CN103910865A - 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 that contains small molecules polyether glycol and preparation method thereof.Small molecules polyether glycol plays similar initiator in the time of catalyst polyethers.In catalyzer, massfraction is 1%-10%.The catalyzer that Catalysts and its preparation method of the present invention is made with traditional method is compared has higher activity; Mainly solve in the past in polyethers is produced, exist the catalyst inducement phase long, need the problems such as initiator induction.Greatly shorten induction time, and do not need to add initiator, saved cost, improved efficiency.
Background technology
As everyone knows, narrow molecular weight distributions and high molecular weight polyether have the stable feature of capability and performance, have a extensive future in fields such as soft bubble urethane, high-rebound polyurethane, polyurethane elastomer, speciality coating, specialty elastomer, hydraulic efficiency oil, metal working fluid and aircraft material quenching mediums.At present, the polyether product on domestic market is substantially with traditional base catalysis explained hereafter, and in product, monohydroxy-alcohol content is high, and average functionality is low, and double bond content is high, capability and performance less stable.
The polyether product that adopts catalytic activity DMC catalysts (DMC) to produce can effectively overcome above shortcoming, is successfully applied in many fields such as elastomerics, polyurethane paint, coating, tackiness agent, obtains good effect.But current DMC catalysts in use also has some problems urgently to be resolved hurrily: as catalyst activity is low, consumption is many; The catalyst inducement phase is long; When each production, need add initiator to cause process loaded down with trivial details, inefficiency etc.
For the solution of these problems, many patents have been carried out report document US3427256 to this, US3427234, US5158922 have reported the technology of preparing DMC catalysts using diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether as complexing agent in succession.Although its performance of the polyether glycol that these catalyzer make has had larger improvement, the degree of unsaturation of polyether glycol is effectively reduced, and because the activity of catalyzer is not high enough, far can not reach the requirement that does not need aftertreatment.
The researchist of Beyer Co., Ltd finds at the trimethyl carbinol under the condition as organic ligand, adds the polycarbonate of certain mass can obviously shorten DMC catalysts and produces the induction time of the reaction of polyether glycol for catalysis propylene oxide, oxyethane.And due to active raising, use the amount of catalyzer greatly to reduce, can remove the process of aftertreatment from.But while producing polyethers at every turn, still need induction, and need add a certain amount of initiator, thereby greatly increased the time of producing, lowered efficiency.
Summary of the invention
One of object of the present invention is when solving above-mentioned production polyether glycol, need temporal induction reaction, and need add a certain amount of initiator, thereby greatly increase the time of producing, lowered the technical problems such as production efficiency and a kind of DMC catalysts that contains small molecules polyether glycol is provided.
Two of object of the present invention is to provide the preparation method of above-mentioned a kind of DMC catalysts that contains small molecules polyether glycol.
Know-why of the present invention
Small molecules polyether glycol plays similar initiator in the time of DMC catalysts catalysis polyethers.
Technical scheme of the present invention
A DMC catalysts that contains small molecules polyether glycol, its general structure is A
a[B
b(CN)
c]
d.r (E
my
n) .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 is identical or different all can;
Y is Cl
-, Br
-, OH
-, CO3
2-, SO4
2-or NO
3 -;
D is ligand, and described ligand is the mixture of Organic Alcohol, ethers or Organic Alcohol and ethers; Wherein said Organic Alcohol is the trimethyl carbinol or propyl carbinol; Described ethers is glycol dimethyl ether;
Z is glycerol;
A, b, c, d, m, n, represents respectively the number of corresponding ion;
R is 0.5-3;
W is 3;
X is 1-2.
The preparation method of above-mentioned a kind of DMC catalysts that contains small molecules polyether glycol, specifically comprises the following steps:
(1), bimetallic cyanide complex is synthetic:
Metal cyanide salt is dissolved in the water and obtains metal cyanides salt brine solution;
Described metal cyanide salt is six cyanogen Cobalt acid potassium, six cyanogen Cobalt acid zinc or potassium hexacynoferrates;
Metal-salt is dissolved in to water and obtains saturated aqueous metal salt;
Described metal-salt is ZnCl
2, ZnBr
2, FeCL
3or FeBr
3in one;
Under the rotating speed that is 8000r/min at rotating speed by metal cyanides salt brine solution, join in saturated aqueous metal salt, be uniformly mixed reaction 0.5h, the reaction solution of gained adds ligand, to forming precipitation, then add the solution being formed by ligand and glycerol, under the agitation condition of 8000r/min, mix 0.5h, obtain mixed solution 1;
Metal cyanides salt brine solution, saturated aqueous metal salt used in above-mentioned reaction process, the amount of ligand, calculates i.e. metal cyanides salt brine solution: saturated aqueous metal salt: ligand is 10-30:20-30:10-15 by volume;
The above-mentioned solution being made up of ligand and glycerol, calculates ligand: glycerol is 10-15ml:0.5-1g by volume; Its consumption calculates and equates with the volume of the ligand adding in reaction solution by ligand;
(2) mixed solution 1, step (1) being obtained filters, the solution that filter cake 1 use of gained is made up of with glycerol ligand mixes 0.5h with it under the rotating speed of 8000r/min, obtain mixed solution 2, mixed solution 2 to gained filters, the filter cake control temperature obtaining is 60-80 ℃ and is dried to constant weight, must contain the DMC catalysts of small molecules polyether glycol;
The above-mentioned solution being made up of ligand and glycerol, calculates ligand: glycerol is 10-15ml:0.5-1g by volume; Its consumption calculates with the volume of the ligand adding in reaction solution in step (1) and equates by ligand.
Above-mentioned a kind of DMC catalysts that contains small molecules polyether glycol, for the preparation of polyether glycol, greatly shortens induction time, and does not need to add initiator, has saved cost, has improved efficiency.
beneficial effect of the present invention
A kind of DMC catalysts that contains small molecules polyether glycol of the present invention, compared with traditional catalyst, owing to containing micromolecular polyethers in catalyzer, can guarantee that catalyzer has very high activity in the early stage, therefore for process for production of polyether polyols, do not need to add inductor to induce.
A kind of DMC catalysts that contains small molecules polyether glycol of the present invention, due to the existence of catalyzer small molecular polyethers, when its production for polyether glycol, greatly shorten induction time, and do not need to add initiator, saved production cost, improved production efficiency.Therefore it has solved in polyethers is produced in the past, exists the catalyst inducement phase long, needs the problems such as initiator.
Embodiment
Below by specific embodiment, the present invention is further set forth, but do not limit the present invention.
embodiment 1
A DMC catalysts that contains small molecules polyether glycol, its general structure is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Zn;
E is Zn;
B is Co;
Y is Cl
-;
D is the trimethyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 3,1,6,2,1,2;
R is 1;
W is 3;
X is 2.
Above-mentioned a kind of DMC catalysts that contains small molecules polyether glycol, specifically comprises the following steps:
(1), bimetallic cyanide complex is synthetic:
Metal cyanide salt six cyanogen Cobalt acid potassium are dissolved in the water, and to obtain mass percent concentration be 10% six cyanogen Cobalt acid aqueous solutions of potassium solution;
Metal-salt ZnCl
2be dissolved in water and obtain saturated ZnCl
2the aqueous solution;
Under the rotating speed that the six cyanogen Cobalt acid aqueous solutions of potassium that are 10% by 20ml mass percent concentration are 8000r/min at rotating speed, join the ZnCl that 20ml is saturated
2in the aqueous solution, be uniformly mixed reaction 0.5h, the reaction solution of gained adds the 15ml ligand trimethyl carbinol, to forming precipitation, then add the solution being formed with 1g glycerol by the 15ml ligand trimethyl carbinol to mix 0.5h under the agitation condition of 8000r/min, obtain mixed solution 1;
(2), the mixed solution 1 of step (1) gained is filtered, the filter cake of gained uses the solution being made up of with 1g glycerol the 15ml ligand trimethyl carbinol to mix 0.5h again under the rotating speed of 8000r/min, obtain mixed solution 2, mixed solution 2 to gained filters, the filter cake control temperature obtaining is 60-80 ℃ and is dried to constant weight, must contain the DMC catalysts A of small molecules polyether glycol, i.e. Zn
3[Co (CN)
6]
2.rZnCl
2.w trimethyl carbinol .x glycerol.
embodiment 2
A DMC catalysts that contains small molecules polyether glycol, its general structure is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Zn;
E is Zn;
B is Co;
Y is Cl
-;
D is propyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 3,1,6,2,1,2;
R is 1;
W is 3;
X is 1.
The preparation method of above-mentioned a kind of DMC catalysts that contains small molecules polyether glycol, specifically comprises the following steps:
(1), bimetallic cyanide complex is synthetic:
Metal cyanide salt six cyanogen Cobalt acid potassium are dissolved in the water, and to obtain mass percent concentration be 10% six cyanogen Cobalt acid aqueous solutions of potassium solution;
Metal-salt ZnCl
2be dissolved in water and obtain saturated ZnCl
2the aqueous solution;
Under the rotating speed that the six cyanogen Cobalt acid aqueous solutions of potassium that are 10% by 30ml mass percent concentration are 8000r/min at rotating speed, join the ZnCl that 30ml is saturated
2in the aqueous solution, be uniformly mixed reaction 0.5h, the reaction solution of gained adds 10ml ligand propyl carbinol, to forming precipitation, then add the solution being formed with 0.5g glycerol by 10ml ligand propyl carbinol to mix 0.5h under the agitation condition of 8000r/min, obtain mixed solution 1;
(2), by step (1) mixed solution 1 filter, the filter cake of gained uses the solution being made up of with 0.5g glycerol 10ml ligand propyl carbinol to mix 0.5h under the rotating speed of 8000r/min, obtain mixed solution 2, mixed solution 2 to gained filters, the filter cake control temperature of gained is 60-80 ℃ and is dried to constant weight, must contain the DMC catalysts B of small molecules polyether glycol, i.e. Zn
3[Co (CN)
6]
2.rZnCl
2.w propyl carbinol .x glycerol.
embodiment 3
A DMC catalysts that contains small molecules polyether glycol, its general structure is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Zn;
E is Zn;
B is Co;
Y is Cl
-;
D is the trimethyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 3,1,6,2,1,2;
R is 2;
W is 3;
X is 2.
The preparation method of above-mentioned a kind of DMC catalysts that contains small molecules polyether glycol, specifically comprises the following steps:
(1), bimetallic cyanide complex is synthetic:
Metal cyanide salt six cyanogen Cobalt acid potassium are dissolved in the water, and to obtain mass percent concentration be 10% six cyanogen Cobalt acid aqueous solutions of potassium solution;
Metal-salt ZnCl
2be dissolved in water and obtain saturated ZnCl
2the aqueous solution;
Under the rotating speed that the six cyanogen Cobalt acid aqueous solutions of potassium that are 10% by 40ml mass percent concentration are 8000r/min at rotating speed, join the ZnCl that 20ml is saturated
2in the aqueous solution, be uniformly mixed reaction 0.5h, the reaction solution of gained adds the 15ml ligand trimethyl carbinol, to forming precipitation, then add the solution being formed with 1g glycerol by the 15ml ligand trimethyl carbinol to mix 0.5h under the agitation condition of 8000r/min, obtain mixed solution 1;
(2), the mixed solution 1 of step (1) gained is filtered, gained filter cake uses the solution being made up of with 1.5g glycerol the 15ml ligand trimethyl carbinol to mix 0.5h under the rotating speed of 8000r/min, obtain mixed solution 2, mixed solution 2 to gained filters, the filter cake control temperature obtaining is 60-80 ℃ and is dried to constant weight, must contain the DMC catalysts C of small molecules polyether glycol, i.e. Zn
3[Co (CN)
6]
2.rZnCl
2.w trimethyl carbinol .x glycerol.
embodiment 4
A DMC catalysts that contains small molecules polyether glycol, its general structure is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Fe;
E is Fe;
B is Co;
Y is Br
-;
D is the trimethyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 1,1,6,1,1,3;
R is 0.5;
W is 3;
X is 2.
The preparation method of above-mentioned a kind of DMC catalysts that contains small molecules polyether glycol, specifically comprises the following steps:
(1), bimetallic cyanide complex is synthetic:
Metal cyanide salt six cyanogen Cobalt acid potassium are dissolved in the water, and to obtain mass percent concentration be 10% six cyanogen Cobalt acid aqueous solutions of potassium solution;
Metal-salt FeBr
3be dissolved in water and obtain saturated FeBr
3the aqueous solution;
Under the rotating speed that the six cyanogen Cobalt acid aqueous solutions of potassium that are 10% by 10ml mass percent concentration are 8000r/min at rotating speed, join the FeBr that 20ml is saturated
3in the aqueous solution, be uniformly mixed reaction 0.5h, the reaction solution of gained adds the 15ml ligand trimethyl carbinol, to forming precipitation, then add the solution being formed with 1g glycerol by the 15ml ligand trimethyl carbinol to mix 0.5h under the agitation condition of 8000r/min, obtain mixed solution 1;
(2), step (1) gained mixed solution 1 is filtered, the filter cake obtaining uses the solution being made up of with 1g glycerol the 15ml ligand trimethyl carbinol to mix 0.5h under the rotating speed of 8000r/min, obtain mixed solution 2, mixed solution 2 to gained filters, the filter cake control temperature obtaining is 60-80 ℃ and is dried to constant weight, the DMC catalysts D that must contain small molecules polyether glycol is Fe[Co (CN)
6] .rFeBr
3.w trimethyl carbinol .x glycerol.
application Example 1(does not add initiator)
The DMC catalysts that contains small molecules polyether glycol of above-described embodiment 1-4 gained is applied to the building-up reactions of polyether glycol, specifically comprise the steps: in the 2L autoclave with agitator, heat exchanger, vacuumize also inflated with nitrogen displacement three times, remove moisture and volatile matter; While being heated to temperature of reaction, add reactor to carry out polyreaction the above-mentioned DMC catalysts that contains small molecules polyether glycol and propylene oxide; In the time that pressure starts to decline, reaction starts, and writes down reaction induction time; Reflection pressure maintains 0.06MP, then through aging, decompression removes the volatile matter in reactor, obtains final product.
application comparative examples 1(adds initiator glycerol)
The DMC catalysts that contains small molecules polyether glycol of above-described embodiment 1-4 gained is applied to the building-up reactions of polyether glycol, specifically comprises the steps: in the 2L autoclave with agitator, heat exchanger, by initiator
glyceroladd in autoclave, at 100 1 130 ℃, vacuumize, then with nitrogen replacement several, to remove moisture and volatile matter; While being heated to temperature of reaction, add reactor to carry out polyreaction the DMC catalysts that contains small molecules polyether glycol and propylene oxide; In the time that reflection pressure starts significantly to decline, write down reaction induction time; Reflection pressure maintains 0.06MP, then through aging, decompression removes the volatile matter in reactor, obtains final product.
When its synthesizing polyether glycol, needed induction time is as following table:
Result by above-mentioned Application Example and application comparative examples can be found out, a kind of DMC catalysts that contains small molecules polyether glycol of the present invention, and during for the production of polyether glycol, compared with not adding initiator, induction time is shorter.Therefore it has solved in polyethers is produced in the past, exists the catalyst inducement phase long, needs the problems such as initiator.In addition, owing to greatly shortening induction time, and do not need to add initiator, therefore reduced production cost, improved production efficiency.
Foregoing is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. contain a DMC catalysts for small molecules polyether glycol, the general structure that contains the DMC catalysts of small molecules polyether glycol described in it is characterized in that is A
a[B
b(CN)
c]
d.r (E
my
n) .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 is identical or different all can;
Y is Cl
-, Br
-, OH
-, CO3
2-, SO4
2-or NO
3 -;
D is ligand, and described ligand is the mixture of Organic Alcohol or ethers or Organic Alcohol and ethers; Wherein said Organic Alcohol is the trimethyl carbinol or propyl carbinol; Described ethers is glycol dimethyl ether;
Z is glycerol;
A, b, c, d, m, n, represents respectively the number of corresponding ion;
R is 0.5-3;
W is 3;
X is 1-2.
2. the DMC catalysts that contains small molecules polyether glycol as claimed in claim 1, the general structure that contains the DMC catalysts of small molecules polyether glycol described in it is characterized in that is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Zn;
E is Zn;
B is Co;
Y is Cl
-;
D is the trimethyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 3,1,6,2,1,2;
R is 1;
W is 3;
X is 2.
3. the DMC catalysts that contains small molecules polyether glycol as claimed in claim 1, the general structure that contains the DMC catalysts of small molecules polyether glycol described in it is characterized in that is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Zn;
E is Zn;
B is Co;
Y is Cl
-;
D is propyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 3,1,6,2,1,2;
R is 1;
W is 3;
X is 1.
4. the DMC catalysts that contains small molecules polyether glycol as claimed in claim 1, the general structure that contains the DMC catalysts of small molecules polyether glycol described in it is characterized in that is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Zn;
E is Zn;
B is Co;
Y is Cl
-;
D is the trimethyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 3,1,6,2,1,2;
R is 2;
W is 3;
X is 2.
5. the DMC catalysts that contains small molecules polyether glycol as claimed in claim 1, the general structure that contains the DMC catalysts of small molecules polyether glycol described in it is characterized in that is A
a[B
b(CN)
c]
d.r (E
my
n) .wD.xZ;
Wherein: A is Fe;
E is Fe;
B is Co;
Y is Br
-;
D is the trimethyl carbinol;
Z is glycerol;
A, b, c, d, m, n, the number that represents respectively corresponding ion is 1,1,6,1,1,3;
R is 0.5;
W is 3;
X is 2.
6. the preparation method of a kind of DMC catalysts that contains small molecules polyether glycol as claimed in claim 1, is characterized in that specifically comprising the following steps:
(1), bimetallic cyanide complex is synthetic:
Metal cyanide salt is dissolved in the water and obtains metal cyanides salt brine solution;
Described metal cyanide salt is six cyanogen Cobalt acid potassium, six cyanogen Cobalt acid zinc or potassium hexacynoferrates;
Metal-salt is dissolved in to water and obtains saturated aqueous metal salt;
Described metal-salt is ZnCl
2, ZnBr
2, FeCL
3, FeBr
3in one;
Under the rotating speed that is 8000r/min at rotating speed by metal cyanides salt brine solution, join in saturated aqueous metal salt, be uniformly mixed reaction 0.5h, the reaction solution of gained adds ligand, to forming precipitation, then add the solution being formed by ligand and glycerol, under the agitation condition of 8000r/min, mix 0.5h, obtain mixed solution 1;
Metal cyanides salt brine solution, saturated aqueous metal salt used in above-mentioned reaction process, the amount of ligand, calculates i.e. metal cyanides salt brine solution: saturated aqueous metal salt: ligand is 10-30:20-30:10-15 by volume;
The above-mentioned solution being made up of ligand and glycerol, calculates ligand: glycerol is 10-15ml:0.5-1g by volume; Its consumption calculates and equates with the volume of the ligand adding in reaction solution by ligand;
(2) mixed solution 1, step (1) being obtained filters, the solution that filter cake 1 use of gained is made up of with glycerol ligand mixes 0.5h with it under the rotating speed of 8000r/min, obtain mixed solution 2, mixed solution 2 to gained filters, the filter cake control temperature obtaining is 60-80 ℃ and is dried to constant weight, must contain the DMC catalysts of small molecules polyether glycol;
The above-mentioned solution being made up of ligand and glycerol, calculates ligand: glycerol is 10-15ml:0.5-1g by volume; Its consumption calculates with the volume of the ligand adding in reaction solution in step (1) and equates by ligand.
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| CN114133416A (en) * | 2020-09-03 | 2022-03-04 | 万华化学集团股份有限公司 | Preparation method of DMC catalyst and DMC catalyst prepared by same |
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| CN103910865B (en) | 2017-02-01 |
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