CN105566114B - A kind of clean preparation method of single functionality acrylate reactive diluent - Google Patents
A kind of clean preparation method of single functionality acrylate reactive diluent Download PDFInfo
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- CN105566114B CN105566114B CN201510178842.0A CN201510178842A CN105566114B CN 105566114 B CN105566114 B CN 105566114B CN 201510178842 A CN201510178842 A CN 201510178842A CN 105566114 B CN105566114 B CN 105566114B
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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
It is poly- comprising following step the invention discloses a kind of clean preparation method of single functionality acrylate reactive diluent：（1）Esterification；（2）The esterification generation water added in step 1, stirs stratification, separates water layer, this water layer makees the raw material of next esterification；（3）Reaction dissolvent is evaporated in vacuo, distillation detects acid number after terminating；（4）Epoxy ring opening reaction removes residual acid；（5）Detect product index.This method does not use neutralization, the traditional treatment method of washing, does not use neutralization, adsorbent absorption, the processing method of filtering yet.It neither produces organic wastewater, does not also produce solid chemical sludge, is a kind of clean preparation method for complying fully with the requirement of industry clean manufacturing, and production process does not have loss of material, and all processes are completed in same reactor, have good economic benefit.
Description
Technical field
The invention belongs to the fields such as radiation curable coating, ink, adhesive, are related to a kind of single functionality acrylate reactive
The clean preparation method of diluent.
Background technology
Radiation curing is to trigger to have the crosslinking of chemically active liquid material rapid polymerization, wink using ultraviolet light or electron beam
Between be solidified into a kind of advanced material process for treating surface of solid-state material.It has the characteristics that quick-drying, energy-conservation and environment-friendly.Closely
As the enhancing of people's energy conservation and environmental awareness, radiation-curable products varieties and characteristicses constantly strengthen over year, application field is constantly expanded,
Yield quickly increases, and impetus development is swift and violent.Reactive diluent is a kind of organic molecule for being contained in polymerizable functional group, is radiation
An important composition in curing materials.Single functionality acrylate reactive diluent generally have viscosity it is low, dilution property it is strong, solidification
The features such as volume contraction is few, therefore it is usually used in the occasion of requirement lower shrinkage.Particularly simple function end group containing methoxy（Methyl）Acrylic acid
Ester monomer, not only shrinkage is low, high conversion rate, while curing rate is fast, equivalent to even more than polyfunctional monomer, makes its use
It is more and more extensive on the way.
Existing acrylate production technology typically divides water using first alcohol and acroleic acid esterification, afterwards plus in buck and excessive third
Olefin(e) acid and catalyst, then wash salt caused by neutralization, last desolvation.Acidic catalyst and excessive third in the production technology
Olefin(e) acid will all wash removing, and this will produce a large amount of high COD industrial organic waste water, and processing is difficult, processing cost is high, and processing is bad
Environment can be polluted.Meanwhile washing product can lose portioned product, reduce product yield, increase production cost, do not meet
The requirement of cleaner Production in Chemical Industry.
A kind of MPEG acrylate, methoxyl group DPG propylene are disclosed in the A of patent CN 102675097
The clean preparation method of acid esters or methoxyl group tripropylene glycol acrylate.First divide alcohol and acroleic acid esterification to water, add piece alkali and
A small amount of water neutralizes, and the rear salt for adding the absorption of multi-silicate magnesium adsorbent and neutralizing generation, decompression dehydration desolventizing, filters out multi-silicate magnesium
And its salt of absorption, add alkaline calcium bentonite, calcium oxide decolourizes, de- minor amount of water, Determining Micro Acid, after the alkalescence for filtering addition
Calcium-base bentonite, calcium oxide.This approach avoid washing product, the shortcomings that overcoming conventional method, organic wastewater will not be produced,
But add the acrylic acid that in alkali and equally have lost catalyst and excess；Multi-silicate magnesium, alkaline calcium bentonite after absorption,
The filter residues such as calcium oxide are solid waste, it is necessary to properly dispose；Post-processing step is on the high side, operates duration.
The content of the invention
For above-mentioned technical disadvantages, the present invention is provided in a kind of production process, neither produces organic wastewater, is not also produced solid
Body chemical sludge, and production process does not have loss of material, complies fully with the single functionality acrylate of industry clean manufacturing requirement
The clean preparation method of reactive diluent.
The technical solution adopted in the present invention is：A kind of clean manufacturing side of single functionality acrylate reactive diluent
Method, it is characterised in that：It is poly- comprising following specific step：
（1）Esterification：Monohydric alcohol in molar ratio：Acrylic acid=1:1-1.2 is added in reactor, continuously adds band water
Solvent, catalyst, polymerization inhibitor, antioxygen are lost lustre agent, and the gaseous mixture of air or nitrogen and air, heating are passed through from reactor bottom
80-120 DEG C of refuxing esterification divides water, and acid number is detected when substantially anhydrous separate and is necessarily less than 30mgKOH/g, is cooled after qualified cold
But to 50 DEG C, wherein, added in the ratio for accounting for alkyd gross mass, band aqueous solvent 30-100%, catalyst 0.5-5%, polymerization inhibitor
0.3-3%, antioxygen are lost lustre agent 0.1-0.5%；（2）The esterification generation water added in step 1, stirs stratification, separates to contain and urges
The superacid water layer of agent and part, this water layer make the raw material of next esterification；（3）Reaction dissolvent, distillation knot is evaporated in vacuo
Acid number is detected after beam；（4）Epoxy ring opening reaction removes residual acid：Add gross mass 0.1-3% epoxide opening catalyst, acid mole
The 100-110 DEG C of reaction of number 1.0-1.05 band epoxy compounds and residual acid open loop；（5）Detect product index：Outward appearance is clear
It is clear bright, total ester content >=96%, color number≤100APHA, acid number≤1mgKOH/g, moisture content≤0.15%.
The monohydric alcohol is laruyl alcohol, phenmethylol, furancarbinol, MPEG, methoxyl group DPG, methoxyl group
The methoxy poly (ethylene glycol) of tripropylene glycol, molecular weight 350,400,550,1000,2000.
The monohydric alcohol：Acrylic acid=1:1.05-1.1.
The band aqueous solvent be toluene, benzene, dimethylbenzene, thiacyclohexane, methyl cyclohexanol, normal hexane, normal heptane and they
Mixture.
The catalyst is p-methyl benzenesulfonic acid, benzene sulfonic acid, the one or more to Loprazolam and its derivative
Arbitrary proportion mixture.
The polymerization inhibitor is MEHQ, one kind of DBPC 2,6 ditertiary butyl p cresol or interworking thing.
The antioxygen lose lustre agent be hypophosphorous acid the aqueous solution or sodium hypophosphite.
The epoxide opening catalyst is triethylamine, N, N- dimethyl benzylamines, DMA, trimethyl benzyl
Ammonium chloride, triphenylphosphine, antimony triphenyl, chromium acetylacetonate, one or more kinds of arbitrary proportions of first ethyl phosphonium bromide ammonium mix
Compound.
The band epoxy compounds be epoxy prapanol, epoxychloropropane, epoxy-cyclohexane,（Methyl）Acrylic acid shrinks sweet
Alcohol diglycidyl ether, 3,4- epoxide rings be for alcohol glycidol ether, bicyclopentadiene dioxide, 1,2- rings for grease, ring
Base formic acid -3,4- epoxy cyclohexyl methyl esters, hexanedioic acid are double（3,4- epoxy cyclohexyl methyl esters）, epoxide number rubs for 0.44-0.6
You/100 grams of epoxy resin and other monocyclic oxygen or multi-epoxy glycidol ether.
The molal quantity calculation formula that is of the present invention with epoxy compounds acid be：Molal quantity=gross mass * acid numbers of acid/
56050。
The present invention is by improving the removal of esterification rear catalyst and the processing method of excessive propene acid.With in step 1
Esterification generation water washing after water layer contain partial catalyst and part excessive propene acid, this water layer makees next esterification
Used during raw material input production next time, avoid the waste of catalyst and excessive propene acid.The acrylic acid remained in product is used again
Band epoxy compounds esterification by ring opening, generation product is acrylate reactive diluent analog, character and acrylate reactive
Diluent is essentially identical, and product is not adversely affected.I.e. excessive propene acid is partly into next time in product in the present invention
Production participates in esterification again, and another part reaches with generating acrylate reactive diluent analog with epoxy compounds
Except the purpose of excessive propene acid.
The present invention have selected band epoxy compounds and excessive propene acid be converted into acrylate reactive diluent analog.
Band epoxy compounds can be with acrylic acid quantitative reaction, and reaction condition is gentle, and reaction does not have accessory substance output, product and propylene
Acid esters reactive diluent character, performance are similar, do not influence character, the performance of product.
This method does not use neutralization, the traditional treatment method of washing, does not use neutralization, adsorbent absorption, the place of filtering yet
Reason method.It neither produces organic wastewater, does not also produce solid chemical sludge, is that one kind complies fully with the requirement of industry clean manufacturing
Clean preparation method, and production process does not have loss of material, and all processes are completed in same reactor, has good
Economic benefit.
Embodiment
It is further described below according to embodiment
Embodiment 1：
600KG toluene, methoxy poly (ethylene glycol) are added into 2 tons of stainless steel cauldrons（Molecular weight 350）700KG, propylene
Sour 155.5KG, MEHQ 10KG, p-methyl benzenesulfonic acid 14KG, aqueous hypophosphorous acid 2KG；Stirring is opened, bottom is empty
Air compressor is passed through air, and heat up 100-110 degree reflux water-dividings, and when substantially anhydrous separate, sampling detection acid number is less than
30mgKOH/g, cool to 50 degree；The esterification generation water added in step 1, stirs stratification, separate containing catalyst and
The superacid water layer in part, this water layer make the raw material of next esterification；Reaction dissolvent is evaporated in vacuo, distillation detects acid after terminating
Value；Triphenyl phosphorus 5KG is added, epoxy prapanol 17.4KG, 100-110 DEG C is reacted 5 hours, sampling detection, when acid number is less than 1
Stop during mgKOH/g, cooling to discharge produces methoxy poly (ethylene glycol)（350）Acrylate.Detect product index：Outward appearance is clear
It is clear bright, total ester content >=98.2%, color 40APHA, acid number 0.4372mgKOH/g, moisture content 0.11%.
Embodiment 2:
600KG thiacyclohexanes, phenmethylol 756KG, acrylic acid 544KG, para hydroxybenzene first are added into 2 tons of stainless steel cauldrons
Ether 15.6KG, p-methyl benzenesulfonic acid 19.5KG, aqueous hypophosphorous acid 4KG；Stirring is opened, bottom is passed through sky with air compressor
Gas, heat up 100-110 degree reflux water-dividings, and when substantially anhydrous separate, sampling detection acid number is less than 30mgKOH/g, cools
To 50 degree；The esterification generation water added in step 1, stirs stratification, separates containing the superacid water layer of catalyst and part, this
Water layer makees the raw material of next esterification；Reaction dissolvent is evaporated in vacuo, distillation detects acid number after terminating；Triphenyl phosphorus 9KG is added,
GMA 45KG, 100-110 DEG C is reacted 5 hours, sampling detection, is stopped when acid number is less than 1 mgKOH/g
Only, cool to discharge and produce benzyl acrylate.Detect product index：Outward appearance clear, total ester content >=97.6%, color
Number 90APHA, acid number 0.4839mgKOH/g, moisture content 0.13%..
Embodiment 3:
600KG toluene, furancarbinol 618KG, acrylic acid 490KG, para hydroxybenzene first are added into 2 tons of stainless steel cauldrons
Ether 10KG, p-methyl benzenesulfonic acid 13KG, aqueous hypophosphorous acid 3KG；Stirring is opened, bottom is passed through air with air compressor, rises
Warm 100-110 degree reflux water-dividing, when substantially anhydrous separate, sampling detection acid number is less than 30mgKOH/g, cools to 50
Degree；The esterification generation water added in step 1, stirs stratification, separates containing the superacid water layer of catalyst and part, this water layer
Make the raw material of next esterification；Reaction dissolvent is evaporated in vacuo, distillation detects acid number after terminating；Add triphenyl phosphorus 7KG, epoxy
Chloropropane 25KG, 100-110 DEG C is reacted 5 hours, sampling detection, is stopped when acid number is less than 1 mgKOH/g, is cooled out
Expect to produce methoxyl group tripropylene glycol acrylate.Detect product index：Outward appearance clear, total ester content >=98.3%, color number
50APHA, acid number 0.3486mgKOH/g, moisture content 0.11%.
Embodiment of the present invention is only the description carried out to the preferred embodiment of the present invention, not to the present invention
Spirit and scope are defined, and on the premise of design philosophy of the present invention is not departed from, engineers and technicians are to this hair in this area
The all variations and modifications that bright technical scheme is made, protection scope of the present invention, the claimed skill of the present invention all should be fallen into
Art content, all record in detail in the claims.
Claims (8)
- A kind of 1. clean preparation method of single functionality acrylate reactive diluent, it is characterised in that：Include following specific step It is poly-：（1）Esterification：Monohydric alcohol in molar ratio：Acrylic acid=1:1-1.2 add reactor in, continuously add band aqueous solvent, Catalyst, polymerization inhibitor, antioxygen are lost lustre agent, and the gaseous mixture of air or nitrogen and air is passed through from reactor bottom, and heat up 80-120 DEG C refuxing esterification divides water, and acid number is detected when substantially anhydrous separate and is necessarily less than 30mgKOH/g, it is qualified after cooling down to 50 DEG C, wherein, added in the ratio for accounting for alkyd gross mass, band aqueous solvent 30-100%, catalyst 0.5-5%, polymerization inhibitor 0.3- 3%th, antioxygen is lost lustre agent 0.1-0.5%；（2）The esterification generation water added in step 1, stirs stratification, separate containing catalyst and The superacid water layer in part, this water layer make the raw material of next esterification；（3）Reaction dissolvent is evaporated in vacuo, distillation is examined after terminating Survey acid number；（4）Epoxy ring opening reaction removes residual acid：Add gross mass 0.1-3% epoxide opening catalyst, sour molal quantity The 100-110 DEG C of reaction of 1.0-1.05 band epoxy compounds and residual acid open loop；（5）Detect product index：Outward appearance is clarified It is transparent, total ester content >=96%, color number≤100APHA, acid number≤1mgKOH/g, moisture content≤0.15%；Wherein described band oxo-compound be epoxy prapanol, epoxychloropropane, epoxy-cyclohexane, glycidyl acrylate, GMA, ring alcohol glycidol ether, bicyclopentadiene dioxide, 1,2- rings alcohol 2-glycidyl Ether, 3,4- epoxy cyclohexyl formic acid -3,4- epoxy cyclohexyls methyl esters, hexanedioic acid are double（3,4- epoxy cyclohexyl methyl esters）, ring Oxygen value is 0.44-0.6 moles/100 grams of epoxy resin and monocyclic oxygen or multi-epoxy glycidol ether.
- 2. clean preparation method according to claim 1, it is characterised in that：The monohydric alcohol is laruyl alcohol, phenmethylol, furan Mutter methanol, MPEG, methoxyl group DPG, methoxyl group tripropylene glycol, molecular weight 350,400,550,1000, 2000 methoxy poly (ethylene glycol).
- 3. clean preparation method according to claim 1, it is characterised in that：The monohydric alcohol：Acrylic acid=1:1.05- 1.1。
- 4. clean preparation method according to claim 1, it is characterised in that：The band aqueous solvent is toluene, benzene, diformazan Benzene, thiacyclohexane, methyl cyclohexanol, normal hexane, normal heptane and their mixture.
- 5. clean preparation method according to claim 1, it is characterised in that：Described catalyst be p-methyl benzenesulfonic acid, Benzene sulfonic acid, one or more kinds of arbitrary proportion mixtures to Loprazolam and its derivative.
- 6. clean preparation method according to claim 1, it is characterised in that：Described polymerization inhibitor be MEHQ, One kind or interworking thing of DBPC 2,6 ditertiary butyl p cresol.
- 7. clean preparation method according to claim 1, it is characterised in that：Described antioxygen lose lustre agent be hypophosphorous acid water Solution or sodium hypophosphite.
- 8. clean preparation method according to claim 1, it is characterised in that：The epoxide opening catalyst be triethylamine, N, N- dimethyl benzylamine, DMA, trimethyl benzyl ammonia chloride, triphenylphosphine, antimony triphenyl, acetylacetone,2,4-pentanedione One or more kinds of arbitrary proportion mixtures of chromium, first ethyl phosphonium bromide ammonium.
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| 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 |
| CN111285764B (en) * | 2019-01-14 | 2023-08-01 | 广东博兴新材料科技有限公司 | Treatment method for reutilization of (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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| CN1434020A (en) * | 2002-01-11 | 2003-08-06 | Dsm有限公司 | Process for preparing acrylic ester (methacrylic) |
| CN1659211A (en) * | 2002-06-11 | 2005-08-24 | 巴斯福股份公司 | (meth)acrylic esters of polyalkoxylated trimethylolpropane |
| CN102491896A (en) * | 2011-11-22 | 2012-06-13 | 江苏利田科技股份有限公司 | Clean production method of dipropylene glycol diacrylate (DPGDA) or tripropylene glycol diacrylate (TPGDA) |
| CN103553920A (en) * | 2013-09-26 | 2014-02-05 | 上海维凯化学品有限公司 | Preparation method of phenoxy benzyl acrylic ester |
| CN103819337A (en) * | 2013-09-29 | 2014-05-28 | 安庆飞凯高分子材料有限公司 | Method for preparing trifunctional-group pentaerythritol acrylate |
-
2015
- 2015-04-16 CN CN201510178842.0A patent/CN105566114B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1278240A (en) * | 1997-10-31 | 2000-12-27 | 国际人造丝公司 | Sulfur removal process from an acrylate stream |
| CN1434020A (en) * | 2002-01-11 | 2003-08-06 | Dsm有限公司 | Process for preparing acrylic ester (methacrylic) |
| CN1659211A (en) * | 2002-06-11 | 2005-08-24 | 巴斯福股份公司 | (meth)acrylic esters of polyalkoxylated trimethylolpropane |
| CN102491896A (en) * | 2011-11-22 | 2012-06-13 | 江苏利田科技股份有限公司 | Clean production method of dipropylene glycol diacrylate (DPGDA) or tripropylene glycol diacrylate (TPGDA) |
| CN103553920A (en) * | 2013-09-26 | 2014-02-05 | 上海维凯化学品有限公司 | Preparation method of phenoxy benzyl acrylic ester |
| CN103819337A (en) * | 2013-09-29 | 2014-05-28 | 安庆飞凯高分子材料有限公司 | Method for preparing trifunctional-group pentaerythritol acrylate |
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