond content is high, capability and performance less stable.
And adopt the polyether product that catalysis activity DMC catalysts (dmc) produce then can effectively overcome with
Upper shortcoming, has successfully applied in the many such as elastomer, polyurethane paint, coating, binding agent fields, has obtained good effect.But
Current DMC catalysts also have some problems demand to solve in use: as low in catalyst activity, consumption is many；Urge
Agent induction period is long；Initiator need to be added to cause process loaded down with trivial details when producing every time, inefficiency etc..
For the solution of these problems, many patents this has been carried out report document us3427256, us3427234,
Us5158922 reports in succession using diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether as chelating agent system
The technology of standby DMC catalysts.Although its performance of polyether polyol that these catalyst are obtained has larger improvement,
The degree of unsaturation of polyether polyol is effectively reduced, but because the activity of catalyst is not high enough, is not required to far from reaching
Want the requirement of post processing.
The research worker of Beyer Co., Ltd finds, under conditions of the tert-butyl alcohol is as organic ligand, to add the poly- of certain mass
Carbonic ester can substantially shorten that DMC catalysts are used for being catalyzed expoxy propane, oxirane carries out producing polyether polyols
The induction time of the reaction of alcohol.And due to active raising, the amount using catalyst greatly reduces, and can remove post processing from
Process.But produce every time it is still desirable to induce during polyethers, and a certain amount of initiator need to be added, thus considerably increasing
The time producing, reduce efficiency.
Content of the invention
When an object of the present invention is to solve above-mentioned production polyether polyol, require time for induced reaction, and
And a certain amount of initiator need to be added, thus considerably increasing the time of production, reducing the technical problems such as production efficiency and carrying
For a kind of DMC catalysts containing small molecule polyether polyol.
The second object of the present invention is to provide a kind of above-mentioned double metal cyanide containing small molecule polyether polyol to urge
The preparation method of agent.
The know-why of the present invention
Small molecule polyether polyol plays the effect of similar initiator when DMC catalysts are catalyzed polyethers.
Technical scheme
A kind of DMC catalysts containing small molecule polyether polyol, its general structure is aa[bb(cn)c]d.r(emyn).wd.xz；
Wherein: a is zn, fe, al, co, cu, cr, mn or pb；
E is zn, fe, al, co, cu, cr, mn or pb;
B is fe, co, al or cr;
Above-mentioned a, b, e are identical or different；
Y is cl-、br-、oh-、co32-、so42-Or no3 -；
D is ligand, and described ligand is the mixture of Organic Alcohol, ethers or Organic Alcohol and ethers；Wherein said
Organic Alcohol is the tert-butyl alcohol or n-butyl alcohol；Described ethers is glycol dimethyl ether；
Z is glycerol；
A, b, c, d, m, n, represent the number of corresponding ion respectively；
R is 0.5-3；
W is 3；
X is 1-2.
A kind of preparation method of above-mentioned DMC catalysts containing small molecule polyether polyol, specifically includes
Following steps:
(1), the synthesis of bimetallic cyanide complex:
Metal cyanide salt is dissolved in the water and obtains metal cyanides saline solution；
Described metal cyanide salt is six potassium cyanates, six cyanic acid zinc or potassium hexacynoferrate；
Dissolving metal salts are obtained saturation aqueous metal salt in water；
Described slaine is zncl2、znbr2、fecl3Or febr3One of；
Metal cyanides saline solution is added under the rotating speed for 8000r/min for the rotating speed saturation aqueous metal salt
In, stir hybrid reaction 0.5h, the reactant liquor of gained adds ligand, to forming precipitation, be subsequently adding by ligand and the third three
The solution of alcohol composition, mixes 0.5h under the stirring condition of 8000r/min, obtains mixed liquor 1；
Metal cyanides saline solution used in above-mentioned course of reaction, saturation aqueous metal salt, the amount of ligand, press
Volume ratio calculates, i.e. metal cyanides saline solution: saturation aqueous metal salt: ligand is 10-30:20-30:10-15；
The above-mentioned solution being made up of ligand and glycerol, calculates, ligand by volume: glycerol is 10-15ml:
0.5-1g；It is equal with the volume of the ligand adding in reactant liquor that its consumption presses ligand calculating；
(2), the mixed liquor 1 obtaining step (1) filters, and the filter cake 1 of gained is molten be made up of ligand and glycerol
Liquid mixed 0.5h under the rotating speed of 8000r/min, obtains mixed liquor 2, the mixed liquor 2 of gained is filtered, will obtain
Filter cake control temperature be 60-80 DEG C of drying to constant weight, obtain final product double metal cyanide-catalyzed containing small molecule polyether polyol
Agent；
The above-mentioned solution being made up of ligand and glycerol, calculates, ligand by volume: glycerol is 10-15ml:
0.5-1g；It is equal with the volume of the ligand adding in reactant liquor in step (1) that its consumption presses ligand calculating.
A kind of above-mentioned DMC catalysts containing small molecule polyether polyol are used for the system of polyether polyol
Standby, greatly shorten induction time, and do not need to add initiator, saved cost, improve efficiency.
Beneficial effects of the present invention
A kind of DMC catalysts containing small molecule polyether polyol of the present invention, with traditional catalyst phase
Than, due in catalyst the polyethers containing small molecule it is ensured that catalyst has very high activity in the early stage, therefore with
It is not necessary to add derivant to be induced in process for production of polyether polyols.
A kind of DMC catalysts containing small molecule polyether polyol of the present invention, due to little point in catalyst
The presence of sub- polyethers, when it is used for the production of polyether polyol, greatly shortens induction time, and does not need to add initiator,
Save production cost, improve production efficiency.Therefore which solve in conventional polyethers produces, there is catalyst induction period
Long, the problems such as need initiator.
Specific embodiment
Below by specific embodiment, the present invention is expanded on further, but is not intended to limit the present invention.
Embodiment 1
A kind of DMC catalysts containing small molecule polyether polyol, its general structure is aa[bb(cn)c]d.r(emyn).wd.xz；
Wherein: a is zn；
E is zn;
B is co;
Y is cl-；
D is the tert-butyl alcohol；
Z is glycerol；
A, b, c, d, m, n, represent that the number of corresponding ion is 3,1,6,2,1,2 respectively；
R is 1；
W is 3；
X is 2.
A kind of above-mentioned DMC catalysts containing small molecule polyether polyol, specifically include following steps:
(1), the synthesis of bimetallic cyanide complex:
Metal cyanide salt six potassium cyanate is dissolved in the water six potassium cyanates obtaining that mass percent concentration is 10%
Aqueous solution；
Slaine zncl2It is dissolved in the zncl that water obtains saturation2Aqueous solution；
By 20ml mass percent concentration be 10% six cyanic acid aqueous solutions of potassium under the rotating speed for 8000r/min for the rotating speed
It is added to the zncl of 20ml saturation2In aqueous solution, stir hybrid reaction 0.5h, the reactant liquor of gained adds the tertiary fourth of 15ml ligand
Alcohol, to forming precipitation, is subsequently adding the stirring in 8000r/min for the solution being made up of the 15ml ligand tert-butyl alcohol with 1g glycerol
Under the conditions of mix 0.5h, obtain mixed liquor 1；
(2), the mixed liquor 1 of step (1) gained is filtered, the filter cake of gained is again with by the 15ml ligand tert-butyl alcohol
Mix 0.5h with the solution of 1g glycerol composition under the rotating speed of 8000r/min, obtain mixed liquor 2, the mixed liquor 2 of gained is entered
Row filters, and the filter cake obtaining is controlled temperature for 60-80 DEG C of drying to constant weight, obtains final product the double gold containing small molecule polyether polyol
Belong to cyanide catalyst a, i.e. zn3[co(cn)6]2.rzncl2.w tert-butyl alcohol .x glycerol.
Embodiment 2
A kind of DMC catalysts containing small molecule polyether polyol, its general structure is aa[bb(cn)c]d.r(emyn).wd.xz；
Wherein: a is zn；
E is zn;
B is co;
Y is cl-；
D is n-butyl alcohol；
Z is glycerol；
A, b, c, d, m, n, represent that the number of corresponding ion is 3,1,6,2,1,2 respectively；
R is 1；
W is 3；
X is 1.
A kind of preparation method of above-mentioned DMC catalysts containing small molecule polyether polyol, specifically includes
Following steps:
(1), the synthesis of bimetallic cyanide complex:
Metal cyanide salt six potassium cyanate is dissolved in the water six potassium cyanates obtaining that mass percent concentration is 10%
Aqueous solution；
Slaine zncl2It is dissolved in the zncl that water obtains saturation2Aqueous solution；
By 30ml mass percent concentration be 10% six cyanic acid aqueous solutions of potassium under the rotating speed for 8000r/min for the rotating speed
It is added to the zncl of 30ml saturation2In aqueous solution, stir hybrid reaction 0.5h, the reactant liquor of gained adds the positive fourth of 10ml ligand
Alcohol, to forming precipitation, is subsequently adding solution the stirring in 8000r/min being made up of 10ml ligand n-butyl alcohol with 0.5g glycerol
Carry out under the conditions of mixing mixing 0.5h, obtain mixed liquor 1；
(2), by step (1) mixed liquor 1 filter, the filter cake of gained is with by 10ml ligand n-butyl alcohol and 0.5g the third three
The solution of alcohol composition mixes 0.5h under the rotating speed of 8000r/min, obtains mixed liquor 2, the mixed liquor 2 of gained is filtered,
The filter cake of gained controls temperature for 60-80 DEG C of drying to constant weight, obtains final product the double metal cyanide containing small molecule polyether polyol
Catalyst b, i.e. zn3[co(cn)6]2.rzncl2.w n-butyl alcohol .x glycerol.
Embodiment 3
A kind of DMC catalysts containing small molecule polyether polyol, its general structure is aa[bb(cn)c]d.r(emyn).wd.xz；
Wherein: a is zn；
E is zn;
B is co;
Y is cl-；
D is the tert-butyl alcohol；
Z is glycerol；
A, b, c, d, m, n, represent that the number of corresponding ion is 3,1,6,2,1,2 respectively；
R is 2；
W is 3；
X is 2.
A kind of preparation method of above-mentioned DMC catalysts containing small molecule polyether polyol, specifically includes
Following steps:
(1), the synthesis of bimetallic cyanide complex:
Metal cyanide salt six potassium cyanate is dissolved in the water six potassium cyanates obtaining that mass percent concentration is 10%
Aqueous solution；
Slaine zncl2It is dissolved in the zncl that water obtains saturation2Aqueous solution；
By 40ml mass percent concentration be 10% six cyanic acid aqueous solutions of potassium under the rotating speed for 8000r/min for the rotating speed
It is added to the zncl of 20ml saturation2In aqueous solution, stir hybrid reaction 0.5h, the reactant liquor of gained adds the tertiary fourth of 15ml ligand
Alcohol, to forming precipitation, is subsequently adding the stirring in 8000r/min for the solution being made up of the 15ml ligand tert-butyl alcohol with 1g glycerol
Under the conditions of mix 0.5h, obtain mixed liquor 1；
(2), the mixed liquor 1 of step (1) gained is filtered, gained filter cake is with by the 15ml ligand tert-butyl alcohol and 1.5g the third three
The solution of alcohol composition mixes 0.5h under the rotating speed of 8000r/min, obtains mixed liquor 2, the mixed liquor 2 of gained is filtered,
The filter cake obtaining is controlled temperature for 60-80 DEG C of drying to constant weight, obtains final product the bimetallic cyaniding containing small molecule polyether polyol
Thing catalyst c, i.e. zn3[co(cn)6]2.rzncl2.w tert-butyl alcohol .x glycerol.
Embodiment 4
A kind of DMC catalysts containing small molecule polyether polyol, its general structure is aa[bb(cn)c]d.r(emyn).wd.xz；
Wherein: a is fe；
E is fe;
B is co;
Y is br-；
D is the tert-butyl alcohol；
Z is glycerol；
A, b, c, d, m, n, represent that the number of corresponding ion is 1,1,6,1,1,3 respectively；
R is 0.5；
W is 3；
X is 2.
A kind of preparation method of above-mentioned DMC catalysts containing small molecule polyether polyol, specifically includes
Following steps:
(1), the synthesis of bimetallic cyanide complex:
Metal cyanide salt six potassium cyanate is dissolved in the water six potassium cyanates obtaining that mass percent concentration is 10%
Aqueous solution；
Slaine febr3It is dissolved in the febr that water obtains saturation3Aqueous solution；
By 10ml mass percent concentration be 10% six cyanic acid aqueous solutions of potassium under the rotating speed for 8000r/min for the rotating speed
It is added to the febr of 20ml saturation3In aqueous solution, stir hybrid reaction 0.5h, the reactant liquor of gained adds the tertiary fourth of 15ml ligand
Alcohol, to forming precipitation, is subsequently adding the stirring in 8000r/min for the solution being made up of the 15ml ligand tert-butyl alcohol with 1g glycerol
Under the conditions of mix 0.5h, obtain mixed liquor 1；
(2), step (1) gained mixed liquor 1 is filtered, the filter cake obtaining is with by the 15ml ligand tert-butyl alcohol and 1g glycerol
The solution of composition mixes 0.5h under the rotating speed of 8000r/min, obtains mixed liquor 2, the mixed liquor 2 of gained is filtered, will
The filter cake obtaining controls temperature for 60-80 DEG C of drying to constant weight, obtains final product the double metal cyanide containing small molecule polyether polyol
Catalyst d is fe [co (cn)6].rfebr3.w tert-butyl alcohol .x glycerol.
Application Example 1(is added without initiator)
The DMC catalysts containing small molecule polyether polyol of above-described embodiment 1-4 gained are applied to gather
The synthetic reaction of ethoxylated polyhydric alcohol, specifically includes following steps: with agitator, the 2l autoclave of heat-exchange device, carry out
Evacuation inflated with nitrogen are replaced three times, remove moisture and volatile matter；When being heated to reaction temperature, by above-mentioned containing small molecule polyethers
The DMC catalysts of polyhydric alcohol and expoxy propane add reactor to carry out polyreaction；When pressure begins to decline,
Reaction starts, and writes down reaction induction time；Reflection pressure maintains 0.06mp, then through aging, waving in removed under reduced pressure reactor
Stimulating food, obtains final product.
Application comparative examples 1(add initiator glycerol)
The DMC catalysts containing small molecule polyether polyol of above-described embodiment 1-4 gained are applied to gather
The synthetic reaction of ethoxylated polyhydric alcohol, specifically includes following steps: with agitator, the 2l autoclave of heat-exchange device, will rise
Beginning agent glycerol adds in autoclave, evacuation at 100 1 130 DEG C, then with nitrogen displacement for several times, to remove moisture and volatilization
Thing；When being heated to reaction temperature, the DMC catalysts containing small molecule polyether polyol are added with expoxy propane
Reactor carries out polyreaction；When reflecting that pressure starts to be remarkably decreased, write down reaction induction time；Reflection pressure maintains
0.06mp, then through aging, in removed under reduced pressure reactor volatile matter, obtain final product.
During its synthesizing polyether glycol, required induction time is as follows:
Contained little by one kind that the result of above-mentioned Application Example and application comparative examples can be seen that the present invention
The DMC catalysts of molecule polyether polyol, during for producing polyether polyol, compared with being not added with initiator, induction
Time is shorter.Therefore which solve in conventional polyethers produces, it is long to there is catalyst induction period, the problems such as need initiator.Separately
Outward, due to greatly shortening induction time, and do not need to add initiator, therefore reduce production cost, improve production effect
Rate.
The above is only the basic explanation under present inventive concept, and according to technical scheme made any etc.
Effect conversion, all should belong to protection scope of the present invention.
Claims (1)
1. a kind of preparation method of the DMC catalysts containing small molecule polyether polyol, described containing little
The general structure of the DMC catalysts of molecule polyether polyol is aa[bb(cn)c]d.r(emyn).wd.xz；
Wherein: a is zn or fe；
E is zn or fe;
B is fe or co;
Above-mentioned a, b, e are identical or different；
Y is cl-Or br-；
D is ligand, and described ligand is Organic Alcohol or the mixture of ethers or Organic Alcohol and ethers；Wherein said is organic
Alcohol is the tert-butyl alcohol or n-butyl alcohol；Described ethers is glycol dimethyl ether；
Z is glycerol；
A, b, c, d, m, n, represent the number of corresponding ion respectively；
R is 0.5-3；
W is 3；
X is 1-2；
It is characterized in that the method specifically includes following steps:
(1) synthesis of bimetallic cyanide complex:
Metal cyanide salt is dissolved in the water and obtains metal cyanides saline solution；
Described metal cyanide salt is Cobalt Potassium Cyanide, zinc hexacyanocobaltate or potassium hexacynoferrate；
Dissolving metal salts are obtained saturation aqueous metal salt in water；
Described slaine is zncl2、znbr2、fecl3,febr3One of；
Metal cyanides saline solution is added in saturation aqueous metal salt under the rotating speed for 8000r/min for the rotating speed, stirs
Mix hybrid reaction 0.5h, the reactant liquor of gained is added ligand, to forming precipitation, is subsequently adding and is made up of with glycerol ligand
Solution, under the stirring condition of 8000r/min mix 0.5h, obtain mixed liquor 1；
Metal cyanides saline solution used in above-mentioned course of reaction, saturation aqueous metal salt, the amount of ligand, by volume
Ratio calculating, i.e. metal cyanides saline solution: saturation aqueous metal salt: ligand is 10-30:20-30:10-15；
The above-mentioned solution being made up of ligand and glycerol, calculates, ligand by volume: glycerol is 10-15ml:0.4-
0.8ml；It is equal with the volume of the ligand adding in reactant liquor that its consumption presses ligand calculating；
(2) mixed liquor 1 obtaining step (1) filters, and the filter cake 1 of gained is with being made up of with glycerol ligand
Solution under the rotating speed of 8000r/min mixed 0.5h, obtain mixed liquor 2, the mixed liquor 2 to gained
Filtered, the filter cake obtaining is controlled temperature for 60-80 DEG C of drying to constant weight, obtains final product containing small molecule polyethers
The DMC catalysts of polyhydric alcohol；
The above-mentioned solution being made up of ligand and glycerol, calculates, ligand by volume: glycerol is 10-15ml:0.4-
0.8ml；It is equal with the volume of the ligand adding in reactant liquor in step (1) that its consumption presses ligand calculating.
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