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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- acid
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- epoxy
- esterification
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- -1 acrylic ester Chemical class 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- 239000003085 diluting agent Substances 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000005886 esterification reaction Methods 0.000 claims abstract description 24
- 230000032050 esterification Effects 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 150000002118 epoxides Chemical group 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 239000003930 superacid Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001427 mPEG Polymers 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229960004217 benzyl alcohol Drugs 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 3
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 claims description 2
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000006386 neutralization reaction Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- 239000010815 organic waste Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 239000002894 chemical waste Substances 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 238000005070 sampling Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910000281 calcium bentonite Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NQOGBCBPDVTBFM-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(C)COC(C)CO NQOGBCBPDVTBFM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- YATYDCQGPUOZGZ-UHFFFAOYSA-N 2-(2-hydroxypropoxy)propan-1-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(C)CO YATYDCQGPUOZGZ-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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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| 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 |
| CN115894227A (en) * | 2022-10-19 | 2023-04-04 | 珠海展辰新材料股份有限公司 | UV monomer and its preparation method |
| CN117025060A (en) * | 2023-08-19 | 2023-11-10 | 韶关南田精细化工技术有限公司 | A kind of cationic iron printing coating and preparation method thereof |
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