CN107253911A - A kind of lactate synthesis method of polyalcohol acrylate - Google Patents
A kind of lactate synthesis method of polyalcohol acrylate Download PDFInfo
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- CN107253911A CN107253911A CN201710457398.5A CN201710457398A CN107253911A CN 107253911 A CN107253911 A CN 107253911A CN 201710457398 A CN201710457398 A CN 201710457398A CN 107253911 A CN107253911 A CN 107253911A
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- Prior art keywords
- toluene
- polyalcohol
- synthesis method
- water
- hexamethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Abstract
The invention discloses a kind of lactate synthesis method of polyalcohol acrylate, this method is using polyalcohol and acrylic acid as primary raw material, using the mixed solvent of toluene or toluene and hexamethylene as solvent, between absolute pressure 20KPa ~ 70KPa, esterification occurs at a temperature of 75 ~ 100 DEG C, then by refined, precipitation, the polyalcohol acrylate for being filtrated to get high-purity.High income of the present invention, reaction temperature is lower, and more preferably, synthetic reaction is safer for inhibition.COD total amounts in waste water of the present invention are less, environmentally friendly to require, achieve extraordinary technique effect.
Description
Technical field
The present invention relates to a kind of synthetic method of polyalcohol acrylate in UV industries, more particularly to a kind of high income, conjunction
The lactate synthesis method for the polyalcohol acrylate that high polymer is few during, synthetic reaction is safer, waste water is less, belonging to
Learn synthesis technical field.
Background technology
In routinely production UV monomers, the synthesis of acrylic acid and polyalcohol is divided into esterification, refined, precipitation, filtering four
It is typically synthesis under normal pressure in individual part, esterification process, it is a variety of using thiacyclohexane, normal heptane, toluene, butyl acetate, both the above
Or a variety of mixed solvents is as solvent, the functions such as dissolving, band water, inhibition are typically served to.The water produced in esterification process passes through
Taken away with the azeotropic of above solvent, after layering, moisture goes out, solvent refluxing, until esterification terminates.After esterification terminates, using heat
Water, solid caustic soda（Or the aqueous solution of solid caustic soda）, salt solution etc. washed, and stands a point water.Then desolvation, and filtering
Obtain finished product.In existing technical process, no matter using which kind of dicyandiamide solution, there are respective shortcoming, the solution that can not all integrate
The problem of certainly improving yield, reduce high polymer, improve reaction safety, reduce waste water COD total emission volumn.
The content of the invention
Goal of the invention：The purpose of the present invention is more to pacify there is provided a kind of high income, synthetic reaction in view of the shortcomings of the prior art
Entirely, the synthetic method of the lower polyalcohol acrylate of COD total amounts in waste water.
Technical scheme, to realize object above, the technical solution adopted by the present invention is：
A kind of lactate synthesis method of polyalcohol acrylate, it comprises the following steps：
（1）, take polyalcohol and acrylic acid to be added in reaction vessel, the mixing for then adding toluene or toluene and hexamethylene is molten
Agent, MEHQ, copper sulphate and pyrovinic acid, heat temperature raising, and open vavuum pump and vacuumize, keep reaction system negative pressure
Reaction system absolute pressure is kept between 20KPa ~ 70KPa, temperature control is between 75 ~ 100 DEG C, the water reaction generation of reaction generation
Water with acrylic acid, toluene or toluene and hexamethylene mixed solvent azeotropic and vapour-liquid carried out by filled column exchanged, vapour phase
It is cooled to be layered after liquid, lower floor's water is constantly separated, the mixed solvent conduct of upper strata acrylic acid and toluene or toluene and hexamethylene
The phegma of filled column, flows through filled column, eventually flows to reactor.Until the acid number of reaction system is in 30 ~ 55mgKOH/g；
（2）Then 50 ~ 65 DEG C are cooled to, and adds toluene, water washing is then added and stands a point water, then add sodium carbonate
Solution and sodium hydrate aqueous solution are neutralized, and stand a point water；
（3）After neutralization terminates, MEHQ is added, then vacuum desolvation, removing toluene and hexamethylene, temperature control is 85
~ 92 DEG C, vacuum absolute pressure is controlled in 10 ~ 25Kpa, obtained polyalcohol acrylate.
Preferably, pacify on the lactate synthesis method of above-described a kind of polyalcohol acrylate, reaction vessel
Equipped with electric mixing device, thermometer, water knockout drum and condenser, vavuum pump.
Preferably, a kind of lactate synthesis method of above-described polyalcohol acrylate, step（1）Reactant
Be absolute pressure between 25KPa ~ 65KPa, temperature control is between 78 ~ 95 DEG C.
Preferably, a kind of lactate synthesis method of above-described polyalcohol acrylate, polyalcohol, propylene
The quality amount ratio of mixed solvent, the MEHQ of acid, toluene or toluene and hexamethylene, copper sulphate and pyrovinic acid for 1 ~
1.5：2~2.5：2.5~7：0.1~0.15：0.0015~0.004：0.0015~0.003：0.06~0.15.
Preferably, the lactate synthesis method of above-described a kind of polyalcohol acrylate, it is characterised in that many
First alcohol is pentaerythrite, bipentaerythrite and trimethylolpropane.
Preferably, a kind of lactate synthesis method of above-described polyalcohol acrylate, it is characterised in that sulphur
Sour copper can be substituted with copper chloride.
The lactate synthesis method of polyalcohol acrylate of the present invention, toluene be usual commercial toluene, and toluene with
The mixed solvent of hexamethylene refers to toluene level more than 50%（Mass ratio）, cyclohexane content is less than 50%（Mass ratio）Mixing it is molten
Agent.In course of reaction of the present invention, toluene（Or the mixed solvent of toluene and hexamethylene）Being total in effect not exclusively esterification process
Boiling band water, while also functioning to the effects such as dissolving, inhibition, regulation reaction temperature and reduction reaction viscosity.
Beneficial effect：Compared to the prior art, the present invention has the following advantages：
1st, high income of the present invention, high income 2 ~ 11% of the yield than existing synthesis technique of new synthesis process.
2nd, high polymer is few in building-up process of the present invention, is conducive to improving product quality.New technology is received due to improving finished product
Rate, therefore high polymer content is lower by 1 ~ 3% than the high polymer content of existing synthesis technique.
3rd, synthetic reaction of the present invention is safer.Using inhibition of the toluene to acrylic acid, while using negative pressure technique, temperature
Degree is lower, therefore inhibition is more preferably, and synthetic reaction is safer.
4th, the COD total amounts in waste water of the present invention are less, environmentally friendly to require.Due to the high income of new technology, therefore
Acrylate and high polymer in waste water is less, and the COD total amounts directly resulted in waste water reduce more than 30%, and it is very good to achieve
Technique effect.
Embodiment
The preparation of the pentaerythritol triacrylate of embodiment 1
110g seasons are sequentially added in equipped with electric stirring, thermometer, water knockout drum, filled column, condenser, the reaction bulb of vavuum pump
Penta tetrol, 188g acrylic acid, 100g toluene and 60g hexamethylenes, 0.3g MEHQs, 0.3g copper sulphate, 6g pyrovinic acids,
Heat temperature raising, and open vavuum pump and vacuumize, keeps system absolute pressure between 22KPa ~ 60KPa, temperature control 80 ~ 82 DEG C it
Between, reaction generation water is with toluene azeotropic and cools down layering, water is constantly separated, up to reaction system acid number 40 ~
45mgKOH/g.60 ~ 65 DEG C are cooled to, and adds 250g toluene.Then 50g water washings are added and a point water is stood, then added
110g aqueous sodium carbonates and 120g sodium hydrate aqueous solutions neutralize and stand a point water.After neutralization terminates, 0.07g is added to hydroxyl
Methyl phenyl ethers anisole, then vacuum desolvation, removes toluene, and temperature control is 88 ~ 92 DEG C, and vacuum is 10 ~ 25Kpa (absolute pressure), is obtained
Pentaerythritol triacrylate.The finished product index of pentaerythritol triacrylate is：Acid number≤0.1mgKOH/g, color and luster≤
25APHA.Finished product 218g is filtered to obtain, yield is 90% (in terms of pentaerythrite):
The preparation of the double pentaerythritol C5 methacrylate of embodiment 2
100g is sequentially added in equipped with electric stirring, thermometer, water knockout drum, filled column, condenser, the reaction bulb of vavuum pump double
Pentaerythrite, 200g acrylic acid, 380g toluene, 10g hexamethylenes, 0.1g MEHQs, 0.25g copper sulphate, 15g methyl sulphurs
Acid, heat temperature raising, and open vavuum pump and vacuumize, keep system absolute pressure between 40KPa ~ 60KPa, temperature control is 85 ~ 90
Between DEG C, reaction generation water is with toluene, hexamethylene azeotropic and cools down layering, water is constantly separated, up to reaction system acid
Value is in 50 ~ 55mgKOH/g.50 ~ 55 DEG C are cooled to, and adds 300g toluene.Then 100g water washings are added and a point water is stood, so
Add 220g aqueous sodium carbonates afterwards and 550g sodium hydrate aqueous solutions neutralize and stand a point water.After neutralization terminates, 0.09g is added
MEHQ, then vacuum desolvation, removes toluene and hexamethylene, and temperature control is 88 ~ 92 DEG C, and vacuum is 10 ~ 25Kpa
(absolute pressure), obtained bipentaerythrite acrylate.The index of double pentaerythritol C5 methacrylate is：Acid number≤0.1mgKOH/
G, color and luster≤25APHA.Finished product 182g is filtered to obtain, yield is 88% (in terms of bipentaerythrite).
The preparation of the trimethylolpropane trimethacrylate of embodiment 3
130g tri- is sequentially added in equipped with electric stirring, thermometer, water knockout drum, filled column, condenser, the reaction bulb of vavuum pump
Hydroxymethyl-propane, 220g acrylic acid, 60g toluene and 30g hexamethylenes, 0.1g MEHQs, 0.15g copper chlorides, 12g methyl
Sulfonic acid, heat temperature raising, and open vavuum pump and vacuumize keeps system absolute pressure between 30KPa ~ 55KPa, temperature control 85 ~
Between 90 DEG C, reaction generation water is with toluene azeotropic and cools down layering, water is constantly separated, up to reaction system acid number 30
~35mgKOH/g.50 ~ 55 DEG C are cooled to, and adds 180g toluene.Then 100g water washings are added and a point water is stood, then added
115g aqueous sodium carbonates and 800g sodium hydrate aqueous solutions neutralize and stand a point water.After neutralization terminates, 0.06g is added to hydroxyl
Methyl phenyl ethers anisole, then vacuum desolvation, removes toluene, and temperature control is 88 ~ 92 DEG C, and vacuum is 10 ~ 25Kpa (absolute pressure), is obtained
Trimethylolpropane trimethacrylate.The index of trimethylolpropane trimethacrylate is：Acid number≤0.1mgKOH/g, color and luster≤
25APHA, ester content >=98%.Finished product 281g is filtered to obtain, yield is 98% (in terms of trimethylolpropane).
The comparative example of embodiment 4
110g pentaerythrites, 195g third are sequentially added in equipped with electric stirring, thermometer, water knockout drum, the reaction bulb of condenser
Olefin(e) acid, 220g toluene, 7.7g p-methyl benzenesulfonic acid, 0.66g p-tert-Butylcatechols, 0.33g phenthazine, 1.1g activated carbons, often
Pressure is heated to system in reflux state, toluene azeotrope with water will react the water of generation constantly by water knockout drum take out of system it
Outside, until there is no water from going out and reacting liquid temperature is stable, can be considered esterification terminal, whole esterification reaction process reaction
System temperature is controlled between for 103 ~ 115 DEG C, and the acid number of reaction system is about 40 ~ 45mgKOH/g.70 ~ 80 DEG C are cooled to,
88g solid sodium hydroxides are added into reaction solution, heating again makes system keep re-injection state 1 ~ 1.5 hour, the water of generation
Water is taken out of outside system with toluene azeotropic.After the completion of neutralization, system is cooled to 30 ~ 40 DEG C, filters off solid matter, adds 0.7g pairs
Removing toluene under hydroxyanisol, vacuum state, the final temperature of removing toluene process is 100 ± 5 DEG C, vacuum is 40 ~
50mmHg.Acid number≤0.1mgKOH/g of obtained pentaerythritol triacrylate, color and luster≤40APHA.Filter to obtain finished product
196g, yield is 81% (in terms of pentaerythrite).
The embodiment of the present invention 1 to 3 is compared with comparative example 4, and yield is higher, and obtained polyalcohol acrylate color and luster is excellent, and
Acrylate and high polymer in reaction waste is less, and the COD total amounts directly resulted in waste water reduce more than 30%, achieve non-
Often good unexpected technique effect.
Described above is only the preferred embodiment of the present invention, it is noted that come for those skilled in the art
Say, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (7)
1. a kind of lactate synthesis method of polyalcohol acrylate, it is characterised in that it comprises the following steps：
（1）, take polyalcohol and acrylic acid to be added in reaction vessel, the mixing for then adding toluene or toluene and hexamethylene is molten
Agent, MEHQ, copper sulphate and pyrovinic acid, heat temperature raising, and open vavuum pump and vacuumize, keep reaction system to bear
Pressure, vacuum degree control absolute pressure is between 20KPa ~ 70KPa, and temperature control reacts the water of generation with third between 75 ~ 100 DEG C
The mixed solvent azeotropic of olefin(e) acid and toluene or toluene and hexamethylene simultaneously carries out gas-liquid by filled column and exchanged, and gas phase is cooled to liquid
After be layered, lower floor's water is constantly separated, and the mixed solvent of upper strata acrylic acid and toluene or toluene and hexamethylene is returned as filled column
Flow liquid, flows through filled column, eventually flows to reactor, until the acid number of reaction system is in 30 ~ 55mgKOH/g；
（2）Then 50 ~ 65 DEG C are cooled to, and adds toluene, water washing is then added and stands a point water, then add sodium carbonate
Solution and sodium hydrate aqueous solution are neutralized, and stand a point water；
（3）After neutralization terminates, MEHQ is added, then vacuum desolvation, the mixing of removing toluene or toluene and hexamethylene
Solvent, temperature control is 85 ~ 92 DEG C, and vacuum absolute pressure is controlled in 10 ~ 25Kpa, obtained polyalcohol acrylate.
2. a kind of lactate synthesis method of polyalcohol acrylate according to claim 1, it is characterised in that reaction vessel
On electric mixing device, thermometer, filled column, water knockout drum and condenser, vavuum pump are installed.
3. a kind of lactate synthesis method of polyalcohol acrylate according to claim 1, it is characterised in that polyalcohol,
The quality amount ratio of mixed solvent, the MEHQ of acrylic acid, toluene or toluene and hexamethylene, copper sulphate and pyrovinic acid
For 1 ~ 1.5：2~2.5：2.5~7：0.1~0.15：0.0015~0.004：0.0015~0.003：0.06~0.15.
4. a kind of lactate synthesis method of polyalcohol acrylate according to claim 1, it is characterised in that step（1）
Reaction system Stress control is between absolute pressure 25KPa ~ 65KPa, and temperature control is between 78 ~ 95 DEG C.
5. a kind of lactate synthesis method of polyalcohol acrylate according to any one of claims 1 to 3, its feature exists
In polyalcohol is pentaerythrite, bipentaerythrite, trimethylolpropane, dipropylene glycol, polyethers 202, tripropylene glycol
Deng containing alcohol more than two or two hydroxyls.
6. the lactate synthesis method of a kind of polyalcohol acrylate according to claim 4, it is characterised in that copper sulphate can
Substituted with copper chloride.
7. the lactate synthesis method of a kind of polyalcohol acrylate according to claim 5, it is characterised in that toluene and ring
The mixed solvent of hexane refers to toluene weight/mass percentage composition more than 50%, and mixing of the hexamethylene weight/mass percentage composition less than 50% is molten
Agent.
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| CN201710457398.5A CN107253911A (en) | 2017-06-16 | 2017-06-16 | A kind of lactate synthesis method of polyalcohol acrylate |
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| CN201710457398.5A CN107253911A (en) | 2017-06-16 | 2017-06-16 | A kind of lactate synthesis method of polyalcohol acrylate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191650A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of pentaerythrite tetra-acetate |
| CN108752201A (en) * | 2018-06-25 | 2018-11-06 | 南通百川新材料有限公司 | A kind of green synthesis process of trimethylolpropane trimethacrylate |
| CN110452191A (en) * | 2019-06-28 | 2019-11-15 | 广东博兴新材料科技有限公司 | A kind of application of modification acrylate, preparation method and its conductive adhesive |
| CN110734370A (en) * | 2019-10-21 | 2020-01-31 | 江苏利田科技股份有限公司 | Method and device for recovering acrylic acid from UV (ultraviolet) light curing monomer crude products |
| CN115304479A (en) * | 2022-07-22 | 2022-11-08 | 嘉宝莉化工集团股份有限公司 | Preparation method and application of washing-free solvent-free modified UV monomer |
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| CN104876822A (en) * | 2014-02-28 | 2015-09-02 | 上海飞凯光电材料股份有限公司 | Pentaerythritol tetraacrylate preparation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191650A (en) * | 2017-12-25 | 2018-06-22 | 江苏雷蒙新材料有限公司 | A kind of preparation method of pentaerythrite tetra-acetate |
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| CN110452191A (en) * | 2019-06-28 | 2019-11-15 | 广东博兴新材料科技有限公司 | A kind of application of modification acrylate, preparation method and its conductive adhesive |
| CN110452191B (en) * | 2019-06-28 | 2021-06-08 | 广东博兴新材料科技有限公司 | Modified acrylate, preparation method and application of conductive adhesive |
| CN110734370A (en) * | 2019-10-21 | 2020-01-31 | 江苏利田科技股份有限公司 | Method and device for recovering acrylic acid from UV (ultraviolet) light curing monomer crude products |
| CN110734370B (en) * | 2019-10-21 | 2022-11-22 | 江苏利田科技有限公司 | Method and device for recovering acrylic acid in UV (ultraviolet) photocuring monomer crude product |
| CN115304479A (en) * | 2022-07-22 | 2022-11-08 | 嘉宝莉化工集团股份有限公司 | Preparation method and application of washing-free solvent-free modified UV monomer |
| CN115304479B (en) * | 2022-07-22 | 2023-08-15 | 嘉宝莉化工集团股份有限公司 | Preparation method and application of water-washing-free solvent-free modified UV monomer |
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