CN1032252C - Acid-catalyzed fabrication of precursors for use in making polyols and ethylene oxide capping of polyols made using double metal cyanide catalysts - Google Patents

Acid-catalyzed fabrication of precursors for use in making polyols and ethylene oxide capping of polyols made using double metal cyanide catalysts Download PDF

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CN1032252C
CN1032252C CN91103436.6A CN91103436A CN1032252C CN 1032252 C CN1032252 C CN 1032252C CN 91103436 A CN91103436 A CN 91103436A CN 1032252 C CN1032252 C CN 1032252C
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polyvalent alcohol
alkaline
alkali metal
catalyst
described method
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CN1057644A (en
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基拉恩·B·钱达列
约翰·W·勒史
迈可尔·M·马丁内斯
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Olin Corp
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Olin Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's

Abstract

A process for removing double metal cyanide complex catalyst residues from a catalyst-residue containing polyol characterized by: (a) treating a double metal cyanide complex catalyst-residue containing polyol with an alkali metal alkoxide or alkaline earth metal alkoxide in order to provide a treated polyol wherein said catalyst-residue is converted into insoluble ionic species, (b) contacting said treated polyol with ethylene oxide to produce an ethylene oxide-capped polyol wherein at least a portion of the secondary hydroxyl groups on said polyol are converted into primary hydroxyl groups, and (c) separating said insoluble ionic species from said ethylene oxide-capped polyol by filtration in order to provide a purified polyol that is essentially free of catalyst-residue. Also claimed is a process for preparing a purified polyol that is free of acid catalyst residues.

Description

Purification of polyol removes the method for resistates
Utilizing the double metal cyanide catalyst preparation macromolecule polyol, is very sophisticated technically.For example, United States Patent (USP) 3,829,505 (transferring GeneralTire and RubberCompany) disclose the preparation method with this class Preparation of Catalyst high molecular weight diol and triol etc.The polyvalent alcohol that can make with this class catalyzer has higher molecular weight and lower end group degree of unsaturation than the polyvalent alcohol that can make with general KOH catalyzer.Above-mentioned United States Patent (USP) 3,829,505 disclosed above-mentioned high molecular weight polyols products can be used for preparing nonionogenic tenside, lubricant and refrigerant, weaving sizing material, packaging film, in addition, by itself and polymeric polyisocyanate are reacted, also can be used for preparing rigidity or flexible polyurethane.
In order to prepare polyvalent alcohol with double metal cyanide complex catalysts, must make reagent with the propoxylation initiator, reason be resemble glycerol and so on non-propoxylation initiator under the situation that double metal cyanide coordination (" DMC ") catalyzer is arranged not with propylene oxide reaction.This reaction obviously caused because of dmc catalyst is insoluble to initiator.
In view of the above problems, generally be under the situation that potassium hydroxide (" KOH ") catalyzer is arranged, to prepare the propoxylation initiator precursor by propylene oxide and initiator (for example glycerol) reaction, regrettably, even have the KOH catalyzer of trace to be present in the propoxylation precursor, also can reduce the catalytic activity of the dmc catalyst that is used for producing continuously polyol reaction.Therefore, must be used for the KOH catalyzer that dmc catalyst removes this precursor before preparing polyvalent alcohol at the propoxylation precursor.
All can reach the purpose that removes KOH catalyzer in the propoxylation precursor by any method in many methods of being introduced in the patent documentation, but the used step that removes the KOH catalyzer is not only expensive but also time-consuming.Therefore, polyvalent alcohol manufacturing firm all necessarily wishes to have a kind of such novel method that required propoxylation precursor is provided very much, and promptly it is without the KOH catalyzer, and need not any catalyst separating step before this class precursor is used for DMC catalytic preparation polyvalent alcohol.
Polyvalent alcohol with double metal cyanide catalyst preparation contains catalyst residue, this remaining can the interference mutually with the polyvalent alcohol that constantly utilizes in the reaction process that produces polyurethane continuously.More precisely, catalyst residue can cause unwelcome side reaction, thereby produces the unwanted by-products that resembles allophanate and so on.Past attempts has the people to plan to remove catalyst residue in the polyvalent alcohol after making polyvalent alcohol.For example, United States Patent (USP) 4,355,188 reports, by a kind of highly basic (being selected from potassium hydroxide, potassium metal and sodium Metal 99.5) is added to (be intended to catalyst residue is changed into the ionic species material) in polyvalent alcohol-catalyst residue mixture with above-mentioned alkali with add oxyethane when polyvalent alcohol contacts, can remove DMC catalysts remnants effectively.Tell the ionic species material by filtering (for example by contacting) then, to obtain the purification polyvalent alcohol of essentially no catalyst residue with a kind of ion exchange resin.Regrettably, the use of oxyhydroxide can produce water, thereby make water is arranged in the polyvalent alcohol.The mixture of this polynary alcohol and water that is produced has proposed the difficult problem that will expend a large amount of energy.In addition, using and handling, the danger of presence of fire and blast in addition sodium Metal 99.5 or potassium metal.
United States Patent (USP) 4,721,818 disclose a kind of method that removes DMC catalysts remnants in the polyvalent alcohol, this method comprises a kind of alkali-metal hydride is added in the mixture of dibasic alcohol and catalyst residue, so that double metal cyanide complex catalysts changed into the insoluble ionic species material that can tell from polyvalent alcohol.By filtering, remove this class insoluble substance then.Regrettably, use alkalimetal hydride that the danger of blasting with fire is arranged, therefore utilizing above-mentioned substance is unwelcome equally.
In view of the importance with high molecular weight polyols that double metal cyanide complex catalysts produces growing, the company that makes polyurethanes all wishes have some to tell the novel method of catalyst residue very much, especially wish to have a kind of danger that neither can cause above-mentioned blast and fire, can not produce disagreeable water again, not have the novel method of relevant therewith separation problem again.
With regard to one aspect of the present invention, the present invention relates to a kind of method that removes the double metal cyanide complex catalysts remnants in the polyvalent alcohol that contains catalyst residue, the included step of this method has:
(a) handle the polyvalent alcohol that contains double metal cyanide complex catalysts remnants with a kind of alkali metal alcoholates or alkaline-earth alkoxides, to obtain a kind of processing polyvalent alcohol that catalyst residue is changed into insoluble ionic species material;
(b) this processing polyvalent alcohol is contacted with oxyethane, with produce a kind of ethylene oxide-capped and interior in the former secondary hydroxyl on this polyvalent alcohol of at least a portion changed into the polyvalent alcohol of primary hydroxyl; With
(c) by filtering, from this ethylene oxide-capped polyvalent alcohol, tell insoluble ionic species material, to obtain a kind of purification polyvalent alcohol of essentially no catalyst residue.
With regard to another aspect of the present invention, the present invention relates to a kind of methods of not having alcohol of making more, the included step of this method has:
(a) under the situation that a kind of acid catalyst (preferably Lewis acid or protonic acid) arranged, by propylene oxide and poly-hydroxy initiator for reaction, make a kind of propoxylation poly-hydroxy initiator, described reaction is to carry out under the situation of no KOH catalyzer, to make a kind of propoxylation poly-hydroxy initiator that contains acid catalyst remnants and no KOH catalyst residue; With
(b) having under the situation of double metal cyanide complex catalysts, making above-mentioned propoxylation poly-hydroxy initiator and a kind of alkylene H-H reaction that contains acid catalyst remnants, to make polyvalent alcohol.
With regard to another aspect again of the present invention, the present invention relates to realize step in the aforesaid method (a) and aforesaid method (b) simultaneously with an easy steps.
With regard to another aspect again more of the present invention, the present invention relates to the polyvalent alcohol product that makes with above-mentioned each side method.
Read following to the present invention detailed description after, be bound to be well understood to all respects of the present invention.
The present invention is now unexpected to be found, handles the end capped polyvalent alcohol of oxyethane (EO) with alkali metal alcoholates or alkaline-earth alkoxides, with regard to removing the double metal cyanide complex catalysts remnants that contain in the above-mentioned remaining polyvalent alcohol, is favourable.Though can follow without any specific theory, the present inventor infers that this (" EO ") end blocking method has two key advantage when be used for the inventive method, that is: (a) can go up polynary unit alcohol extremely that a part of secondary hydroxyl changes into primary hydroxyl; (b) help alkali metal alcoholates or alkaline-earth alkoxides to make the catalyst residue precipitation.
Relevant another advantage of the present invention is, though be convenient to this prior art compound that removes usefulness or combustible especially, or volatile (being sodium Metal 99.5, potassium metal and alkalimetal hydride), or produce disagreeable, that be difficult to remove, be present in water byproduct in the polyvalent alcohol, it then is non-flammable or unexplosive being used for alkali metal alcoholates of the present invention or alkaline-earth alkoxides, and produces the by-product alcohol that easily removes.This by-product alcohol is suitable for being removed from polyvalent alcohol with simple distillating method, because this alcohol (especially rudimentary alkoxide) has the advantage of lower boiling character.
The alkali metal alcoholates or the alkaline-earth alkoxides that can be used for the inventive method, the carbonatoms that per molecule had should be between 1 and 8 generally between 1 and 23, and be more suitable between 1 and 6.The example of the alkali metal alcohol that is suitable for has sodium methylate, potassium methylate, lithium methoxide, also has ethylate, propylate, butanolate, amylalcohol salt and dodecane alkoxide or the like in addition.The example of the alkaline-earth alkoxides that is suitable for has the calcium salt and the magnesium salts of similar above-mentioned alkoxide.
The present invention also is surprised to find that, uses acid catalyst in preparation propoxylation polyvalent alcohol precursor, and this makes and might purify the propoxylation precursor, directly make polyvalent alcohol in the DMC catalyzed reaction.Therefore, acid catalyst can not make the dmc catalyst deactivation or dmc catalyst do not risen under the situation of disadvantageous effect, for preparation propoxylation precursor provides needed katalysis.This beyond thought result, to those so far for avoid because of KOH catalyzer or KOH catalyst residue make the dmc catalyst deactivation have to before dmc catalyst contacts concerning the DMC-catalytic polyol manufacturing firm that the propoxylation precursor purifies, be significant certainly.
The acid catalyst that can be used for the inventive method is Lewis acid, for example BF preferably 3Et 2O (boron-trifluoride etherate), SbF 5(antimony pentafluoride), SbCl 5(antimony pentachloride), F 3CSO 3H (trifluoromethayl sulfonic acid) also has protonic acid, for example HBF in addition 4(Tetrafluoroboric acid), H 2SO 4(sulfuric acid) and their mixture or the like.The maximum of acid catalyst, the reaction mixture amount by producing the propoxy-precursor generally is no more than 1% (weight), and preferably the acid catalysis dosage in the reaction mixture is about 50 and about 1, between the 500ppm.The acid catalyst consumption surpasses 1% this upper limit, may produce unwelcome side reaction.
That make according to the inventive method and be used for polyvalent alcohol of the present invention, generally be have under the situation of DMC catalysts by the mixture of propylene oxide or propylene oxide and a kind of alkylene oxide arbitrarily or the condensation of the alkylene oxide mixture that progressively is summed into and a kind of poly-hydroxy initiator make.The example of alkylene oxide has oxyethane, propylene oxide, butylene oxide ring, epoxy pentane, oxidation virtue alkene (for example Styrene oxide 98min.) and their mixture or the like.The most desirable alkylene oxide is the mixture of propylene oxide or it and oxyethane during with alkoxylate arbitrarily or progressively.
The poly-hydroxy initiator that is used to prepare the polyol reaction agent has following compounds and their mixture: aliphatic triol, for example glycerol, propoxylation glycerol adducts, TriMethylolPropane(TMP), triethylol propane, Trimethylolhexane; And glycol, ethylene glycol, 1 for example, ammediol, dipropylene glycol, butyleneglycol and pentanediol or the like.In addition, can be used for simple function of the present invention and initiator high functionality and also have for example butanols, sucrose, sorbose and tetramethylolmethane or the like.Except above-mentioned points, also has United States Patent (USP) 4,472,560 and 4,477,589 (Shell ChemicalCompany) and United States Patent (USP)s 3,941, other poly-hydroxy initiator that is suitable for that 849 and 4,355,188 (General Tire and RubberCompany) are introduced.Wherein the most desirable poly-hydroxy initiator has glycerol, TriMethylolPropane(TMP), Diethylene Glycol, dipropylene glycol and tripropylene glycol.
The condensation reaction of alkylene oxide-poly-hydroxy initiator is to carry out having under the situation of DMC catalysts.Still do not having under the governed situation of any specific theory, the present inventor infers that undersaturated end group can be created in the monofunctional species that has the chain termination agent effect in the elastomerics forming process.In synthetic by the polyvalent alcohol of KOH katalysis, the degree of unsaturation that is produced increases with normal increase.Operational condition when molecular weight is increased is fixed after all.In other words, use alkaline catalysts to prepare the hydroxy-end capped polyethenoxy ether of high-molecular weight, can cause hydroxy functionality to lose in a large number.Katalysis by double cyanide can produce low-down saturation ratio, thereby makes made polyvalent alcohol have higher equivalent.The equivalent of polyvalent alcohol generally arrives in about 20,000 the scope about 1,000, is preferably in about 1,500 in about 5,000 scope, but can makes equivalent lower or higher on demand.
For the double metal cyanide coordination class Catalysts and its preparation method that is suitable for, at United States Patent (USP) 4,472,560 and 4,477, among 589 (the ShellChemical Company) and at United States Patent (USP) 3,941,849 and 4,335, among 188 (the GeneralTireand Rubber Company), description is arranged all.
It is found that a kind of double metal cyanide complex catalysts of particularly suitable is six cyanogen metal zinc, its general formula is as follows: Zn 3(M (CN) 6) 2XZnCl 2YGLYMEzH 2In the O formula: M can be Co (III), or Cr (III) or Fe (II) or Fe (III); X, y and z can be mark, integer or zero, and its value is different because of the preparation title complex method of reality, preferably between each leisure 0 and 15.
Any alkali metal alcoholates or alkaline-earth alkoxides all can be used in the practical application of the present invention.Preferred alkoxide is the alkoxide of sodium, potassium, lithium, magnesium and calcium, or their mixture.Total consumption of alkoxide is for can change into double metal cyanide complex catalysts remnants the needed amount of insoluble ionic species material effectively.Hydroxyl on the general consideration polyvalent alcohol is 1: 1 to 500: 1 to the mol ratio of alkali metal alcoholates or alkaline-earth alkoxides.Though be not essential, in order to improve the formation speed of insoluble ionic species metallics, preferably mixture heating up.Finding, is that heating was favourable in nearly 5 hours under about 40 ℃ to about 100 ℃ in temperature range.
After double metal cyanide complex catalysts remnants are changed into insoluble ionic species metallics, available conventional process (for example using diatomaceous filtration method), or according to United States Patent (USP) 4,355, the method described in 188 (promptly by a kind of acidic ion exchange resin) is told polyvalent alcohol.
In another example of the present invention, find, as long as before separation, a spot of Magnesium Silicate q-agent, pure aluminium silicate or their mixture are added in the mixture, can easily tell soluble ion form metallics in the polyvalent alcohol with filtration method.Above-mentioned silicate can use separately or use with general flocculating aids (for example diatomite).With silicate handle to remove help to separate, also find it also can be with the alkoxide of polyvalent alcohol its change into the alkali metal hydroxide that hydroxyl and absorption are produced.
The add-on of silicate generally is that the polyol blends about 1 that per 100 weight parts contain catalyst residue arrives about 5 weight parts.Before filtration, mixture to be arrived about 150 ℃ of following heating 1 to 12 hour for about 80 ℃ in temperature.Selected silicate preferably broken powdered and have big surface-area.
Here used " molecular weight " number-average molecular weight that this term refers to.
Embodiment 1
Step (A)--use the double metal cyanide catalyst preparation high molecular weight polyols
100 gram (0.667 equivalent) propoxylation glycerol precursors (molecular weight 450, equivalent 150) are put into 1 liter of autoclave.Add 0.64 gram, six cyanogen and close cobalt zinc ethylene glycol dimethyl ether complex (Zn 3(Co (CN 6) 2) glyme) and with nitrogen blowing mixt three times, be heated to 100 ℃ then.Add 30 gram (0.517 equivalent) propylene oxide (PO), after 15 minutes initial inductive phase, observe pressure and descend, this show catalyzer be have active.In 90 minutes time, other 600 gram (10.33 equivalent) propylene oxide are added in the reactor.This moment, pressure was still 4.35 * 10 -3Below the Pa, this shows that PO is swift in response.When dropping to, pressure is lower than 1.45 * 10 -3During Pa, from reactor, shift out 550 gram products, think that the oxide compound that adds in addition provides the space.In 1 hour time other 195 gram (3.36 equivalent) propylene oxide being added to 180 grams (0.164 equivalent) still stays in the product in the reactor.Make product continue reaction 30 minutes.
Step (B)--with potassium methylate catalyzer is transformed
Add 1.9 gram (0.027 equivalent) potassium methylates so that the catalyst residue ionization, then under 100 ℃ to mixture coupling vacuum stripping 1 hour
Step (C)--ethoxylation
In 1 hour time, add 60 gram (1.36 equivalent) oxyethane, under 100 ℃, make this mixture continue reaction 2 hours then.
Step (D)--purify and remove catalyzer
4.3 gram water and 8.7 gram acidic sodium pyrophosphates (SAPP) are added in the mixture, and mixture was heated 1 hour down at 110 ℃, coupling vacuum stripping is 1 hour then.Add 8.7 gram Magnesium Silicate q-agents and 4.3 gram diatomite, and under 100 ℃, stirred the mixture 1 hour.To mixture coupling vacuum stripping 2 hours, filter then.The analytical results of products therefrom is, the OH number is 22, and EO is 11%, and primary hydroxyl is 74.1%.The atomic absorption method of products therefrom and the analytical results of x-ray fluorescence method are under the limit of detection of 1ppm, not detect cobalt or zinc.
Embodiment 2
Make catalyst ionization with sodium ethylate
Repeat the method described in the embodiment 1, different is to replace potassium methylate with sodium ethylate, and the analytical results of products therefrom shows that under the limit of detection of 1ppm, product does not contain cobalt or zinc.
Comparative Examples A
Prepare high molecular weight polyols under the situation that without alkali metal alcoholates catalyzer is transformed handling with DMC catalysts and Magnesium Silicate q-agent
Prepare polyvalent alcohol according to method described in the embodiment 1a, do not carry out making the step 1b and the ethoxyquin step 1c of catalyzer conversion, with SAPP and Magnesium Silicate q-agent polyvalent alcohol is handled according to method described in the embodiment 1d with alkoxide.The analytical results of products therefrom shows that product contains 110ppm cobalt and 280ppm zinc.
Embodiment 3
Step (A)--use SbF 5Preparation of Catalyst propoxylation glycerol precursor
100 gram (1.09 moles, 3.26 equivalents) glycerol are added to reflux exchanger to be housed and to be filled with cover with in the flask of nitrogen.After adding 0.10 gram (0.00046 mole) antimony pentafluoride, stir the mixture, in 1 hour time, add 400 gram (6.89 equivalent) propylene oxide by dropping funnel.Flask is placed in the ice bath cools off, be lower than 34 ℃ to keep temperature.After adding alkane, stirred the mixture 0.5 hour, make great efforts to steam unreacted propylene oxide then, the result can not steam propylene oxide, and this shows that all propylene oxide all react.The theoretical molecular of products therefrom is 460.The gel permeation chromatography of products therefrom (GPC) method analytical results is that molecular weight is 439.
Produced many kinds of propoxylation precursors with glycerol and dipropylene glycol, the method for preparing these precursors is identical, but used catalyzer difference.Relevant data sees Table 1 and table 2.
Table 1
Prepare precursor by glycerol
Catalyzer The catalyst levels gram Glycerol consumption gram The propylene oxide gram of reaction Hydroxyl value (estimated value) Equivalent (estimated value) Molecular-weight average (GPC method)
SbF 5 SbF 5 BF 3 HBF 4 HBF 4 CF 3SO 3H CF 3SO 3H BF 3 BF 3 BF 3 SbCl 5 0.3 0.1 0.1 0.3 0.1 0.3 0.1 1.15 0.20 0.13 0.33 100 100 100 100 100 100 100 100 100 100 50 400 400 400 400 264 400 316 400 400 400 150 365 365 365 365 502 365 439 365 365 365 457 153.6 153.6 153.6 153.6 111.7 153.6 127.7 153.6 153.6 153.6 122.8 - 439 - 483 - 483 - 481 496 391 -
Table 2
Prepare precursor by dipropylene glycol
Catalyzer The catalyst levels gram Glycerol consumption gram The propylene oxide of reaction, gram Hydroxyl value (estimated value) Equivalent (estimated value) Molecular-weight average (GPC method)
SbF 5 SbF 5 HBF 4 BF 3 SbCl 5 SbCl 5 0.05 0.1 0.2 0.5 0.08 0.25 50 50 50 50 50 50 200 200 143 200 70 87.5 167.4 167.4 216.6 167.4 348.4 304.0 335 335 259 335 161 184.5 761 779 - 583 - 383
Step (B)--with dmc catalyst with in order to SbF 5The preceding system that makes
Be equipped with polyvalent alcohol
Restrain (0.748 equivalent) with SbF with 100 5The propoxylation glycerol precursor that catalyzer makes is added in 1 liter of autoclave.Add 0.64 gram, six cyanogen and close cobalt zinc catalyst (Zn 3(Co (CN 6) 2)), use the nitrogen wash autoclave then three times.With mixture heating up to 100 ℃.Add 30 gram propylene oxide,, thereby show that it reacts in view of pressure descends.Be lower than 2.9 * 10 to keep-up pressure -3The speed of Pa is sent into propylene oxide in the reactor, adds 609 gram PO in 2 hours, and shift out and make the mixture of staying in the reactor to 548 gram mixtures this moment from reactor be 162.1 grams, so that provide the space for advancing epoxide again.Other 340 gram propylene oxide are sent into reactor in 1.5 hours time, to make the polyvalent alcohol of molecular weight 10,000 and OH several 16.75.
By identical method, in order to BF 3/ glycerol/PO and HBF 4/ glycerol/PO and SbF 5The precursor that/glycerol/DPG makes closes the polyvalent alcohol that the cobalt zinc catalyst is made molecular weight 10,000 with six cyanogen respectively.
With regard to all situations, the activity of dmc catalyst can not reduce because of containing acid in the precursor.
Embodiment 4
With glycerol/SbF 5/ dmc catalyst/propylene oxide directly prepares polyvalent alcohol
33 gram (0.358 mole, 1.07 equivalents) glycerol are added in the reactor.Add 0.64 gram, six cyanogen and close cobalt zinc and 0.10 gram antimony pentafluoride, use the nitrogen wash mixture then.Keep mixture under 30 ℃, and in 1.5 hours time, add 133 gram (2.29 equivalent) propylene oxide at leisure.Then with mixture heating up to 100 ℃.Do not produce pressure, this shows that all propylene oxide all react.To keep pressure 2.9 * 10 -3The speed of Pa is sent into other 615 gram (10.6 equivalent) propylene oxide in the reactor, and this needs 2 hours approximately.A part (625 gram) said mixture is shifted out from reactor, and making the mixture of staying in the reactor is 148.6 grams, so that provide the space for other adds epoxide.With retaining ring Ethylene Oxide pressure 2.9 * 10 -3The speed of Pa is sent other 516 gram propylene oxide into (this needs 2 hours approximately) in the reactor, to make the polyvalent alcohol of molecular weight 10,000, OH several 17.

Claims (9)

1. method that removes double metal cyanide complex catalysts remnants in the polyvalent alcohol that contains catalyst residue is characterized in that:
(a) handle the polyvalent alcohol that contains double metal cyanide complex catalysts remnants with a kind of alkali metal alcoholates or alkaline-earth alkoxides, obtaining a kind of polyvalent alcohol that catalyst residue is changed into the processing of insoluble ionic species material,
(b) polyvalent alcohol of this processing is contacted with oxyethane, with produce a kind of ethylene oxide-capped and wherein the former secondary hydroxyl on this polyvalent alcohol of at least a portion changed into the polyvalent alcohol of primary hydroxyl; With
(c) add trisodium phosphate also by filtering, from this ethylene oxide-capped polyvalent alcohol, tell insoluble ionic species material, to obtain a kind of purification polyvalent alcohol of essentially no catalyst residue.
2. the described method of claim 1 is characterized in that, the consumption of described alkali metal alcoholates or alkaline-earth alkoxides be enough to guarantee hydroxyl on the polyvalent alcohol to the mol ratio of alkali metal alcoholates or alkaline-earth alkoxides between 1: 1 and 500: 1.
3. the described method of claim 1 is characterized in that, the contained carbon atom of described alkali metal alcoholates or alkaline-earth alkoxides per molecule is between 1 and 23.
4. the described method of claim 1 is characterized in that, the contained carbon atom of described alkali metal alcoholates or alkaline-earth alkoxides per molecule is between 1 and 8.
5. the described method of claim 1 is characterized in that, described alkali metal alcoholates or alkaline-earth alkoxides are selected from methylate, ethylate, propylate, butanolate, the amylalcohol salt of sodium, potassium, lithium, calcium and magnesium, and their mixture.
6. the described method of claim 1 is characterized in that, described filtration is that spent ion exchange resin is realized.
7. the described method of claim 1 is characterized in that, before a spot of Magnesium Silicate q-agent, pure aluminium silicate or their mixture is added in the described polyvalent alcohol that contains catalyst residue, to help the separation of step (c) in step (c).
8. the described method of claim 1, its feature also is, by this other step of fractionation described purification polyvalent alcohol is distilled, to remove the by-product alcohol in the described purification polyvalent alcohol.
9. the described method of claim 1 is characterized in that, step (a) and step (b) are carried out simultaneously or sequentially.
CN91103436.6A 1990-03-30 1991-05-27 Acid-catalyzed fabrication of precursors for use in making polyols and ethylene oxide capping of polyols made using double metal cyanide catalysts Expired - Fee Related CN1032252C (en)

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US53037990A 1990-03-30 1990-03-30
US07/530,366 US5391722A (en) 1990-03-30 1990-03-30 Acid-catalyzed fabrication of precursors for use in making polyols using double metal cyanide catalysts
US530,379 1990-05-30
US530,366 1990-05-30

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AR246286A1 (en) 1994-07-29
WO1991018909A1 (en) 1991-12-12
AU7792991A (en) 1991-12-31
EP0532520A4 (en) 1993-05-19
MY106397A (en) 1995-05-30
CN1120546A (en) 1996-04-17
EP0532520A1 (en) 1993-03-24
CN1057644A (en) 1992-01-08

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