CN1240745C - Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst - Google Patents
Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst Download PDFInfo
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- CN1240745C CN1240745C CN 200310101835 CN200310101835A CN1240745C CN 1240745 C CN1240745 C CN 1240745C CN 200310101835 CN200310101835 CN 200310101835 CN 200310101835 A CN200310101835 A CN 200310101835A CN 1240745 C CN1240745 C CN 1240745C
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- calcium sulfate
- epoxysuccinic acid
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- sodium hydroxide
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Abstract
The present invention relates to a method for preparing polyeposysuecinic acid, which uses calcium sulphate as a catalyst. The present invention comprises the following operation steps: step 1, epoxy succinic acid is dissolved into deionized water, and the quality ratio of the epoxy succinic acid and the deionized water is 1: 1 to 1: 3; step 2, sodium hydroxide is added, the quality ratio of the epoxy succinic acid and the sodium hydroxide is 1: 0.1 to 1: 0.2, and epoxy succinic acid sodium is generated after alkalization by controlling the temperature below 80 DEG C; step 3, a calcium sulphate catalyst is added, and the quality ratio of the epoxy succinic acid and the calcium sulphate is 1: 0.02 to 1: 0.2. The temperature of polymerization reaction is 90 to 105 DEG C, the time of polymerization reaction is 3 to 6 hours, and then the crude product of polyeposysuecinic acid is produced. Then, after filtration and refining operation, the polyeposysuecinic acid is obtained. The calcium sulphate catalyst has the advantages of no corrosion, no moisture absorption, no water solubility and difficult deterioration. The method has the advantages of stable reaction for synthesizing the polyeposysuecinic acid, short technical process, high product yield, easy product separation and high relative molecular mass.
Description
Technical field
The present invention relates to a kind of method by the synthetic polyepoxy sodium succinate of Epoxysuccinic acid, this method is to be catalyzer with calcium sulfate.
Background technology
Poly-epoxy succinic acid is a kind of water-soluble polymers with powerful chelating and scale inhibition performance, and not phosphorous in its molecular structure, nitrogen element can not cause body eutrophication, and biological degradability is good, is a kind of green polymer.It is strong to calcium, magnesium, the isoionic chelating ability of iron, and has threshold effect, and scale inhibition performance is good, is applicable to high-alkali high solid water system, and high concentration multiple and zero blowdown are handled, and are the renewal products of existing Scale inhibitors.
The structural formula of the poly-epoxy succinic acid that United States Patent (USP) " Detergent formulations " (US3,776,850) proposes is:
Wherein R is H or other appointment group, and n is preferably 2-6 from 2-40.When n is 3 or 4, compound scale removal better performances.Its preparation method is to be that catalyzer is from the Epoxysuccinic acid monomer polymerization with the boron trifluoride.This method can be prepared the poly-epoxy succinic acid mixture of very low n=3 of content and n=4, but is difficult to realize industrialization.
United States Patent (USP) " Ether hydroxypolycarboxylate detergency builders " (US4,654,159) proposes following structural formula:
In the formula, M is H, NH
4Or alkali metal cation, R is H or C
1-4Alkyl, n are more preferably 2～10 from 2～15, and preferably 2～4.Its preparation method is in liquid phase medium, the calcium hydroxide reaction that the epoxy succinic hydrochlorate of solubility is suitable with molar weight, and the reactant esterification separates ester from reaction mixture, the ester saponification is generated an alkali metal salt of poly-epoxy succinic acid again.The reaction conditions of epoxy succinic hydrochlorate and calcium hydroxide: will be equivalent to output at least 5%, preferably 1/2 of 10%～80% mole calcium hydroxide amount adds in the epoxy succinic acid salt solution of pH value 5～7, be heated to 100 ℃ and constant temperature 2h, the calcium hydroxide that adds all the other 1/2 amounts then is heated to 100 ℃ and constant temperature 2h.This method productive rate is higher, and synthetic product is effective to polyvalent cations such as chelating calcium, magnesium, and can be used as washing auxiliary detergent, to substitute phosphorus be auxiliary agent.But this method is strong as the calcium hydroxide corrodibility of catalyzer, easily moisture absorption and apt to deteriorate, and reaction product need pass through ion-exchange, esterification and processing such as carboxylate separation and saponification, and it is low etc. that the target product relative molecular mass is crossed.
Summary of the invention
The purpose of this invention is to provide a kind of method that with calcium sulfate is catalyzer from the synthetic polyepoxy sodium succinate of Epoxysuccinic acid.The calcium sulfate catalyzer has non-hygroscopic, the non-advantage such as water-soluble and not perishable of no burn into.This method is synthesized the polyepoxy sodium succinate reacting balance, and technical process is short, the product yield height, and product separation is easy, and relative molecular mass is higher.
The present invention is a kind of method that is catalyzer from the synthetic polyepoxy sodium succinate of Epoxysuccinic acid with calcium sulfate.Comprise following operation steps:
(1) Epoxysuccinic acid is dissolved in the deionized water, the mass ratio of Epoxysuccinic acid and deionized water is 1: 1～1: 3;
(2) add sodium hydroxide, the mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.1～1: 0.2; Temperature is controlled at below 80 ℃ and generates epoxy sodium succinate through alkalization;
(3) add catalyst sulfuric acid calcium, the mass ratio of Epoxysuccinic acid and calcium sulfate is 1: 0.02～1: 0.3; Polymeric reaction temperature is 90～105 ℃, and polymerization reaction time is 3～6h, i.e. system
Get the polyepoxy sodium succinate crude product, the refining after filtration then polyepoxy sodium succinate that obtains.
The mass ratio of Epoxysuccinic acid of the present invention and deionized water is preferably 1: 2～and 1: 2.2.
The mass ratio of Epoxysuccinic acid of the present invention and sodium hydroxide is preferably 1: 0.15～and 1: 0.17.
The mass ratio of Epoxysuccinic acid of the present invention and calcium sulfate is preferably 1: 0.06～and 1: 0.11.
Polymeric reaction temperature of the present invention is preferably 90～100 ℃, and polymerization reaction time is 4h.
The mass ratio of Epoxysuccinic acid of the present invention and deionized water is 1: 1～1: 3, and preferably 1: 2～1: 2.2, the product solid content reduced during hypervolia, and operation was stable inadequately when the water yield was very few.The mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.1～1: 0.2, and preferably 1: 0.15～1: 0.17, amount of sodium hydroxide too much reduced with the very few product relative molecular mass that all can make.The temperature of reaction of Epoxysuccinic acid and sodium hydroxide is no more than 80 ℃, can cause the epoxy succinic acid hydrolysis when temperature is too high.The mass ratio of Epoxysuccinic acid and calcium sulfate is 1: 0.02～1: 0.3, preferably 1: 0.06～1: 0.11, suitably reduce the calcium sulfate amount product relative molecular mass is improved, but product yield is reduced when very few, the product relative molecular mass is reduced.The adding temperature of calcium sulfate without limits, preferably 70～100 ℃.The polymeric reaction temperature of Epoxysuccinic acid is 90～105 ℃ behind the adding catalyst sulfuric acid calcium, and preferably 90～100 ℃, polymerization reaction time is 4h.The polyepoxy sodium succinate of preparation adopts the gel chromatography relative molecular mass.The method that provides with invention can obtain product yield up to 100%, relative molecular mass is 300～1500 polyepoxy sodium succinate.The structural formula of the polyepoxy sodium succinate A that makes is:
The raw material Epoxysuccinic acid that the present invention uses, calcium sulfate (CaSO for example
4.2H
2O) and sodium hydroxide can adopt commercially available technical grade product, the calcium sulfate catalyzer is compared with the calcium hydroxide catalyzer, calcium sulfate has non-hygroscopic, the non-advantage such as water-soluble and not perishable of no burn into, and calcium sulfate adds alkali can not generate calcium hydroxide, is a kind of safer, stable catalyst more.With calcium sulfate is that catalyzer synthesizes polyepoxy sodium succinate from Epoxysuccinic acid, reacting balance, and technical process is simple, the product yield height, the product relative molecular mass is higher.The polyepoxy sodium succinate of the inventive method preparation has threshold effect, is a kind of Scale inhibitors of excellent performance, and calcium ion is had very high tolerance, is applicable to that high-alkali high solid water is.
Embodiment
Embodiment 1: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4 in the polyepoxy sodium succinate structural formula～9).
Embodiment 2: under constantly stirring, 100g Epoxysuccinic acid, 15g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 3: under constantly stirring, 100g Epoxysuccinic acid, 17g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 4: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 200g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 5: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 220g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 6: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 60 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 7: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 80 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 8: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 70 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 9: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 100 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 10: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 6.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 600～1500 (being equivalent to n=5～12).
Embodiment 11: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 11.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 300～800 (being equivalent to n=2～7).
Embodiment 12: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 95 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 13: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 100 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 14: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 3.5h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 15: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 5h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1500 (being equivalent to n=4～12).
Embodiment 16: under constantly stirring, 100g Epoxysuccinic acid, 10g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 300～900 (being equivalent to n=2～8).
Embodiment 17: under constantly stirring, 100g Epoxysuccinic acid, 20g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 300～900 (being equivalent to n=2～8).
Embodiment 18: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 100g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 40%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 19: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 300g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 20%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 20: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 3.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 93%, solid content 30%, relative molecular mass 600～1500 (being equivalent to n=5～12).
Embodiment 21: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 22.0g, react 4h down at 98 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 300～800 (being equivalent to n=2～7).
Embodiment 22: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 90 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Embodiment 23: under constantly stirring, 100g Epoxysuccinic acid, 16g sodium hydroxide are added in the 217g deionized water, keep temperature of reaction to be no more than 65 ℃, get the Epoxysuccinic acid sodium solution, in the time of 80 ℃, add calcium sulfate 8.0g, react 4h down at 105 ℃, remove by filter calcium sulfate, promptly make polyepoxy sodium succinate, yield 100%, solid content 30%, relative molecular mass 400～1000 (being equivalent to n=4～9).
Claims (5)
1, a kind of is the polyepoxy sodium succinate preparation method of catalyzer with calcium sulfate, comprises following operation steps:
(1) Epoxysuccinic acid is dissolved in the deionized water, the mass ratio of Epoxysuccinic acid and deionized water is 1: 1～1: 3;
(2) add sodium hydroxide, the mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.1～1: 0.2; Temperature is controlled at below 80 ℃ and generates epoxy sodium succinate through alkalization;
(3) add catalyst sulfuric acid calcium, the mass ratio of Epoxysuccinic acid and calcium sulfate is 1: 0.02～1: 0.3; Polymeric reaction temperature is 90～105 ℃, and polymerization reaction time is 3～6h, promptly makes the polyepoxy sodium succinate crude product, the refining after filtration then polyepoxy sodium succinate that obtains.
2, method according to claim 1 is characterized in that: the mass ratio of Epoxysuccinic acid and deionized water is 1: 2～1: 2.2.
3, method according to claim 1 is characterized in that: the mass ratio of Epoxysuccinic acid and sodium hydroxide is 1: 0.15～1: 0.17.
4, method according to claim 1 is characterized in that: the mass ratio of Epoxysuccinic acid and calcium sulfate is 1: 0.06～1: 0.11.
5, method according to claim 1 is characterized in that: polymeric reaction temperature is 90～100 ℃, and polymerization reaction time is 4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310101835 CN1240745C (en) | 2003-10-20 | 2003-10-20 | Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst |
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| CN 200310101835 CN1240745C (en) | 2003-10-20 | 2003-10-20 | Prepn process of polyepoxy succinic acid with calcium sulfate as catalyst |
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| CN1240745C true CN1240745C (en) | 2006-02-08 |
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| 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 |
| CN112642490A (en) * | 2019-10-12 | 2021-04-13 | 兰溪市向荣电子电器有限公司 | Preparation method of high-efficiency catalyst for hard anodizing of cast aluminum and die-cast aluminum |
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