CN104926677A - Production process of beta-hydroxyalkylamide - Google Patents
Production process of beta-hydroxyalkylamide Download PDFInfo
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Abstract
The invention discloses a production process of beta-hydroxyalkylamide. According to the invention, when a reaction is finished, phosphoric or phosphorous acid is added, such that alkaline components such as catalysts and alkanolamine left in a product are removed, or part of hydroxyl group in the product is further esterified. According to the invention, the hydroxyalkylamide provided by the invention has less alkaline impurities, or further contains phosphate or phosphite products. When the beta-hydroxyalkylamide is used as a powdery paint curing agent, application performances such as weather resistance and yellowing resistance can be improved.
Description
Technical field
The present invention relates to the field of chemical synthesis, specifically a kind of production technique of beta-hydroxy alkylamide.
Background technology
US Patent No. 4,076,917 and US 4,727,111 disclose the method for synthesizing beta-hydroxy alkylamide solidifying agent with alkyl carboxylates and β-alkanolamine under basic catalyst condition, and have employed methyl alcohol, purifying that acetone and other organic solvent crystallization processes achieves target product.US 0,055,595 A1 then reports the preparation method of a kind of hydroxyalkyl virtue acid amides, and the method is using the organic solvent such as benzene, toluene as reaction medium, makes reactant ammonia solution conversion wherein, crystallization product simultaneously.Must use a certain amount of recrystallisation solvent in these existing production technique, not only increase solvent consumption and post-processing step, and the volatilization of recrystallisation solvent can cause environmental pollution.
US Patent No. 5,101,073 discloses solvent-free what slurry sedimentation process carries out pure solid hydroxyalkyl amide product, this technique utilizes to make the constantly sedimentation from reaction system what slurry of hydroxyalkyl amide product under maintenance certain temperature condition, impel reaction to carry out to the direction obtaining target product, thus the beta-hydroxy alkylamide product of higher degree can be obtained without the need to solvent crystallization.But when the β hydroxyalkyl amide target product fusing point of preparation is lower, when can not settle from molten system, what slurry sedimentation rule cannot be proved effective.In addition, because what slurry settling process have collected materials all in reaction system, in therefore obtained target product, inevitably there is basic catalyst and the unreacted alkaline impurities such as alkanolamine completely.This type of impurity has had a strong impact on target product application performance in powder coating systems, as yellowing resistance and weathering resistance deterioration etc.
Summary of the invention
For solving the problem, the invention discloses a kind of production technique strengthening the beta-hydroxy alkylamide of powder paint solidifying agent anti-yellowing property, eliminate the residual alkaline components such as catalyzer, alkanolamine in the product, or the part of hydroxyl esterification making in product further, enhance the application performance such as yellowing resistance and weathering resistance of product.
A production technique for beta-hydroxy alkylamide, comprises the following steps:
(1) β-alkanolamine and basic catalyst are dropped in reactor, 80-150 DEG C are heated under the protection of rare gas element, after gas to the pressure in still extracted out in still reaches 0.03-0.05MPa, alkyl carboxylates is dripped in 1-3 hours, and constantly ammonolysis reaction is carried out in stirring, continues to steam the alcohol of releasing in reaction process simultaneously;
(2) alkyl carboxylates drips complete, continues to be incubated ammonolysis reaction after 0.5-2 hours under 0.03-0.05MPa, regulates pressure in still to be normal pressure, adds the aqueous solution of phosphoric acid or phosphorous acid, be fully uniformly mixed in reaction mixture;
(3) reaction system be warming up to 150-200 DEG C and be incubated, the rare gas element being not less than 0.1MPa to charged pressure in reaction system by the gas dispersion apparatus bottom reactor carries out bubbling purging, inflation is stopped after continuing inflation 2-10min, underpressure distillation to still forces down in 0.005MPa and continues to vacuumize 5-20min, then stop vacuumizing, and then be filled with rare gas element and carry out bubbling purging, inflation is stopped to carry out underpressure distillation, alternate intervals like this carries out inflation and underpressure distillation 2-5 times, till absence of liquid material steams;
(4) after steaming liquid substance, remaining reaction product is cooled to 80-100 DEG C, blowing, then cools, pulverizes, and obtains white powder product.
The mol ratio of described alkyl carboxylates and β-alkanolamine is 1:2-2.1, described alkyl carboxylates and the mass ratio of basic catalyst are 1:0.00001-0.05, described phosphoric acid or phosphorous acid minimum be mol ratio 1:1-1.2 of hydroxide ion in its hydrogen ion and basic catalyst, described phosphoric acid or phosphorous acid maximum are that in its hydroxyl and β-alkanolamine, the mol ratio of hydroxyl is 1:8, and described phosphoric acid or the concentration of aqueous solution of phosphorous acid are 20-50%(w/w).
The present invention is by adding basic catalyst residual after phosphoric acid or phosphorous acid eliminative reaction, greatly reduce the generation of side reaction in following purification steps, the phosphoric acid simultaneously added or phosphorous acid energy partial esterification beta-hydroxy alkylamide, the performance such as its weather-proof, color inhibition as powder paint solidifying agent significantly improves.
Embodiment
According to the present invention, a kind of production technique of β hydroxyalkyl amide, can be described by the following examples, but be not limited to the following examples.
embodiment 1
By 210.0g(2mol) diethanolamine and 2.8g sodium methylate mixture drop into bottom has in the reactor of gas dispersion apparatus, are heated to 130 DEG C under nitrogen protection.After pressure reaches 0.05MPa in extraction gas reactor to still, in 2h, drip 174.0g(1mol) dimethyl adipate, continuous stirring reaction, and synchronously steam the methyl alcohol of releasing in reaction process.Again after 2h reaction, 90.5g20% phosphate aqueous solution is added in reaction mixture, after being fully uniformly mixed, reaction system be warming up to 200 DEG C and be incubated, in reaction system, nitrogen bubble is filled with and constantly stirring with 0.5MPa pressure durations 5min by the gas dispersion apparatus bottom reactor, then logical nitrogen is stopped, decompression steams liquid substance to still pressure and reaches 0.003MPa and continue to vacuumize 15min, stop vacuumizing being filled with nitrogen 3min by preceding method again, then inflation is stopped to carry out underpressure distillation again, repeatable operation like this 3 times, absence of liquid material steams again, reaction system is cooled to 90 DEG C, blowing, pulverize after further cooling, obtain white unrestricted flow shape product 329g.
comparative example
By 210.0g(2mol) diethanolamine and 2.8g sodium methylate mixture drop into bottom has in the reactor of gas dispersion apparatus, are heated to 130 DEG C under nitrogen protection.After pressure reaches 0.05MPa in extraction gas reactor to still, in 2h, drip 174.0g(1mol) dimethyl adipate, continuous stirring reaction, and synchronously steam the methyl alcohol of releasing in reaction process.Again after 2h reaction, 3.0g acetic acid is added in reaction mixture, after being fully uniformly mixed, reaction system be warming up to 200 DEG C and be incubated, in reaction system, nitrogen bubble is filled with and constantly stirring with 0.5MPa pressure durations 5min by the gas dispersion apparatus bottom reactor, then logical nitrogen is stopped, decompression steams liquid substance to still pressure and reaches 0.003MPa and continue to vacuumize 15min, stop vacuumizing being filled with nitrogen 3min by preceding method again, then inflation is stopped to carry out underpressure distillation again, repeatable operation like this 3 times, absence of liquid material steams again, reaction system is cooled to 90 DEG C, blowing, pulverize after further cooling, obtain white unrestricted flow shape product 324g.
embodiment 2
By 210.0g(2.0mol) diethanolamine and 2.8g sodium methylate mixture drop into bottom has in the reactor of gas dispersion apparatus, are heated to 130 DEG C under nitrogen protection.After pressure reaches 0.05MPa in extraction gas reactor to still, in 2h, drip 174.0g(1mol) dimethyl adipate, continuous stirring reaction, and synchronously steam the methyl alcohol of releasing in reaction process.Again after 2h reaction, 8g20% phosphate aqueous solution is added in reaction mixture, after being fully uniformly mixed, reaction system be warming up to 200 DEG C and be incubated, in reaction system, nitrogen bubble is filled with and constantly stirring with 0.5MPa pressure durations 5min by the gas dispersion apparatus bottom reactor, then logical nitrogen is stopped, decompression steams liquid substance to still pressure and reaches 0.003MPa and continue to vacuumize 15min, stop vacuumizing being filled with nitrogen 3min by preceding method again, then inflation is stopped to carry out underpressure distillation again, repeatable operation like this 3 times, absence of liquid material steams again, reaction system is cooled to 90 DEG C, blowing, pulverize after further cooling, obtain white unrestricted flow shape product 323g.
embodiment 3
By 210.0g(2.0mol) diethanolamine and 2.8g sodium methylate mixture drop into bottom has in the reactor of gas dispersion apparatus, are heated to 130 DEG C under nitrogen protection.After pressure reaches 0.05MPa in extraction gas reactor to still, in 2h, drip 174.0g(1mol) dimethyl adipate, continuous stirring reaction, and synchronously steam the methyl alcohol of releasing in reaction process.Again after 2h reaction, 113g20% phosphorous acid aqueous solution is added in reaction mixture, after being fully uniformly mixed, reaction system be warming up to 200 DEG C and be incubated, in reaction system, nitrogen bubble is filled with and constantly stirring with 0.5MPa pressure durations 5min by the gas dispersion apparatus bottom reactor, then logical nitrogen is stopped, decompression steams liquid substance to still pressure and reaches 0.003MPa and continue to vacuumize 15min, stop vacuumizing being filled with nitrogen 3min by preceding method again, then inflation is stopped to carry out underpressure distillation again, repeatable operation like this 3 times, absence of liquid material steams again, reaction system is cooled to 90 DEG C, blowing, pulverize after further cooling, obtain white unrestricted flow shape product 336g.
embodiment 4
By 210.0g(2.0mol) diethanolamine and 2.8g sodium methylate mixture drop into bottom has in the reactor of gas dispersion apparatus, are heated to 130 DEG C under nitrogen protection.After pressure reaches 0.05MPa in extraction gas reactor to still, in 2h, drip 174.0g(1mol) dimethyl succinate, continuous stirring reaction, and synchronously steam the methyl alcohol of releasing in reaction process.Again after 2h reaction, 10.5g20% phosphorous acid aqueous solution is added in reaction mixture, after being fully uniformly mixed, reaction system be warming up to 200 DEG C and be incubated, in reaction system, nitrogen bubble is filled with and constantly stirring with 0.5MPa pressure durations 5min by the gas dispersion apparatus bottom reactor, then logical nitrogen is stopped, decompression steams liquid substance to still pressure and reaches 0.003MPa and continue to vacuumize 15min, stop vacuumizing being filled with nitrogen 3min by preceding method again, then inflation is stopped to carry out underpressure distillation again, repeatable operation like this 3 times, absence of liquid material steams again, reaction system is cooled to 90 DEG C, blowing, pulverize after further cooling, obtain white unrestricted flow shape product 324g.
Mixed in the high intensity mixer of 3000rmp/2 minute by each composition in table 1, then in the type use for laboratory twin screw extruder of ZS-30, melting mixing is extruded, and temperature is 110 DEG C.Extrudate cools, and coffee mill is pulverized, and crosses 160 mesh sieves.The mode of the electrostatic spraying used for powder coating obtained is sprayed on Q-Panel model, and each sample sprays the model of 80 ± 5 μm of thickness respectively; Model after spraying is respectively at 190 DEG C, 15 minutes, and 220 DEG C, 20 minutes, under 230 DEG C, 30 minutes conditions, baking formed film.BYK-Spainish CC-6807 type colour-difference meter is adopted to test △ b and the △ E value of above film respectively.Separately get the film model that baking in 190 DEG C, 15 minutes is formed, survey impact, levelling and QUV-B(500 hour) protect light rate.The results detailed in Table 1.
Relatively overbaking stability approach
Overbaking stability coefficient △ b, △ E numerical value are less, and the weathering resistance of powder paint solidifying agent, yellowing resistance and over-all properties are stronger; By filling a prescription in the comparison of different storing temperature, the overbaking stability coefficient △ b drawn after the time, △ E to each in experiment, weathering resistance, the yellowing resistance of products obtained therefrom of the present invention are obviously better than original product.
Table 1
SJ5122: Anhui Shenjian New Material Co., Ltd. Primid polyester in table 1 formula, acid number 30-34mgKOH/g; W-44: Guizhou China adds the barium sulfate that meticulous mining industry company limited produces; R902: the Rutile type Titanium Dioxide that E.I.Du Pont Company produces; The polyacrylate flow agent that PV88:Worlee company produces; SA500: the level and smooth degasifier of powder coating, Liuan Jietongda Chemical Co., Ltd.'s product.
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets with reference to each above-mentioned embodiment to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (2)
1. a production technique for beta-hydroxy alkylamide, is characterized in that: comprise the following steps:
(1) β-alkanolamine and basic catalyst are dropped in reactor, 80-150 DEG C are heated under the protection of rare gas element, after gas to the pressure in still extracted out in still reaches 0.03-0.05MPa, alkyl carboxylates is dripped in 1-3 hours, and constantly ammonolysis reaction is carried out in stirring, continues to steam the alcohol of releasing in reaction process simultaneously;
(2) alkyl carboxylates drips complete, continues to be incubated ammonolysis reaction after 0.5-2 hours under 0.03-0.05MPa, regulates pressure in still to be normal pressure, adds the aqueous solution of phosphoric acid or phosphorous acid, be fully uniformly mixed in reaction mixture;
(3) reaction system be warming up to 150-200 DEG C and be incubated, the rare gas element being not less than 0.1MPa to charged pressure in reaction system by the gas dispersion apparatus bottom reactor carries out bubbling purging, inflation is stopped after continuing inflation 2-10min, underpressure distillation to still forces down in 0.005MPa and continues to vacuumize 5-20min, then stop vacuumizing, and then be filled with rare gas element and carry out bubbling purging, inflation is stopped to carry out underpressure distillation, alternate intervals like this carries out inflation and underpressure distillation 2-5 times, till absence of liquid material steams;
(4) after steaming liquid substance, remaining reaction product is cooled to 80-100 DEG C, blowing, then cools, pulverizes, and obtains white powder product.
2. the production technique of described a kind of beta-hydroxy alkylamide according to claim 1, it is characterized in that: the mol ratio of described alkyl carboxylates and β-alkanolamine is 1:2-2.1, described alkyl carboxylates and the mass ratio of basic catalyst are 1:0.00001-0.05, described phosphoric acid or phosphorous acid minimum be mol ratio 1:1-1.2 of hydroxide ion in its hydrogen ion and basic catalyst, described phosphoric acid or phosphorous acid maximum are that in its hydroxyl and β-alkanolamine, the mol ratio of hydroxyl is 1:8, described phosphoric acid or the concentration of aqueous solution of phosphorous acid are 20-50%(w/w).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203555A (en) * | 2017-12-29 | 2018-06-26 | 六安科瑞达新型材料有限公司 | A kind of synthetic method of beta-hydroxy alkylamide |
| CN109535024A (en) * | 2018-11-27 | 2019-03-29 | 黄山华惠科技有限公司 | A kind of color inhibition type beta-hydroxy alkylamide curing agent and the preparation method and application thereof |
| CN110642742A (en) * | 2019-09-18 | 2020-01-03 | 甘肃青宇新材料有限公司 | Preparation method of beta-hydroxyalkylamide curing agent |
| CN112142612A (en) * | 2019-06-28 | 2020-12-29 | 南京红宝丽醇胺化学有限公司 | Method for preparing beta-hydroxyalkyl amide by extraction and purification |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1489485A (en) * | 1974-03-25 | 1977-10-19 | Rohm & Haas | Method for curing polymers |
| US4727111A (en) * | 1986-09-29 | 1988-02-23 | Ppg Industries, Inc. | Powder coating compositions based on mixtures of acid group-containing materials and beta-hydroxyalkylamides |
| CN1057519C (en) * | 1992-02-28 | 2000-10-18 | 罗姆和哈斯公司 | Production of beta-hydroxyalkylamides |
| CN101704762B (en) * | 2009-11-13 | 2013-01-09 | 六安市捷通达化工有限责任公司 | Production technology of beta-hydroxyalkylamide |
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2014
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203555A (en) * | 2017-12-29 | 2018-06-26 | 六安科瑞达新型材料有限公司 | A kind of synthetic method of beta-hydroxy alkylamide |
| CN109535024A (en) * | 2018-11-27 | 2019-03-29 | 黄山华惠科技有限公司 | A kind of color inhibition type beta-hydroxy alkylamide curing agent and the preparation method and application thereof |
| CN109535024B (en) * | 2018-11-27 | 2021-08-31 | 黄山华惠科技有限公司 | Anti-yellowing beta-hydroxyalkylamide curing agent and preparation method and application thereof |
| CN112142612A (en) * | 2019-06-28 | 2020-12-29 | 南京红宝丽醇胺化学有限公司 | Method for preparing beta-hydroxyalkyl amide by extraction and purification |
| CN110642742A (en) * | 2019-09-18 | 2020-01-03 | 甘肃青宇新材料有限公司 | Preparation method of beta-hydroxyalkylamide curing agent |
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Address after: 237000 Anhui city in Lu'an Province, Beijiao, ten Patentee after: Lu'an Jietongda new materials Co. Ltd. Address before: 237000 Anhui city in Lu'an Province, Beijiao, ten Patentee before: Liu'an Jietongda Chemical Co., Ltd. |
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