CN101717498A - Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof - Google Patents
Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof Download PDFInfo
- Publication number
- CN101717498A CN101717498A CN200910250594A CN200910250594A CN101717498A CN 101717498 A CN101717498 A CN 101717498A CN 200910250594 A CN200910250594 A CN 200910250594A CN 200910250594 A CN200910250594 A CN 200910250594A CN 101717498 A CN101717498 A CN 101717498A
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- reaction
- concentration
- temperature
- solution
- 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.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a synthesis method of high-concentration polyepoxysuccinic acid and salt thereof. The method comprises the following main processes: simultaneously adding maleic anhydride and sodium hydrate into water in a mode of feeding in batches; controlling the pH value of solution at 5-7 and the reaction temperature at 40-60 DEG C; adding sodium tngstate into a hydrolysis product as expoxidation catalyst at 50-60 DEG C; carrying out expoxidation reaction by adding hydrogen peroxide; adding sodium hydrate solution at the same time; controlling the pH value at 4-7; finishing the expoxidation reaction; stirring; raising the temperature to above 80 DEG C; adding initiator calcium oxide; and after polymerization, lowering the temperature and filtering to obtain the polyepoxysuccinic acid and salt solution thereof. In the preparation method, a one-pot synthesis is adopted, and therefore, the preparation method has the advantages of simple and unique technology, high product concentration, high raw material conversion rate, ideal molecular weight distribution and favorable industrial operability.
Description
Technical field
But the present invention refers to a kind of synthetic method of high density poly-epoxy succinic acid and its esters (PESA) of suitability for industrialized production.
Background technology
Poly-epoxy succinic acid and its esters are emerging a kind of scale-inhibiting dispersion agent for water treatment nineties in last century, have favorable biological degradability, and be environmentally friendly, therefore is called as the green scale dispersion agent, and market outlook are good.This product also can be widely used in the daily use chemicals in the prescription such as articles for washing, toothpaste, substitutes the phosphorated compound.Its molecular formula is as follows:
(I) n represents the polymerization degree in the formula, the integer for 〉=2.M is H
+, Na
+, K
+, NH
4 +, Ca
2+, Mg
2+Or its mixture.
U.S. Pat 5028415 has been described the synthetic method of PESA, is about to neutralize with sodium hydroxide after the maleic anhydride hydrolysis, carries out epoxidation reaction simultaneously with hydrogen peroxide and sodium hydroxide solution again, and the gained epoxide is separated out with the acetone crystallization, carries out polymerization again.
Because have the problem that intermediate product solubleness is little, stir difficulty in the maleic anhydride hydrolytic process, therefore the epoxidation product concentration that obtains is low.When it is carried out crystallization, need to use a large amount of acetone, the recycling difficulty is difficult to carry out suitability for industrialized production.If the non-crystallizable direct polymerization of epoxide, resulting polymers concentration low (about 20% or lower) then need take other concentration method just can obtain the product of high density, and lower concentration polymerizable molecular amount distributes undesirablely, and scale inhibition effect is bad.
Summary of the invention
The technical problem to be solved in the present invention provides the synthetic method of high density poly-epoxy succinic acid and its esters, this method adopts one-pot synthesis, the reaction conditions gentleness, products therefrom concentration height, the feed stock conversion height, have the favorable industrial operability, avoided the difficulty of suitability for industrialized production in the prior art.Utilize technological process described in the invention, can produce the polymkeric substance shown in (I) easily, its distribution of polymerization degree is at the product of the arbitrary proportion of n 〉=2.
The technical problem to be solved in the present invention is realized by following scheme: the synthetic method of high density poly-epoxy succinic acid and its esters, with the maleic anhydride is starting raw material, through hydrolysis, epoxidation, polymerization, obtain desired product, it is characterized in that: simultaneously add in entry in the mode of batch charging maleic anhydride and sodium hydroxide, sodium hydroxide is 1.2～2 to the mol ratio of maleic anhydride, the pH value of control solution is 5～7,40～60 ℃ of temperature of reaction, under 50～60 ℃, in hydrolysate, add sodium wolframate as epoxidation catalyst, the molar weight of sodium wolframate is 0.001～0.1 of a maleic anhydride, 60～70 ℃ of controlled temperature, the hydrogen peroxide that adds concentration 27.5～50% carries out epoxidation reaction, the sodium hydroxide solution that adds concentration 25～50% simultaneously, the control pH value is 4～7, used hydrogen peroxide is 1～2 to the mol ratio of maleic anhydride, reaction times is 0.5～3 hour, epoxidation reaction finishes, remaining on 60～70 ℃ stirred 1～3 hour, be warmed up to more than 80 ℃, add initiator and carry out polyreaction, initiator is a calcium oxide, used molar weight is 0.02～0.2 of a maleic anhydride, the time of polyreaction is 2～4 hours, and temperature of reaction is 80～100 ℃, is more preferably 86～94 ℃, polyreaction finishes, cooling is filtered, and promptly obtains poly-epoxy succinic acid and saline solution thereof, and production concentration is 35～55%, feed stock conversion 95～100%, the may command polymerization degree 2～4 about 80～90%.As the more high-load product of needs, can be behind the product that present method is produced, utilize known method (as recrystallization, concentrate etc.) to purify or subsequent operations.
Advantage of the present invention is: this preparation method adopts one-pot synthesis, technology is simply unique, products therefrom concentration height (35～55%), feed stock conversion height (95～100%), molecular weight distribution ideal (the may command polymerization degree 2～4 about 80～90%) has the favorable industrial operability.
Description of drawings
Accompanying drawing 1 is the process flow sheet of this synthetic method
Embodiment
Embodiment:
5000 liters of reactors, band mechanical stirring, PH meter, heating jacket and refrigerated brine coil pipe are equipped with two header tanks.In reactor, squeeze into 1200 liters of deionized waters, in two hours, add maleic anhydride 1000kg and sodium hydroxide 600kg simultaneously uniformly, by 45 ℃ of refrigerated brine control reaction temperature.Added material back insulated and stirred 1 hour.When reaction solution is between 56 ℃, add the 60kg sodium wolframate, be warmed up to 68 ℃, begin to add 1400kg hydrogen peroxide (concentration 27.5%), the pH value that adds 40% sodium hydroxide solution control reaction solution simultaneously is 6.Adding the material back keeps stirring 2 hours under this temperature.Be warmed up to 86 ℃, add the 60kg calcium oxide, kept 3 hours at 90 ℃.Through cooling, filtration, obtain outward appearance near colourless poly-epoxy succinic acid and saline solution product 4400kg thereof, solid content 42.6%.Detect through HPLC, feed stock conversion 99.7%, various polymer contents are 24.4% (n=2), 33.6% (n=3), 30.7% (n=4), 10.6% (n 〉=5).
Claims (1)
1. the synthetic method of high density poly-epoxy succinic acid and its esters, with the maleic anhydride is starting raw material, through hydrolysis, epoxidation, polymerization, obtain desired product, it is characterized in that: simultaneously add in entry in the mode of batch charging maleic anhydride and sodium hydroxide, sodium hydroxide is 1.2～2 to the mol ratio of maleic anhydride, the pH value of control solution is 5～7,40～60 ℃ of temperature of reaction, under 50～60 ℃, in hydrolysate, add sodium wolframate as epoxidation catalyst, the molar weight of sodium wolframate is 0.001～0.1 of a maleic anhydride, 60～70 ℃ of controlled temperature, the hydrogen peroxide that adds concentration 27.5～50% carries out epoxidation reaction, the sodium hydroxide solution that adds concentration 25～50% simultaneously, the control pH value is 4～7, used hydrogen peroxide is 1～2 to the mol ratio of maleic anhydride, reaction times is 0.5～3 hour, epoxidation reaction finishes, remaining on 60～70 ℃ stirred 1～3 hour, be warmed up to more than 80 ℃, add initiator and carry out polyreaction, initiator is a calcium oxide, and used molar weight is 0.02～0.2 of a maleic anhydride, the time of polyreaction is 2～4 hours, temperature of reaction is 80～100 ℃, and polyreaction finishes, and cooling is filtered, promptly obtain poly-epoxy succinic acid and saline solution thereof, production concentration is 35～55%, feed stock conversion 95～100%, the may command polymerization degree 2～4 about 80～90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910250594A CN101717498A (en) | 2009-12-16 | 2009-12-16 | Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910250594A CN101717498A (en) | 2009-12-16 | 2009-12-16 | Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101717498A true CN101717498A (en) | 2010-06-02 |
Family
ID=42432142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910250594A Pending CN101717498A (en) | 2009-12-16 | 2009-12-16 | Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101717498A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432567A (en) * | 2011-11-07 | 2012-05-02 | 中国科学院青岛生物能源与过程研究所 | Method for preparing epoxy succinate |
| CN103183789A (en) * | 2011-12-28 | 2013-07-03 | 康吉诺（北京）科技有限公司 | Nano heavy calcium carbonate grinding-assisted dispersion polymerization inhibitor and preparation method and application thereof |
| CN103709387A (en) * | 2013-12-19 | 2014-04-09 | 南宁市化工研究设计院 | Production method of polyepoxysuccinic acid |
| CN105906795A (en) * | 2016-04-21 | 2016-08-31 | 华东理工大学 | Synthetic method for basic oil of perfluoropolyether lubricant oil |
-
2009
- 2009-12-16 CN CN200910250594A patent/CN101717498A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432567A (en) * | 2011-11-07 | 2012-05-02 | 中国科学院青岛生物能源与过程研究所 | Method for preparing epoxy succinate |
| CN102432567B (en) * | 2011-11-07 | 2015-01-07 | 中国科学院青岛生物能源与过程研究所 | Method for preparing epoxy succinate |
| CN103183789A (en) * | 2011-12-28 | 2013-07-03 | 康吉诺（北京）科技有限公司 | Nano heavy calcium carbonate grinding-assisted dispersion polymerization inhibitor and preparation method and application thereof |
| CN103183789B (en) * | 2011-12-28 | 2015-12-02 | 康吉诺（北京）科技有限公司 | Nano heavy calcium carbonate disperse and grind aid stopper and its preparation method and application |
| CN103709387A (en) * | 2013-12-19 | 2014-04-09 | 南宁市化工研究设计院 | Production method of polyepoxysuccinic acid |
| CN103709387B (en) * | 2013-12-19 | 2016-04-27 | 南宁市化工研究设计院 | Production method of polyepoxysuccinic acid |
| CN105906795A (en) * | 2016-04-21 | 2016-08-31 | 华东理工大学 | Synthetic method for basic oil of perfluoropolyether lubricant oil |
| CN105906795B (en) * | 2016-04-21 | 2019-06-07 | 华东理工大学 | A kind of synthetic method of perfluoro polyether oil base oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1834092B (en) | Preparation of pramipexole | |
| CN102250261B (en) | New method for producing iron dextran | |
| CN101717498A (en) | Synthesis method of high-concentration polyepoxysuccinic acid and salt thereof | |
| CN105753818B (en) | The method of synthesizing epoxy calcium succinate suspension and the method for production L (+) tartaric acid | |
| CN102875594A (en) | Continuous synthesis technique of hydroxyethylidenediphosphonic acid | |
| CN101381294A (en) | Industrial production method of 1,3-cyclohexanedione | |
| CN101648878A (en) | Preparation method of dimethyldiallylammonium chloride with low salt | |
| CN112592296B (en) | Method for producing sodium isethionate by continuous reaction | |
| CN107400069B (en) | Preparation method of lauroyl arginine ethyl ester hydrochloride | |
| KR101952060B1 (en) | Method for preparing furan-2,5-dicarboxylic acid (FDCA) from solid salt | |
| CN104262991B (en) | A kind of method of semi-continuous production white dyes | |
| CN108530301B (en) | Synthetic method of 2,4, 6-trifluorobenzylamine | |
| CN115557928A (en) | Synthetic method of 2-chlorothiophene-5-formic acid | |
| CN101723842B (en) | Method for preparing ethylene diamine tetraacetic acid (EDTA) disodium salt | |
| CN111574416B (en) | Method for preparing tiamulin from isothiourea salt and pleuromutilin p-toluenesulfonate | |
| CN102585196A (en) | Synthetic method for polyepoxysuccinic acid serving as scale and corrosion inhibitor | |
| CN110713444A (en) | Preparation method of caprylyl hydroximic acid | |
| CN102584636A (en) | Synthetic method of kreatine | |
| CN107216240B (en) | Synthesis method of octoxy glycerol | |
| CN103739723A (en) | Method for preparing octenyl succinate starch ester | |
| CN102432567B (en) | Method for preparing epoxy succinate | |
| CN101265183A (en) | Method for preparing 2,3,4-trimethoxybenzoic acid | |
| JP3998747B2 (en) | Process for producing hydroxyiminodisuccinic acid alkali metal salt | |
| US20240025756A1 (en) | Method for producing calcium sulfate hemihydrate whiskers by using fermentation broth for producing lactic acid with calcium salt method as raw material and synchronously recovering lactic acid monomer | |
| CN103087307A (en) | Preparation method of sodium polyepoxysuccinate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100602 |