CN105330537A - Preparation method of methoxyethyl acrylate - Google Patents
Preparation method of methoxyethyl acrylate Download PDFInfo
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- CN105330537A CN105330537A CN201510852633.XA CN201510852633A CN105330537A CN 105330537 A CN105330537 A CN 105330537A CN 201510852633 A CN201510852633 A CN 201510852633A CN 105330537 A CN105330537 A CN 105330537A
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- acrylate
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- methoxyethyl acrylate
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- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 59
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 7
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- -1 tetramethyl piperidine nitrogen oxygen free radical Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- QRIXUJIWPKIHGR-UHFFFAOYSA-N [Zn].C(C)C(=O)C(=O)C Chemical compound [Zn].C(C)C(=O)C(=O)C QRIXUJIWPKIHGR-UHFFFAOYSA-N 0.000 claims description 4
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical class ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- CKJMHSMEPSUICM-UHFFFAOYSA-N di-tert-butyl nitroxide Chemical class CC(C)(C)N([O])C(C)(C)C CKJMHSMEPSUICM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 13
- 230000035484 reaction time Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 150000002148 esters Chemical group 0.000 abstract description 2
- 238000000066 reactive distillation Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- 238000010533 azeotropic distillation Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical class CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229920005559 polyacrylic rubber Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 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
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of methoxyethyl acrylate. The preparation method is characterized in that methyl acrylate and methyl cellosolve are taken as raw materials; in the presence of a catalyst and a polymerization inhibitor, a reactive distillation ester exchange process is adopted for reaction; the catalysis in the reaction is realized by using zinc acetylacetonate, and methanol generated by reaction is timely removed by azeotropic distillation, so that a reaction product containing the methoxyethyl acrylate is obtained; the dosage mole ratio of the methyl acrylate to the methyl cellosolve is (1.0-5.0) to 1, the usage of the catalyst is 0.01 to 1.0 percent of total mass of raw materials, and the usage of the polymerization inhibitor is 0.02 to 2.0 percent of total mass of the raw materials. The method has better catalytic effect for preparing the methoxyethyl acrylate; according to the method, the movement of the reaction towards the direction of generating the methoxyethyl acrylate is promoted, reaction time is shortened, the content of polymer is obviously reduced, and the efficiency of a reaction still is improved.
Description
Technical field
The present invention relates to a kind of preparation method of Chemicals, be related specifically to a kind of preparation method of methoxyethyl acrylate.
Background technology
Methoxyethyl acrylate is a kind of important two-component acrylicester adhesive and thermosetting acrylic resin, and it is high temperature resistant/and oil-proofness makes it can be used as the comonomer of polyacrylic elastomer.Can be used as barrier coat and tackiness agent in addition, PVC impact modifying agent, contact lens.There is provided good bounding force, chemical resistance, elasticity, impact, weathering resistance and low-shrinkage.It or UV solidify the splendid reactive diluent of series.The preparation method of prior art methoxyethyl acrylate mainly contains direct esterification and ester-interchange method.
CN102850217A discloses the preparation method of one (methyl) methoxyethyl acrylate, is with (methyl) methyl acrylate and ethylene glycol-methyl ether for raw material, under composite catalyst and stopper effect, generates (methyl) methoxyethyl acrylate.Described catalyzer is that organic tin catalyzer is or/and organic titanium class catalyzer.
TQ225.13+1 describes a kind of with the methoxyethyl acrylate green syt route of the solvent-free participation of heteropolyacid (silicotungstic acid) catalysis.Adopt ethylene glycol monomethyl ether and vinylformic acid direct esterification and obtain, productive rate is 93.2%.
0258-3283(2008) 12-0947-01 describes a kind of synthetic method of methoxyethyl acrylate.Employing tosic acid is catalyzer, and Resorcinol is stopper, and utilize ethylene glycol monomethyl ether and vinylformic acid direct esterification and obtain, water entrainer is toluene, productive rate nearly 70%.
CN101475475 discloses a kind of method being prepared vinylformic acid alkoxyalkyl methacrylate or methacrylic ethyl ester by esterification process operational path, be with acrylic or methacrylic acid and ethylene glycol monoalkyl ether for raw material, with SO
4 2-/ TiO
2solid super-strong acid is catalyzer, thiodiphenylamine or thiodiphenylamine-Resorcinol-copper powder are stopper, toluene is water entrainer, direct esterification acrylic acid synthesizing alkoxyalkyl methacrylate or methacrylic ethyl ester, the method catalyzer and product separation are easily, little to equipment corrosion.
US6008404 discloses the transesterification reaction that a kind of alkyl methacrylate and alcohols carry out, and catalyzer is alkali metal alcoholates, and stopper is bromine salt.
US2002111511 discloses a kind of Exchange Ester Process of methylpropionate class, and used catalyst is a) alkali metal cyanate or thiocyanate-, b) alkaline earth metal oxide, alkali metal hydroxide or halogenide, the mixture of the two.
The catalyzer mentioned in above-mentioned document and patent, kind is more, and different, organic tin catalyzer or/and compound catalyst (based on the organic tin catalyzer) relative price of organic titanium class catalyzer costly, cost is higher; There is the problems such as the loss of active ingredient solution-off and carbon distribution inactivation in heteropolyacid (silicotungstic acid) catalyzer; Solid super-strong acid SO
4 2-/ TiO
2, an acidic catalyst such as toluene sulfonic acide, it generally all has certain acidity, has certain requirement to equipment, apparatus and operational condition etc., and long reaction time, side reaction are many, serious three wastes; Alkali metal alcoholates, alkali metal cyanate or thiocyanate-and alkaline earth metal oxide, alkali metal hydroxide or the mixture etc. both halogenide are mentioned specific to preparing methoxyethyl acrylate.The direct esterification reaction adopted in report, there is complicated operation, easily causes the problems such as environmental pollution in this method more in technique.
Summary of the invention
Object of the present invention is exactly to solve the problem, and provides the preparation method of the methoxyethyl acrylate that a kind of reaction efficiency is high, cost is low.
In order to achieve the above object, present invention employs following technical scheme: a kind of preparation method of methoxyethyl acrylate, is characterized in that: adopt acrylate and methyl cellosolve reaction, react and carry out catalysis by zinc acetylacetonate.
The reaction of acrylate and methyl cellosolve is, getting methyl acrylate and methyl cellosolve is 1.0 ~ 5.0:1 batching in molar ratio, add together in reactor, then the methyl ethyl diketone zinc catalyst of the total mass 0.01% ~ 1.0% being equivalent to methyl acrylate and methyl cellosolve is added, and stopper, open and stir, heat temperature raising, after tower top temperature rises, after tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column ratio, controlling reflux ratio makes tower top temperature be stabilized in 61 ~ 66 DEG C, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature has when obviously rising, stop heating, cooling, temperature controls at 60-80 DEG C, reaction solution is moved on to separating still underpressure distillation, first excessive methyl acrylate is removed, then Removal of catalyst, stopper and heavy component, the methoxyethyl acrylate product that purity is greater than 99.5% can be obtained from tower top.
Reaction solution removes the vacuum degree control of methyl acrylate at 10 ~ 15kPa when moving on to separating still underpressure distillation, tower top temperature controls at 40 ~ 50 DEG C.
Methoxyethyl methacrylate distillation vacuum degree control at 0.01 ~ 2kPa, tower top temperature controls at 66 ~ 100 DEG C.
The consumption mol ratio of described methyl acrylate and methyl cellosolve is 2.0 ~ 3.0:1.
The consumption of described methyl ethyl diketone zinc catalyst is raw material total mass 0.01% ~ 1.0%.
Stopper consumption is equivalent to the total mass 0.02% ~ 2.0% of methyl acrylate and methyl cellosolve.
Described stopper is the one in nitroxyl oxides of free radical inhibitor, is di-tert-butyl nitroxide or 2,2,6,6-tetramethyl--4-hydroxy piperidine-1-oxygen nitroxyl free radical or tetramethyl piperidine nitrogen oxygen free radical tris phosphite
.
The temperature of reaction of acrylate and methyl cellosolve controls at 80 ~ 130 DEG C.
The reaction of acrylate and methyl cellosolve is under agitation carried out, and stir speed (S.S.) is 100-500rpm.
The preparation method of methoxyethyl acrylate of the present invention, owing to have employed above technical scheme, makes it compared with prior art, has following advantage and disadvantage:
Owing to employing efficient catalyzer, shorten the reaction times, reduce polymer content, improve quality product and yield.Catalyst levels is few, and cost is low.Reactive distillation process technology, by excessive methyl acrylate and the formation of methanol azeotrope, removes by-product carbinol in time, facilitate reaction and want that the direction generating methoxyethyl acrylate is moved, shorten the reaction times, significantly reduce polymer content, improve the efficiency of reactor.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the preparation method of methoxyethyl acrylate of the present invention.
Shown in process flow sheet, 1 is reactor, and 2 is one-level rectifying tower, and 3 is azeotrope receiving tank, and 4 is separating still, and 5 is two-stage rectification tower, and 6 is Light ends receiving tank, and 7 is intermediate component receiving tank, and 8 is product receiving tank.
Embodiment
The preparation method of methoxyethyl acrylate of the present invention is: getting methyl acrylate and methyl cellosolve is 2.0 ~ 3.0:1 batching in molar ratio, adds together in reactor.Then the catalyzer of the total mass 0.01% ~ 1.0% being equivalent to methyl acrylate and methyl cellosolve is added, and be equivalent to the stopper of total mass 0.02% ~ 2.0% of methyl acrylate and methyl cellosolve, open and stir, heat temperature raising, after tower top temperature rises, after tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column ratio, controlling reflux ratio makes tower top temperature be stabilized in 61 ~ 66 DEG C, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature has when obviously rising, stop heating, cooling (controlling at 60-80 DEG C).Reaction solution is moved on to separating still underpressure distillation, first (vacuum degree control is at 10 ~ 15kPa to remove excessive methyl acrylate, tower top temperature controls at 40 ~ 50 DEG C), then Removal of catalyst, stopper and heavy component, can from tower top obtain purity be greater than 99.5% methoxyethyl acrylate product (methoxyethyl acrylate product distillation vacuum degree control at 0.01 ~ 2kPa, tower top temperature controls at 66 ~ 100 DEG C).
The present invention is further illustrated below by embodiment.Embodiment 1
5 liters of reactors, on reactor, rectifying tower is φ 50*2.5mm, tower height 1000mm
Add 2263g methyl acrylate and 1000g methyl cellosolve in a kettle., add 65.3g dibutyl tin sulfide as catalyzer, add 6.53g tetramethyl piperidine nitrogen oxygen free radical tris phosphite as stopper.
Open and stir, heat temperature raising, when reactor temperature rises to 90 ~ 100 DEG C, tower top starts discharging, total reflux, when tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column than system, reflux ratio is 6:1 ~ 6:2, tower top temperature is made to be stabilized in 61 ~ 66 DEG C by regulating reflux ratio, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature have when obviously rising, and stops heating, cooling, sampling analysis.
Reaction solution composition (passing through gas chromatography determination):
Methyl alcohol 0.12%
Methyl cellosolve 8.63%
Methyl acrylate 27.24%
Methoxyethyl acrylate 59.22%
Heavy constituent 2.83%
Reaction solution is moved on to separating still, start decompression separation, under 10 ~ 15kPa condition, remove excessive methyl methacrylate, then Removal of catalyst, stopper and heavy component under 1 ~ 2000Pa condition, obtains at product receiving tank the methoxyethyl acrylate product 1631g that purity is greater than 99.8%.
Embodiment 2
5 liters of reactors, on reactor, rectifying tower is φ 50*2.5mm, tower height 1000mm
Add 2037g methyl acrylate and 1200g methyl cellosolve in a kettle., the mixture adding 64.7g Dibutyltin oxide and tetrabutyl titanate, as catalyzer (the two quality proportioning 3:1), adds 6.47g tetramethyl piperidine nitrogen oxygen free radical tris phosphite as stopper.
Open and stir, heat temperature raising, when reactor temperature rises to 90 ~ 100 DEG C, tower top starts discharging, total reflux, when tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column than system, reflux ratio is 6:1 ~ 6:2, tower top temperature is made to be stabilized in 61 ~ 66 DEG C by regulating reflux ratio, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature have when obviously rising, and stops heating, cooling, sampling analysis.
Reaction solution composition (passing through gas chromatography determination):
Methyl alcohol 0.05%
Methyl cellosolve 7.27%
Methyl acrylate 27.11%
Methoxyethyl acrylate 61.55%
Heavy constituent 2.92%
Reaction solution is moved on to separating still, start decompression separation, under 10 ~ 15kPa condition, remove excessive methyl methacrylate, then Removal of catalyst, stopper and heavy component under 1 ~ 2000Pa condition, obtains at product receiving tank the methoxyethyl acrylate product 1783g that purity is greater than 99.8%.
Embodiment 3
5 liters of reactors, on reactor, rectifying tower is φ 50*2.5mm, tower height 1000mm
Add 2263g methyl acrylate and 1000g methyl cellosolve in a kettle., add 16.32g zinc acetylacetonate, add 3.26g tetramethyl piperidine nitrogen oxygen free radical tris phosphite as stopper.
Open and stir, heat temperature raising, when reactor temperature rises to 90 ~ 100 DEG C, tower top starts discharging, total reflux, when tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column than system, reflux ratio is 6:1 ~ 6:2, tower top temperature is made to be stabilized in 61 ~ 66 DEG C by regulating reflux ratio, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature have when obviously rising, and stops heating, cooling, sampling analysis.
Reaction solution composition (passing through gas chromatography determination):
Methyl alcohol 0.4%
Methyl cellosolve 6.82%
Methyl acrylate 31.33%
Methoxyethyl acrylate 60.38%
Heavy constituent 0.81%
Reaction solution is moved on to separating still, start decompression separation, under 10 ~ 15kPa condition, remove excessive methyl methacrylate, then Removal of catalyst, stopper and heavy component under 1 ~ 2000Pa condition, obtains at product receiving tank the methoxyethyl acrylate product 1793g that purity is greater than 99.8%.
Embodiment 4
5 liters of reactors, on reactor, rectifying tower is φ 50*2.5mm, tower height 1000mm
Add 2037g methyl acrylate and 1200g methyl cellosolve in a kettle., add 22.66g zinc acetylacetonate, add 3.24g tetramethyl piperidine nitrogen oxygen free radical tris phosphite as stopper.
Open and stir, heat temperature raising, when reactor temperature rises to 90 ~ 100 DEG C, tower top starts discharging, total reflux, when tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column than system, reflux ratio is 6:1 ~ 6:2, tower top temperature is made to be stabilized in 61 ~ 66 DEG C by regulating reflux ratio, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature have when obviously rising, and stops heating, cooling, sampling analysis.
Reaction solution composition (passing through gas chromatography determination):
Methyl alcohol 0.4%
Methyl cellosolve 7.31%
Methyl acrylate 27.50%
Methoxyethyl acrylate 64.01%
Heavy constituent 0.35%
Reaction solution is moved on to separating still, start decompression separation, under 10 ~ 15kPa condition, remove excessive methyl methacrylate, then Removal of catalyst, stopper and heavy component under 1 ~ 2000Pa condition, obtains at product receiving tank the methoxyethyl acrylate product 1750g that purity is greater than 99.8%.
Embodiment 5
1000 liters of reactors, on reactor, rectifying tower is φ 400*5mm, tower height 6800mm
Add 680kg methyl acrylate and 300kg methyl cellosolve in a kettle., add 5.88kg zinc acetylacetonate, add 0.98kg tetramethyl piperidine nitrogen oxygen free radical tris phosphite as stopper.
Open and stir, heat temperature raising, when reactor temperature rises to 90 ~ 100 DEG C, tower top starts discharging, total reflux, when tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column than system, reflux ratio is 6:1 ~ 6:2, tower top temperature is made to be stabilized in 61 ~ 66 DEG C by regulating reflux ratio, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature have when obviously rising, and stops heating, cooling, sampling analysis.
Reaction solution composition (passing through gas chromatography determination):
Methyl alcohol 0.06%
Methyl cellosolve 9.27%
Methyl acrylate 23.46%
Methoxyethyl acrylate 65.88%
Heavy constituent 0.61%
Reaction solution is moved on to separating still, start decompression separation, under 10 ~ 15kPa condition, remove excessive methyl methacrylate, then Removal of catalyst, stopper and heavy component under 1 ~ 2000Pa condition, obtains at product receiving tank the methoxyethyl acrylate product 559kg that purity is greater than 99.8%.
Claims (10)
1. a preparation method for methoxyethyl acrylate, is characterized in that: adopt acrylate and methyl cellosolve reaction, react and carry out catalysis by zinc acetylacetonate.
2. the preparation method of a kind of methoxyethyl acrylate according to claim 1, is characterized in that: the reaction of acrylate and methyl cellosolve is, getting methyl acrylate and methyl cellosolve is 1.0 ~ 5.0:1 batching in molar ratio, add together in reactor, then the methyl ethyl diketone zinc catalyst of the total mass 0.01% ~ 1.0% being equivalent to methyl acrylate and methyl cellosolve is added, and stopper, open and stir, heat temperature raising, after tower top temperature rises, after tower top temperature is stabilized in 61 ~ 63 DEG C, open trim the top of column ratio, controlling reflux ratio makes tower top temperature be stabilized in 61 ~ 66 DEG C, treat between still temperature rise to 115 ~ 125 DEG C, and tower top temperature has when obviously rising, stop heating, cooling, temperature controls at 60-80 DEG C, reaction solution is moved on to separating still underpressure distillation, first excessive methyl acrylate is removed, then Removal of catalyst, stopper and heavy component, the methoxyethyl acrylate product that purity is greater than 99.5% can be obtained from tower top.
3. the preparation method of a kind of methoxyethyl acrylate according to claim 2, is characterized in that: remove the vacuum degree control of methyl acrylate when reaction solution moves on to separating still underpressure distillation at 10 ~ 15kPa, tower top temperature controls at 40 ~ 50 DEG C.
4. the preparation method of a kind of methoxyethyl acrylate according to claim 2, is characterized in that: methoxyethyl methacrylate distillation vacuum degree control at 0.01 ~ 2kPa, tower top temperature controls at 66 ~ 100 DEG C.
5. the preparation method of a kind of methoxyethyl acrylate according to claim 2, is characterized in that: the consumption mol ratio of described methyl acrylate and methyl cellosolve is 2.0 ~ 3.0:1.
6. the preparation method of a kind of methoxyethyl acrylate according to claim 2, is characterized in that: the consumption of described methyl ethyl diketone zinc catalyst is raw material total mass 0.01% ~ 1.0%.
7. the preparation method of a kind of methoxyethyl acrylate according to claim 2, is characterized in that: stopper consumption is equivalent to the total mass 0.02% ~ 2.0% of methyl acrylate and methyl cellosolve.
8. the preparation method of a kind of methoxyethyl acrylate according to claim 2 or 7, it is characterized in that: described stopper is the one in nitroxyl oxides of free radical inhibitor, for di-tert-butyl nitroxide or 2,2,6,6-tetramethyl--4-hydroxy piperidine-1-oxygen nitroxyl free radical or tetramethyl piperidine nitrogen oxygen free radical tris phosphite
.
9. the preparation method of a kind of methoxyethyl acrylate according to claim 2, is characterized in that: the temperature of reaction of acrylate and methyl cellosolve controls at 80 ~ 130 DEG C.
10. the preparation method of a kind of methoxyethyl acrylate according to claim 2, is characterized in that: the reaction of acrylate and methyl cellosolve is under agitation carried out, and stir speed (S.S.) is 100-500rpm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110713438A (en) * | 2019-05-29 | 2020-01-21 | 抚顺东联安信化学有限公司 | Production process of ethylene glycol di (meth) acrylate |
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