CN1861612A - Production process of solid alkylphosphonate - Google Patents
Production process of solid alkylphosphonate Download PDFInfo
- Publication number
- CN1861612A CN1861612A CN200610021129.6A CN200610021129A CN1861612A CN 1861612 A CN1861612 A CN 1861612A CN 200610021129 A CN200610021129 A CN 200610021129A CN 1861612 A CN1861612 A CN 1861612A
- Authority
- CN
- China
- Prior art keywords
- alkyl phosphate
- low
- carbon alcohol
- alkylphosphonate
- phosphoric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A process for preparing monoalkyl phosphate solid includes such steps as preparing raw liquid from industrial-pure monoalkyl phosphate and organic solvent, washing for removing acid, alkalizing to become salt, and distill drying.
Description
Technical field
The invention belongs to the production method of industrial surfactants such as a kind of daily chemicals and light industry, weaving.Particularly a kind of alkyl carbon atoms number that adopts is that 10～18 monoalkyl phosphoric acid esters is the raw material production high-purity C
10-C
18The method of solid alkylphosphonate.
Background technology
Alkylphosphonate is a kind of anion surfactant of excellent property, has characteristics such as easily wetting, acid-and base-resisting, and is good to the skin affinity, chemical ﹠ blended fabric is had excellent antistatic and smoothness, waste paper is had good deinking performance.Therefore, at household chemicals, be used widely in the industrial production such as chemical fibre, weaving, papermaking, plastics.But the alkylphosphonate product that generally adopts generally forms by the direct neutralization of monoalkyl phosphoric acid esters at present, and product form is emulsion, solid content 30～40%.From the thermodynamics angle, the emulsion state instability, very easily layering in storage and transportation, the storage and transport of liquid product are extremely inconvenient in addition, storage period is short, foreign matter content is higher relatively, is used for products productions such as makeup, skin care and then easily causes allergicly, thereby has greatly limited applying of it.At the not anti-storage of alkyl phosphate salt product emulsion, easy stratified defective, be that CN1634938A, denomination of invention are in the patent documentation of " a kind of preparation method of alkyl phosphate salt " at publication number, a kind of employing Fatty Alcohol(C12-C14 and C12-C18) and P are disclosed
2O
5Carrying out esterification carries out neutralization reaction and just makes the alkyl phosphate salt product emulsion to generate alkyl phosphate and then to add the alkali aqueous solution that contains carboxymethyl cellulose.Though this patented technology is by adding carboxymethyl cellulose in process of production improving the stability of emulsion, and technology is also simpler; Because its product still is an emulsion, though prolonged the stationary phase of product to a certain extent, but still can not overcome disadvantages such as product emulsion inherent poor stability, not anti-storage, transportation inconvenience, the material that is added still is retained in the emulsion in addition, not only influenced its purity, but also overslaugh its apply.
Summary of the invention
The objective of the invention is a kind of production method of producing solid alkylphosphonate of development research, realize the pulverulent solids alkylphosphonate of production high purity, good stability, conveniently storing, to transport and to satisfy the production requirement of products such as high-quality daily-use chemical industry, and purpose such as broadened application scope.
Solution of the present invention is to be main raw material with the pure monoalkyl phosphoric acid esters of general industry, after it is dissolved in organic solvent (or directly adopt solvent method manufacture order alkyl phosphate and without the slip of distillatory monoalkyl phosphoric acid esters and organic solvent) mix with the miscible fluid of water and low-carbon alcohol, standing demix, extract upper strata organic solution then; Miscible fluid with alkali and low-carbon alcohol adds in the organic solution that extracts again, its alkalinisation treatment is got alkylphosphonate paste throw out, through distill drying or in this paste throw out, add low-carbon alcohol, stir mixed after again with this slip distillation, it heats up in a steamer the back thing and is object solid phosphate ester product salt.Therefore, the inventive method comprises:
A, preparation raw material liquid: with the monoalkyl phosphoric acid esters raw material powder be dissolved in be mixed with stock liquid in the organic solvent or directly adopt solvent method manufacture order alkyl phosphate, the slip that contains organic solvent handled without distillation makes stock liquid; The weight ratio of alkyl phosphate and organic solvent is 1: 1～4;
B, washing deacidification: the mixing solutions of water or water and low-carbon alcohol is added in the stock liquid, fully mix back, standing demix, extract upper strata organic solution then; Wherein the weight ratio of water and alkyl phosphate is 1.5～2.5: 1, the weight ratio of low-carbon alcohol and alkyl phosphate is 0～2.5: 1;
C, quaternization: with alkali and low-carbon alcohol miscible after, under agitation condition, slowly add in the organic solution that the B operation is extracted, treat fully to react the paste throw out that after-filtration gets alkyl phosphate salt; In 4～6 hours reaction times, wherein: the mol ratio of alkali and alkyl phosphate is 1.8～2.4: 1, the weight ratio of low-carbon alcohol and alkyl phosphate is 0.8～1.2: 1;
D, distillation; It is dry or add low-carbon alcohol, send into distiller after stirring that C operation gained throw out is sent into distiller distillation, promptly gets solid alkylphosphonate after the distillation drying treatment; When adding low-carbon alcohol, the weight ratio of low-carbon alcohol and raw material alkyl phosphate is 0.1～1: 1.
Above-mentioned monoalkyl phosphoric acid esters raw material is that carbonatoms is 10～18 monoalkyl phosphoric acid esters, and the content of bisalkyl phosphate and residual fat alcohol, residual phosphoric acid is≤10wt% respectively in the raw material.And described organic solvent is C
5-C
18Aliphatic hydrocarbon or/and halohydrocarbon, aromatic hydrocarbons, ether.Described low-carbon alcohol is the Fatty Alcohol(C12-C14 and C12-C18) of carbonatoms≤4 that comprise ethanol, Virahol.At alkali described in the quaternization process is NaOH or KOH, ammoniacal liquor, organic amine.
The present invention is that raw material makes it be dissolved in the organic solvent or the direct intermediate product that adopts with solvent method manufacture order alkyl phosphate owing to adopting the technical pure monoalkyl phosphoric acid esters---without the monoalkyl phosphoric acid esters of distillation processing and the slip of organic solvent, make its generation be insoluble in the alkyl phosphate salt of organic solvent by washing and alkalinisation treatment, the alcohols impurity etc. that is dissolved in organic solvent is then removed with filtrate, at last by the distillation of paste alkyl phosphate salt is dry or add low-carbon alcohol, dry to take residual water and organic solvent out of through distilling again to it.Carry out synchronously and make highly purified Powdered alkylphosphonate product thereby make the manufacture order alkyl phosphate salt and purify.Thereby the present invention to have production technique easy, reliable, the purity of product is high and be pressed powder, can satisfy the requirement of products productions such as high-quality daily-use chemical industry; And both be convenient to store, transportation, have good stability, characteristics such as applied widely again.
Embodiment
Embodiment 1
A, preparation raw material liquid:, be dissolved in the 40ml normal hexane, and change in the separating funnel with technical pure onodoidecyl phosphonic acid ester 20g (wherein remaining acid and remaining pure content are respectively 4.2wt% and 1.5wt%);
B, washing deacidification: will add in the separating funnel, by the miscible fluid that 40ml water and 12ml Virahol are prepared, extract the upper strata organic solvent then through vibration, standing demix, stand-by;
C, quaternization: with concentration is that 70% potassium hydroxide aqueous solution and 30ml industrial alcohol are mixed with mixed solution and slowly drip in the organic solvent that is extracted by the B operation, reaction 5.5 hours under agitation condition, gets the paste throw out through suction filtration then;
D, distillation: in gained paste throw out, add the 6ml Virahol, stir after 15 minutes, send into and distill the dry 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium product 21.82g of getting in the distiller.
Products obtained therefrom its remaining acid and pure content after testing is respectively 0.37wt% and 0.5wt%.
Embodiment 2:
The A stock liquid is formulated by the single hexadecanyl phosphate 20g and the 38ml ether that contain remaining sour 3.8wt%, remaining pure 1.8wt%, places separating funnel;
B, washing deacidification: will add in the stock liquid by 35ml water and the formulated mixed solution of 10ml Virahol, behind vibration, standing demix, extract the upper strata organic solvent, stand-by;
C, quaternization: with concentration is that 70% potassium hydroxide aqueous solution 10g and 25ml ethanol are mixed with mixed solution and slowly are added dropwise to and extracts in the stand-by organic solvent, and reaction is after 5 hours under agitation condition, and suction filtration gets the paste throw out;
D, distillation drying: after in by C operation gained throw out, adding the 6ml Virahol and stirring 10 minutes, be drying to obtain the single hexadecanyl phosphate potassium of 20.75g product through distillation.
Products obtained therefrom is through check, and remaining acid and pure content are respectively 0.35wt% and 0.6wt%.
Embodiment 3:
A, employing contain remaining acid and the pure single octadecyl phosphoric acid ester 20g that is respectively 3.5wt% and 2.1wt% is dissolved in the mixed solution of 40ml normal hexane and toluene, also places separating funnel;
B, washing deacidification: 37ml water and 12ml alcoholic acid mixed solution are added in the stock liquid of being prepared by A, and all the other are identical with embodiment 1;
C, quaternization: with concentration be that 50% aqueous sodium hydroxide solution 9.2g and 28ml alcohol mixeding liquid slowly are added dropwise in B operation gained organic solvent, stirring reaction after 4.5 hours suction filtration get the paste throw out;
D, distillation are dry: the direct vacuum distillation drying of gained paste throw out, promptly get 19.118g list octadecyl phosphoric acid ester sodium product.
Through check, contain remaining acid in the product and alcohol is respectively 0.32wt% and 0.8wt%.
Embodiment 4:
A, present embodiment directly adopt the slip 50kg that handles without last distillation of solvent method manufacture order 1-isobutyl-3,5-dimethylhexylphosphoric acid to place in the retort of belt stirrer as stock liquid, contain in the feed liquid: onodoidecyl phosphonic acid ester 37.9wt%, organic solvent 58.3wt%, remaining sour 1.7wt%, remaining pure 2.1wt%;
B, washing deacidification: in the stock liquid in 38L water and the 13L alcoholic acid mixed solution adding retort, fully mix back, standing demix, extract upper strata organic solvent, stand-by then;
C, quaternization: with concentration is that 28% strong aqua 30kg and 28L alcohol mixeding liquid slowly add in the above-mentioned raw materials liquid, stirring reaction after 5 hours suction filtration get the paste throw out;
D, distillation: in gained paste throw out, add 10L ethanol, stirring after 25 minutes, through distilling the dry 19.224kg onodoidecyl phosphonic acid ester ammonia product salt that gets.
Remaining acid and pure content are respectively 0.30wt% and 0.8wt% in the check products obtained therefrom.
Claims (5)
1, a kind of production method of solid alkylphosphonate comprises:
A, preparation raw material liquid: with the monoalkyl phosphoric acid esters raw material powder be dissolved in be mixed with stock liquid in the organic solvent or directly adopt solvent method manufacture order alkyl phosphate, the slip that contains organic solvent handled without distillation makes stock liquid; The weight ratio of alkyl phosphate and organic solvent is 1: 1～4;
B, washing deacidification: the mixing solutions of water or water and low-carbon alcohol is added in the stock liquid, fully mix back, standing demix, extract upper strata organic solution then; Wherein the weight ratio of water and alkyl phosphate is 1.5～2.5: 1, the weight ratio of low-carbon alcohol and alkyl phosphate is 0～2.5: 1;
C, quaternization: with alkali and low-carbon alcohol miscible after, under agitation condition, slowly add in the organic solution that the B operation is extracted, treat fully to react the paste throw out that after-filtration gets alkyl phosphate salt; In 4～6 hours reaction times, wherein: the mol ratio of alkali and alkyl phosphate is 1.8～2.4: 1, the weight ratio of low-carbon alcohol and alkyl phosphate is 0.8～1.2: 1;
D, distillation: it is dry or add low-carbon alcohol, send into distiller after stirring that C operation gained throw out is sent into distiller distillation, promptly gets solid alkylphosphonate through the distillation drying treatment; When adding low-carbon alcohol, the weight ratio of low-carbon alcohol and raw material alkyl phosphate is 0.1～1: 1.
2, press the production method of the described solid alkylphosphonate of claim 1; It is characterized in that described monoalkyl phosphoric acid esters raw material is that carbonatoms is 10～18 monoalkyl phosphoric acid esters, in the raw material content of bisalkyl phosphate and residual fat alcohol, residual phosphoric acid respectively≤10wt%.
3, press the production method of the described solid monoalkyl phosphoric acid esters of claim 1; It is characterized in that described organic solvent is C
5-C
18Aliphatic hydrocarbon or/and halohydrocarbon, aromatic hydrocarbons, ether.
4, press the production method of the described solid alkylphosphonate of claim 1; It is characterized in that described low-carbon alcohol is the Fatty Alcohol(C12-C14 and C12-C18) of carbonatoms≤4 that comprise ethanol, Virahol.
5, press the production method of the described solid alkylphosphonate of claim 1; It is characterized in that described alkali is NaOH or KOH, ammoniacal liquor, organic amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100211296A CN1861612B (en) | 2006-06-09 | 2006-06-09 | Production process of solid alkylphosphonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100211296A CN1861612B (en) | 2006-06-09 | 2006-06-09 | Production process of solid alkylphosphonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1861612A true CN1861612A (en) | 2006-11-15 |
| CN1861612B CN1861612B (en) | 2011-06-01 |
Family
ID=37389154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100211296A Expired - Fee Related CN1861612B (en) | 2006-06-09 | 2006-06-09 | Production process of solid alkylphosphonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1861612B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450953B (en) * | 2008-12-30 | 2011-09-28 | 南京华狮化工有限公司 | Method for preparing monoalkyl phosphoric acid esters and salt thereof |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634938A (en) * | 2003-12-30 | 2005-07-06 | 中国石化上海石油化工股份有限公司 | Process for preparing alkyl phosphate |
-
2006
- 2006-06-09 CN CN2006100211296A patent/CN1861612B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450953B (en) * | 2008-12-30 | 2011-09-28 | 南京华狮化工有限公司 | Method for preparing monoalkyl phosphoric acid esters and salt thereof |
| CN109516623A (en) * | 2018-11-16 | 2019-03-26 | 浙江万盛股份有限公司 | A kind of method of comprehensive utilization of tri butylethyl phosphate waste water |
| CN109516623B (en) * | 2018-11-16 | 2021-06-01 | 浙江万盛股份有限公司 | Comprehensive utilization method of tributoxyethyl phosphate wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1861612B (en) | 2011-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11572418B2 (en) | Nanocellulose compositions and processes to produce same | |
| US11932706B2 (en) | Processes and apparatus for producing nanocellulose, and compositions and products produced therefrom | |
| US11827771B2 (en) | Oleophilic and hydrophobic nanocellulose materials | |
| WO2014113884A1 (en) | Process for isolating cellulose from cellulosic biomass, isolated cellulose of type i and composite materials comprising same | |
| WO2015200584A1 (en) | Processes for producing nanocellulose-lignin composite materials, and compositions obtained therefrom | |
| Uyar et al. | Electrospun polyethylene oxide (PEO) nanofibers containing cyclodextrin inclusion complex | |
| CA2996423A1 (en) | Nanocellulose production co-located at a pulp and paper mill | |
| US20200148843A1 (en) | Nanocellulose-reinforced cellulose fibers | |
| US20200140658A1 (en) | Hydrophobic nanocellulose-coated paper and paperboard | |
| CN1861612B (en) | Production process of solid alkylphosphonate | |
| Zhang et al. | Separation cellulose nanocrystals from microcrystalline cellulose using hydrated deep eutectic solvent and high shear force | |
| Wu et al. | Structural and rheological properties of nanocellulose with different polymorphs, nanocelluloses I and II, prepared by natural deep eutectic solvents from sugarcane bagasse | |
| Jančíková et al. | The role of deep eutectic solvents in the production of cellulose nanomaterials from biomass | |
| WO2016109479A1 (en) | Processes for producing pharmaceutical excipients from lignocellulosic biomass, and pharmaceutical excipients obtained therefrom | |
| CN106496337B (en) | The preparation method of microcrystalline cellulose | |
| CN1939926A (en) | Production of glyphosate by glycine method | |
| CN1490337A (en) | Superhigh viscosity carboxymethyl sodium starch and its preparation | |
| CN1884288B (en) | Process for manufacturing monoalkyl phosphate ester | |
| CN102046534B (en) | Process for continuous production of fibrous basic magnesium sulfate particle | |
| Yang | Manufacturing of nanocrystalline cellulose | |
| CN110092947A (en) | A kind of micro-nano cellulose compound, and its preparation method and application | |
| US11324830B2 (en) | Processes for producing pharmaceutical excipients from lignocellulosic biomass, and pharmaceutical excipients obtained therefrom | |
| Li et al. | Preparation of cellulose nanofibrils (CNF) with uniform diameter distribution from okara by ultrasonic and high-speed stirring treatment method using deep eutectic solvent | |
| CN107879944A (en) | A kind of method for preparing butyrobetaine | |
| Xia et al. | DEGRADATION AND STABILITY OF PULP TREATED IN HETEROGENEOUS AND HOMOGENEOUS PHASES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110601 Termination date: 20120609 |