CN109503825A - The production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether - Google Patents

The production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether Download PDF

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Publication number
CN109503825A
CN109503825A CN201811378187.3A CN201811378187A CN109503825A CN 109503825 A CN109503825 A CN 109503825A CN 201811378187 A CN201811378187 A CN 201811378187A CN 109503825 A CN109503825 A CN 109503825A
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secondary alcohol
alcohol polyoxyethylene
polyoxyethylene ether
low
ethylene oxide
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CN109503825B (en
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徐兴建
张江锋
陈静
王建臣
侯海育
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Shanghai Duolun Chemical Co Ltd
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Shanghai Duolun Chemical Co Ltd
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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
    • C08G65/26—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
    • C08G65/2609—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 containing aliphatic 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
    • C08G65/2654—Aluminium or boron; Compounds thereof
    • 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

Abstract

The production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether, it reacts to obtain high ethylene oxide adduct number secondary alcohol polyoxyethylene ether under base catalysis with ethylene oxide including low ethoxymer distribution secondary alcohol polyoxyethylene ether, the low ethoxymer distribution secondary alcohol polyoxyethylene ether is using the preparation method preparation included the following steps: in the presence of acidic, secondary alcohol and reacting ethylene oxide obtain low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 1；Crude product 1 is mixed with water, and the above stratification of cloud point obtains oily phase crude product 2；Vacuum distillation removes the secondary alcohol contained in crude product 2, crude product 3；Crude product 3 mixes to obtain mixture A with water；Mixture A is uniformly mixed to obtain mixture B with fluorine boron remover；Moisture in removing mixture B obtains mixture C；Mixture C is mixed with filter aid, and filtering must refine low ethoxymer distribution secondary alcohol polyoxyethylene ether.

Description

The production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether
Technical field
The present invention relates to the production methods of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether.
Background technique
Secondary alcohol polyoxyethylene ether is a kind of almost colourless, tasteless, transparent liquid at normal temperature, and pour point and viscosity are compared with primary Alcohol system nonionic surfactant is low, and easy to use.Secondary alcohol polyoxyethylene ether application field is extensive, and depth and range are not Disconnected to expand, the market demand is rapidly increasing.By technology and size limit, substantially matter is poor at present, measures less, the situation that valence is high, As solved, the core competitiveness of home products will be increased.
The country is in terms of secondary alcohol epoxidation reaction, to the exploratory development of catalyst, reaction condition, kinetics, reaction The problems such as form, the separation and refining method of epoxides, final product quality, carries out in-depth study, and due to the hydroxyl of secondary alcohol and primary Alcohol is different in structure and in chemical characteristic, when with ethyleneoxide addition, if using its reaction speed of basic catalyst Smaller, as a result ethyoxyl distribution range is very wide in addition product, it becomes virtually impossible to alcohol ethoxylate, therefore the second of secondary alcohol be made Friedel-Crafts type acidic catalyst such as BF is generally selected in the selection of oxygroup catalyst both at home and abroad3、BF3Etherate, AlCl3、H2SO4、HClO4、H3PO4Deng wherein with BF3Diethyl ether solution is most appropriate, secondary under the conditions of existing for the acidic catalyst Quickly, secondary alcohol ethoxy compound is made in the ethoxylation of alcohol.
But the by-product that existing preparation method generates has dioxanes, remaining fluorine element, boron element, generates in reaction process Carbonyl aldehyde compound and free unreacting alcohol etc., especially remaining fluorine element and boron element, and when fluorination boric acid will be contained Property catalyst made from secondary alcohol polyoxyethylene ether be the obtained more high ethylene oxide addition of initiator base catalysis ethyleneoxide addition Number secondary alcohol polyoxyethylene ether product coloration apperance is muddy, limits the application range of product.
Summary of the invention
Present invention mainly solves be that existing secondary alcohol polyoxyethylene ether preparation method obtains high ethylene oxide adduct number secondary alcohol The fluorine and boron impurity content height of polyoxyethylene ether and saturate technical problem provide a kind of system of new secondary alcohol polyoxyethylene ether Preparation Method, low, the of light color and high transparency advantage of this method fluorine boron impurity content.
In order to solve the above technical problems, technical scheme is as follows:
The production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether, including low ethoxymer distribution secondary alcohol polyoxy Vinethene reacts to obtain high ethylene oxide adduct number secondary alcohol polyoxyethylene ether, the low epoxy second under base catalysis with ethylene oxide Alkane adduct number secondary alcohol polyoxyethylene ether is using the preparation method preparation included the following steps:
(1) in the presence of acidic, secondary alcohol and reacting ethylene oxide obtain low ethoxymer distribution secondary alcohol polyoxy Vinethene crude product 1；The acidic catalyst includes boron trifluoride；
(2) low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 1 is mixed with water, secondary in low ethoxymer distribution The above stratification of the cloud point of alcohol polyoxyethylene ether, obtains oily phase, and oil is mutually that low ethoxymer distribution secondary alcohol polyoxyethylene ether is thick Product 2；
(3) vacuum distillation removes the step of containing in low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 2 (1) not The secondary alcohol of reaction obtains low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 3；
(4) low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 3 mixes to obtain mixture A with water；
(5) mixture A is uniformly mixed to obtain mixture B with fluorine boron remover；
(6) by heat and/or vacuum processing, the moisture removed in mixture B obtains mixture C；
(7) mixture C is mixed with filter aid, and filtering must refine low ethoxymer distribution secondary alcohol polyoxyethylene ether；
Fluorine boron remover includes selected from by sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, calcium carbonate, hydroxide At least one of substance group composed by magnesium, magnesia, magnesium carbonate, aluminium hydroxide, aluminium oxide and aluminium carbonate；
The low ethoxymer distribution secondary alcohol polyoxyethylene ether meets following general formula:
R-(O-CH2CH2)n-OH；
Wherein R is the secondary alkyl that carbon number is 8~18；N is ethoxymer distribution, n > 0 and is lower than 6；
The molar ratio of step (1) ethylene oxide and secondary alcohol is Q, and n/Q is 0.25~12.
Since step (5) has used the fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxy of purification is reduced The content of fluorine and boron impurity in ethylene ether product, to correspondingly reduce high ethylene oxide adduct number secondary alcohol polyoxyethylene ether product The content of middle fluorine and boron impurity, obtained high ethylene oxide adduct number secondary alcohol polyoxyethylene ether product colour is shallow and transparency is high.
As R non limiting example containing carbon number, 8,9,10,11,12,13,14,15,16,17,18, etc..Described is secondary Alcohol can be the secondary alcohol that R is single carbon number within the scope of C8-C18, be also possible to carbon number and be formed in those of C8~C18 secondary alcohol Substance group in two or more mixture.
As n non limiting example, n can be 0.5,0.8,1,1.2,1.4,1.6,1.8,2,2.2,2.4,2.6,2.8, 3,3.2,3.4,3.6,3.8,4,4.2,4.4,4.6,4.8,5.0,5.2,5.4,5.6,5.8, etc..But it is preferred that n=1~3.
As n/Q value non limiting example, such as, but not limited to 0.28,0.5,1,1.5,1.7,2,2.5,3,3.6,4, 4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10,11, etc..
Key problem in technology of the invention is the use of step (5) fluorine boron remover, to low ethoxymer distribution secondary alcohol polyoxy Vinethene reacts to obtain the reaction process item of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether under base catalysis with ethylene oxide Part is not particularly limited.And one skilled in the art will appreciate that refine low ethoxymer distribution secondary alcohol polyoxyethylene ether end For hydroxyl, and those skilled in the art are under alkaline condition, the compound of hydroxyl and reacting for ethylene oxide are ripe Know.
As non limiting example, the alkali can be alkali metal hydroxide and/or the alkali metal alcohol of C1~C2 alcohol Salt.
In above-mentioned technical proposal, the alkali metal hydroxide more commonly used sodium hydroxide and/or potassium hydroxide.
In above-mentioned technical proposal, the preferred methanol of C1~C2 alcohol and/or ethyl alcohol.
In above-mentioned technical proposal, the preferred sodium alkoxide of alkali metal alcoholates and/or potassium alcoholate.
As non limiting example, the dosage of alkali is high ethylene oxide adduct number secondary alcohol polyoxy second in reaction under base catalysis The 0.05~1% of alkene ether weight.Such as, but not limited to 0.10%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc..
As non limiting example, the pressure reacted in reaction under base catalysis is 0.05~0.5MPa.Such as it is but unlimited In 0.08MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.30MPa, 0.35MPa, 0.40MPa, 0.45MPa, etc..
As non limiting example, the temperature reacted in reaction under base catalysis is 95~170 DEG C.Such as, but not limited to 100 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, etc..
In above-mentioned technical proposal, the high ethylene oxide adduct number secondary alcohol polyoxyethylene ether preferably conforms to following general formula:
R-(OCH2CH2)mOH；
Wherein, m is the ethoxymer distribution of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether, and m≤50.
The size of m is not particularly limited, as long as being greater than the specific value of n, and m≤50 are only preferred.M value is non- Restricted citing can be 4,5,6,7,8,9,10,15,20,25,30,35,40,45, etc..
In above-mentioned technical proposal, m is preferably 4~50.
In above-mentioned technical proposal, the concrete technology condition of step (1) is not particularly limited, and those skilled in the art can close Reason selection, such as, but not limited to:
The optional boron trifluoride of acidic catalyst；
The dosage of acidic catalyst can be the 0.05 of low 1 weight of ethoxymer distribution secondary alcohol polyoxyethylene ether crude product ~1%；Such as, but not limited to 0.10,0.15,0.20,0.25,0.30,0.35,0.40,0.45,0.50,0.55,0.60, 0.65,0.70,0.75,0.80,0.85,0.90,0.95, etc..
Optional 0~the 0.5MPa of pressure of step (1) reaction；Such as, but not limited to 0.05,0.10,0.15,0.20,0.25, 0.30,0.35,0.40,0.45, etc..
Optional 10~120 DEG C of temperature of step (1) reaction；Such as, but not limited to 20,25,30,35,40,45,50,55, 60,65,70,75,80,85,90,95,100,105,110,115, etc..
As known to those skilled in the art, room temperature is gas when boron trifluoride pure state, using inconvenient with storage and transportation.To solve Using convenient with storage and transportation, alcohol, ether, solution form storage and transportation and use in ketone equal solvent are usually dissolved in boron trifluoride.Such as But it is not limited to boron trifluoride, by weight, the concentration of boron trifluoride can be 10~50%, and (such as the concentration of boron trifluoride can be with It is 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.).The boron trifluoride used in the specific embodiment of the invention It is all made of the boron trifluoride ether solution that boron trifluoride weight concentration is 46.5%, but metering is still carried out with boron trifluoride.
In above-mentioned technical proposal, the dosage of water is not particularly limited in step (2), as long as secondary in low ethoxymer distribution It is more than the cloud point of alcohol polyoxyethylene ether can amount needed for static layering, this those skilled in the art can be reasonably selected And it need not make the creative labor.But the matter of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 1 and water in step (2) Amount is than preferably 0.2~20.Such as, but not limited to 0.5,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5, 8,8.5,9,9.5,10,12,15,17,19, etc..
To those skilled in the art, in above-mentioned technical proposal, the temperature of step (2) mixing and mixed time do not have There are special requirement, those skilled in the art can reasonably select and need not make the creative labor.
In above-mentioned technical proposal, the process conditions that step (3) vacuum distillation removes are not particularly limited, those skilled in the art It can reasonably select.But it is preferred that the temperature distilled is normally controlled in steaming to be advisable lower than secondary alcohol polyoxyethylene ether thermal decomposition temperature Evaporating temperature is 180 DEG C hereinafter, such as 140~180 DEG C, and further non limiting example is 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, etc.；The pressure (gauge pressure) of distillation is preferably greater than -0.1MPa and -0.090MPa or less.Example Such as, but not limited to, -0.099MPa, -0.098MPa, -0.097MPa, -0.096MPa, -0.095MPa, - 0.094MPa, -0.092MPa, -0.091MPa, etc..
In above-mentioned technical proposal, the dosage of water is that low ethoxymer distribution secondary alcohol polyoxyethylene ether slightly produces in step (4) The 0.5~10% of 3 weight of product.Such as, but not limited to 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc..Still more preferably 1~5%.
To those skilled in the art, in above-mentioned technical proposal, the temperature of step (4) mixing and mixed time do not have There are special requirement, those skilled in the art can reasonably select and need not make the creative labor.
As non limiting example, the temperature of step (4) mixing is chosen as 25~100 DEG C.In this temperature range, as Step (4) temperature point value be such as, but not limited to 30 DEG C, 35 DEG C, 40 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, etc..More preferable 25~70 DEG C.
The time mixed in step (4) is not particularly limited, one skilled in the art will appreciate that incorporation time increase is conducive to Mixing is abundant, but comprehensively considering economic aim general control in the mixed time is 10~100 minutes.Such as, but not limited to 15 points Clock, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 points Clock, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, etc.；It is preferred that 30~60 minutes.
In above-mentioned technical proposal, by weight, preferred steps (5) fluorine boron remover dosage is equivalent to step (1) acidity and urges 0.5~10 times of agent dosage.Such as, but not limited to 0.7 times, 0.9 times, 1 times, 1.2 times, 1.5 times, 2 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, 5.5 times, 6 times, 6.5 times, 7 Again, 7.5 times, 8 times, 8.5 times, 9 times, 9.5 times, etc.；More preferably 0.5~6 times；Further 2~4 times；Most preferably 2.9~ 3.5 again.
To those skilled in the art, in above-mentioned technical proposal, the temperature of step (5) mixing and mixed time do not have There are special requirement, those skilled in the art can reasonably select and need not make the creative labor.
In above-mentioned technical proposal, the temperature of step (5) mixing is chosen as 25~100 DEG C.In this temperature range, as step Suddenly (5) mixing temperature point value be such as, but not limited to 30 DEG C, 35 DEG C, 40 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, etc..More preferable 25~70 DEG C.
The time mixed in step (5) is not particularly limited, one skilled in the art will appreciate that incorporation time increase is conducive to Mixing is abundant, but comprehensively considering economic aim general control in the mixed time is 10~180 minutes.Such as, but not limited to 15 points Clock, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 points Clock, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, 120 points Clock, etc..More preferable 60~120 minutes.
In above-mentioned technical proposal, step (6) is specific hot and/or vacuum processing in order to remove the moisture in mixture B Process conditions are not particularly limited, and those skilled in the art can reasonably select, and need not make the creative labor.
In above-mentioned technical proposal, for step (6) simultaneously using heat and for being vacuum-treated, the temperature of processing is preferably 50 ~200 DEG C.Such as, but not limited to 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, etc..
In above-mentioned technical proposal, for step (6) simultaneously using heat and for being vacuum-treated, the pressure of processing is greater than- 0.1MPa and be less than 0MPa, such as, but not limited to -0.099MPa, -0.098MPa, -0.097MPa, -0.095MPa, - 0.093MPa, -0.090MPa, -0.085MPa, -0.08MPa, -0.075MPa, -0.07MPa, -0.065MPa, - 0.06MPa, -0.055MPa, -0.05MPa, -0.045MPa, -0.04MPa, -0.035MPa, -0.03MPa, - 0.025MPa, -0.02MPa, -0.015MPa, -0.01MPa, etc.；Preferably -0.098MPa~-0.05MPa.
In above-mentioned technical proposal, for step (6) simultaneously using heat and for being vacuum-treated, the time of processing is preferably 30 ~300 minutes.Such as, but not limited to 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 points Clock, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, 180 minutes, 190 minutes, 200 minutes, 210 minutes, 220 minutes, 230 minutes, 240 minutes, 250 minutes, 260 minutes, 270 minutes, 280 minutes, 290 minutes, etc..
To those skilled in the art, in above-mentioned technical proposal, the temperature of step (7) mixing and mixed time do not have There are special requirement, those skilled in the art can reasonably select and need not make the creative labor.
The time mixed in step (7) is not particularly limited, one skilled in the art will appreciate that incorporation time increase is conducive to Mixing is abundant, but comprehensively considering economic aim general control in the mixed time is 30~120 minutes.Such as, but not limited to 35 points Clock, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 points Clock, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, 120 minutes, 125 minutes, etc..More preferable 60~90 points Clock.
In above-mentioned technical proposal, the temperature of step (7) mixing can be 20~150 DEG C.Such as, but not limited to 25 DEG C, 30 ℃、35℃、40℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, etc..
In above-mentioned technical proposal, if pursuing the transparency of product, the filtering for step (7), such as filtering be not transparent, can To take repetition to filter, unlimited number can best condition until obtained filtrate is transparent.
In above-mentioned technical proposal, the dosage of filter aid is not particularly limited, those skilled in the art can reasonably select And need not make the creative labor, such as, but not limited to filter aid dosage is the 0.1~1% of mixture C quality.
In above-mentioned technical proposal, the filter aid is not particularly limited, and those skilled in the art can reasonably select and not It must make the creative labor, such as the filter aid can be selected from by atlapulgite, attapulgite, montmorillonite, kaolin, alum Stone, tufa stone, diatomite, magnesium silicate, perlite, silica, active carbon, epoxy resin, 4A molecular sieve, gama-alumina and At least one of substance group composed by ZSM-5 molecular sieve.
In above-mentioned technical proposal, the preferably described fluorine boron remover includes calcium hydroxide and magnesium carbonate simultaneously.It was found that fluorine When boron remover includes calcium hydroxide and magnesium carbonate simultaneously, the two is reducing fluorine impurity content, is reducing boron impurity content and reduction There is synergistic effect in terms of coloration.At this point, the specific ratio of calcium hydroxide and magnesium carbonate is not particularly limited, any ratio Obtain comparable synergy.Such as, but not limited to the weight ratio of calcium hydroxide and magnesium carbonate is 1~10, in this weight ratio range The point value of interior non-limiting weight ratio can be 1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9, 9.9, etc..The weight ratio of calcium hydroxide and magnesium carbonate further optional 1~8, the weight ratio of calcium hydroxide and magnesium carbonate more into One step optional 3~5.
In above-mentioned technical proposal, the preferably described fluorine boron remover includes calcium hydroxide and aluminium carbonate simultaneously.It was found that fluorine When boron remover includes calcium hydroxide and aluminium carbonate simultaneously, the two is reducing fluorine impurity content, is reducing boron impurity content and reduction There is synergistic effect in terms of coloration.At this point, the specific ratio of calcium hydroxide and aluminium carbonate is not particularly limited, any ratio Obtain comparable synergy.Such as, but not limited to the weight ratio of calcium hydroxide and aluminium carbonate is 1~40, in this weight ratio range The point value of interior non-limiting weight ratio can be 5,10,15,20,25,30,35, etc..The weight ratio of calcium hydroxide and aluminium carbonate Further optional 5~30, the weight ratio further optional 10~20 of calcium hydroxide and aluminium carbonate.
The content of fluorine and boron in the specific embodiment of the invention, analysis method are respectively as follows:
1, the measurement of fluorine ion
1.1, principle
Using lanthanum fluoride electrode as indicator electrode, saturated calomel electrode (or silver chloride electrode) is reference electrode, when depositing in water In fluorine ion, electrode response will be generated on negative electrode.
Working battery is expressed as follows:
When total ionic strength is definite value in control water, the electromotive force E of battery changes with fluorinion concentration in solution undetermined And change:
E and lgCFBe in line relationship, and 2.303RT/F is the slope (being 59.1 at 25 DEG C) of the straight line
The pH for measuring solution is 5~9.The influence of interfering ion and acidity is eliminated with total ionic strength buffer solution.
The concentration limit of method be 0.05 milligram of fluorine/liter, measurement the upper limit up to 4000 milligrams of fluorine/liter.
1.2, instrument
Precision acidity meter
Fluorinion combination electrode
Magnetic stirrer
1.3, reagent
1.3.1, fluorine standard solution:
0.2210 gram of sodium fluoride (, dry cooling 40~45 minutes dry in 500~650 DEG C) is weighed, is dissolved, is transferred to water In 1000 milliliters of volumetric flasks, it is diluted to graticule.Every milliliter of this solution contains 100 microgram fluorine, stores in polyethylene bottle.
1.3.2, total ionic strength buffer
58.8 grams of trisodium citrate dihydrates and 85 grams of sodium nitrate are weighed, are dissolved in water, with the aqueous hydrochloric acid solution tune of 6mol/L PH to 5.5~6.0 is saved, is transferred in 1000 milliliters of volumetric flasks, is diluted with water to graticule.This solution is 0.2M sodium citrate -1M nitre Sour sodium.
1.4, step
1.4.1, instrument calibration
It is carried out by instrument operation instructions.
1.4.2, draw standard curve
(1) be separately added into a series of 100 milliliters of volumetric flasks containing 20,100,500,1000,2000,3000,4000, 5000, the standard solution of 6000,7000 microgram fluorine, then 20 milliliters of total ionic strength buffers are separately added into, it is diluted with water to mark Line.Respective concentration is respectively 0.20,1.00,5.00,10.0,20.0,30.0,40.0,50.0,60.0,70.0 mg/litre fluorine. It shakes up, is transferred in 100 milliliters of beakers.
(2) it inserts electrodes into solution, starts magnetic stirrer, stir 1~3 minute, current potential starts to read after stablizing.Again Before discharge electrode, it not stir, in order to avoid enter air around crystal and the reading of mistake or pointer is caused to shake.It is measured each time Before, it will be rinsed with water electrode, and blotted with filter paper.
(3) on semilogarithmic paper, E-logC is drawnF -Curve.
1.4.3, the measurement of sample
W grams of polyethers sample (according to fluorine content height) is weighed, is put into 100 milliliters of volumetric flasks, 20 milliliters of total ions is added Intensity buffer solution is diluted with water to graticule, and uniformly mixes to obtain sample test liquid, and 70 milliliters of sample test liquid is taken to set 100 millis It rises in beaker, is operated by step (2) program determination in the 1.4.2 for drawing standard curve, millivolt numerical value is read, from standard curve It looks into and takes fluorinion concentration value C mg/litre fluorine.
W is related with the content of fluorine in polyethers sample, corresponding according to substantially fluorinated volume selects suitable W value in polyethers sample Relationship is as follows:
Polyethers sample fluorine element content, ppmw W, gram
Greater than 1000 and 5000 or less 1.0~1.3
Greater than 500 and 1000 or less 3.0~3.5
Greater than 100 and 500 or less 7.0~7.5
100 or less 8.0~8.5
1.5, it calculates
Calculation formula are as follows:
Fluorine element content (ppmw)=100C/W in polyethers sample；
C is the numerical value as unit of Funing tablet for the sample solution that standard curve is read is by mg/litre；
W is the numerical value of polyethers example weight in grams.
1.6, points for attention
(1) standard curve measures at the same temperature in sample, can eliminate influence caused by the temperature difference；
(2) measurement is advisable with polyethylene beaker；
(3) it is noted that eliminating the bubble of electrode surface.
2, ICP-AES method measures boron element
2.1, principle
When doing quantitative analysis with ICP-AES, under certain condition, the intensity of spectral line I and constituent content C to be measured are in certain line Sexual intercourse: I=aC (wherein a is constant), according to this feature, at element respective wavelength, by the mark for preparing various concentration Quasi- solution surveys its spectral intensity, draws standard curve, and the concentration of the element in sample is measured using calibration curve method.
2.2, instrument and experiment condition
U.S.'s Varian inductive coupling plasma emission spectrum；VISTA-PRO (vertical quarter bend)；
ICP-AES operating condition: radio-frequency generator power 1100W；Sample introduction is atomized argon pressure 200kPa；Plasma air-flow Measure 15.0L/min；Secondary air amount 1.5L/min；Observation degree: 10mm；Analysis spectral line wavelength 249.772nm.
2.3, experiment reagent:
Boron standard solution mother liquor: weighing 0.57g boric acid, dissolved with water, is transferred in 1000 milliliters of volumetric flasks, is diluted to mark Line.This solution boron concentration is 100mg/L；
Aqueous hydrochloric acid solution, weight concentration 1%.
2.4, step
2.4.1, the drafting of working curve
(1) it is separately added into a series of 100 milliliters of volumetric flasks micro- containing 20,100,500,1000,2000,3000,4000 The standard solution of gram boron, is diluted with water to graticule.Respective concentration be respectively 0.20,1.00,5.00,10.0,20.0,30.0, The standard series of 40.0 mg/litre boron, is measured according to the instrument condition of step 2.2, using boron element concentration as abscissa, spectrum Line intensity is that ordinate draws working curve.
2.4, sample measures
W grams of polyethers sample (according to boron content height) is weighed in 200ml polytetrafluoroethylene beaker, it is dense that 50ml weight is added The aqueous hydrochloric acid solution that degree is 1%, cap upper surface ware heat slightly boiled 5min on electric hot plate.Remove cooling.It is transferred to 100ml modeling Expect in volumetric flask, the aqueous hydrochloric acid solution constant volume for being 1% with weight concentration shakes up, and filters, as sample solution.
Sample solution is measured according to the above instrument condition, boron element concentration C mg/litre is read on curve.
W is related with the content of boron in polyethers sample, corresponding according to substantially fluorinated volume selects suitable W value in polyethers sample Relationship is as follows:
Polyethers sample boron content, ppmw W, gram
Greater than 1000 and 5000 or less 1.0~1.3
Greater than 500 and 1000 or less 3.0~3.5
Greater than 100 and 500 or less 7.0~7.5
100 or less 8.0~8.5
2.5, it calculates
Calculation formula are as follows:
Boron content (ppmw)=100C/W in polyethers sample；
C is the numerical value as unit of boron element concentration for the sample solution that standard curve is read is by mg/litre；
W is the numerical value of polyethers example weight in grams.
3, appearance and color
Appearance is using range estimation (at 25 DEG C)；Color uses GB/T 9282-1988, and " transparency liquid is with platinum-cobalt ranking face Color " measurement.
4, hydroxyl value
The hydroxyl value of secondary alcohol polyoxyethylene ether is surveyed using GB/T7383-2007 " measurement of nonionic surfactant hydroxyl value " It is fixed, and ethoxymer distribution is calculated according to hydroxyl value according to following formula:
N=[(56110/OHV)-Mw]/44.052
In formula: n- ethoxymer distribution
The comparable mgKOH number of 56110-1 hydroxy, mgKOH；
The hydroxyl value of OHV- secondary alcohol polyoxyethylene ether, mgKOH/g；
The molecular weight of Mw- secondary alcohol；
44.052- the molecular weight of ethylene oxide.
Inventor can greatly reduce secondary alcohol polyoxyethylene ether product it is discovered by experiment that after using the method for the present invention In fluorine, boron content；And when the fluorine boron remover includes simultaneously calcium hydroxide and magnesium carbonate or the fluorine boron remover When simultaneously including calcium hydroxide and aluminium carbonate, hence it is evident that reduce the coloration of secondary alcohol polyoxyethylene ether product and increase secondary alcohol polyoxy second The transparency of alkene ether product.
In the present invention, if not specializing, pressure is in terms of gauge pressure.
The present invention is described in detail combined with specific embodiments below.
Specific embodiment
[embodiment 1]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, 5.50 grams of fluorine boron removers (group becomes calcium hydroxide) is added stirring 120 minutes Obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 2]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, is added 5.50 grams of fluorine boron removers (group becomes magnesium carbonate) stirring 120 minutes To mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 3]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, is added 5.50 grams of fluorine boron removers (group becomes aluminium carbonate) stirring 120 minutes To mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 4]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, 5.50 grams of fluorine boron removers (group becomes sodium hydroxide) is added stirring 120 minutes Obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 5]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, 5.50 grams of fluorine boron removers (group becomes potassium hydroxide) is added stirring 120 minutes Obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[comparative example]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, fluorine boron remover is not added but stirring obtains mixture B in 120 minutes；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 6]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, 5.50 grams of fluorine boron removers is added (for the mixing of calcium hydroxide and magnesium hydroxide The weight ratio of object, calcium hydroxide and magnesium hydroxide is 5) to stir 120 minutes to obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 7]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, 5.50 grams of fluorine boron removers is added (for the mixing of calcium hydroxide and magnesium hydroxide The weight ratio of object, calcium hydroxide and magnesium hydroxide is 3) to stir 120 minutes to obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 8]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, remain temperature-resistant, be added 5.50 grams of fluorine boron removers (for the mixture of calcium hydroxide and aluminium carbonate, The weight ratio of calcium hydroxide and aluminium carbonate is 10) to stir 120 minutes to obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 9]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, remain temperature-resistant, be added 5.50 grams of fluorine boron removers (for the mixture of calcium hydroxide and aluminium carbonate, The weight ratio of calcium hydroxide and aluminium carbonate is 20) to stir 120 minutes to obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 10]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, 5.50 grams of fluorine boron removers is added (for the mixing of calcium hydroxide and sodium hydroxide The weight ratio of object, calcium hydroxide and sodium hydroxide is 20) to stir 120 minutes to obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
[embodiment 11]
One, the preparation of secondary alcohol polyoxyethylene ether
(1) 1 mole of C13 secondary alcohol and 1.68g boron trifluoride is added in the autoclave with stirring of 1L, seals reaction kettle, Open stirring.Three times using the air in nitrogen replacement reaction kettle, ethylene oxide, control reaction temperature are then passed through into reaction kettle Degree 70 DEG C and reaction pressure be 0.2MPa, until be passed through ethylene oxide total amount be 1.8 moles, until reactor pressure no longer under Drop, shows to complete slaking reaction, is cooled to 50 DEG C, obtain 280 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1；
(2) water of 70g, stirring are added in 280 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 1 60 DEG C are warming up to, and stratification 45 minutes at this temperature, obtaining oily phase is low ethoxymer distribution secondary alcohol polyoxyethylene ether Crude product 2；
(3) low ethoxymer distribution secondary alcohol polyoxyethylene is distilled off in the pressure of 160 DEG C and -0.092MPa Unreacted secondary alcohol in ether crude product 2 obtains 168 grams of low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3；
(4) 8 grams of pure water are added in 168 grams of Xiang Shangshu low ethoxymer distribution secondary alcohol polyoxyethylene ether crude products 3,90 Mixture A is stirred 30 minutes to obtain at a temperature of DEG C；
(5) then, it remains temperature-resistant, 5.50 grams of fluorine boron removers is added (for the mixing of calcium hydroxide and potassium hydroxide The weight ratio of object, calcium hydroxide and potassium hydroxide is 20) to stir 120 minutes to obtain mixture B；
(6) pressure vacuum in 85 DEG C and -0.093MPa is dehydrated 120 minutes to obtain mixture C；
(7) 60 DEG C are cooled to, 1.0 grams of atlapulgites are added and stir 45 minutes, filters to obtain the low ethoxymer distribution of purification Secondary alcohol polyoxyethylene ether；The OHV measured be 168, calculate accordingly ethoxymer distribution be 3；
(8) in Xiang Shangshu autoclave, the low ethoxymer distribution secondary alcohol polyoxyethylene of 150 grams of (0.45 mole) purifications is added Ether and 0.6 gram of sodium hydroxide seal reaction kettle, open stirring.Three times using the air in nitrogen replacement reaction kettle, then to anti- It answers and is passed through ethylene oxide in kettle, 150 DEG C of control reaction temperature and reaction pressure are 0.2MPa, until being passed through the total amount of ethylene oxide It is 120 grams, until reactor pressure no longer declines, shows to complete slaking reaction to get high ethylene oxide adduct number secondary alcohol polyoxy second Alkene ether products: C13 secondary alcohol polyoxyethylene (9) ether.
Two, remaining fluorine and boron content and high epoxy second in low ethoxymer distribution secondary alcohol polyoxyethylene ether are refined The appearance and coloration of alkane adduct number secondary alcohol polyoxyethylene ether
For convenient for comparing, by the composition of fluorine boron remover, the low ethoxymer distribution secondary alcohol polyoxyethylene of the purification measured The appearance and coloration of remaining fluorine and boron content and high ethylene oxide adduct number secondary alcohol polyoxyethylene ether are listed in table 1 in ether.For Measurement result is listed in table 1 convenient for comparing.
Table 1

Claims (10)

1. the production method of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether, including low ethoxymer distribution secondary alcohol polyoxy second Alkene ether reacts to obtain high ethylene oxide adduct number secondary alcohol polyoxyethylene ether, the low ethylene oxide under base catalysis with ethylene oxide Adduct number secondary alcohol polyoxyethylene ether is using the preparation method preparation included the following steps:
(1) in the presence of acidic, secondary alcohol and reacting ethylene oxide obtain low ethoxymer distribution secondary alcohol polyoxyethylene Ether crude product 1；The acidic catalyst includes boron trifluoride；
(2) low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 1 is mixed with water, poly- in low ethoxymer distribution secondary alcohol The above stratification of the cloud point of ethylene oxide ether, obtains oily phase, and oil is mutually low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 2；
(3) vacuum distillation removes the step of containing in low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 2 (1) unreacted Secondary alcohol, obtain low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 3；
(4) low ethoxymer distribution secondary alcohol polyoxyethylene ether crude product 3 mixes to obtain mixture A with water；
(5) mixture A is uniformly mixed to obtain mixture B with fluorine boron remover；
(6) by heat and/or vacuum processing, the moisture removed in mixture B obtains mixture C；
(7) mixture C is mixed with filter aid, and filtering must refine low ethoxymer distribution secondary alcohol polyoxyethylene ether；
Fluorine boron remover includes selected from by sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, calcium carbonate, magnesium hydroxide, oxygen At least one of substance group composed by change magnesium, magnesium carbonate, aluminium hydroxide, aluminium oxide and aluminium carbonate；
The low ethoxymer distribution secondary alcohol polyoxyethylene ether meets following general formula:
R-(O-CH2CH2)n-OH；
Wherein R is the secondary alkyl that carbon number is 8~18；N is ethoxymer distribution, n > 0 and is lower than 6；
The molar ratio of step (1) ethylene oxide and secondary alcohol is Q, and n/Q is 0.25~12.
2. production method according to claim 1, it is characterized in that the alkali is alkali metal hydroxide and/or C1~C2 alcohol Alkali metal alcoholates.
3. production method according to claim 1, it is characterized in that the dosage of alkali is high ethylene oxide in reaction under base catalysis The 0.05~1% of adduct number secondary alcohol polyoxyethylene ether weight.
4. production method according to claim 1, it is characterized in that the pressure reacted in reaction under base catalysis be 0.05~ 0.5MPa。
5. production method according to claim 1, it is characterized in that the temperature reacted in reaction under base catalysis is 95~170 ℃。
6. institute's production method according to claim 1, it is characterized in that the high ethylene oxide adduct number secondary alcohol polyoxyethylene ether meets Following general formula:
R-(OCH2CH2)mOH；
Wherein, m is the ethoxymer distribution of high ethylene oxide adduct number secondary alcohol polyoxyethylene ether, and m≤50.
7. production method according to claim 1, it is characterized in that low ethoxymer distribution secondary alcohol polyoxyethylene in step (2) The mass ratio of ether crude product 1 and water is 0.2~20.
8. production method according to claim 1, it is characterized in that the dosage of water is that low ethoxymer distribution is secondary in step (4) The 0.5~10% of 3 weight of alcohol polyoxyethylene ether crude product.
9. production method according to claim 1, it is characterized in that it is characterized in that the temperature of step (4) mixing is 25~100 DEG C.
10. production method according to claim 1, it is characterized in that by weight, step (5) fluorine boron remover dosage is equivalent to 0.5~10 times of step (1) acidic catalyst dosage.
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