CN102153484A - Quaternarization method of (dialkyl) aminoethyl methacrylate - Google Patents
Quaternarization method of (dialkyl) aminoethyl methacrylate Download PDFInfo
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- CN102153484A CN102153484A CN2011100082008A CN201110008200A CN102153484A CN 102153484 A CN102153484 A CN 102153484A CN 2011100082008 A CN2011100082008 A CN 2011100082008A CN 201110008200 A CN201110008200 A CN 201110008200A CN 102153484 A CN102153484 A CN 102153484A
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- ethyl ester
- acid dialkyl
- halohydrocarbon
- propenoic acid
- methacrylic acid
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Abstract
The invention relates to a quaternarization method of (dialkyl) aminoethyl methacrylate, belonging to the field of chemical products. The quaternarization method of (dialkyl) aminoethyl methacrylate comprises the following steps of: (1) adding halogenated hydrocarbon in a pressure reaction kettle; (2) adding (dialkyl) aminoethyl methacrylate of a polymerization inhibitor in the pressure reaction kettle at 20-40 DEG C and stirring for reacting, wherein (dialkyl) dimethylaminoethyl methacrylate contains 300-3000ppm of polymerization inhibitor, and the mole ratio of halogenated hydrocarbon to (dialkyl) aminoethyl methacrylate in the reaction is (2-20):1; (3) after the reaction is finished, cooling, filtering and separating, drying at low temperature to obtain the quaternary ammonium salt of dialkyl aminoethyl methacrylate; and (4) freezing the filtrate for recycling, wherein the main component of the filtrate is halogenated hydrocarbon which can be reused in the reaction process of the method. The quaternarization method of (dialkyl) aminoethyl methacrylate has the advantages of simple reaction process, easiness for control and high safety, can be used for producing solid products and is easy for industrial production.
Description
One, technical field
The present invention relates to the quaternized method of a kind of (methyl) propenoic acid dialkyl amino ethyl ester, belong to the Chemicals field.
Two, background technology
The quaternary ammonium salt of propenoic acid dialkyl amino ethyl ester and methacrylic acid dialkyl amido ethyl ester is undersaturated cationic monomer, is one of critical materials of cationic polyacrylamide, at aspects such as environmental protection, papermaking, oil recovery, soil improvements important use is arranged.
The manufacture method of the unsaturated quaternary ammonium salt of narration such as Chinese patent CN1174188, CN1337936, CN1296942, CN1337935, CN1384095 is carried out in the aqueous solution.Because quaternizing agent hydrochloric ether such as methyl chloride, solubleness is very little in water, and conversion unit need be strengthened stirring, and speed of response is slow.The final product of reaction is an aqueous solution form.Because (methyl) propenoic acid dialkyl amino ethyl ester is water-soluble big, the boiling point height adopts conventional extraction, evaporation technology, is difficult to remove from final product, thereby has influence on the copolymerization performance of the quaternary ammonium salt of (methyl) propenoic acid dialkyl amino ethyl ester.Simultaneously, the quaternary ammonium salt of (methyl) propenoic acid dialkyl amino ethyl ester very easily dissolves in water, and conventional concentration method can not obtain the quaternary ammonium salt solid crystal of (methyl) propenoic acid dialkyl amino ethyl ester.
Huang Shiqiangs etc. (chemistry and bonding 1997,3,128) have been introduced organic solvent and have been had down the synthetic method of unsaturated quaternary ammonium salt.Organic solvents such as acetonitrile, acetone and ether, highly volatile, inflammable and explosive, the industrially scalable preparation for the quaternary ammonium salt of (methyl) propenoic acid dialkyl amino ethyl ester needs great amount of investment to be used for safety precaution, and running cost is high.
Three, summary of the invention
The objective of the invention is to overcome the deficiency of aforesaid method, provide that a kind of reaction process is simple, control is easy, safe, can obtain solid phase prod, be easy to the quaternized method of (methyl) propenoic acid dialkyl amino ethyl ester of suitability for industrialized production.
The quaternized method of the present invention's (methyl) propenoic acid dialkyl amino ethyl ester may further comprise the steps:
1) halohydrocarbon is joined in the withstand voltage reactor;
2) under 20-40 ℃ of temperature, will contain stopper 300-3000ppm (methyl) propenoic acid dialkyl amino ethyl ester and join withstand voltage reactor, stirring reaction; Its mol ratio one halohydrocarbon: (methyl) propenoic acid dialkyl amino ethyl ester is 2-20: 1;
3) after reaction finishes, cooling, filtering separation, cryodrying obtains (methyl) propenoic acid dialkyl amino ethyl ester quaternary ammonium salt;
4) filtrate is through freezing recovery, and main component is a halohydrocarbon, and can circulate is used for said process.
(methyl) propenoic acid dialkyl amino ethyl ester is meant dimethylaminoethyl acrylate, perhaps dimethylaminoethyl methacrylate.
A described halohydrocarbon is meant a methyl halide, a halo ethane, a halogenopropane, perhaps butyl halide etc.; Halohydrocarbon is meant hydrochloric ether and hydrobromic ether.
Described stopper is a Resorcinol, or tertiarybutylhydroquinone, or other are applicable to the stopper of acrylic ester compound.
Carry out heating and cooling by reacting kettle jacketing in the described step 2, keep temperature in the kettle 35-40 ℃, stirred 1-3 hour;
After reaction finishes, adopt close filter to carry out filter operation, the solid cryodrying obtains (methyl) propenoic acid dialkyl amino ethyl ester quaternary ammonium salt.
Reaction finishes the filtrate behind the after-filtration, and main component is a halohydrocarbon, can adopt conventional liquifying method, avoids loss through volatilization, the circulation quaterisation.
The quaternized method of (methyl) of the present invention propenoic acid dialkyl amino ethyl ester, reaction process is simple, control is easy, safe, can obtain solid phase prod, is easy to suitability for industrialized production.
Four, embodiment
Following embodiment is used for illustrating the present invention, scope of the present invention is not construed as limiting.
Embodiment 1
In 1000 liters of withstand voltage reactors, add methyl chloride 500Kg (9.90 kilomol), under the agitation condition, slowly be warmed up to 36-38 ℃.In reactor, be metered into the dimethylaminoethyl methacrylate that contains hydroquinone of polymerization retarder 1000ppm then, amount to 157.21Kg (1.0 kilomol), added in 1 hour, carry out heating and cooling by reacting kettle jacketing, keep temperature in the kettle 36-38 ℃, stirred 2 hours.
Cooling, material filters through close filter, and solid crystal is the quaternary ammonium salt of dimethylaminoethyl methacrylate, and after the collection, the decompression cryodrying obtains finished product.Excessive methyl chloride is present in the filtrate, and a part of methyl chloride is vaporized, and through after the freezing recovery, can circulate and use quaterisation.
Embodiment 2
In 1000 liters of withstand voltage reactors, add monochlorethane 500Kg (7.75 kilomol), under the agitation condition, slowly be warmed up to 35-38 ℃.In reactor, be metered into the dimethylaminoethyl acrylate that contains hydroquinone of polymerization retarder 2000ppm then, amount to 143.18Kg (1.0 kilomol), added in 1 hour, carry out heating and cooling by reacting kettle jacketing, keep temperature in the kettle 35-38 ℃, stirred 2 hours.
Cooling, material filters through close filter, and solid crystal is the quaternary ammonium salt of dimethylaminoethyl acrylate, and after the collection, cryodrying obtains finished product.Excessive monochlorethane is present in the filtrate, and a part of monochlorethane is vaporized, and through after the freezing recovery, can circulate and use quaterisation.
Embodiment 3
In 1000 liters of withstand voltage reactors, add the recovery monochlorethane 420Kg of example 2, replenish fresh monochlorethane 100Kg, under the agitation condition, slowly be warmed up to 36-39 ℃.In reactor, be metered into the dimethylaminoethyl acrylate that contains stopper tertiarybutylhydroquinone 1000ppm then, amount to 143.18Kg, added in 1 hour, carry out heating and cooling, keep temperature in the kettle 36-39 ℃, stirred 2 hours by reacting kettle jacketing.
After reaction finished, material filtered through close filter, and solid crystal is the quaternary ammonium salt of dimethylaminoethyl acrylate, and after the collection, cryodrying obtains finished product.Excessive monochlorethane is present in the filtrate, and a part of monochlorethane is vaporized, and through after the freezing recovery, can circulate and use quaterisation.
Embodiment 4
In 1000 liters of withstand voltage reactors, add 1-N-PROPYLE BROMIDE 500Kg (4.07 kilomol), under the agitation condition, slowly be warmed up to 37-39 ℃.In reactor, be metered into the dimethylaminoethyl methacrylate that contains hydroquinone of polymerization retarder 2500ppm then, amount to 157.21Kg (1.0 kilomol), added in 1 hour, carry out heating and cooling by reacting kettle jacketing, keep temperature in the kettle 37-39 ℃, stirred 2.5 hours.
Cooling, material filters through close filter, and solid crystal is the quaternary ammonium salt of dimethylaminoethyl methacrylate, and after the collection, the decompression cryodrying obtains finished product.Excessive 1-N-PROPYLE BROMIDE is present in the filtrate, and a part of 1-N-PROPYLE BROMIDE is vaporized, and through after the freezing recovery, can circulate and use quaterisation.
The quaternized method of the above embodiment of the invention (methyl) propenoic acid dialkyl amino ethyl ester, reaction process is simple, control is easy, safe, can obtain solid phase prod, is easy to suitability for industrialized production.
Claims (10)
1. the quaternized method of propenoic acid dialkyl amino ethyl ester is characterized in that may further comprise the steps:
1) halohydrocarbon is joined in the withstand voltage reactor;
2) the propenoic acid dialkyl amino ethyl ester that will contain stopper under 20-40 ℃ of temperature joins withstand voltage reactor, stirring reaction;
Containing stopper in the dimethylaminoethyl acrylate is 300-3000ppm;
One halohydrocarbon: the mol ratio of propenoic acid dialkyl amino ethyl ester is 2-20: 1;
3) after reaction finishes, cooling, filtering separation, cryodrying obtains propenoic acid dialkyl amino ethyl ester quaternary ammonium salt;
4) filtrate is through freezing recovery, and main component is a halohydrocarbon, and can circulate is used for said process.
2. the quaternized method of propenoic acid dialkyl amino ethyl ester as claimed in claim 1 is characterized in that a described halohydrocarbon is meant a methyl halide, a halo ethane, a halogenopropane and a butyl halide etc.; Halohydrocarbon is meant hydrochloric ether and hydrobromic ether.
3. the quaternized method of propenoic acid dialkyl amino ethyl ester as claimed in claim 1 is characterized in that described stopper is a Resorcinol, or tertiarybutylhydroquinone, or other are applicable to the stopper of acrylic ester compound.
4. the quaternized method of propenoic acid dialkyl amino ethyl ester as claimed in claim 1 is characterized in that carrying out heating and cooling by reacting kettle jacketing in the described step 2, keeps temperature in the kettle 35-40 ℃, stirs 1-3 hour.
5. the quaternized method of propenoic acid dialkyl amino ethyl ester as claimed in claim 1 after it is characterized in that reacting end, adopts close filter to carry out filter operation, and the solid cryodrying obtains propenoic acid dialkyl amino ethyl ester quaternary ammonium salt.
6. the quaternized method of methacrylic acid dialkyl amido ethyl ester is characterized in that may further comprise the steps:
1) halohydrocarbon is joined in the withstand voltage reactor;
2) the methacrylic acid dialkyl amido ethyl ester that will add stopper under 20-40 ℃ of temperature joins withstand voltage reactor, stirring reaction;
Containing stopper in the dimethylaminoethyl methacrylate is 300-3000ppm;
One halohydrocarbon: the mol ratio of methacrylic acid dialkyl amido ethyl ester is 2-20: 1;
3) after reaction finishes, cooling, filtering separation, cryodrying obtains methacrylic acid dialkyl amido ethyl ester quaternary ammonium salt;
4) filtrate is through freezing recovery, and main component is a halohydrocarbon, and can circulate is used for said process.
7. the quaternized method of methacrylic acid dialkyl amido ethyl ester as claimed in claim 6 is characterized in that a described halohydrocarbon is meant a methyl halide, a halo ethane, a halogenopropane and a butyl halide etc.; Halohydrocarbon is meant hydrochloric ether and hydrobromic ether.
8. the quaternized method of methacrylic acid dialkyl amido ethyl ester as claimed in claim 6 is characterized in that described stopper is a Resorcinol, or tertiarybutylhydroquinone, or other are applicable to the stopper of methyl acrylic ester compound.
9. the quaternized method of methacrylic acid dialkyl amido ethyl ester as claimed in claim 6 is characterized in that carrying out heating and cooling by reacting kettle jacketing in the described step 2, keeps temperature in the kettle 35-40 ℃, stirs 1-3 hour.
10. the quaternized method of methacrylic acid dialkyl amido ethyl ester as claimed in claim 6 after it is characterized in that reacting end, adopts close filter to carry out filter operation, and the solid cryodrying obtains methacrylic acid dialkyl amido ethyl ester quaternary ammonium salt.
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| CN2011100082008A CN102153484A (en) | 2011-01-07 | 2011-01-07 | Quaternarization method of (dialkyl) aminoethyl methacrylate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185640A (en) * | 2021-05-07 | 2021-07-30 | 南京大学 | Hydrophobic modified cationic starch flocculant and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101815699A (en) * | 2008-01-17 | 2010-08-25 | Mt奥科高分子株式会社 | Process for producing quaternary salt of dialkylaminoalkyl (meth)acrylate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101815699A (en) * | 2008-01-17 | 2010-08-25 | Mt奥科高分子株式会社 | Process for producing quaternary salt of dialkylaminoalkyl (meth)acrylate |
Non-Patent Citations (1)
| Title |
|---|
| 孙中新等: "甲基丙烯酰氧乙基三甲基氯化铵生产技术及现状", 《齐鲁石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185640A (en) * | 2021-05-07 | 2021-07-30 | 南京大学 | Hydrophobic modified cationic starch flocculant and preparation method and application thereof |
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Application publication date: 20110817 |