CN105566114A - Clean production method for monofuction acrylic ester reactive diluent - Google Patents
Clean production method for monofuction acrylic ester reactive diluent Download PDFInfo
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- CN105566114A CN105566114A CN201510178842.0A CN201510178842A CN105566114A CN 105566114 A CN105566114 A CN 105566114A CN 201510178842 A CN201510178842 A CN 201510178842A CN 105566114 A CN105566114 A CN 105566114A
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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
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
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Abstract
The invention discloses a clean production method for a monofuction acrylic ester reactive diluent. The clean production method comprises the following steps: (1) performing esterification reaction; (2) adding the esterification generated water in step 1, stirring, leaving to stand to layer, and separating a water layer, wherein the water layer is taken as a raw material for next esterification reaction; (3) performing vacuum distillation on a reaction solvent, and detecting the acid value after distillation; (4) performing epoxide ring-opening reaction to remove residual acid; (5) inspecting product indexes. Conventional treatment methods such as neutralization and washing are not used, and treatment methods such as neutralization, adsorption with an adsorbent, and filtration are not used either. Both organic waste water and solid chemical waste slag are not generated, so that the clean production method can completely meet the clean production requirements of the industry; moreover as material loss is avoided in the production process, and the process is completed within one same reaction kettle, good economic benefits are achieved.
Description
Technical field
The invention belongs to the fields such as radiation curable coating, ink, tackiness agent, relate to a kind of clean preparation method of single functionality acrylate reactive thinner.
Background technology
Radiation curing utilizes UV-light or electron beam initiation to have chemically active liquid material rapid polymerization to be cross-linked, and instantaneous solidification becomes a kind of advanced material process for treating surface of solid-state material.It has the features such as quick-drying, energy-conservation and environmental friendliness.In recent years along with the enhancing of people's energy-conserving and environment-protective consciousness, radiation-curable products varieties and characteristics constantly strengthens, and Application Areas is constantly expanded, and output increases fast, and impetus development is swift and violent.Reactive thinner is a kind of organic molecule being contained in polymerizable functional group, is an important composition in radiation curing material.Single functionality acrylate reactive thinner has the features such as viscosity is low, dilution property is strong, and solidification volumetric shrinkage is few usually, therefore is usually used in the occasion of requirement lower shrinkage.Particularly simple function is containing methoxy end group (methyl) acrylate monomer, and not only shrinkability is low, and transformation efficiency is high, and curing speed is fast simultaneously, is equivalent to even exceed polyfunctionality monomer, makes its purposes more and more extensive.
Existing acrylate production technique generally adopts first alcohol and acroleic acid esterification to divide water, after to add in buck and excessive propene acid and catalyzer, then the salt that washing neutralization produces, last desolvation.In this production technique, an acidic catalyst and excessive vinylformic acid all will wash removing, and this will produce the industrial organic waste water of a large amount of high COD, and process is difficult, processing costs is high, processes bad meeting to environment.Meanwhile, washing product can lose portioned product, reduces product yield, increases production cost, does not meet the requirement of cleaner Production in Chemical Industry.
The clean preparation method of a kind of MPEG acrylate, methoxyl group dipropylene glycol acrylate or methoxyl group tripropylene glycol acrylate is disclosed in patent CN102675097A.First divide water by alcohol and acroleic acid esterification, add sheet alkali and the neutralization of a small amount of water, after the salt that to add in multi-silicate magnesium adsorbent and generate, decompression dehydration desolventizing, filter out the salt of multi-silicate magnesium and absorption thereof, add alkaline calcium bentonite, calcium oxide decolouring, de-minor amount of water, Determining Micro Acid, after filtering the alkaline calcium bentonite, the calcium oxide that add.This approach avoid washing product, overcome the shortcoming of traditional method, can not organic waste water be produced, but, add in alkali and have lost catalyzer and excessive vinylformic acid equally; The filter residue such as multi-silicate magnesium, alkaline calcium bentonite, calcium oxide after absorption is solid waste, needs properly to dispose; Post-processing step is on the high side, operation duration.
Summary of the invention
For above-mentioned technical disadvantages, the invention provides in a kind of production process, neither produce organic waste water, also do not produce solid chemical sludge, and production process does not have loss of material, meet the clean preparation method of the single functionality acrylate reactive thinner of industry cleaner production requirement completely.
The technical solution adopted in the present invention is: a kind of clean preparation method of single functionality acrylate reactive thinner, is characterized in that: comprise following concrete step poly-:
(1) esterification: monohydroxy-alcohol in molar ratio: vinylformic acid=1:1-1.2 adds in reactor, continue to add band water solvent, catalyzer, stopper, antioxygen lose lustre agent, the gas mixture of air or nitrogen and air is passed into from reactor bottom, an intensification 80-120 DEG C refuxing esterification divides water, detect acid number when substantially anhydrous separating and must be less than 30mgKOH/g, qualified rear cooling down to 50 DEG C, wherein, add in the ratio accounting for alkyd total mass, band water solvent 30-100%, catalyzer 0.5-5%, stopper 0.3-3%, antioxygen are lost lustre agent 0.1-0.5%; (2) esterification added in step 1 generates water, and stir stratification, separate containing catalyzer and the superacid water layer of part, this water layer makes the raw material of next esterification; (3) vacuum distilling reaction solvent, distillation terminates rear detection acid number; (4) epoxy addition reaction is except residual acid: add the epoxide opening catalyst of total mass 0.1-3%, the band epoxy compounds of sour mole number 1.0-1.05 and residual acid open loop 100-110 DEG C and react; (5) testing product index: outward appearance clear, total ester content >=96%, look number≤100APHA, acid number≤1mgKOH/g, water ratio≤0.15%.
The methoxy poly (ethylene glycol) that described monohydroxy-alcohol is lauryl alcohol, phenylcarbinol, furfuralcohol, MPEG, methoxyl group dipropylene glycol, methoxyl group tripropylene glycol, molecular weight are 350,400,550,1000,2000.
Described monohydroxy-alcohol: vinylformic acid=1:1.05-1.1.
Described band water solvent is toluene, benzene, dimethylbenzene, cyclohexane, methyl cyclohexanol, normal hexane, normal heptane and their mixture.
Described catalyzer is p-methyl benzenesulfonic acid, Phenylsulfonic acid, one or more arbitrary proportion mixture to methanesulfonic and derivative thereof.
Described stopper is MEHQ, the one of 2,6 ditertiary butyl p cresol or interworking thing.
The agent of losing lustre of described antioxygen is the aqueous solution or the inferior sodium phosphate of Hypophosporous Acid, 50.
Described epoxide opening catalyst is one or more arbitrary proportion mixture of triethylamine, N, N-dimethyl benzylamine, DMA, trimethyl benzyl ammonia chloride, triphenylphosphine, antimony triphenyl, chromium acetylacetonate, the first and second base brometo de amonios.
Described band epoxy compounds is R-GLYCIDOL, epoxy chloropropane, epoxy-cyclohexane, (methyl) glycidyl acrylate, ring alcohol glycidyl ether, bicyclopentadiene dioxide, 1,2-ring is alcohol diglycidylether, 3,4-epoxy cyclohexyl formic acid-3,4-epoxy cyclohexyl methyl esters, adipic acid two (3,4-epoxy cyclohexyl methyl esters), oxirane value is the epoxy resin of 0.44-0.6 mole/100 grams and other monocycle oxygen or multi-epoxy glycidyl ether.
The calculation formula that the mole number of band epoxy compounds of the present invention acid is is: mole number=total mass * acid number/56050 of acid.
The removal of the present invention by improvement esterification rear catalyst and the treatment process of excessive propene acid.Contain partially catalyzed agent and the acid of part excessive propene with the water layer after the esterification generation water washing in step 1, use when this water layer does raw material input production next time of next esterification, avoid the waste of catalyzer and excessive propene acid.Vinylformic acid residual in product is again with band epoxy compounds esterification by ring opening, and generating product is acrylate reactive thinner analogue, and proterties is substantially identical with acrylate reactive thinner, does not have disadvantageous effect to product.Namely in the present invention, in product, an excessive propene acid part enters to produce next time and again participates in esterification, and another part generates acrylate reactive thinner analogue with band epoxy compounds, reaches the object of removal excessive propene acid.
The present invention have selected band epoxy compounds and excessive propene acid is converted into acrylate reactive thinner analogue.Band epoxy compounds can with vinylformic acid quantitative reaction, reaction conditions is gentle, and reaction does not have by product output, and product and acrylate reactive thinner proterties, performance are similar, do not affect the proterties of product, performance.
Present method does not adopt the traditional treatment method of neutralization, washing, does not adopt the treatment process of neutralization, adsorbent, filtration yet.It neither produces organic waste water, does not also produce solid chemical sludge, and be a kind of clean preparation method meeting industry cleaner production requirement completely, and production process does not have loss of material, all processes all complete in same reactor, have good economic benefit.
Embodiment
Be further described according to embodiment below
Embodiment 1:
600KG toluene is added, methoxy poly (ethylene glycol) (molecular weight 350) 700KG, vinylformic acid 155.5KG, MEHQ 10KG, p-methyl benzenesulfonic acid 14KG, aqueous hypophosphorous acid 2KG in 2 tons of stainless steel cauldrons; Open and stir, pass into air, intensification 100-110 degree reflux water-dividing at the bottom of still with air compressor, when substantially anhydrous separating, sampling detects acid number and is less than 30mgKOH/g, cools to 50 degree; The esterification added in step 1 generates water, and stir stratification, separate containing catalyzer and the superacid water layer of part, this water layer makes the raw material of next esterification; Vacuum distilling reaction solvent, distillation terminates rear detection acid number; Add triphenyl phosphorus 5KG, R-GLYCIDOL 17.4KG, 100-110 DEG C is reacted 5 hours, and sampling detects, and stop when acid number is less than 1mgKOH/g, namely the discharging that cools obtains methoxy poly (ethylene glycol) (350) acrylate.Testing product index: outward appearance clear, total ester content >=98.2%, look 40APHA, acid number 0.4372mgKOH/g, water ratio 0.11%.
Embodiment 2:
600KG cyclohexane is added, phenylcarbinol 756KG, vinylformic acid 544KG, MEHQ 15.6KG, p-methyl benzenesulfonic acid 19.5KG, aqueous hypophosphorous acid 4KG in 2 tons of stainless steel cauldrons; Open and stir, pass into air, intensification 100-110 degree reflux water-dividing at the bottom of still with air compressor, when substantially anhydrous separating, sampling detects acid number and is less than 30mgKOH/g, cools to 50 degree; The esterification added in step 1 generates water, and stir stratification, separate containing catalyzer and the superacid water layer of part, this water layer makes the raw material of next esterification; Vacuum distilling reaction solvent, distillation terminates rear detection acid number; Add triphenyl phosphorus 9KG, glycidyl methacrylate 45KG, 100-110 DEG C is reacted 5 hours, and sampling detects, and stop when acid number is less than 1mgKOH/g, namely the discharging that cools obtains benzyl acrylate.Testing product index: outward appearance clear, total ester content >=97.6%, look 90APHA, acid number 0.4839mgKOH/g, water ratio 0.13%.。
Embodiment 3:
600KG toluene is added, furfuralcohol 618KG, vinylformic acid 490KG, MEHQ 10KG, p-methyl benzenesulfonic acid 13KG, aqueous hypophosphorous acid 3KG in 2 tons of stainless steel cauldrons; Open and stir, pass into air, intensification 100-110 degree reflux water-dividing at the bottom of still with air compressor, when substantially anhydrous separating, sampling detects acid number and is less than 30mgKOH/g, cools to 50 degree; The esterification added in step 1 generates water, and stir stratification, separate containing catalyzer and the superacid water layer of part, this water layer makes the raw material of next esterification; Vacuum distilling reaction solvent, distillation terminates rear detection acid number; Add triphenyl phosphorus 7KG, epoxy chloropropane 25KG, 100-110 DEG C is reacted 5 hours, and sampling detects, and stop when acid number is less than 1mgKOH/g, namely the discharging that cools obtains methoxyl group tripropylene glycol acrylate.Testing product index: outward appearance clear, total ester content >=98.3%, look 50APHA, acid number 0.3486mgKOH/g, water ratio 0.11%.
Embodiment of the present invention is only the description carried out the preferred embodiment of the present invention; not design of the present invention and scope are limited; under the prerequisite not departing from design philosophy of the present invention; the various modification that in this area, engineering technical personnel make technical scheme of the present invention and improvement; protection scope of the present invention all should be fallen into; the technology contents of request protection of the present invention, all records in detail in the claims.
Claims (9)
1. a clean preparation method for single functionality acrylate reactive thinner, is characterized in that: comprise following concrete step poly-:
(1) esterification: monohydroxy-alcohol in molar ratio: vinylformic acid=1:1-1.2 adds in reactor, continue to add band water solvent, catalyzer, stopper, antioxygen lose lustre agent, the gas mixture of air or nitrogen and air is passed into from reactor bottom, an intensification 80-120 DEG C refuxing esterification divides water, detect acid number when substantially anhydrous separating and must be less than 30mgKOH/g, qualified rear cooling down to 50 DEG C, wherein, add in the ratio accounting for alkyd total mass, band water solvent 30-100%, catalyzer 0.5-5%, stopper 0.3-3%, antioxygen are lost lustre agent 0.1-0.5%; (2) esterification added in step 1 generates water, and stir stratification, separate containing catalyzer and the superacid water layer of part, this water layer makes the raw material of next esterification; (3) vacuum distilling reaction solvent, distillation terminates rear detection acid number; (4) epoxy addition reaction is except residual acid: add the epoxide opening catalyst of total mass 0.1-3%, the band epoxy compounds of sour mole number 1.0-1.05 and residual acid open loop 100-110 DEG C and react; (5) testing product index: outward appearance clear, total ester content >=96%, look number≤100APHA, acid number≤1mgKOH/g, water ratio≤0.15%.
2. clean preparation method according to claim 1, is characterized in that: the methoxy poly (ethylene glycol) that described monohydroxy-alcohol is lauryl alcohol, phenylcarbinol, furfuralcohol, MPEG, methoxyl group dipropylene glycol, methoxyl group tripropylene glycol, molecular weight are 350,400,550,1000,2000.
3. clean preparation method according to claim 1, is characterized in that: described monohydroxy-alcohol: vinylformic acid=1:1.05-1.1.
4. clean preparation method according to claim 1, is characterized in that: described band water solvent is toluene, benzene, dimethylbenzene, cyclohexane, methyl cyclohexanol, normal hexane, normal heptane and their mixture.
5. clean preparation method according to claim 1, is characterized in that: described catalyzer is p-methyl benzenesulfonic acid, Phenylsulfonic acid, one or more arbitrary proportion mixture to methanesulfonic and derivative thereof.
6. clean preparation method according to claim 1, is characterized in that: described stopper is MEHQ, the one of 2,6 ditertiary butyl p cresol or interworking thing.
7. clean preparation method according to claim 1, is characterized in that: the agent of losing lustre of described antioxygen is the aqueous solution or the inferior sodium phosphate of Hypophosporous Acid, 50.
8. clean preparation method according to claim 1, it is characterized in that: described epoxide opening catalyst is triethylamine, N, one or more arbitrary proportion mixture of N-dimethyl benzylamine, DMA, trimethyl benzyl ammonia chloride, triphenylphosphine, antimony triphenyl, chromium acetylacetonate, the first and second base brometo de amonios.
9. clean preparation method according to claim 1, it is characterized in that: described band epoxy compounds is R-GLYCIDOL, epoxy chloropropane, epoxy-cyclohexane, glycidyl acrylate, glycidyl methacrylate, ring alcohol glycidyl ether, bicyclopentadiene dioxide, 1,2-ring is alcohol diglycidylether, 3,4-epoxy cyclohexyl formic acid-3,4-epoxy cyclohexyl methyl esters, adipic acid two (3,4-epoxy cyclohexyl methyl esters), oxirane value is the epoxy resin of 0.44-0.6 mole/100 grams and monocycle oxygen or multi-epoxy glycidyl ether.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734586A (en) * | 2019-01-14 | 2019-05-10 | 广东博兴新材料科技有限公司 | A kind of processing method that esterification hair answers in system (methyl) acrylic acid to recycle |
| CN109880062A (en) * | 2019-01-14 | 2019-06-14 | 广东博兴新材料科技有限公司 | A kind of cross-linkable solidifying material and its continuous production method |
| CN117025060A (en) * | 2023-08-19 | 2023-11-10 | 韶关南田精细化工技术有限公司 | Cationic iron printing coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109734586A (en) * | 2019-01-14 | 2019-05-10 | 广东博兴新材料科技有限公司 | A kind of processing method that esterification hair answers in system (methyl) acrylic acid to recycle |
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| CN109734586B (en) * | 2019-01-14 | 2020-05-15 | 广东博兴新材料科技有限公司 | Treatment method for recycling (methyl) acrylic acid in esterification reaction system |
| CN117025060A (en) * | 2023-08-19 | 2023-11-10 | 韶关南田精细化工技术有限公司 | Cationic iron printing coating and preparation method thereof |
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