CN101914076B - Method for preparing non-toxic environmental-friendly epoxy plasticizer - Google Patents
Method for preparing non-toxic environmental-friendly epoxy plasticizer Download PDFInfo
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- CN101914076B CN101914076B CN201010235389XA CN201010235389A CN101914076B CN 101914076 B CN101914076 B CN 101914076B CN 201010235389X A CN201010235389X A CN 201010235389XA CN 201010235389 A CN201010235389 A CN 201010235389A CN 101914076 B CN101914076 B CN 101914076B
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Abstract
The invention relates to a method for preparing a non-toxic environmental-friendly epoxy plasticizer, which is characterized by preparing the non-toxic environmental-friendly epoxy plasticizer by adopting fatty acid methyl ester as a raw material, hydrogen peroxide as oxidant and organic acid as an oxygen carrier. A non-toxic environmental-friendly epoxy plasticizer rough product is prepared by adopting a closed-end cooling circulation device through a one-step method without using any solvent, stabilizer and acid catalyst; and by water-washing, distilling, distributing and neutralizing with soda ash or calcium carbonate solution (pH is adjusted to 6.5-7.0), a chemical factor which probably pollutes the product is eliminated, a sewage treatment load is greatly reduced, and simultaneously, the production cost is also reduced. The preparation method of the invention has no poison, environmental protection, safety, water saving, stability, short production cycle and low energy consumption.
Description
(1) technical field
The present invention relates to a kind of compound method of plastics additive, particularly a kind of method for preparing non-toxic environmental-friendly epoxy plasticizer.
(2) background technology
The China recent years various places are investment construction large-tonnage ethylene project in succession, thereby whole plastic working industry also increasing the softening agent demand year by year, also has some amount softening agent products export in addition.
The external research aspect that Study of Plasticizer is mainly concentrated on now non-toxic plasticizers such as terephthalate, phosphoric acid ester, epoxy ester series, fatty acid ester, polyester, trimellitate class; Also abandon traditional vitriol oil class selecting for use of catalyzer, adopted to equipment corrosion catalyzer such as little, the solid ion super acids that the generation pollution is few, organic acid, heteropolyacid.Yet; State's internal plasticizer is main with O-phthalic acids softening agent such as DOP, DBP mainly now; Research for non-toxic plasticizers such as citrate, inclined to one side benzoic ether classes also rests on the sulphuric acid catalysis stage, and therefore, it is extremely urgent to develop a kind of novel environment friendly softening agent.
Utilize the epoxy plasticizer quality product of fatty acid methyl ester preparation to compare with vegetables oil such as Plasticizer Epoxidized Soybean Oil; The epoxy plasticizer of fatty acid methyl ester preparation not only can replace the DOP softening agent to produce PVC product nontoxic, environmental protection fully; Be used for food product pack, medical article material, toy and water supply line etc.; Also as celluosic resin and elastomeric non-toxic plasticizer and tenderizer, in processing products, add epoxy aliphatic acid methyl ester and can obviously improve physical properties of articles and prolong digestion time simultaneously; With metal(lic)stabilizer and times spent such as barium, cadmium, zinc, good synergy is arranged.In addition, because of it also has good lubricity, consistency and dispersion performance, go back useful as surfactants and dispersion agent and be applied to production industries such as epoxy coating and epoxy resin.
Solventless method synthesizing epoxy softening agent so far, epoxidation reaction uses formic acid to be organic acid mostly, and the vitriol oil is made catalyzer; Under stirring state, slowly drip ydrogen peroxide 50, dropwise insulation backflow then, whole process approximately continues 16-20 hour; Production cycle is long, and the vitriol oil and formic acid are middle strong acid in addition, and the finished product acid number is difficult to control; Institute's water amount of blowdown increases production cost and increases, because epoxidation reaction is quick thermopositive reaction, sets off an explosion easily in case reacting liquid temperature control is improper.
(3) summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, a kind of asepsis environment-protecting, safety, water saving, stable, with short production cycle, method for preparing non-toxic environmental-friendly epoxy plasticizer that energy consumption is low are provided.
The objective of the invention is to realize like this:
A kind of method for preparing non-toxic environmental-friendly epoxy plasticizer is characterized in that: the employing fatty acid methyl ester is a raw material, and ydrogen peroxide 50 is the oxygen supply agent, and organic acid is made oxygen carrier, makes non-toxic environmental-friendly epoxy plasticizer, and it comprises the steps:
A) fatty acid methyl ester and organic acid are dropped in the reaction kettle, heat up, open stirring and move closed cooling-cycle device, be warmed up to 40-45 ℃ and stop heating;
B) open the cooling water valve of reaction kettle, drip ydrogen peroxide 50 with the speed of 50-65g/s, reacting liquid temperature is controlled at 40-60 ℃, and the dropping time is 2-3 hour;
C) after ydrogen peroxide 50 dripped and finishes, insulation backflow 2-3 hour guaranteed that epoxidation reaction is abundant;
D) to the thick product of epoxy plasticizer wash, neutralization, underpressure distillation, stop to stir and closing closed cooling-cycle device, decompression dehydration obtains the non-toxic environmental-friendly epoxy plasticizer product.
Said organic acid add-on accounts for fatty acid methyl ester quality proportion 5%-15%.
The add-on of said ydrogen peroxide 50 accounts for fatty acid methyl ester quality proportion 25%-35%.
Described organic acid is Glacial acetic acid min. 99.5 or formic acid.
Said closed cooling-cycle device is meant that reaction kettle comprises a upper inlet and one outlet down, uses pump and pipeline to be delivered to said upper inlet by reaction solution from the said outlet down of reaction kettle, makes reaction solution in pump around circuit system of the outside formation of reaction kettle.
The pipeline outer setting of said closed cooling-cycle device has cooling water pipeline.
The hot water that said closed cooling-cycle device cooling back forms is used for the thick product water washing process of epoxy plasticizer.
Compared with prior art, the invention has the beneficial effects as follows:
A) the invention reside under the condition of not using any solvent, stablizer and an acidic catalyst with the fatty acid methyl ester is raw material, and ydrogen peroxide 50 is for to oxysome, and Glacial acetic acid min. 99.5 is made oxygen carrier; Adopt closed cooling-cycle device single stage method to make the thick product of non-toxic environmental-friendly epoxy type softening agent; Process washing, distillation, branch water with soda ash or calcium carbonate soln neutralization (Ph is transferred to 6.5-7.0), have been eliminated the chemical factor of possibility polluted product; A large amount of WWT burdens that reduce have also reduced production cost simultaneously.
B) the present invention uses Glacial acetic acid min. 99.5 to be organic acid, does not use an acidic catalyst, adopts closed cooling-cycle device; Form a refrigeration cycle return-flow system, the temperature that can fast reaction be produced reduces, thereby can realize dripping fast ydrogen peroxide 50; Make epoxidation reaction fast, evenly fully carry out; And reach equilibrium state, be equivalent to play catalyst action, whole epoxidation reaction is saved half the time than traditional processing technology simultaneously.
C) epoxy plasticizer head product washing is used and is reclaimed recirculated cooling water institute depleted hot water, reduces the WWT burden, has also reduced production cost simultaneously.
D) use Glacial acetic acid min. 99.5 to be organic acid, make the epoxidation reaction milder, prevent that the epoxidation reaction heat release is too fast and explosion caused.
The epoxidation of fatty acid methyl ester is the epoxidation of carbon-carbon double bond in the lipid acid, and its chemical reaction mechanism is:
CH3COOH+H2O2→CH3COOOH+H2O
(4) embodiment
Embodiment 1.
In the 3000L reaction kettle, fatty acid methyl ester and Glacial acetic acid min. 99.5 (accounting for fatty acid methyl ester quality proportion 15%) are dropped in the reaction kettle with corresponding proportion, heat up, open and stir and move closed cooling-cycle device; Be warmed up to 45 ℃ and stop heating, open the cooling water valve of reaction kettle, with the speed dropping ydrogen peroxide 50 (accounting for fatty acid methyl ester quality proportion 35%) of 65g/s; Reacting liquid temperature is controlled at 40-60 ℃; The dropping time is 2 hours, and ydrogen peroxide 50 drips and finishes back insulation backflow 2 hours, guarantees that epoxidation reaction is abundant; To the thick product of epoxy plasticizer wash, neutralization, underpressure distillation 1.5 hours; Stop to stir and closing closed cooling-cycle device, decompression dehydration obtains non-toxic environmental-friendly epoxy plasticizer.
Closed cooling-cycle device refers to upper inlet of reaction kettle needs and one outlet down, use the Fluroplast-4 pump by reaction solution from reaction kettle down outlet be delivered to upper inlet, make reaction solution form a pump around circuit system in that reaction kettle is outside.
Closed cooling-cycle device pipeline outer setting has cooling water pipeline, and the hot water that the cooling back forms is used for the thick product water washing process of epoxy plasticizer.
N-process uses soda ash or lime carbonate to be acid acceptor, and pH value is transferred to 6.5-6.8.
Embodiment 2.
In the 3000L reaction kettle, fatty acid methyl ester and Glacial acetic acid min. 99.5 (accounting for fatty acid methyl ester quality proportion 10%) drop in the reaction kettle with corresponding proportion, heat up, open and stir and move closed cooling-cycle device; Be warmed up to 40 ℃ and stop heating, open the cooling water valve of reaction kettle, with the speed dropping ydrogen peroxide 50 (accounting for fatty acid methyl ester quality proportion 35%) of 55g/s; Reacting liquid temperature is controlled at 40-60 ℃; The dropping time is 3 hours, and ydrogen peroxide 50 drips and finishes back insulation backflow 3 hours, guarantees that epoxidation reaction is abundant; To the thick product of epoxy plasticizer wash, neutralization, underpressure distillation 1.5 hours; Stop to stir and closing closed cooling-cycle device, decompression dehydration obtains non-toxic environmental-friendly epoxy plasticizer.
Embodiment 3.
In the 3000L reaction kettle, fatty acid methyl ester and Glacial acetic acid min. 99.5 (accounting for fatty acid methyl ester quality proportion 15%) are dropped in the reaction kettle with corresponding proportion, heat up and the unlatching stirring; Be warmed up to 43 ℃ and stop heating, open the cooling water valve of reaction kettle, with the speed dropping ydrogen peroxide 50 (accounting for methyl-formiate quality proportion 35%) of 20g/s; Reacting liquid temperature is controlled at 40-60 ℃, and the dropping time is 6 hours, and ydrogen peroxide 50 drips and finishes back insulation backflow 8 hours; Guarantee that epoxidation reaction is abundant; To the thick product of epoxy plasticizer wash, neutralization, underpressure distillation 2.5 hours, decompression dehydration obtains non-toxic environmental-friendly epoxy plasticizer.
Embodiment 4.
In the 3000L reaction kettle, fatty acid methyl ester and formic acid (accounting for fatty acid methyl ester quality proportion 15%) are dropped in the reaction kettle with corresponding proportion, heat up and the unlatching stirring; Be warmed up to 45 ℃ and stop heating, open the cooling water valve of reaction kettle, with the speed dropping ydrogen peroxide 50 (accounting for methyl-formiate quality proportion 35%) of 20g/s; Reacting liquid temperature is controlled at 40-60 ℃, and the dropping time is 6 hours, and ydrogen peroxide 50 drips and finishes back insulation backflow 8 hours; Guarantee that epoxidation reaction is abundant; To the thick product of epoxy plasticizer wash, neutralization, underpressure distillation 2.5 hours, decompression dehydration obtains non-toxic environmental-friendly epoxy plasticizer.
Claims (1)
1. a method for preparing non-toxic environmental-friendly epoxy plasticizer is characterized in that: in the 3000L reaction kettle, fatty acid methyl ester and Glacial acetic acid min. 99.5 are dropped in the reaction kettle with corresponding proportion; Said Glacial acetic acid min. 99.5 accounts for fatty acid methyl ester quality proportion 15%, heats up, opens stirring and moves closed cooling-cycle device, is warmed up to 45 ℃ and stops heating; Open the cooling water valve of reaction kettle, with the speed dropping ydrogen peroxide 50 of 65g/s, said ydrogen peroxide 50 accounts for fatty acid methyl ester quality proportion 35%; Reacting liquid temperature is controlled at 40-60 ℃, and the dropping time is 2 hours, and ydrogen peroxide 50 drips and finishes back insulation backflow 2 hours; Guarantee that epoxidation reaction is abundant, to the thick product of epoxy plasticizer wash, neutralization, underpressure distillation 1.5 hours, stop to stir and closing closed cooling-cycle device; Decompression dehydration obtains non-toxic environmental-friendly epoxy plasticizer;
Said closed cooling-cycle device refers to upper inlet of reaction kettle needs and one outlet down, use the Fluroplast-4 pump by reaction solution from reaction kettle down outlet be delivered to upper inlet, make reaction solution form a pump around circuit system in that reaction kettle is outside.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010235389XA CN101914076B (en) | 2010-07-26 | 2010-07-26 | Method for preparing non-toxic environmental-friendly epoxy plasticizer |
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| CN201010235389XA CN101914076B (en) | 2010-07-26 | 2010-07-26 | Method for preparing non-toxic environmental-friendly epoxy plasticizer |
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| CN101914076B true CN101914076B (en) | 2012-08-22 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102212189B (en) * | 2011-05-11 | 2012-09-05 | 江南大学 | Preparation method for epoxy polyester plasticizer |
| CN102503912B (en) * | 2011-10-26 | 2013-11-27 | 邹平福海科技发展有限公司 | High epoxide number environment-friendly plasticizer production process |
| CN103361186B (en) * | 2012-03-30 | 2015-03-18 | 中国石油化工股份有限公司 | Method for producing plasticizer by using biodiesel |
| CN103305347B (en) * | 2013-07-03 | 2014-09-03 | 江南大学 | Method for preparing environment-friendly plasticizer by high concentration hydrogen peroxide epoxidized oil |
| CN103483296A (en) * | 2013-09-23 | 2014-01-01 | 广州市海珥玛植物油脂有限公司 | Synthesis process of diacetyl epoxy glyceryl oleate |
| CN103773609A (en) * | 2013-10-29 | 2014-05-07 | 尚诚德 | Method for preparing plastic plasticizer by using illegally recycled waste cooking oil |
| CN103846071B (en) * | 2014-03-13 | 2016-01-20 | 安徽天意环保科技有限公司 | Autocontrol method in a kind of epoxy plasticizer production and device |
| CN106699698B (en) * | 2016-12-27 | 2019-09-10 | 江苏向阳科技有限公司 | A kind of biology plasticizer epoxy aliphatic acid methyl ester process units and production method |
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| EP1343860B1 (en) * | 2000-12-21 | 2012-01-25 | AarhusKarlshamn Denmark A/S | A process for preparing vegetable oil fractions rich in non-tocolic, high-melting, unsaponifiable matter |
| CN1919905A (en) * | 2006-09-04 | 2007-02-28 | 罗春妹 | Preparation method of nontoxic plasticizer |
| CN100590188C (en) * | 2007-05-22 | 2010-02-17 | 江阴市向阳科技有限公司 | Method for producing epoxy plasticizer using waste grease |
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Address after: Xiangyang Road, Xiangyang Village town of Hua Jiangsu city of Jiangyin province No. 8-5 214421 Patentee after: Jiangsu Xiangyang Technology Co. Ltd. Address before: Xiangyang Road, Xiangyang Village town of Hua Jiangsu city of Jiangyin province No. 8-5 214421 Patentee before: JIANGYIN XIANGYANG TECHNOLOGY CO., LTD. |