CN103874720B - The manufacture method of alkylene oxide addition product - Google Patents
The manufacture method of alkylene oxide addition product Download PDFInfo
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- CN103874720B CN103874720B CN201280049761.5A CN201280049761A CN103874720B CN 103874720 B CN103874720 B CN 103874720B CN 201280049761 A CN201280049761 A CN 201280049761A CN 103874720 B CN103874720 B CN 103874720B
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- alkylene oxide
- oxide addition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
Abstract
The present invention provides the manufacture method of a kind of alkylene oxide addition product, comprising: (A) limit keeps the temperature at more than 90 DEG C and less than 130 DEG C, while to by the presence of alkoxylate solid catalyst in the compound containing reactive hydrogen and/or fatty acid alkyl esters addition alkylene oxide and the alkylene oxide addition crude product that obtains adds organic carboxylic acid aqueous solution, by 5 mass %, pH when measuring at 25 DEG C adjusts the operation to 5～7, and (B) is then, the amount of moisture adjusting the alkylene oxide addition crude product to more than 50 DEG C less than 80 DEG C is adjusted the operation to more than 8 mass % 12 mass %.In accordance with the invention it is possible to effectively the PAG of catalyst and by-product separated from alkylene oxide addition product and remove.
Description
Technical field
The present invention relates to the manufacture method of a kind of alkylene oxide (alkylene oxide) addition product, it can hold from target product
Change places and separate and remove catalyst and accessory substance.
Background technology
Addition alkylene oxide in the compound containing reactive hydrogen such as higher alcohol, higher amines, higher fatty acid alkyl ester and manufacture poly-
Alkylene oxides fundamental mode nonionic surfactant, owing to can become the addition mole of the alkylene oxide of hydrophilic group by suitably adjustment
Number and at random control Hydrophilic-Lipophilic Balance (HLB), be therefore widely used in washing, emulsify, the various uses such as dispersion.
As the preparation of this alkylene oxide addition product, there is the alkane using alkoxylate solid catalyst, particularly alkali modification to process
Epoxide solid catalyst obtains the method for the reactant of alkylene oxide addition molal quantity narrowly distributing.But, exist and ask as follows
Topic: when using solid catalyst, generates the by-product such as high molecular weight polyethylene glycol of weight average molecular weight more than 10,000 in reactant liquor
Thing, become using as the alkylene oxide addition product of object separate from solid catalyst time troublesome reason.Specifically, deposit
In following problem: filter cloth mesh blocking when solid catalyst filtration being separated, alkylene oxide addition product are mixed into and separate discarded " giving up
Filter cake " resulted in yield reduce, muddy etc. as the alkylene oxide addition product of object produces, need to solve these classes
Topic.
For above-mentioned problem, carry out the separation of catalyst and the method for removing well as efficiency, it is proposed that make as cohesion
The method (patent document 1) that the acrylic acid series polymeric compounds of accelerator contacts with alkylene oxide addition crude product with water.By making pair
The PAG cohesion produced so that it is the method separating with alkoxylate solid catalyst and removing.But, the method
For the crude product that the by-product amount addition molal quantity many, alkylene oxide of HMW PAG is high, filterability is also
Not necessarily abundant, and there is the shortcoming such as the increase of discarded object, cost increase.
It addition, disclose pH and the method (patent document 2) of amount of moisture adjusting alkylene oxide addition crude product.But,
In the method, also having to filter needs long period, the discarded problem filtering filter cake amount many etc. not yet to solve.
Prior art literature
Patent document 1: Japanese Patent Laid-Open 9-262456 publication
Patent document 2: International Publication 2008/078768
Summary of the invention
The problem that invention is to be solved
It is an object of the invention to provide the manufacture method of a kind of alkylene oxide addition product, this manufacture method is using alkoxylate use
Solid catalyst manufactures in the method for alkylene oxide addition product, it is possible to effectively by the PAG of catalyst and by-product from ring
Oxygen alkane addition product separates and removes.
For the method solving problem
The present inventor etc. are repeated further investigation, it was found that alkoxylate solid catalyst will used to obtain
Alkylene oxide addition crude product adds organic carboxylic acid aqueous solution on the basis of heating, after cooling, when suitably adjusting amount of moisture, Gu
Body catalyst and PAG are effectively formed condensation product, thus complete the present invention.
That is, the present invention provides the manufacture method of a kind of alkylene oxide addition product, comprising: (A) limit keeps the temperature at 90 DEG C
Above and less than 130 DEG C, while to by the presence of alkoxylate solid catalyst at the compound containing reactive hydrogen and/or
Addition alkylene oxide on fatty acid alkyl esters and the alkylene oxide addition crude product that obtains adds organic carboxylic acid aqueous solution, by 5 mass
The operation that %, pH when measuring at 25 DEG C adjust to 5～7, and
(B) then, the amount of moisture adjusting the alkylene oxide addition crude product to more than 50 DEG C less than 80 DEG C is adjusted to 8 mass
Operation below more than % 12 mass %.
The effect of invention
In accordance with the invention it is possible to make solid catalyst and PAG accessory substance, easily and efficiency adds from alkylene oxide well
Become in thing and separate and remove.It is as a result, it is possible to cut down the amount of the alkylene oxide addition product being mixed in discarded object, and therefore alkylene oxide adds
The yield becoming thing uprises.Meanwhile, it is capable to obtain solid catalyst and the polyalkylene of residual in obtained alkylene oxide addition product
The amount of glycol high alkylene oxide addition product few, clarification.
Detailed description of the invention
Operation (A)
In the presence of alkoxylate solid catalyst, to the compound containing reactive hydrogen and/or fatty acid alkyl esters addition epoxy
Alkane makes it react and obtains alkylene oxide addition crude product.
(alkoxylate solid catalyst)
As " alkoxylate solid catalyst " that the present invention uses, such as, the oxygen of interpolation metal ion can be listed
Change magnesium (Japanese Patent Laid-fair 6-15038 publication, Japanese Patent Laid-Open 7-227540 publication, Japanese Patent Laid-Open
Flat 6-198169 publication, Japanese Patent Laid-Open 6-182206 publication, Japanese Patent Laid-Open 5-170688 publication),
Calcined hydrotalcite (Japanese Patent Laid-Open 2-71841 publication), aluminum magnesium hydroxide calcining matter (Japanese Patent Laid-Open
8-268919 publication) etc. the alkoxylate solid catalyst of Al-Mg Containing Oxide Catalyst etc..Above-mentioned catalyst is also
Can be processed by alkali modification and carry out surface modification (Japanese Patent Laid-Open 8-169860 publication, Japanese Patent Laid-Open
8-169861 publication).Particularly, if the catalyst using alkali modification to process reacts, then the unreacted fat of remaining
The amount of fat acid alkyl ester is few, it is possible to obtain the product that alkylene oxide addition molal quantity distributed pole is narrow.In the present invention, it is preferred to make
The catalyst of surface modification has been carried out with being processed by alkali modification by aluminum magnesium hydroxide calcining matter.
As aforementioned aluminum magnesium hydroxide calcining matter, it is not particularly limited, suitably can select according to purpose, such as, can arrange
Enumerate the material described in Japanese Patent Laid-Open 8-268919 publication.Specifically, the aluminium-magnesium shown in following formula (I)
Metal composite oxide meets, and it can be obtained by the co-precipitation thing roasting by aluminium hydroxide and magnesium hydroxide.
nMgO·Al2O3·mH2O (I)
In formula (I), n and m is positive number, and there is no particular limitation, but n is preferably 1～3, particularly about 2.5 Ke Te
It is not preferably by.M suitably can select according to purpose.
In the roasting condition of catalyst, sintering temperature suitably can select according to purpose, but from playing catalyst activity and pressing down
From the viewpoint of the growing amount of accessory substance processed, preferably 400～950 DEG C, more preferably 800～900 DEG C.Roasting time can
Suitably to select, but when carrying out roasting in aforesaid scope, usually 2～4 hours.
If sintering temperature is too low, then exist can not play catalyst activity, accessory substance generate the many problem of quantitative change.
On the other hand, if sintering temperature is too high, then there are the following problems: owing to being produced caused catalyst granules by caking
Specific surface area is few, aluminium and the composite oxides recurring structure change of magnesium, therefore relevant to the ring-opening polymerization of alkylene oxide
Catalyst acid point is few, reactivity reduces.
That is, from the point of view of guaranteeing reactivity height, reducing amount of by-products the two viewpoint, the roasting condition expectation of catalyst is carried out
Appropriate managerial.At this point it is possible to using the specific surface area of catalyst granules as the index of process management.Other also have based on ammonia
The strength detection of the surface acid point of absorption method etc., the survey of spinel degree based on the crystallographic structural analysis utilizing X-ray diffraction
Fixed is also effective index.
During using specific surface area as the index of catalyst proterties, it is possible to use with BET surface area determinator (bavin field science device
Tool Industrial Co., Ltd, surface area determination unit SA-1000 etc.) value that measures, the specific surface area of catalyst granules is preferably
100～200m2/g。
Particle diameter for catalyst granules is not particularly limited, and usually as average grain diameter, is the scope of 10～1000 μm.
The average grain diameter of catalyst refers to use laser scattering type particle size distribution device LA-920(HORIBA strain formula meeting
Society manufacture), be measured using acetonitrile as decentralized medium, the value calculated as median diameter.
It addition, as being processed the catalyst that aforementioned aluminum magnesium hydroxide calcining matter is carried out surfaction by alkali modification, do not have
Limit especially, can suitably select according to purpose, such as, aforesaid Japanese Patent Laid-Open 8-169860 can be listed
Material etc. number described in publication, Japanese Patent Laid-Open 8-169861 publication.Specifically, can be by aforementioned hydroxide
Magnalium calcining matter metal hydroxides or metal alkoxide carry out surface modification, make modified aluminium hydroxide magnesium calcining matter and urge
Agent.As the hydroxide of aforementioned metal hydroxide, preferably alkali metal or alkaline-earth metal, wherein, more preferably hydrogen
Sodium oxide molybdena, potassium hydroxide.As the alkoxide of aforementioned metal alkoxide, preferably alkali metal or alkaline-earth metal, wherein, more preferably
For sodium alkoxide, potassium alcoholate.The carbon number of alkoxide is preferably 1～4.
Alkali modification is processed and can be carried out by following method: such as, by catalyst alkali metal or the hydroxide of alkaline-earth metal
After thing or alkoxide are modified, the method used as anti-applications catalyst；In alkoxylate reactor, by raw material
Fatty acid alkyl esters and metal hydroxides or metal alkoxide mix, and carry out the method etc. of catalyst modification in the feed.That is,
Alkali modification processes and can carry out when preparing catalyst, it is also possible to carry out by adding alkali when addition reaction.
Above-mentioned catalytic agent can be used alone one, it is also possible to and with two or more.
The particle diameter of catalyst is not particularly limited, generally, when alkylene oxide addition reaction, inside such as catalyst granules
The accumulation of reaction heat or the generation of high-molecular weight by-products, the generation of pressure differential drastically, machinery based on stirring vane etc.
Shearing, make catalyst granules be disintegrated, therefore the particle diameter of catalyst can change.
And then, the most as described later, in order to improve the activity of catalyst, by adding polyalcohol in reactant mixture
And make catalyst fine further.Therefore, for the particle diameter of catalyst contained in reacted crude product, as averagely
Particle diameter can be such as 0.1 μm～500 μm.
As the consumption of Above-mentioned catalytic agent, as long as the amount that reaction can suitably be carried out, then it is not particularly limited, can basis
The activity etc. of the catalyst used suitably selects, relative to previous reaction raw material (fatty acid alkyl esters and alkylene oxide)
Gross mass, preferably 0.01～5 mass %, more preferably 0.03～1 mass %, particularly preferably 0.05～0.2 mass %.
By making the consumption of catalyst be aforementioned preferred scope such that it is able to make reaction suitably carry out.
(compound containing reactive hydrogen)
In the present invention, as the compound containing reactive hydrogen, it is not particularly limited, suitably can select according to purpose, example
As, alcohol, amine, acid amides, phenol and derivative thereof, mercaptan and derivative etc. thereof can be listed.In these, preferably alcohol, more
It is preferably the alcohol represented by following formula (1).
R1OH (1)
In formula (1), R1It is not particularly limited, suitably can select according to the performance etc. required by the product to be obtained
Select, such as, straight or branched alkyl, straight or branched thiazolinyl etc. can be listed.R1Carbon number it is not also specifically limited,
Suitably can select according to purpose, preferably 1～40, more preferably 3～30, particularly preferably 6～22.
As the object lesson of alcohol, can list n-octyl alcohol, Decanol, n-dodecane alcohol, tetradecanol, positive hexadecanol,
It is former that positive octadecyl alcolol, oleyl alcohol, eicosanol (Eicosanol), docosyl alcohol, nonyl alcohol, tip-nip, tridecanol etc. have carbon
The higher aliphatic primary alcohol of the saturated or undersaturated straight chained alkyl of subnumber 8～22；2-Ethylhexyl Alcohol, carbon number 16～36
The branched alkyl primary alconol such as gerber special type alcohol；With secondary alcohol such as sec-n-octyl alcohol, 2-decyl alcohol, 2-dodecanols；Further, benzylalcohol etc..
As the object lesson of amine, octylame, dioctylamine, lauryl amine, dilaurylamine (DLA), stearylamine, distearyl amine can be listed
Primary or secondary amine etc. the saturated or unsaturated alkyl with carbon number 8～24；The polyamines such as ethylenediamine, diethylenetriamine etc..
As the object lesson of acid amides, the carbon number such as lauric monoethanolamide, lauric acid diethyl amide can be listed
The alkanolamide of 12～18.
In these compounds containing reactive hydrogen, preferably the straight or branched of carbon number 8～22 is saturated or undersaturated
Alcohol.
(fatty acid alkyl esters)
In the present invention, as fatty acid alkyl esters, it is not particularly limited, suitably can select according to purpose.Aforementioned
Fatty acid ester represents with following formula (2):
R2COOR3(2)
In formula, R2And R3For straight or branched alkyl or straight or branched thiazolinyl.
R2Carbon number, the most preferably 1～40, more preferably 3～30, particularly preferably 5～21.R3Carbon former
Subnumber, the most preferably 1～30, more preferably 1～10, particularly preferably 1～4.
Fatty acid alkyl esters can be used alone one, it is also possible to and with two or more.As fatty acid alkyl esters, it is also possible to
Use the triglycerides of the fatty acid ester as glycerine.
The consumption of fatty acid alkyl esters is not particularly limited, can be according to the product amount to be obtained, catalyst or ring described later
The consumption of oxygen alkane etc. and suitably select.
(alkylene oxide)
As the alkylene oxide used in the present invention, as long as can be with the aforementioned compound containing reactive hydrogen and/or fatty acid alkyl esters
React and obtain the material of alkylene oxide addition product, be just not particularly limited, suitably can select according to purpose, but the most preferred
Alkylene oxide for carbon number 2～4.Specifically, it is possible to use oxirane, expoxy propane, epoxy butane etc., this
Can use in the way of the mixture of one or two or more kinds a bit.
(alkylene oxide addition crude product)
In the present invention, the most every 1 mole containing the compound of reactive hydrogen and/or the fatty acid alkyl esters addition ring of 1～50 mole
Oxygen alkane person, the more preferably addition alkylene oxide person of 3～30 moles, the ring of the alkylene oxide of particularly preferred addition 5～20 moles
Oxygen alkane.When alkylene oxide addition product is nonionic surfactant, preferably there is its HLB(lattice Lifei's method) become 3～20
The material of structure.
The consumption of aforementioned epoxy alkane is not particularly limited, can according to use aforementioned fatty acids Arrcostab kind, be intended to obtain
The performance required by product etc. suitably select, but relative to the consumption of 1 mole of aforementioned fatty acids Arrcostab, preferably 1～
50 moles, more preferably 3～30 moles, particularly preferably 5～20 moles.
(any composition that can use in the addition reaction of operation (A))
The reaction of operation (A) can also be added low molecular polylol and carry out.By low molecular polylol is added reactant
In system, catalyst fine, the effect of its activity raising can be obtained.
As foregoing polyols, as long as there are more than 2 hydroxyls in intramolecular and be obtained in that miniaturization Above-mentioned catalytic agent is imitated
The material of fruit, then be not particularly limited, for example, it is possible to according to purpose from emulsifying aforementioned fatty acids Arrcostab or divide
Dissipate in the compound of homogenization and suitably select, preferably glycerine, ethylene glycol, diethylene glycol etc..Among these, particularly preferably
Glycerine.Foregoing polyols can be used alone one, it is also possible to and with two or more.
The consumption of foregoing polyols is not particularly limited, and suitably can select according to purpose, but former relative to previous reaction
The gross mass of material (compound containing reactive hydrogen and/or fatty acid alkyl esters and alkylene oxide), preferably 0.02～0.5 mass %.
It addition, relative to the quality of Above-mentioned catalytic agent, preferably more than 1.0 times, more preferably more than 1.25 times.Polynary by making
The consumption of alcohol is the aforementioned scope being preferably, it is possible to rapidly and sufficiently by catalyst fine.
(the operation order of operation (A) and reaction condition)
Alkylene oxide addition crude product can be easily prepared by above-mentioned raw materials according to known operation order and reaction condition.Reaction
Temperature is preferably 80～230 DEG C, although reaction pressure also depends on reaction temperature, but preferably 0～2MPa, more preferably
0.2～0.8MPa, it is also possible under conditions of nitrogen dilutes, carry out alkylene oxide addition reaction as required.
Above-mentioned reaction such as can add the compound containing reactive hydrogen and/or fatty acid alkyl esters and alkoxylate in autoclave
With solid catalyst, in a nitrogen atmosphere, at the temperature, pressure condition of regulation, import alkylene oxide and carry out.
(interpolation of the organic carboxyl acid aqueous solution)
While the alkylene oxide addition crude product obtained in above-mentioned operation is maintained at more than 90 DEG C and the temperature of less than 130 DEG C, Bian Xiang
Wherein add organic carboxylic acid aqueous solution, 5 mass %, pH at 25 DEG C are adjusted to 5～7.In other words, by 5 mass %,
PH when measuring at 25 DEG C becomes the organic carboxyl acid aqueous solution of the amount of 5～7 and adds to crude product.The organic carboxyl acid aqueous solution
Organic carboxyl acid concentration does not limit, but preferably 3～20 mass %.
As organic carboxyl acid, preferably malic acid, lactic acid, citric acid, glycolic, acetic acid or their hydrate.More excellent
Elect malic acid, lactic acid, citric acid, glycolic, citric acid or their hydrate as.Most preferably citric acid or they
Hydrate.These acid can be used alone one, it is also possible to and with two or more.Although letting loose in any theory, but push away
Survey organic carboxyl acid to be adsorbed in solid catalyst and PAG accessory substance and form condensation product.
When adding organic carboxylic acid aqueous solution, the temperature of crude product is maintained at more than 90 DEG C less than 130 DEG C.It is preferably kept in
More than 100 DEG C less than 125 DEG C.If less than 90 DEG C, then discarded object amount increases.It is considered as owing to organic acid is at solid catalysis
The absorption of agent is insufficient.If more than 130 DEG C, then the vapour pressure of water uprises, and operability is deteriorated.That adds in crude product is organic
The temperature of carboxylic acid aqueous solution is not particularly limited.When adding the temperature organic carboxyl acid aqueous solution less than 90 DEG C, although crude product
Temperature temporarily reduces, even if the temperature of crude product is temporarily deviate from the scope of more than 90 DEG C less than 130 DEG C, to discarded object amount,
Operability does not has considerable influence yet.
Generally take 5～30 minutes, be preferably 10～20 minutes and the interpolation of the organic carboxyl acid aqueous solution is slightly produced to alkylene oxide addition
In thing.
If adding the pH of the crude product after organic carboxylic acid aqueous solution less than 5, then owing to organic carboxyl acid is in the absorption of solid catalyst
Insufficient, thus discarded object amount increases.In the case of pH is more than 7, owing to organic carboxyl acid is in the absorption of solid catalyst
The most insufficient, therefore discarded object amount increases.
After adding organic carboxylic acid aqueous solution, in order to crude product and organic carboxyl acid are uniformly mixed, although also depend on mixing speed,
But preferably carrying out the stirring of more than 5 minutes, preferred mixing time is 5 minutes～60 minutes.If mixing time is less than 5
Minute, then exist cannot be sufficiently mixed the organic carboxyl acid aqueous solution and the situation of alkylene oxide addition crude product, exist cannot by from
The heart separates the situation being sufficiently separated solid catalyst and PAG.On the other hand, when mixing time was more than 60 minutes,
More preferable mixing effect cannot be obtained, there is the unfavorable condition that required time extends.
Stirring can use tank diameter to carry out.About stirring condition, it is possible to use oar or screw, turbo blade or anchor formula leaf
The common agitating device such as sheet.Mixing speed arbitrarily can set under conditions of can carrying out all mixing, but be preferably with
The stirring required drive of per unit volume is calculated as 0.1～0.9kW/m3Scope.
During stirring the temperature of the mixture of the organic carboxyl acid aqueous solution and alkylene oxide addition crude product be maintained at more than 90 DEG C 130 DEG C with
Under.More preferably more than 100 DEG C less than 125 DEG C.
(operation (B))
Then, adjusting to the temperature of more than 50 DEG C less than 80 DEG C, preferably adjusting the temperature to more than 60 DEG C less than 75 DEG C
After degree, the amount of moisture of crude product is adjusted to more than 8 mass % 12 mass %.If in this temperature range, the most such as
Can cool down after reaching 80 DEG C, limit is continued cooling limit and is adjusted amount of moisture, it is also possible to after cooling reaches 80 DEG C, stops cooling so
Rear adjustment amount of moisture.
If temperature is less than 50 DEG C, then solid catalyst is insufficient with the formation of the condensation product of PAG is carried out, it is impossible to fill
Divide and remove solid catalyst and PAG, the problem that there is gonorrhoea.If it addition, temperature is more than 80 DEG C, then due to poly-
Aklylene glycol dissolves, and therefore cannot fully remove PAG from alkylene oxide addition product, cause gonorrhoea.
The time that the crude product of more than 90 DEG C less than 130 DEG C adjusts the temperature to more than 50 DEG C less than 80 DEG C limits the most especially
System.Usually 30～60 minutes.
Cooling can be carried out by being placed by crude product, it is also possible to is passed through cooling in sleeve pipe or inside coil in tank diameter
Water etc. and carry out.
Amount of moisture is below more than 8 mass % 12 mass %, more than preferably 9 mass % below 11 mass %.Amount of moisture is not
During foot 8 mass %, owing to not carrying out the cohesion of HMW PAG, it is impossible to fully divide from alkylene oxide addition product
From removing PAG, therefore turbidity deteriorates.If it addition, amount of moisture is more than 12 mass %, then due to polyalkylene two
Alcohol dissolves, and therefore cannot fully remove PAG from alkylene oxide addition product, cause gonorrhoea.
The amount of moisture being cooled to the crude product after the temperature of more than 50 DEG C less than 80 DEG C is usual less than 8 mass %.Therefore, moisture
The adjustment of amount is generally carried out by adding water in crude product.The water used in the present invention is not particularly limited, the most permissible
Use distilled water or ion exchange water.Amount of moisture generally takes 5～30 minutes, preferably within 10～20 minutes, is adjusted.
Amount of moisture in the present invention measures the alkylene oxide addition crude product liquid that can use after adding organic carboxylic acid aqueous solution, utilizes
Karl Fischer (Karl Fischer) method is tried to achieve by measuring moisture.As karl Fischer moisture meter, such as, can use flat
The AQV-7 etc. that natural pond Industry Co., Ltd manufactures.
(any operation)
After operation (B), by centrifugation or common filter operation, poly-by alkoxylate catalyst and by-product
The condensation product of aklylene glycol or its mixture separates from alkylene oxide addition product, removes from alkylene oxide addition product.All right
Before removing catalyst etc., alkylene oxide addition product is stirred.The temperature of alkylene oxide addition product now be preferably 30～
60 DEG C, more preferably 40～60 DEG C.Mixing time is preferably 10～120 minutes, more preferably 30～60 minutes.Stirring
Speed can arbitrarily can set under conditions of all mixing, but be preferably and be calculated as with the stirring required drive of per unit volume
0.1～0.9kW/m3Scope.Stirring can use the common agitating device of record relevant to operation (A).
The alkylene oxide addition product so obtained is clarification and homogeneous outward appearance.
The clarification of alkylene oxide addition product can be evaluated by the turbidity at 50 DEG C.Turbidity can pass through integrating sphere type turbidity
Meter (SEP-PT-760D etc. of Mitsubishi chemical Co., Ltd) is measured.The unit of turbidity is ppm, clarifies, turbid
The numerical value of degree is the least.
Turbidity at 50 DEG C of obtained alkylene oxide addition product is preferably less than 2ppm, more preferably less than 1.5ppm, more
It is preferably less than 1ppm.If turbidity is more than 2ppm, the most visually can confirm that trace gonorrhoea, in allocating the products such as washing agent into
Time, there is the situation producing muddiness in product appearance.
It addition, the homogeneity of alkylene oxide addition product is with when being visually confirmed to be the outward appearance at 50 DEG C in putting into transparent vessel, show
For deposit-free or the state of floating material.If alkylene oxide addition product has sediment or floating material, then allocate the product of washing agent etc. into
Time in product, there is the situation of the problems such as the muddiness or the precipitation that produce product in product appearance.
In the case of separating based on common filter operation, use the double of such as cellulose and polyester preferably as filter paper
Metafiltration paper, wire mesh type filter etc., in decompression or add pressure, at temperature 35～100 DEG C, particularly 40～85 DEG C
Under the conditions of filter.Now, preferably by using filter aid to improve filterability.As filter aid, it is possible to use ability
Arbitrary filter aid known to field technique personnel, such as, as containing 80～95% principal component SiO2The silicon of noncrystalline silicic acid
Diatomaceous earth, include, for example out Radiolite100, Radiolite200, Radiolite500, Radiolite600,
Radiolite900, Zemlite Super(ゼ system ラ イ ト ス パ) M, Zemlite Super1, Zemlite Super
56、Zemlite Super2、Celite501、Celite503、Celite535、Celite545、Hyflo Super-Cel、Standard
Super-Cel, Filter-Cel etc..As containing about 70% principal component SiO2Alumina silicate, such as, can list Topco31,
Topco34 etc., as cellulose-based filter aid, can list KC FLOCK, SW40, BW20, BW40, BW100,
BW200, BNB20 etc., each can be individually or to use with the form of two or more mixtures.The consumption of filter aid is relative
It is preferably about 0.05～5 mass % in crude product, particularly preferably 0.1～2 mass %.
The temperature of crude product during filtration is preferably 40 DEG C～60 DEG C, more preferably more than 45 DEG C less than 55 DEG C.If temperature surpasses
Cross 60 DEG C, then high due to the dissolubility of the PAG relative to alkylene oxide addition product, therefore PAG cannot
It is sufficiently separated, there is the situation of obtained alkylene oxide addition product gonorrhoea.On the other hand, if temperature is less than 40 DEG C, then epoxy
The viscosity of alkane addition crude product uprises, it is impossible to fully carries out being separated off of solid catalyst and PAG, there is institute
The situation of the alkylene oxide addition product gonorrhoea obtained.
On the other hand, when using centrifugal separating device, the decanter type discharged continuously by the solid content of separation is preferably used
(decanter type) centrifugal separator.
Decanting centrifuge possesses that to make direction of rotation be one, has some speed differences and the outside rotating cylinder of High Rotation Speed
And conveying worm.Supply to the heavier agglomerate of proportion in the liquid to be treated within rotating cylinder, become attaching by centrifugal force
In the state of rotating cylinder inwall, the position separated with liquid component is scraped by conveying worm, is removed.
Decanting centrifuge has " vertical type ", " horizontal type " according to the setting direction difference of rotary body, permissible in the present invention
Use any one.It addition, as carrying out the mode of liquor charging in device, have liquor charging direction and a rotating body liquid moving direction
Identical " parallel type " and " to streaming " to reverse direction flowing, arbitrary form is the most separable.
As the example of decanting centrifuge, the BDN type etc. that Tomoe Engineering Co., Ltd. manufactures can be listed.
In centrifugal separation process, the temperature of crude product is preferably 40 DEG C～60 DEG C, more preferably more than 45 DEG C less than 55 DEG C.
If temperature is more than 60 DEG C, then high due to the dissolubility of the PAG relative to alkylene oxide addition product, therefore poly-Asia
Alkyl diol cannot be sufficiently separated, and there is the situation of obtained alkylene oxide addition product gonorrhoea.On the other hand, if temperature is less than
40 DEG C, then the viscosity of alkylene oxide addition crude product uprises, it is impossible to fully carry out the separation of solid catalyst and PAG
Remove, there is the situation of obtained alkylene oxide addition product gonorrhoea.
As the operating condition of decanting centrifuge, " centrifugal force " is preferably the scope of 1500G～3500G, more excellent
Elect 1500G～3000G as.If centrifugal force is too small, then cannot fully remove solid catalyst from alkylene oxide addition product and gather
The condensation product of alkylene oxide, exists in obtained alkylene oxide addition product gonorrhoea or separation liquid and is mixed into sedimentary situation.The opposing party
Face, when centrifugal force is excessive, presses strongly due to the condensation product of centrifugation and is attached to the inwall of rotating cylinder, therefore can not enter smoothly
The discharge of row condensation product based on conveying worm, exists in separation liquid and is mixed into sedimentary situation.
The rotary speed of the rotating cylinder of decanting centrifuge is preferred with the difference of the rotary speed of conveying worm i.e. " differential "
It is the scope of 5～20rpm, more preferably 10～the scope of 15rpm.If differential is too small, then owing to separating in rotating cylinder
Holdup time of solid content elongated, in rotating cylinder, solid content becomes big relative to the ratio separating liquid, therefore exists and separates liquid
In be mixed into sedimentary situation.
On the other hand, if differential is excessive, then the holdup time of the solid content owing to separating in rotating cylinder shortens, and therefore separates
The liquid holdup of solid content uprise, there is the situation that the amount of discarded object increases.
In separation of solid and liquid based on decanting centrifuge, in the case of being mixed into bubble in alkylene oxide addition product, also may be used
With additional " bubble removal step " by using defoaming device to be removed bubble.As defoaming device, vacuum can be selected to take off
The various devices such as bubble machine, pressure defoaming machine, stirring deaeration machine, centrifugal defoaming machine.Particularly, horizontal field makes made ASP
The deaeration pumps such as type, from the viewpoint of can carrying out continuous print process and can being also used as shifting pump, are preferred in the present invention.
Embodiment
It is exemplified below out embodiment and comparative example specifically describes the present invention, but the present invention is not by any limit of these embodiments
Fixed.
(preparation of catalyst)
Use tunnel oven at 880 DEG C, spend 3 hours to by 2.5MgO Al as roasting band by the time2O3·mH2O
The aluminum magnesium hydroxide (Kyowa Chemical Industry Co., Ltd manufactures, Kyoward300) of chemical composition carries out roasting, obtains magnesium
Aluminum composite metal oxide catalyst fines.
Embodiment 1
(operation (A))
Methyl laurate (Lion Chemical(ラ イ オ Application ケ ミ カ Le) strain formula meeting is added in 15kL stirred tank
Society manufactures, PASTELL M12) 1840kg, (Lion Chemical Co., Ltd. manufactures methyl myristate, PASTELL
M14) 660kg, O composite metallic oxide catalyst 10kg prepared above, relative as the glycerine 12.5kg(of polyalcohol
Total amount in methyl laurate and methyl myristate is 0.5 weight %), it is subsequently adding potassium hydroxide 0.5kg, stirs 10
Minute, the alkali modification carrying out catalyst processes.
Afterwards, limit stirring mixing, while to carrying out nitrogen displacement in reactive tank, till being heated up to 100 DEG C, at below 1.3kPa
Reduced pressure under carry out 30 minutes dehydration.
Then, till being heated up to 180 DEG C, under conditions of upper pressure limit value is 0.49MPa, oxirane 7480kg is imported
(15 times moles of fatty acid methyl ester).
After carrying out the slaking reaction of 0.5 hour further, till being cooled to 80 DEG C, obtain ethyleneoxide addition crude product (ring
Oxidative ethane average addition molal quantity=15) 10000kg.In this crude product, containing polyethylene glycol 0.9 weight as accessory substance
Amount %.
It addition, oxirane average addition molal quantity by high performance liquid chromatography (HPLC) method measure (condition determination post:
GL Sciences (ジ エ Le サ イ エ Application ス) Co., Ltd. manufactures Intersil C8(particle diameter 5 μm, internal diameter 4.6mm × length
Degree 250mm), mobile phase: acetonitrile/water (volume ratio 60/40) 1mL/ minute, (the strain formula meeting of differential refraction rate detector
Community day, vertical making was manufactured, L-7490), column temperature: 15 DEG C, injection rate: 200 μ L).
(survey it addition, the concentration of accessory substance polyethylene glycol contained in crude product is measured by gel permeation chromatography (GPC) method
Fixed condition post: Shodex Co., Ltd. manufactures GF-310HQ, mobile phase: acetonitrile/water (volume ratio 45/55) 1mL/ divides
Clock, differential refraction rate detector (Shimadzu Scisakusho Ltd manufactures, RID-6A), column temperature: 30 DEG C), inject
Amount: 200 μ L).
Separately, citric acid monohydrate compound 11kg is dissolved in purified water 121kg of normal temperature, prepares citric acid monohydrate compound
The aqueous solution.
Crude product 9000kg obtained above is added in 15kL tank diameter, is heated up to 120 DEG C while stirring.By interior for stirring
The temperature of crude product be maintained at 120 DEG C, limit stirring (the stirring required drive of per unit volume: about 0.5kw/m3) limit exists
The citric acid monohydrate compound aqueous solution is added in 10 minutes.The interpolation of the citric acid monohydrate compound aqueous solution just complete after crude product
Temperature is 118 DEG C.From tank diameter, choose a small amount of crude product, be diluted with water to 20 times (5 weight %), survey at 25 DEG C
Determine pH.PH is 5.8.
After crude product in tank diameter is heated up to 120 DEG C, while temperature to be controlled the scope at 120 ± 2 DEG C, while carry out 10
Minute stirring.
(operation (B))
After this, aforementioned crude product is cooled to 70 DEG C.It is added to purified water 879kg of normal temperature, makes crude product
Amount of moisture is 10%.
Then, till being cooled to 50 DEG C after, while temperature to be held in 50 DEG C, while carry out 60 points with oblique leaf paddle stirring vane
Clock stirring (the stirring required drive of per unit volume: about 0.5kw/m3).Thus, polyethylene glycol and the catalysis of accessory substance are made
Agent cohesion forms solid content and is dispersed in crude product.
From above-mentioned crude product, remove polyethylene glycol by centrifugation and catalyst cohesion forms solid content.
Specifically, the crude product of 50 DEG C obtained in operation (B) is extremely settled with the flow velocity supply of every 1 hour 1000kg
In formula centrifugal separator (Tomoe Engineering Co., Ltd.'s BDN-34 type, the radius of rotating cylinder: 0.18m).Make the rotation of rotating cylinder
Revolution is 3250rpm(centrifugal separating effect: 2100G), making rotating cylinder is 15rpm with the differential of conveying worm.Pass through
It is centrifuged crude product under this condition separating, thus is divided into solid content and separates liquid, discharge from whizzer respectively.
Use deaeration pump (Co., Ltd. Yokota Seisakusho ASP-0310S), with the processing speed pair of every 1 hour 10000kg
Separation liquid from centrifugal separator carries out deaeration continuously and processes, and removes and separates bubble contained in liquid, obtains highly finished product (ring
The water dilution product of oxidative ethane addition product) 9790kg(yield 97.9%).
The weight of the solid content (condensation product containing solid catalyst and polyethylene glycol and moisture) separated with centrifugal separator is
210kg.The solid content (discarded object) separated is 2.1% relative to the weight ratio of obtained highly finished product.
Highly finished product are precipitation, the floating materials etc. not being visually observed, and confirm as homogeneous.It addition, highly finished product are at 50 DEG C
Turbidity be 0.1ppm, confirm as clarification.
Embodiment 2～embodiment 5
Operation (A) substitutes citric acid, uses glycolic, malic acid, lactic acid or acetic acid respectively, in addition, with reality
Execute example 1 similarly to carry out.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 6～embodiment 7
The temperature of crude product when adding citric acid in operation (A) is set to 90 DEG C, 130 DEG C, in addition, with embodiment
1 is similarly carried out.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 8～embodiment 9
PH in operation (A) is adjusted to 5.0,7.0, in addition, carries out similarly to Example 1.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 10～embodiment 11
Amount of moisture in operation (B) is adjusted to 8%, 12% respectively, in addition, carries out similarly to Example 1.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 12～embodiment 13
The temperature of crude product when adding water in operation (B) is set to 50 DEG C, 130 DEG C, in addition, according to embodiment 1
Carry out.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 14～embodiment 15
The temperature of crude product when adding citric acid in operation (A) is set to 90 DEG C, by amount of moisture in operation (B) respectively
It is adjusted to 8%, 12%, in addition, carries out similarly to Example 1.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 16
The temperature of crude product when adding citric acid in operation (A) is set to 130 DEG C, pH be set to 5.0, by operation (B)
Middle amount of moisture is adjusted to 8%, in addition, carries out similarly to Example 1.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 17
Operation (B) substitutes citric acid and adds lactic acid, pH is set to 5.0, amount of moisture in operation (B) is adjusted to 12%,
In addition, carry out similarly to Example 1.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Embodiment 18
Operation (A) substitutes citric acid at 90 DEG C, adds lactic acid, pH is set to 7.0, by amount of moisture in operation (B)
Adjust to 8%, in addition, carry out according to embodiment 1.Similarly to Example 1, in obtained alkylene oxide addition product
The sediment that is not visually observed, floating material, turbidity is little, therefore confirms that homogeneity and clarification aspect at liquid do not have
Problematic.
Embodiment 19
Operation (A) substitutes citric acid at 90 DEG C, adds lactic acid, pH is set to 7.0, by amount of moisture in operation (B)
It is adjusted to 12%, adds at 50 DEG C, in addition, carry out similarly to Example 1.
Similarly to Example 1, the sediment that is not visually observed in obtained alkylene oxide addition product, floating material, turbid
Spend little, therefore confirm that homogeneity and clarification aspect at liquid are no problem.
Comparative example 1
The temperature adding citric acid in operation (A) is set to 80 DEG C, in addition, carries out similarly to Example 1.
Although turbidity obtains clarification less than 1.5ppm, but discarded object amount relative to obtained highly finished product be 3.0 weight % with
On.
Comparative example 2～comparative example 3
PH in operation (B) is set to 4.0,8.0, in addition, carries out similarly to Example 1.
The turbidity of each comparative example all more than 5ppm, gonorrhoea and cannot obtain clarification, discarded object amount is also relative to obtained
Highly finished product be more than 3.0 weight %.
Comparative example 4
In operation (A), substitute organic carboxyl acid and use hydrochloric acid, in addition, carry out similarly to Example 1.
Turbidity is more than 2ppm, it is impossible to obtain clarification, discarded object amount also relative to obtained highly finished product be 2.5 weight % with
On.
Comparative example 5～comparative example 6
Amount of moisture in operation (B) is adjusted to 5%, 15% respectively, in addition, carries out similarly to Example 1.
Turbidity all more than 5ppm, gonorrhoea and cannot obtain clarification, discarded object amount also relative to obtained highly finished product is
More than 2.5 weight %.
PH is to be 5 weight % with ion exchange water by the concentration dilution of alkylene oxide addition product, utilizes pH meter (east at 25 DEG C
Sub-DKK(デ ィ ケ ケ) Co., Ltd., HM-30V) measure.
Moisture is to utilize karl Fischer moisture meter (Ping Zhao Industry Co., Ltd, AQV-7) to measure.
Alkylene oxide addition product (highly finished product) obtained by utilizing turbidity (unit: ppm) at 50 DEG C to evaluate clarification.
Turbidity is the least, clarification the highest, solid catalyst, PAG separation good.The mensuration of turbidity is to utilize integration
Ball nephelometer (Mitsubishi chemical Co., Ltd SEP-PT-760D) carries out the judgement of following 5 grades.
◎ ◎: turbidity is less than 1ppm
◎: more than turbidity 1ppm, less than 1.5ppm
Zero: more than turbidity 1.5ppm, less than 2ppm
△: more than turbidity 2ppm, less than 5ppm
×: more than turbidity 5ppm
" centrifugal force " of centrifugal separation process is to be calculated by following numerical expression.
Centrifugal force (G)=(π2×R×N2)/(900 × g)
π: pi
The inside radius (m) of R: rotating cylinder
The rotation number (rpm) of N: rotating cylinder
G: acceleration of gravity (m/s2)
The evaluation of manufacturing is to represent with the productivity of obtained alkylene oxide addition product (highly finished product), carries out following 4 grades
Judge.
◎: more than productivity 97.7wt%
Zero: more than productivity 97.5wt%, less than 97.7wt%
△: more than productivity 97wt%, less than 97.5wt%
×: productivity is less than 97wt%
Embodiment is shown in table 1, table 2, and comparative example is shown in table 3.
Claims (6)
1. a manufacture method for alkylene oxide addition product, comprising:
(A) limit keeps the temperature at more than 90 DEG C and less than 130 DEG C, while to by alkoxylate solid
In the presence of catalyst on the compound containing reactive hydrogen and/or fatty acid alkyl esters addition alkylene oxide and obtain
Alkylene oxide addition crude product adds the operation of organic carboxylic acid aqueous solution,
Choose the alkylene oxide addition crude product being added with the organic carboxyl acid aqueous solution in a small amount of described operation (A)
Solution, the pH when solution of the concentration gained being diluted with water to 5 mass % measures at 25 DEG C is 5～7, with
And
(B) then, the amount of moisture adjusting the alkylene oxide addition crude product to more than 50 DEG C less than 80 DEG C is adjusted
Operation below 12 mass % more than 8 mass %.
Manufacture method the most according to claim 1, wherein, in operation (A), by alkylene oxide addition
The temperature of crude product is maintained at more than 100 DEG C less than 125 DEG C.
Manufacture method the most according to claim 1 and 2, wherein, organic carboxyl acid be selected from malic acid,
At least one in the group that lactic acid, citric acid, glycolic and their hydrate are formed.
Manufacture method the most according to claim 1 and 2, wherein, in operation (B), by alkylene oxide
The temperature of addition crude product adjusts to more than 60 DEG C less than 75 DEG C.
Manufacture method the most according to claim 1 and 2, wherein, in operation (B), by adding
Water, adjusts the amount of moisture of alkylene oxide addition crude product to more than 8 mass % 12 mass %.
The manufacture method of alkylene oxide addition product the most according to claim 1 and 2, wherein, at operation (B)
Afterwards, farther include alkylene oxide addition product centrifugation or the operation of filtration.
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| JP2011-250565 | 2011-11-16 | ||
| JP2011250565A JP5711648B2 (en) | 2011-11-16 | 2011-11-16 | Method for producing alkylene oxide adduct |
| PCT/JP2012/079779 WO2013073665A1 (en) | 2011-11-16 | 2012-11-16 | Method for producing alkylene oxide adduct |
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| KR (1) | KR101982367B1 (en) |
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| JP6403325B2 (en) * | 2014-12-26 | 2018-10-10 | ライオン株式会社 | Process for producing fatty acid alkyl ester alkoxylate |
| JP6935059B2 (en) * | 2017-03-30 | 2021-09-15 | 日油株式会社 | A method for purifying polyethylene glycol having one carboxyl group |
| JP6978369B2 (en) * | 2018-03-30 | 2021-12-08 | 株式会社カネカ | Method for manufacturing polyether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0826715A1 (en) * | 1995-03-28 | 1998-03-04 | Lion Corporation | Method for producing an alkylene oxide adduct of a compound having one more active hydrogen |
| CN1759134A (en) * | 2003-02-21 | 2006-04-12 | 拜尔材料科学有限责任公司 | Amine-initiated polyether polyols and a process for their production |
| WO2008078768A1 (en) * | 2006-12-27 | 2008-07-03 | Lion Corporation | Process for production of alkylene oxide adduct |
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| JPS56112931A (en) * | 1980-02-12 | 1981-09-05 | Sanyo Chem Ind Ltd | Polyol composition |
| JP3550248B2 (en) | 1996-03-28 | 2004-08-04 | ライオン株式会社 | Purification method of nonionic surfactant |
| JP2005187415A (en) * | 2003-12-26 | 2005-07-14 | Lion Corp | Fatty acid polyoxyalkylenealkyl ether and method for producing the same |
| JP2005314617A (en) * | 2004-04-30 | 2005-11-10 | Sanyo Chem Ind Ltd | Method for purifying polyether |
| KR101138885B1 (en) | 2007-02-24 | 2012-05-15 | 삼성전자주식회사 | Washing machine door Lock control apparatus and method |
| JP2010006964A (en) * | 2008-06-27 | 2010-01-14 | Lion Corp | Method of producing alkylene oxide addition product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0826715A1 (en) * | 1995-03-28 | 1998-03-04 | Lion Corporation | Method for producing an alkylene oxide adduct of a compound having one more active hydrogen |
| CN1759134A (en) * | 2003-02-21 | 2006-04-12 | 拜尔材料科学有限责任公司 | Amine-initiated polyether polyols and a process for their production |
| WO2008078768A1 (en) * | 2006-12-27 | 2008-07-03 | Lion Corporation | Process for production of alkylene oxide adduct |
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| TWI535756B (en) | 2016-06-01 |
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| WO2013073665A1 (en) | 2013-05-23 |
| KR101982367B1 (en) | 2019-08-28 |
| TW201333070A (en) | 2013-08-16 |
| JP5711648B2 (en) | 2015-05-07 |
| CN103874720A (en) | 2014-06-18 |
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