CN104151541B - The process for purification of polyethers - Google Patents
The process for purification of polyethers Download PDFInfo
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- CN104151541B CN104151541B CN201410399809.6A CN201410399809A CN104151541B CN 104151541 B CN104151541 B CN 104151541B CN 201410399809 A CN201410399809 A CN 201410399809A CN 104151541 B CN104151541 B CN 104151541B
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Abstract
The present invention relates to the process for purification of polyethers, purpose is to provide the process for purification of a kind of new polyethers, use the process for purification of polyethers, comprise the steps: that water, pH adjusting agent, the polyethers of alkali metal containing and solid absorbent are mixed by (1), it is thus achieved that the mixture of pH5～8；(2) insulation absorption；(3) vacuum dehydration；(4) it is filtrated to get refined polyethers；Described solid absorbent is made up of modified-salt and adsorbent parent, and described modified-salt is selected from magnesium sulfate, aluminum sulfate, aluminium potassium sulfate, aluminum sodium sulfate, alkali-metal sulfate, alkali-metal phosphate or the salt of alkali-metal halogen acids；The described adsorbent parent technical scheme of at least one in aluminium oxide, amorphous silica, aluminium silicate or magnesium silicate, can be used in the Refining process of polyethers.
Description
Technical field
The present invention relates to the process for purification of polyethers, particularly relate to the removal methods of alkali metal ion in polyethers.
Background technology
With the compound of alcoholic hydroxy as initiator, with alkali metal hydroxide, (conventional is potassium hydroxide and/or hydrogen-oxygen
Change sodium), alkali metal alcoholates (potassium of such as methanol or ethanol or sodium salt) be catalyst cause oxirane, expoxy propane, 1,2-
When the epoxyalkane homopolymerizations such as epoxy butane or copolymerization, the spike of course of reaction is alcohol negative oxygen ion, with alkali metal ion as institute
State the pairing cation of spike.In order to make product storage stable or the application needs in downstream, usually require that removing catalyst
The alkali metal ion introduced.
Li Junxian etc. disclose employing acid and neutralize, and then use Emathlite or ion exchange resin etc. to take off as adsorbent
Except alkali metal ion method (refined [J] chemical propellant of high activity low-unsaturated polyether polyatomic alcohol and macromolecular material,
2004,2 (6): 32～33.
CN1229806A discloses a kind of process for purification of polyethers, and it uses inorganic salt hydrate to do crystal seed, phenol derivative
Thing does precipitant, adds the adsorbent such as synthetic magnesium silicate, synthetic aluminium silicate, and then dehydration etc. process and obtain refined gathering
Ether.Wherein as precipitant phenol derivatives such as, 2.6-di-tert-butyl-4-methy phenol remains in refined polyethers
Words, also should play the effect of antioxidant.
Summary of the invention
It is an object of the invention to provide a kind of new polyethers process for purification, the method have in refined polyether product alkali metal from
The advantage that sub-content is low.
For solving above-mentioned technical problem, technical scheme is as follows: the process for purification of polyethers, comprises the steps:
(1) water, pH adjusting agent, the polyethers of alkali metal containing and solid absorbent are mixed, it is thus achieved that the mixture of pH5～8；More
Preferably pH is less than 7；
(2) insulation absorption；
(3) vacuum dehydration；
(4) it is filtrated to get refined polyethers；
Described solid absorbent is made up of modified-salt and adsorbent parent, and described modified-salt is selected from magnesium sulfate, aluminum sulfate, sulfur
Acid aluminum potassium, aluminum sodium sulfate, alkali-metal sulfate, alkali-metal phosphate or the salt of alkali-metal halogen acids；Described adsorbent
At least one in aluminium oxide, amorphous silica, aluminium silicate or magnesium silicate of parent；Described polyethers is with hydroxyl chemical combination
Thing is initiator, with alcohol negative oxygen ion as spike, with alkali metal ion for the alcohol negative oxygen ion pairing cation as spike,
Obtained by epoxy alkane ring opening polymerization.
In technique scheme, described modified-salt is containing water of crystallization and/or without water of crystallization.
In technique scheme, described phosphate can be in the normal salt of phosphoric acid, phosphoric acid hydrogen disalt or dihydric phosphate
At least one.
In technique scheme, the salt of described alkali-metal halogen acids select free NaCl, KCl, NaBr, KBr, NaF,
KF、NaHF2Or KHF2At least one in the material group constituted.
In technique scheme, the synthetic method taked of described solid absorbent comprises the following steps:
(I) by the aqueous solution of adsorbent parent Yu described modified-salt；
(II) it is dried.Between step (I) and step (II), preferably include aging step, Aging Temperature preferably 30～50
DEG C, digestion time preferably 4～8 hours.
In technique scheme, described dry temperature is preferably 50～90 DEG C.
In technique scheme, in described solid absorbent, modified-salt is preferably ＞ 0 with the mol ratio of adsorbent parent
And≤0.5.
In technique scheme, described pH adjusting agent can be mineral acid or organic acid.The optional sulfur of described mineral acid
Acid, hydrochloric acid, phosphoric acid, do not have oxidisability and non-volatility due to phosphoric acid, from execute-in-place safe and sanitary meter, preferably phosphoric acid.Institute
The organic acids stated such as, but not limited to, acetic acid, oxalic acid, adipic acid, tartaric acid.
In technique scheme, described epoxyalkane is selected from oxirane, expoxy propane and 1, in 2-epoxy butane
At least one.But it is most commonly that described epoxyalkane is selected from oxirane and/or expoxy propane, when described alkylene oxide
Hydrocarbon is when oxirane and expoxy propane, and described polyethers can be atactic polyether or the block polyether of various sequence.
In technique scheme, the granular size of described solid absorbent is not particularly limited, those skilled in the art
Can select as required.Such as from adsorption rate, the mesh number of described solid absorbent should be more than 100 mesh, and
And the mesh number of granule is the bigger the better.Cause difficulty to follow-up filtration if but granule mesh number is too big, help so that must be aided with
Filtering agent.
In technique scheme, as optimum technical scheme, be described adsorbent parent be amorphous silica, institute
State modified-salt to include selecting free NaF, KF, NaHF2Or KHF2At least one in the material group constituted；And the most optimum technical side
Modified-salt described in case farther includes at least one in described phosphate.
The present invention's it is crucial that the selection of adsorbent, the consumption of adsorbent, the consumption of water, Yi Jibu in concrete steps (1)
Suddenly the temperature range that (2) are incubated, time those skilled in the art of absorption all can determine according to actual needs.With potassium hydroxide
And/or sodium hydroxide is that catalyst causes oxirane and/or Polymerization of Propylene Oxide raw with alcoholic hydroxy compound for initiator
When producing polyethers, the content of the K in polyethers and/Na is generally in the range of 500～6000ppmw.Now, as a example by adsorbent amount
Such as, but not limited to, the 0.1～3% of polyether quality.The consumption of water is such as but not limited to the 0.1～10% of polyether quality.Step (2)
Adsorption temp be not particularly limited, as long as the mixture of the step of making (1) is for above freezing, and the heat decomposition temperature of polyethers
Below, but from being easy to industry and there is adsorption rate double factor consideration faster, preferably 60～120 DEG C, more preferably 60
～80 DEG C.The time of step (2) insulation absorption is preferably greater than 0.5 hour, and insulation absorption prolongation is conducive to reaching to balance, but along with
The contribution reaching adsorption equilibrium is gradually lowered by time lengthening adsorption time, thus insulation adsorption time to can be controlled in 0.5～6 little
Time, it is further suitable that 1～3 hour.
The time that the temperature of step (3) vacuum dehydration, the pressure of dehydration are dehydrated is not particularly limited, as long as can be by step
(2) water dissolved in the mixture after insulation absorption removes.Such as but not limited to, the temperature of vacuum dehydration is 60～100
DEG C, dewatering pressure is-0.02～-0.08MPa, and dewatering time can be 0.5～3 hour.
As the detection of kalium ion and natrium ion in the polyethers of alkali metal containing of raw material and refined polyethers, all use Japan's Shimadzu system
The atomic absorption instrument AA-670 made, is tested by GB12008.4-89.
In detailed description of the invention, the measurement of polyethers hydroxyl value uses national standard " in GB120008.3-1989 polyether polyol
Hydroxy value measuring method " Phthalic Anhydride recorded is measured.
Using the polyethers that the inventive method is refined, the most alkali-metal content low can reach 5ppmw, achieve preferable technology
Effect.
Below in conjunction with specific embodiment, the present invention is described in detail.
Detailed description of the invention
[embodiment 1]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
In the autoclave that the band of 1.5L stirs, add 1 mole of lauryl alcohol and 6 grams of KOH, sealed reactor, open stirring.
Air in use nitrogen replacement reaction kettle three times, then at 60 DEG C and-0.05MPa evacuation 30min.Then in reactor
Being passed through epoxy ethane-epoxy propane mixture (oxirane is 1: 1 with the mol ratio of expoxy propane), controlling reaction temperature is
120 DEG C is 0.2MPa with reaction pressure, until the molal quantity sum being passed through oxirane and expoxy propane is 20 moles, then stops
Stop described mixture thus complete main body reaction.Maintain temperature of reaction kettle to be 120 DEG C and carry out ripening, until reactor pressure is not
Decline again, shown slaking reaction, at pressure and the temperature evacuation 30min of 100 DEG C of-0.05MPa, be down to room temperature and obtain
Described polyethers, recording the content that hydroxyl value is 49.7mgKOH/g, K ion is 3780ppmw.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.2 mole of KF and 0.2 mole
K2HPO4) mixing, 40 DEG C of sealed thermal insulatings 6 hours, then it is dried 12 hours at 70 DEG C, pulverizes, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 2]
1, the synthesis of lauryl alcohol polyoxyethylene (20) ether containing potassium
In the autoclave that the band of 1.5L stirs, add 1 mole of lauryl alcohol and 6 grams of KOH, sealed reactor, open stirring.
Air in use nitrogen replacement reaction kettle three times, then at 60 DEG C and-0.05MPa evacuation 30min.Then in reactor
Being passed through oxirane, control reaction temperature being 120 DEG C is 0.2MPa with reaction pressure, until the molal quantity being passed through oxirane is
20 moles, then stop described mixture thus complete main body reaction.Maintain temperature of reaction kettle to be 120 DEG C and carry out ripening, directly
No longer decline to reactor pressure, shown slaking reaction, at pressure and the temperature evacuation of 100 DEG C of-0.05MPa
30min, is down to room temperature and obtains polyethers, and recording the content that hydroxyl value is 53.6mgKOH/g, K ion is 3960ppmw.
2, the preparation of adsorbent
With embodiment 1.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 3]
1, the synthesis of n-butyl alcohol polyoxypropylene (16) ether containing sodium
In the autoclave that the band of 1.5L stirs, add 1 mole of dipropylene glycol mono-n-butyl ether and 6 grams of NaOH, seal reaction
Still, opens stirring.Air in use nitrogen replacement reaction kettle three times, then at 60 DEG C and-0.05MPa evacuation 30min.So
Being passed through expoxy propane in backward reactor, control reaction temperature being 120 DEG C is 0.2MPa with reaction pressure, until being passed through epoxy third
The molal quantity of alkane is 14 moles, then stops described mixture thus completes main body reaction.Maintaining temperature of reaction kettle is 120 DEG C
Carry out ripening, until reactor pressure no longer declines, shown slaking reaction, in pressure and the temperature of 100 DEG C of-0.05MPa
Degree evacuation 30min, is down to room temperature and obtains polyethers, and recording the content that hydroxyl value is 54.1mgKOH/g, Na ion is 3690ppmw.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.2 mole of NaF and 0.2 mole
Na2HPO4) mixing, 40 DEG C of sealed thermal insulatings 6 hours, then it is dried 12 hours at 70 DEG C, pulverizes, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 4]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.2 mole of KF and 0.2 mole
K3PO4) mixing, 40 DEG C of sealed thermal insulatings 6 hours, then it is dried 12 hours at 70 DEG C, pulverizes, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 5]
1, the synthesis of n-butyl alcohol polyoxypropylene (16) ether containing sodium
Such as embodiment 3.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.2 mole of NaF and 0.2 mole
Na3PO4) mixing, 40 DEG C of sealed thermal insulatings 6 hours, then it is dried 12 hours at 70 DEG C, pulverizes, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 6]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, mix, 40 with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of KF)
DEG C sealed thermal insulating 6 hours, is then dried 12 hours at 70 DEG C, pulverizes, and crosses 100 mesh sieves and obtains adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 7]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of K2HPO4) mixing,
40 DEG C of sealed thermal insulatings 6 hours, are then dried 12 hours at 70 DEG C, pulverize, and cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 8]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of K3PO4) mixing,
40 DEG C of sealed thermal insulatings 6 hours, are then dried 12 hours at 70 DEG C, pulverize, and cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 9]
1, the synthesis of n-butyl alcohol polyoxypropylene (16) ether containing sodium
Such as embodiment 3.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, mix, 40 with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of NaF)
DEG C sealed thermal insulating 6 hours, is then dried 12 hours at 70 DEG C, pulverizes, and crosses 100 mesh sieves and obtains adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 10]
1, the synthesis of n-butyl alcohol polyoxypropylene (16) ether containing sodium
Such as embodiment 3.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of Na2HPO4) mixing,
40 DEG C of sealed thermal insulatings 6 hours, then it is dried 12 hours at 70 DEG C, pulverizes, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 11]
1, the synthesis of n-butyl alcohol polyoxypropylene (16) ether containing sodium
Such as embodiment 3.
2, the preparation of adsorbent
180 mesh amorphous silicas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of Na3PO4) mixing,
40 DEG C of sealed thermal insulatings 6 hours, are then dried 12 hours at 70 DEG C, pulverize, and cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 12]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, the preparation of adsorbent
180 mesh Alpha-aluminas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.2 mole of KF and 0.2 mole of K2HPO4) mixed
Close, 40 DEG C of sealed thermal insulatings 6 hours, be then dried 12 hours at 70 DEG C, pulverize, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 13]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, the preparation of adsorbent
180 mesh Alpha-aluminas 1 mole, mix with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of KF), airtight at 40 DEG C
It is incubated 6 hours, is then dried 12 hours at 70 DEG C, pulverize, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[embodiment 14]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, the preparation of adsorbent
180 mesh Alpha-aluminas 1 mole, with 100 milliliters of modified-salt aqueous solutions (containing 0.4 mole of K2HPO4) mixing, close at 40 DEG C
Close insulation 6 hours, be then dried 12 hours at 70 DEG C, pulverize, cross 100 mesh sieves and obtain adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[comparative example 1]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, adsorbent
Using 180 mesh amorphous silicas is adsorbent.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
[comparative example 2]
1, the synthesis of lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium
Such as embodiment 1.
2, adsorbent
Use the Alpha-alumina of 180 mesh.
3, polyethers is refined
Deionized water 5 grams, the polyethers 100 grams of step 1 are mixed with the adsorbent 1 gram of step 2, is 85w%'s by concentration
Phosphorus acid for adjusting pH is 6；Stir 2 hours at 70 DEG C of constant temperature；Then at 70 DEG C and-0.05MPa evacuation 1 hour.It is filtered hot to
Filtrate clarifies to obtain refined polyethers.
For ease of comparing, the alkali metal ion content measured in the composition of adsorbent and refined polyethers is listed in table 1.
Table 1
Note: polyethers 1 represents lauryl alcohol polyoxyethylene (10) polyoxypropylene (10) ether containing potassium that embodiment 1 synthesizes；Polyethers 2
Represent lauryl alcohol polyoxyethylene (20) ether containing potassium of the 2-in-1 one-tenth of embodiment；Polyethers 3 represents the positive fourth containing sodium that embodiment 3 synthesizes
Alcohol polyoxypropylene (16) ether.
Claims (10)
1. the process for purification of polyethers, comprises the steps:
(1) water, pH adjusting agent, the polyethers of alkali metal containing and solid absorbent are mixed, it is thus achieved that the mixture of pH5～8；
(2) insulation absorption；
(3) vacuum dehydration；
(4) it is filtrated to get refined polyethers；
Described solid absorbent is made up of modified-salt and adsorbent parent, and described modified-salt includes selecting free NaF, KF, NaHF2Or
KHF2At least one in the material group constituted；Described adsorbent parent is amorphous silica；Described polyethers is with hydroxyl
Compound is initiator, with alcohol negative oxygen ion as spike, with alkali metal ion for alcohol negative oxygen ion as spike pairing sun
Ion, is obtained by epoxy alkane ring opening polymerization.
Method the most according to claim 1, is characterized in that described modified-salt farther includes phosphate.
Method the most according to claim 1 and 2, is characterized in that described modified-salt is containing water of crystallization and/or without water of crystallization.
Method the most according to claim 2, is characterized in that described phosphate is the normal salt of phosphoric acid, phosphoric acid hydrogen disalt or phosphorus
At least one in acid dihydride salt.
Method the most according to claim 1, is characterized in that the synthetic method of described solid absorbent comprises the following steps:
(I) by the aqueous solution of adsorbent parent Yu described modified-salt；
(II) it is dried.
Method the most according to claim 5, is characterized in that described dry temperature is 50～90 DEG C.
Method the most according to claim 1, is characterized in that modified-salt and adsorbent parent in described solid absorbent
Mol ratio is ＞ 0 and≤0.5.
Method the most according to claim 1, is characterized in that described pH adjusting agent is mineral acid or organic acid.
Method the most according to claim 1, is characterized in that described epoxyalkane is selected from oxirane, expoxy propane and 1,
At least one in 2-epoxy butane.
Method the most according to claim 1, is characterized in that the mesh number of described solid absorbent is more than 100 mesh.
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