CN1683313A - Epoxy sodium succinate and its process for preparing polymer - Google Patents
Epoxy sodium succinate and its process for preparing polymer Download PDFInfo
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- CN1683313A CN1683313A CN 200410073370 CN200410073370A CN1683313A CN 1683313 A CN1683313 A CN 1683313A CN 200410073370 CN200410073370 CN 200410073370 CN 200410073370 A CN200410073370 A CN 200410073370A CN 1683313 A CN1683313 A CN 1683313A
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Abstract
The present invention is preparation process of sodium epoxy succinate and its polymer. Sodium epoxy succinate is prepared through dissolving maleic anhydride in water, adding sodium hydroxide solution, heating, adding catalyst, adding hydrogen peroxide solution continuously, dropping sodium hydroxide solution, heating to 65-75 deg.c, reaction for 1-1.5 hr, cooling, adding proper amount of acetone to separate sodium epoxy succinate as white precipitate. Sodium epoxy succinate is dissolved in water, and initiator calcium hydroxide is added to react at 90-100 deg.c to obtain sodium epoxy succinate polymer. Or, initiator calcium hydroxide is added directly into the above said reacted solution for reaction of 4-5 hr to obtain sodium epoxy succinate polymer solution, and through further separation, methanol washing to obtain solid sodium epoxy succinate polymer, dissolving in deionized water and vacuum drying to obtain pure solid sodium epoxy succinate polymer.
Description
Technical field
The present invention relates to the preparation method of water conditioner, is the preparation method of epoxy sodium succinate and polymkeric substance thereof specifically.
Background technology
Poly-epoxy succinic acid and salt thereof are a kind of without phosphorus no nitrogen " green " water conditioners.It has inhibition, scale inhibition dual-use function concurrently, and it is good to have a biological degradability, characteristics such as applied range.Can be applied in the Treatment of Industrial Water as Scale inhibitors, dispersion agent, inhibiter, in washing composition, clean-out system, stain remover as sequestrant of metal ion etc.
Preparation method about epoxy sodium succinate and polymkeric substance thereof, United States Patent (USP) (US 4654159) report: MALEIC ANHYDRIDE is dissolved in the water, adds sodium hydroxide and generate maleic acid sodium, be catalyzer with the sodium wolframate, add hydrogen peroxide continuously, keep pH=5～7 with sodium hydroxide, generate epoxy sodium succinate, add calcium hydroxide again is initiator in batches, and the composition that obtains polymkeric substance is distributed as: n=1～2 account for 8%, n=3～6 account for 25%, and n＞6 account for 67%.
The reaction equation of synthetic polyepoxy sodium succinate is as follows:
This patent reports simultaneously, and during the amount that adds calcium hydroxide when polyreaction few (epoxy sodium succinate and calcium hydroxide mol ratio≤1: 0.05), transformation efficiency is low, contains a large amount of unreacted epoxy sodium succinates in the product.When only adding calcium hydroxide amount big (epoxy sodium succinate and calcium hydroxide mol ratio 〉=1: 0.1) when polyreaction, epoxy sodium succinate can transform fully, and the component of n=3 in the product～6 reaches 70%.Adopt aforesaid method, add a large amount of calcium hydroxide when polyreaction, make and contain a large amount of calcium ions in the polymkeric substance, inconvenience is directly used, and the sepn process complexity.
The Chinese patent that application number is 03124258.8, name is called the preparation method of poly-epoxy succinic acid and salt thereof improves this, by epoxy sodium succinate and calcium hydroxide mol ratio is that 1: 0.01～0.05 adding calcium hydroxide is initiator, pH=10～13 that add the sodium hydroxide regulation system simultaneously, can obtain low polyepoxy sodium succinate of calcium ion content or poly-epoxy succinic acid, but this patent is not explained to making the epoxy sodium succinate monomer.
Summary of the invention
The preparation method who the purpose of this invention is to provide epoxy sodium succinate monomer and polymkeric substance thereof.
For achieving the above object, the present invention realizes through the following steps:
At first that MALEIC ANHYDRIDE is soluble in water, add sodium hydroxide solution, heat, when solution temperature reaches 55 ℃, add catalyzer by 0.01～0.1 of MALEIC ANHYDRIDE amount of substance, add superoxol then continuously, total add-on of hydrogen peroxide is 1.0～1.3 times of MALEIC ANHYDRIDE, the pH value of the solution of dropping sodium maintenance simultaneously is between 5～7, and MALEIC ANHYDRIDE and sodium hydroxide mol ratio 1: 1.8～1: 2 dripped in 30～40 minutes, after dropwising, be heated to 65～75 ℃, under this temperature, reacted 1～1.5 hour, carry out the following step then:
(a) reacted solution is cooled to room temperature, add proper amount of acetone then, epoxy sodium succinate is white in color to precipitate and separates out, wash again 2～3 times, get the higher intermediate epoxy sodium succinate of purity, press epoxy sodium succinate soluble in water with deionized water mol ratio 1: 8～10, add initiator calcium hydroxide in batches, calcium hydroxide and epoxy sodium succinate mol ratio 0.01～0.1 are reacted under 90～100 ℃ temperature, the polyepoxy sodium succinate that obtains.
(b) also can directly use above-mentioned reacted solution, add initiator calcium hydroxide with MALEIC ANHYDRIDE mol ratio 0.01～0.1 in batches, reacted under 90～100 ℃ temperature 4～5 hours, the polyepoxy sodium succinate solution that obtains is with pH value to 1～2 of solution behind the hydrochloric acid conditioned reaction.Separate out white solid, with methanol wash for several times, must gather and encircle the succsinic acid solid, poly-ring succsinic acid is dissolved in deionized water, and is with sodium hydrate regulator solution pH value to 9～10, dry that pure solid gathers the ring sodium succinate under vacuum.
It is that 2: 1 or sodium wolframate and ammonium molybdate mol ratio are 2: 1 that catalyzer adopts sodium wolframate and ammonium vanadate mol ratio.
The invention has the advantages that, carry out epoxidation with binary composite catalyst, by the amount of control adding sodium hydroxide, the pH value of regulator solution can realize the higher yields of epoxy sodium succinate between 5～7, significantly reduce the generation of by product.In polyreaction, by adding initiator calcium hydroxide in batches, and the controlled polymerization temperature of reaction can obtain the good polyepoxy sodium succinate of scale-inhibiting properties at 90～100 ℃.The product that obtains is a kind of without phosphorus no nitrogen " green " water conditioner, can directly apply to Treatment of Industrial Water as Scale inhibitors, inhibiter, dispersion agent, and it has inhibition, scale inhibition dual-use function concurrently, and it is good to have a biological degradability, characteristics such as applied range.
Embodiment
Embodiment 1:
1: 8 in molar ratio～10 add MALEIC ANHYDRIDE and water to there-necked flask, stir to make it soluble in water fully, drip proper amount of sodium hydroxide solution, note the control rate of addition, drip in 20～30 minutes.Heating, when solution temperature reaches 55 ℃, add catalyzer by 0.01～0.1 of MALEIC ANHYDRIDE amount of substance, 1.0～1.3 times 30% the hydrogen peroxide that adds the MALEIC ANHYDRIDE amount then continuously, the pH value of the solution of dropping sodium maintenance simultaneously dripped in 30～40 minutes, after dropwising between 5～7, be heated to 65～75 ℃, under this temperature, reacted 1～1.5 hour.Reacted solution is cooled to room temperature, adds acetone, and epoxy sodium succinate is white in color to precipitate and separates out, and washs 2～3 times again, gets the higher epoxy sodium succinate of purity.Epoxy sodium succinate by soluble in water with deionized water mol ratio 1: 8～10, also can directly be used above-mentioned reacted solution, add an amount of initiator calcium hydroxide in batches, under 90～100 ℃ temperature, react 4～5 hours, get polyepoxy sodium succinate.It is characterized in that, add sodium hydroxide, make the pH value of reaction system remain on 5～7, become more readily available epoxy sodium succinate, the epoxy sodium succinate monomer purity height that obtains under the acidic conditions by MALEIC ANHYDRIDE and sodium hydroxide mol ratio 1: 1.8～2.
Below the present invention is described further.
MALEIC ANHYDRIDE is tried one's best in CL and the water, if can not, can suitably heat, but should notice that temperature is no more than 55 ℃, otherwise influence product yield.
One of this synthetic key will be controlled the add-on of sodium hydroxide exactly well, the pH value that keeps solution is between 5～7, the sodium hydroxide that adds and the mol ratio of MALEIC ANHYDRIDE are preferably in 1.8～2: between 1, add too much, solution is alkalescence, and more sodium tartrate is arranged in the reaction product, adds very few, it is acid that solution is, and the oxidation susceptibility of hydrogen peroxide reduces greatly.So reaction is preferably under the slightly acidic condition to be carried out, because strong heat release should note controlling solution temperature.The temperature of reaction soln is controlled at about 55 ℃, drips superoxol and sodium hydroxide simultaneously, in 30 minutes, drip.
Catalyzer adds with solid form, and sodium wolframate and ammonium vanadate mol ratio are that 2: 1 or sodium wolframate and ammonium molybdate mol ratio are that 2: 1 catalyzer have epoxidation performance efficiently.
The epoxidised time also is a link of its key.Solution system is warming up to about 70 ℃ and reacted 1～1.5 hour, and the reaction times will suitably be controlled.Time is oversize, and product unresolvable tartaric acid sodium is too much, and the yield of epoxy sodium succinate is not high, and the time is too short, and then reaction is carried out not exclusively.
When carrying out polyreaction, initiator calcium hydroxide will add in batches, and experiment shows that calcium hydroxide adds in batches, is because initiator amount is relevant with the polymerization degree of polymkeric substance, the increase of initiator amount, and the polymerization degree of synthetic polymer reduces.And the scale-inhibiting properties of product has relation with the polymerization degree, and big or hour, its scale-inhibiting properties is all relatively poor when the polymerization degree of polyepoxy sodium succinate, the polymerization degree has only and just has scale-inhibiting properties preferably within the specific limits.Calcium hydroxide adds in batches, helps the controlled polymerization degree.
Polymeric reaction temperature should be controlled between 90～100 ℃, and temperature is too low, and polyreaction carries out slowly or not reacting, and temperature is too high, and polyreaction is carried out acutely, and polyepoxy sodium succinate content reduces in the product, and scale-inhibiting properties descends.
Embodiment 2:
Take by weighing MALEIC ANHYDRIDE 49g to there-necked flask, stirring makes it soluble in water fully, and the pH value of solution is between 2～3 at this moment, and solution is colourless.Add the sodium hydroxide solution of 80g 50% with dropper to above-mentioned drips of solution, strong reaction heat release this moment, solution colour makes solution temperature be no more than 55 ℃ by the transparent white that becomes, and dropping sodium solution finishes in 15 minutes.Take by weighing the catalyzer (sodium wolframate and ammonium vanadate mol ratio are 2: 1) of 1.7g, join in the solution.Measure 30% hydrogen peroxide of 65ml, slowly drip in 20 minutes introversive above-mentioned solution.When dripping superoxol, regulate the pH value about 7 with pipette Dropwise 5 0% sodium hydroxide.Solution colour by white to canescence.Solution heat temperature raising to 70 ℃, isothermal reaction is 1.5～2 hours under this temperature.Reacted solution is cooled to room temperature, adds organic solvent acetone, and the epoxy sodium succinate white precipitate is separated out, and gets final product for 2 to 3 times with washing with acetone again.
Embodiment 3:
The epoxy sodium succinate of the 0.5mol that makes with embodiment 2 is dissolved in the deionized water of 87.9ml, stirring is dissolved it fully, add initiator calcium hydroxide 1.85g to it more in batches, be heated to 90～100 ℃ with oil bath, under this temperature, reacted 3～4 hours, must gather the ring sodium succinate, by analysis, the composition of polymkeric substance is distributed as: n=1～2 account for 8%, and n=3～6 account for 25%, and n＞6 account for 67%.
Embodiment 4:
Take by weighing MALEIC ANHYDRIDE 49g to there-necked flask, stirring makes it soluble in water fully, and the pH value of solution is between 2～3 at this moment, and solution is colourless.Add the sodium hydroxide solution of 75g 50% with dropper to above-mentioned drips of solution, strong reaction heat release this moment, solution colour makes solution temperature be no more than 55 ℃ by the transparent white that becomes, and dropping sodium solution finishes in 15 minutes.Take by weighing the catalyzer (sodium wolframate and ammonium molybdate mol ratio are 2: 1) of 1.7g, join in the solution.Measure 30% hydrogen peroxide of 65ml, slowly drip in 20 minutes introversive above-mentioned solution.When dripping superoxol, regulate the pH value about 7 with pipette Dropwise 5 0% sodium hydroxide.Solution colour by white to canescence.Solution heat temperature raising to 70 ℃, isothermal reaction is 1.5～2 hours under this temperature.Reacted solution is cooled to room temperature, adds organic solvent acetone, and the epoxy sodium succinate white precipitate is separated out, and gets final product for 2 to 3 times with washing with acetone again.
Embodiment 5:
The epoxy sodium succinate of the 0.5mol that use-case 3 makes is dissolved in the deionized water of 75ml, stirring is dissolved it fully, add initiator calcium hydroxide 1.8g to it more in batches, be heated to 90～100 ℃ with oil bath, under this temperature, reacted 3～4 hours, must gather the ring sodium succinate, by analysis, the composition of polymkeric substance is distributed as: n=1～2 account for 6%, and n=3～6 account for 26%, and n＞6 account for 68%.
Embodiment 6:
Take by weighing MALEIC ANHYDRIDE 49g to there-necked flask, stirring makes it soluble in water fully, and the pH value of solution is between 2～3 at this moment, and solution is colourless.Add the sodium hydroxide solution of 80g 50% with dropper to above-mentioned drips of solution, strong reaction heat release this moment, solution colour makes solution temperature be no more than 55 ℃ by the transparent white that becomes, and dropping sodium solution finishes in 15 minutes.Take by weighing the catalyzer (sodium wolframate and ammonium vanadate mol ratio are 2: 1) of 1.7g, join in the solution.Measure 30% hydrogen peroxide of 65ml, slowly drip in 20 minutes introversive above-mentioned solution.When dripping superoxol, regulate the pH value about 7 with pipette Dropwise 5 0% sodium hydroxide.Solution colour by white to canescence.Solution heat temperature raising to 70 ℃, isothermal reaction is 1.5～2 hours under this temperature.Reacted solution is heated to 90～100 ℃ with oil bath, adds initiator calcium hydroxide 1.85g to it more in batches, under this temperature, reacted 3～4 hours, and must gather the ring sodium succinate, by analysis, the composition of polymkeric substance is distributed as: n=1～2 account for 8%, and n=3～6 account for 45%, and n＞6 account for 47%.
Embodiment 7:
Add 320ml distilled water to the 500ml there-necked flask, take by weighing MALEIC ANHYDRIDE 223g to there-necked flask, stirring makes it soluble in water fully, and the pH value of solution is between 2～3, and solution is colourless.Add the sodium hydroxide solution of 327g 50% to above-mentioned drips of solution, strong reaction heat release this moment, solution colour is by the transparent white that becomes, and the control solution temperature is no more than 55 ℃.After sodium hydroxide solution dropwised, control heater kept solution temperature at 55 ℃, takes by weighing the catalyzer (sodium wolframate and ammonium vanadate mol ratio are 2: 1) of 7.84g, joins in the solution.Take by weighing 30% hydrogen peroxide of 270g, slowly drip in above-mentioned solution, when dripping superoxol, Dropwise 5 0% sodium hydroxide is regulated the pH value about 7.Solution colour by white to canescence.Solution heat temperature raising to 70 ℃, isothermal reaction is 1.5～2 hours under this temperature.Use the oil bath heating instead, add initiator calcium hydroxide 8.4g,, added other initiator calcium hydroxide 8.4g afterreaction again 2～3 hours 90～100 ℃ of reactions 2～3 hours.Poly-by analysis ring sodium succinate accounts for 75%, and sodium tartrate 20% also has other impurity.PH value to 1～2 with solution behind the hydrochloric acid conditioned reaction.Separate out white solid, with methanol wash for several times, must gather and encircle the succsinic acid solid, poly-ring succsinic acid is dissolved in deionized water, and is with sodium hydrate regulator solution pH value to 9～10, dry that pure solid gathers the ring sodium succinate under vacuum.
Claims (2)
1, the preparation method of epoxy sodium succinate and polymkeric substance thereof, at first that MALEIC ANHYDRIDE is soluble in water, add sodium hydroxide solution, heat, when solution temperature reaches 55 ℃, add catalyzer by 0.01～0.1 of MALEIC ANHYDRIDE amount of substance, add superoxol then continuously, total add-on of hydrogen peroxide is 1.0～1.3 times of MALEIC ANHYDRIDE, and dropping sodium keeps the pH value of solution between 5～7 simultaneously, MALEIC ANHYDRIDE and sodium hydroxide mol ratio 1: 1.8～1: 2, in 30～40 minutes, drip, after dropwising, be heated to 65～75 ℃, under this temperature, reacted 1～1.5 hour, and it is characterized in that:
(a) reacted solution is cooled to room temperature, add proper amount of acetone then, epoxy sodium succinate is white in color to precipitate and separates out, get the higher intermediate epoxy sodium succinate of purity, epoxy sodium succinate by soluble in water with deionized water mol ratio 1: 8～10, is added initiator calcium hydroxide, calcium hydroxide and epoxy sodium succinate mol ratio 0.01～0.1 in batches, under 90～100 ℃ temperature, react the polyepoxy sodium succinate that obtains;
(b) also can directly use above-mentioned reacted solution, add initiator calcium hydroxide with MALEIC ANHYDRIDE mol ratio 0.01～0.1 in batches, reacted under 90～100 ℃ temperature 4～5 hours, the polyepoxy sodium succinate solution that obtains is with pH value to 1～2 of solution behind the hydrochloric acid conditioned reaction.Separate out white solid, with methanol wash for several times, must gather and encircle the succsinic acid solid, poly-ring succsinic acid is dissolved in deionized water, and is with sodium hydrate regulator solution pH value to 9～10, dry that pure solid gathers the ring sodium succinate under vacuum;
2, the preparation method of epoxy sodium succinate according to claim 1 and polymkeric substance thereof is characterized in that it is that 2: 1 or sodium wolframate and ammonium molybdate mol ratio are 2: 1 that catalyzer adopts sodium wolframate and ammonium vanadate mol ratio.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602852B (en) * | 2009-07-13 | 2011-04-06 | 山东省泰和水处理有限公司 | Preparation method for polyepoxy sodium succinate for water treatment |
| CN101293945B (en) * | 2007-04-27 | 2011-11-23 | 四川中物凯沃科技有限公司 | Method for preparing modified poly-epoxy succinic acid derivative |
| 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 |
| CN103087307A (en) * | 2013-01-17 | 2013-05-08 | 潍坊泉鑫化工有限公司 | Preparation method of sodium polyepoxysuccinate |
| CN103864233A (en) * | 2014-02-19 | 2014-06-18 | 安徽大学 | Environment-friendly water treatment agent and preparation method thereof |
| CN111808275A (en) * | 2020-05-25 | 2020-10-23 | 河南清水源科技股份有限公司 | Fluorescent polyepoxysuccinic acid sodium and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538362B (en) * | 2008-03-21 | 2011-11-09 | 北京合创同盛科技有限公司 | Method for synthesizing polyepoxysuecinic acid salt |
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- 2004-12-09 CN CN 200410073370 patent/CN1286797C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293945B (en) * | 2007-04-27 | 2011-11-23 | 四川中物凯沃科技有限公司 | Method for preparing modified poly-epoxy succinic acid derivative |
| CN101602852B (en) * | 2009-07-13 | 2011-04-06 | 山东省泰和水处理有限公司 | Preparation method for polyepoxy sodium succinate for water treatment |
| 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 |
| CN103087307A (en) * | 2013-01-17 | 2013-05-08 | 潍坊泉鑫化工有限公司 | Preparation method of sodium polyepoxysuccinate |
| CN103087307B (en) * | 2013-01-17 | 2015-02-11 | 潍坊泉鑫化工有限公司 | Preparation method of sodium polyepoxysuccinate |
| CN103864233A (en) * | 2014-02-19 | 2014-06-18 | 安徽大学 | Environment-friendly water treatment agent and preparation method thereof |
| CN103864233B (en) * | 2014-02-19 | 2016-04-06 | 安徽大学 | A kind of Environment-friendlywater water treatment agent and preparation method thereof |
| CN111808275A (en) * | 2020-05-25 | 2020-10-23 | 河南清水源科技股份有限公司 | Fluorescent polyepoxysuccinic acid sodium and preparation method thereof |
| CN111808275B (en) * | 2020-05-25 | 2023-03-10 | 河南清水源科技股份有限公司 | Fluorescent polyepoxysuccinic acid sodium and preparation method thereof |
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