CN1117790C - Bimetal complex catalyst for synthesizing polyether polyol and its preparing process - Google Patents
Bimetal complex catalyst for synthesizing polyether polyol and its preparing process Download PDFInfo
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- CN1117790C CN1117790C CN 00112555 CN00112555A CN1117790C CN 1117790 C CN1117790 C CN 1117790C CN 00112555 CN00112555 CN 00112555 CN 00112555 A CN00112555 A CN 00112555A CN 1117790 C CN1117790 C CN 1117790C
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Abstract
The present invention relates to a bimetal complex catalyst for synthesizing polyether polyhydric alcohol and a preparation method thereof. The bimetal complex catalyst comprises Zn [Fe(CN)6]2. a. ZnCl. bKCl. C. H2O. dp, wherein P represents tertiary alcohol and a polyether polyhydric alcohol chelating agent; a, b, c and d represent positive numbers or zero. The bimetal complex catalyst is used for an epoxy compound polymerized into polyether polyhydric alcohol in a ring opening mode. Compared with a similar product prepared by adopting potassium hydroxide as a catalyst, the catalyst lowers the unsaturation degree. The catalyst can synthesize polyether polyhydric alcohol with different molecular weight, and is particularly used for synthesizing polyether polyhydric alcohol with high molecular weight and a low unsaturation degree.
Description
The present invention relates to relevant synthesizing polyether glycol bimetal complex catalyst and preparation method thereof, its purposes is the ring-opening polymerization of catalysis epoxidation thing and small molecules polyvalent alcohol, thus the synthesized high-performance polyether glycol.
Polyether glycol is the main raw material of polyester industrial, is widely used in industrial sectors such as coating, tackiness agent, elastomerics, foam article, sealing agent, washing composition and oil development, and has also obtained application at aerospace field.Traditional polyether glycol is to use the small molecules polyvalent alcohol as initiator, and initiation propylene oxide open loop addition polymerization obtains in the presence of potassium hydroxide or sodium hydroxide catalyst, and reaction belongs to anionic reactive.Catalyst system is melted in reactor by initiator and potassium hydroxide catalyst, and 80～90 ℃ of temperature, vacuum decompression dehydration temperaturre are 100～110 ℃, dewaters 1～2 hour.Reaction generates the alcoholic solution of potassium alcoholate, squeeze into autoclave then and carry out ring-opening polymerization, reacted about 4 hours, after polyreaction is finished, owing to adopt potassium hydroxide catalyst, potassium ion has detrimentally affect to synthesis of polyurethane more than surpassing 10ppm, therefore must carry out aftertreatment to polyether glycol, general with treatment agent k adsorption, sodium ion, neutralization is filtered again.Therefore, adopt the potassium hydroxide catalyst operation cumbersome, production efficiency is not high, also influence the raising of productive rate simultaneously, energy consumption is big, the comprehensive cost height, the general treated dose of domestic reduction about 10% of polyether glycol productive rate after refining is if potassium, sodium ion are handled the processing and the quality that totally can not influence urethane.This technology exists propylene oxide isomerization to form the side reaction of vinyl carbinol and living chain to monomeric chain transfer reaction simultaneously, cause the formation of lower molecular weight unit alcohol, thereby the molecular weight of polyethers and functionality are reduced, and institute's synthetic polyether glycol degree of unsaturation is higher simultaneously.These unit alcohol can only form side chain and can not be crosslinked in the netted structure of urethane, objectively play a part chain termination agent, the growth of restriction state polyurethane molecular amount, and finally the physical and mechanical property to goods produces ill effect.
In order to address the above problem, various countries launch active research, disconnect the catalyzer of having sent out the synthetic usefulness of some new polyether glycols mutually, have successfully synthesized high performance low-unsaturated polyether polyatomic alcohol.At the end of the sixties, report state BASF, Mitsui East Asia, Sanyo change into, the catalyzer of the strontium hydroxide of rising sun Shi Xiao Subsidiary Company research, can prepare the polyether glycol of high molecular, low insatiable hunger degree.At the beginning of the eighties, U.S. Conoco Inc and union carbide corporation are made the high polyether glycol of molecular weight with alkaline earth metal compound as catalyzer, simultaneously, the scholar of Tokyo Univ Japan has developed 5,10, and 15,20 tetraphenyl quinoline aluminum complex catalysts can prepare high molecular weight polyether.After particularly the sixties, AM General rubber for tire company found the activity of bimetallic catalyst in the polyethers preparation, various countries had carried out big quantity research to it.The nineties, Japan rising sun Shi Xiao Subsidiary Company adopted bimetal complex to make all good elastic polyurethane body and function polyether glycol of high resilience, mechanical property, thermotolerance and water-repellancy.
The purpose of this invention is to provide the polyethers bimetal complex catalyst, the ring-opening polymerization that this catalyzer can be used for epoxy compounds and low molecular polylol prepares polyether glycol.Can make the polyether glycol of molecular weight from 500～30,000, preferable for the polyether glycol of synthetic 1000～20000 molecular weight, for polyether glycol the best of Synthetic 2 000～10000 molecular weight.
Another object of the present invention provides the preparation method of a kind of synthesizing polyether with bimetal complex catalyst, so that prepare a kind of iron zinc bimetal complex catalyst with cheap cost.
Purpose of the present invention can reach by following measure:
A kind of polyether glycol synthesizes bimetal complex catalyst, it is characterized in that this catalyzer is the complex compound made from the Tripotassium iron hexacyanide and zinc chloride and different sequestrant, and it consists of:
Be sequestrant, a, b, c, d are positive number or zero.
Catalyzer of the present invention adopts order of addition(of ingredients) to form throw out for drip potassium ferricyanide aqueous solution in the ammonification zinc aqueous solution in preparation.Require the Tripotassium iron hexacyanide and ammonification zinc mol ratio 1: 1～12 in feeding intake.Throw out with gained carries out abundant chelating for several times with the tertiary alcohol aqueous solution and polyether glycol solution washing again.More than the throw out of Xing Chenging is collected with centrifugal or filtration method, removes the part by product with washing methods, carries out drying at last and promptly makes stand-by.Above operation is all finished under 0～80 ℃ of temperature.
The ring-opening polymerization that catalyzer of the present invention can be used for epoxy compounds such as propylene oxide, oxyethane, butylene oxide ring prepares polyether glycol.Catalyst levels is 0.001～1% of a reactant weight.Temperature of reaction is at 30～110 ℃, and reaction pressure is no more than under the 1.2MPa carries out, and operation steps all adopts the polyether glycol known method to carry out.
The invention has the advantages that:
This catalyzer utilizes the influence to the metal surrounding environment of iron zinc bimetallic synergy and the special polymeric chelant of various sequestrant, and choose between two kinds of metallic compounds and bimetal compound and sequestrant between optimum proportion, according to optimal sequence each reactant is mixed again, these measures make this catalyzer have high activity to the open loop of epoxy compound polyreaction.Wherein cyclisation thing transformation efficiency is up to more than 95%.These performances of catalyzer of the present invention are considerably beyond classical catalyst system.This catalyzer has very high selectivity simultaneously, owing to adopted rational preparation method and selected cheap raw material for use, reduces amount of chelant, and the cost of catalyzer of the present invention only is equivalent to 20～30% of the present cobalt zinc bimetallic catalyst of announcing.Catalyzer of the present invention is yellow or oyster powder, water insoluble and organic solvent, no pyrophoricity and obvious water absorbability, when room temperature and lucifuge, stable in the air, preserve easily and the operation of available ordinary method, and this catalyst activity height, consumption is few, for preparation high molecular, low-unsaturation-degree high-performance poly ethoxylated polyhydric alcohol provide possibility.And the component homogeneous that obtains, can obtain good reproducibility, superior result of use.
Embodiment 1
Preparation of Catalyst: with 8.0gK
3Fe (CN)
6Add 150ml deionized water wiring solution-forming 1, again with 20gZnCl
2Add 30ml deionized water wiring solution-forming 2, at room temperature solution 1 is dropped in 2, stir, react after 1 hour, handle secondary respectively with the tertiary alcohol aqueous solution and the polyether glycol aqueous solution respectively again, be centrifuged into throw out, vacuum-drying promptly makes this bimetal complex catalyst.Above service temperature is carried out under 0～70 ℃.
Polyether glycol preparation: in 4 gram glycerine, add 0.4 this catalyzer of gram, add and 230 gram propylene oxide, be warming up to 40 ℃.Stop heating, 40 ℃ begin reaction, and reaction can automatically heat up, and temperature is controlled under 40～110 ℃, and pressure is no more than 1.2MPa, reacts i.e. reaction end in 2 hours, obtain molecular weight and be 8000 polyether glycol, degree of unsaturation 0.006.
Embodiment 2
Preparation of Catalyst: with 33.2gK
3Fe (CN)
6Add 150ml deionized water wiring solution-forming 1, again with 13.8gZnCl
2Add 30ml deionized water wiring solution-forming 2, at room temperature solution 1 is dropped in 2, stir, react after 1 hour, handle respectively three times with the tertiary alcohol aqueous solution and the polyether glycol aqueous solution respectively, be centrifuged into throw out, vacuum-drying promptly makes this bimetal complex catalyst.Above service temperature is carried out under 0～70 ℃.
Polyether glycol preparation: in 3 gram glycerine, add 0.25 this catalyzer of gram, add and 230 gram butylene oxide rings, be warming up to 40 ℃.Stop heating, 40 ℃ begin reaction, and reaction can automatically heat up, and temperature is controlled under 40～110 ℃, and pressure is no more than 1.2MPa, reacts i.e. reaction end in 2 hours, obtain molecular weight and be 10000 polyether glycol, degree of unsaturation 0.006.
Embodiment 3
Preparation of Catalyst: with 3.32gK
3Fe (CN)
6Add 150ml deionized water wiring solution-forming 1, again with 13.8gZnCl
2Add 30ml deionized water wiring solution-forming 2, at room temperature solution 1 is dropped in 2, stir, react after 1 hour, handle respectively three times with the tertiary alcohol aqueous solution and the polyether glycol aqueous solution respectively, be centrifuged into throw out, vacuum-drying promptly makes this bimetal complex catalyst.Above service temperature is carried out under 0～70 ℃.
Polyether glycol preparation: in 40 gram glycerine, add 0.2 this catalyzer of gram, add and 230 gram propylene oxide, be warming up to 40 ℃.Stop heating, 40 ℃ begin reaction, and reaction can automatically heat up, and temperature is controlled under 40～110 ℃, and pressure is no more than 1.2MPa, reacts i.e. reaction end in 4 hours, obtain molecular weight and be 800 polyether glycol, degree of unsaturation 0.006.
Embodiment 4
Preparation of Catalyst: with 6.0gK
3Fe (CN)
6Add 150ml deionized water wiring solution-forming 1, again with 20gZnCl
2Add 30ml deionized water wiring solution-forming 2, at room temperature solution 1 is dropped in 2, stir, react after 1 hour, the spent glycol dme aqueous solution and the polyether glycol aqueous solution are handled secondary respectively respectively again, are centrifuged into throw out, and vacuum-drying promptly makes this bimetal complex catalyst.Above service temperature is carried out under 0～70 ℃.
Polyether glycol preparation: in 2 gram glycerine, add 0.5 this catalyzer of gram, add and 250 gram propylene oxide, be warming up to 40 ℃.Stop heating, 40 ℃ begin reaction, and reaction can automatically heat up, and temperature is controlled under 40～110 ℃, and pressure is no more than 1.2MPa, reacts i.e. reaction end in 2 hours, obtain molecular weight and be 15000 polyether glycol, degree of unsaturation 0.006.
Embodiment 5
Preparation of Catalyst: with 5.0gK
3Fe (CN)
6Add 150ml deionized water wiring solution-forming 1, again with 20gZnCl
2Add 30ml deionized water wiring solution-forming 2, at room temperature solution 1 is dropped in 2, stir, react after 1 hour, handle secondary respectively with the tertiary alcohol aqueous solution and the polyether glycol aqueous solution respectively again, be centrifuged into throw out, vacuum-drying promptly makes this bimetal complex catalyst.Above service temperature is carried out under 0～70 ℃.
Polyether glycol preparation: in 1 gram glycerine, add 0.5 this catalyzer of gram, add and 330 gram propylene oxide, be warming up to 40 ℃.Stop heating, 40 ℃ begin reaction, and reaction can automatically heat up, and temperature is controlled under 40～110 ℃, and pressure is no more than 1.2MPa, reacts i.e. reaction end in 6 hours, obtain molecular weight and be 20000 polyether glycol, degree of unsaturation 0.006.
Claims (5)
1. the synthetic bimetal complex catalyst of polyether glycol is characterized in that this catalyzer is the complex compound made from the Tripotassium iron hexacyanide and zinc chloride and different sequestrant, and it consists of:
Be the tertiary alcohol and polyether glycol sequestrant, a, b, c, d are positive number.
2. catalyzer as claimed in claim 1 is characterized in that the mol ratio 1: 1～12 of potassium ferricyanide aqueous solution and solder(ing)acid.
3. method that is used to prepare catalyzer described in the right 1, its order of addition(of ingredients) is that potassium ferricyanide aqueous solution drops to solder(ing)acid, with the throw out several of the tertiary alcohol and polyether glycol aqueous solution chelated iron potassium cyanide and solder(ing)acid reactant, so that form the catalyzer of claim 1.
4. the purposes of the described catalyzer of claim 1, the ring-opening polymerization of its feature catalysis epoxidation thing prepares the polyether glycol of molecular weight 500～30,000, very effective to synthetic low-unsaturation-degree, high molecular weight polyether especially, be reactant weight 0.001～1% at poly-reacting middle catalyst consumption.
5. epoxide as claimed in claim 4, it is characterized by can be oxyethane, propylene oxide, butylene oxide ring.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 00112555 CN1117790C (en) | 2000-09-19 | 2000-09-19 | Bimetal complex catalyst for synthesizing polyether polyol and its preparing process |
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| CN 00112555 CN1117790C (en) | 2000-09-19 | 2000-09-19 | Bimetal complex catalyst for synthesizing polyether polyol and its preparing process |
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| CN1343731A CN1343731A (en) | 2002-04-10 |
| CN1117790C true CN1117790C (en) | 2003-08-13 |
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