CN110981722A - Synthetic method of alcohol-containing methyl acrylate - Google Patents
Synthetic method of alcohol-containing methyl acrylate Download PDFInfo
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- CN110981722A CN110981722A CN201911389911.7A CN201911389911A CN110981722A CN 110981722 A CN110981722 A CN 110981722A CN 201911389911 A CN201911389911 A CN 201911389911A CN 110981722 A CN110981722 A CN 110981722A
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 title claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 8
- 238000004817 gas chromatography Methods 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- RGKUKMROHWBUNQ-UHFFFAOYSA-N methanol;methyl prop-2-enoate Chemical compound OC.COC(=O)C=C RGKUKMROHWBUNQ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- GMBISRIAAXSMQV-UHFFFAOYSA-N O.C(C=C)(=O)OC.CO Chemical compound O.C(C=C)(=O)OC.CO GMBISRIAAXSMQV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (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 synthetic method of alcohol-containing methyl acrylate and application thereof, and the specific method comprises the following steps: the acrylic acid and the methanol are pumped into a mixing kettle, and then the polymerization inhibitor and the catalyst are sequentially stirred fully to be mixed uniformly; then transferring the uniformly mixed materials into a reaction tower kettle, and carrying out heat preservation reaction; and (3) extracting the mixture outside the system to a rectifying tower for separation, and simultaneously adding methanol into the reaction system in batches until the reflux temperature of the materials in the kettle of the reaction tower is reduced to about 65 ℃ to stop the cyclic rectification reaction. The method is characterized in that a methanol-methyl acrylate-water ternary mixed system formed by reaction is separated out by controlling the reaction temperature and the top temperature of the rectifying tower and adopting a method of large excess of methanol to form a methyl acrylate-methanol azeotropic system. The methanol-methyl acrylate mixed solution is directly applied to synthesizing an intermediate 2-dimethyl phosphonate-1, 2, 4-methyl butanetriacate of the high-efficiency water treatment agent PBTCA, reduces the production cost, and is beneficial to realizing the continuous reaction and the large-scale industrial production.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a synthetic method of alcohol-containing methyl acrylate and application thereof.
Background
Methyl acrylate is an important fine chemical raw material with wide application, and is mainly used as an organic synthesis intermediate and a high molecular monomer. The polymer synthesized by the method can be widely applied to the industries of coating, textile, leather making, adhesive and the like, and also has wide application in the production of the industries of paper making, leather making, paint, pharmacy and the like.
At present, the production methods of acrylic acid and esters thereof mainly include a propylene oxidation method, an acrylonitrile hydrolysis method, a vinyl ketone method, a propane oxidation method, an acetylene method, a methyl formate method, and the like. At present, the two-step oxidation process of propylene is almost adopted in the industrial production of acrylic ester, about 95 percent of industrial production devices newly built after 80 years in the 20 th century adopt the two-step oxidation process of propylene, wherein relatively famous companies mainly comprise Japanese catalytic chemistry (NSKK), Japanese Mitsubishi chemistry (MCC) and Germany Basf (BASF), but the methods have the defects of more or less serious pollution, large energy consumption, large toxicity of intermediate products, low yield and the like. In recent years, the research on the production technology of methyl acrylate focuses on the improvement of the process and the research on the catalyst, and the literature reports that the synthesis of methyl acrylate by adopting industrial byproduct methyl acetate and formaldehyde or methylal as raw materials and through one-step aldol condensation reaction belongs to a typical atom economic reaction and meets the requirement of green chemistry. However, the aldol condensation reaction is limited to experimental research stages because the selection of the catalyst is strict and the product yield is not high.
The boiling point of the acrylic acid is much higher than that of the esterification reaction product and unreacted alcohol, and the acrylic acid can be separated from the reaction product liquid for recycling by one step by using a common rectification method. However, if the excessive alcohol is adopted, the purposes of promoting the forward reaction of the reaction and improving the reaction speed can be achieved, but the recovery step of the alcohol is complicated, so that the process flow of a refining system is increased, and the energy consumption of the refining system is also increased, therefore, the reaction temperature and the molar ratio of the excessive acrylic acid to the excessive alcohol are adopted in the existing propylene one-step oxidation process, and the esterification rate is improved. However, in the existing industrial production process of methyl acrylate, no matter the acrylic acid is excessive or the methanol is excessive, a ternary azeotropic system can be formed between the generated product methyl acrylate and water and the methanol, the methyl acrylate needs to be purified by repeatedly extracting and rectifying water, and a large amount of waste water is generated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of alcohol-containing methyl acrylate.
The method for synthesizing the alcohol-containing methyl acrylate is characterized by comprising the following steps:
(1) adding acrylic acid and methanol into a mixing kettle, adding a polymerization inhibitor and a catalyst, and fully stirring to uniformly mix the acrylic acid and the methanol;
(2) transferring the uniformly mixed material in the step (1) into a reaction kettle, heating and raising the temperature under the stirring condition, and then carrying out heat preservation reaction;
(3) controlling the temperature to be 65-70 ℃, extracting outside the system to a rectifying tower for separation, and simultaneously adding methanol into the reaction system until the reflux temperature of materials in the kettle of the reaction tower is reduced to 65 ℃, and stopping the cyclic rectification reaction.
Wherein the mass ratio of the acrylic acid and the methanol in the kettle in the step (1) is 1: 0.44-1.33; preferably, the molar ratio of the acrylic acid to the methanol in the kettle is 1: 0.67-0.89.
Wherein, the polymerization inhibitor in the step (1) is any one of p-hydroxyanisole or hydroquinone or the combination of the p-hydroxyanisole and the hydroquinone; the amount of the acrylic acid is 0.1-1.0% by mass. Preferably, the amount of the polymerization inhibitor accounts for 0.3-0.6% of the mass of the acrylic acid in the kettle.
Wherein, the catalyst in the step (1) is more than one of concentrated sulfuric acid, strong acid cation resin or molecular sieve; the amount of the catalyst accounts for 6-15% of the mass of the acrylic acid in the kettle. Preferably, the catalyst is a composite catalyst consisting of a molecular sieve and a sulfonic acid group strong-acid cation resin, and the mass ratio of the molecular sieve to the resin in the composite catalyst is 1: 3.
Wherein the temperature of the heat preservation reaction in the step (2) is 70-75 ℃.
Wherein the heat preservation reaction time in the step (2) is 1-5 hours, preferably 2-3 hours.
Wherein methanol supplement in the step (3) is supplemented in batches, and the mass ratio of the total methanol supplement to acrylic acid is 3-8: 1. preferably, the mass ratio of the supplemented methanol to the acrylic acid fed into the kettle is (3.5-5): 1.
wherein the mixture extracted from step (3) enters a filler rectifying tower, and azeotrope containing methanol and methyl acrylate is extracted from the top of the tower, wherein the mass ratio of methanol to methyl acrylate is mMethanol：mMethyl ester=52 to 56: 43-48; the tower bottom liquid circulates to the reaction kettle and is continuously brought to the rectifying tower for separation through the supplemented methanol, and meanwhile, the samples are sampled and the esterification reaction process is monitored through the gas chromatography until the esterification rate of the acrylic acid is more than 99.5 percent.
Wherein, the alcohol-containing methyl acrylate is applied to the synthesis of 2-phosphonic acid dimethyl ester-1, 2, 4-butanetricarboxylic acid methyl ester.
The method separates a methanol-methyl acrylate-water ternary mixed system formed by reaction from a formed methyl acrylate-methanol and water-methanol azeotropic system respectively by controlling the reaction temperature and the top temperature of a rectifying tower and adopting a low-temperature condition of less than 75 ℃ and a method of large excess of methanol, so that the reaction yield is effectively improved, and the esterification rate of acrylic acid can reach more than 99.8%; meanwhile, the synthesized alcohol-containing methyl acrylate is applied to the synthesis raw material of the high-efficiency water treatment agent 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid, so that the complicated recovery treatment step of excessive methanol and the generation of a large amount of wastewater are effectively avoided; the method is favorable for improving the utilization rate of equipment, realizing the cyclic utilization of materials, saving energy, reducing consumption, reducing production cost and realizing the continuous reaction and large-scale industrial production.
Has the beneficial effects that:
(1) the method adopts the method of supplementing excessive methanol in batches, on one hand, the forward progress of the esterification reaction is promoted, and simultaneously, the methanol-methyl acrylate-water ternary mixed system formed by the reaction is finally separated out by the formed methyl acrylate-methanol azeotropic system and the water-methanol mixed system respectively, so that the reaction yield is effectively improved, the generation of a large amount of waste water is avoided, and the esterification rate of the acrylic acid can reach more than 99.5 percent;
(2) the method of esterification reaction under low temperature condition and continuous rectification and purification by circulating the bottom liquid of the rectifying tower into the reaction tower kettle is adopted, so that the side reaction incidence is effectively inhibited, the equipment utilization rate is improved, the energy is saved, the consumption is reduced, the production cost is reduced, and the industrial continuous and large-scale production is favorably realized;
(3) collecting the alcohol-containing methyl acrylate (m) from the top of the columnAlcohol(s)：mEsters=52 to 56: 43-48) is directly applied to a raw material for synthesizing a 2-phosphonobutane-1, 2, 4-tricarboxylic acid intermediate of a high-efficiency water treatment agent, so that complicated recovery treatment steps of excessive methanol are effectively avoided, and reasonable utilization of materials is realized.
Detailed Description
Example 1
Respectively putting 100Kg of acrylic acid and 70Kg of methanol into a mixing kettle, then sequentially adding 0.5Kg of p-hydroxyanisole polymerization inhibitor and 12Kg of composite catalyst consisting of perfluorinated strong-acid cation resin and a 3A molecular sieve, wherein the mass ratio of the resin to the molecular sieve is 3:1, and fully stirring to uniformly mix the resin and the molecular sieve; transferring the uniformly mixed materials into a reaction tower kettle, heating and raising the temperature under the stirring condition, keeping the temperature at 72 +/-2 ℃ for reaction for 3 hours, then starting to collect reaction products out of the reaction products to a filler rectifying tower for separation, controlling the tower top temperature of the rectifying tower to be about 62.5 ℃ (the azeotropic temperature of methanol-methyl acrylate) and collecting tower top liquid; the tower bottom liquid circulates to the reaction tower kettle and is continuously brought to the rectifying tower through the supplemented methanol for separation, the reaction is stopped when the material reflux temperature in the reaction tower kettle is reduced to about 65 ℃, the total time of external recovery circulation is recorded for 4 hours, and the methanol quantity supplemented in batches in the reaction system is 423 Kg.
Through detection and calculation: 228.97Kg of alcoholic methyl acrylate was collected from the rectification column, wherein Gas Chromatography (GC) detected: the contents of methyl acrylate and methanol in the mixed system are 47.291% and 52.338% respectively, and the moisture content detected by a micro-water meter is 0.13%; the total esterification rate was 99.78% based on the amount of acrylic acid charged.
Example 2
Respectively putting 100Kg of acrylic acid and 80Kg of methanol into a mixing kettle, then sequentially adding 0.3Kg of p-hydroxyanisole serving as a polymerization inhibitor and 15Kg of perfluorinated strong-acid cation resin serving as a catalyst, and fully stirring to uniformly mix the materials; transferring the uniformly mixed materials into a reaction tower kettle, heating and raising the temperature under the stirring condition, keeping the temperature at 75 ℃ for reaction for 2 hours, then starting to collect reaction products out of the reaction products to a filler rectifying tower for separation, controlling the tower top temperature of the rectifying tower to be about 62.5 ℃ (the azeotropic temperature of methanol-methyl acrylate) and collecting tower top liquid; the tower bottom liquid circulates to the reaction tower kettle and is continuously brought to the rectifying tower through the supplemented methanol for separation, the reaction is stopped when the material reflux temperature in the reaction tower kettle is reduced to about 65 ℃, the total time of external recovery circulation is recorded for 6 hours, and the total methanol supplementation amount in the reaction system in batches is 356 Kg.
Through detection and calculation: 223.33Kg of alcoholic methyl acrylate was collected from the rectification column, wherein Gas Chromatography (GC) detected: the contents of methyl acrylate and methanol in the mixed system are 45.941% and 54.043% respectively, and the water content detected by a micro-water meter is 0.08%; the total esterification rate was 99.51% based on the amount of acrylic acid charged.
Example 3
Respectively putting 200Kg of acrylic acid and 178Kg of methanol into a mixing kettle, then sequentially adding 1.2Kg of p-hydroxyanisole serving as a polymerization inhibitor and 20Kg of perfluorinated strong acid cation resin serving as a catalyst, and fully stirring to uniformly mix the materials; transferring the uniformly mixed materials into a reaction tower kettle, heating and raising the temperature under the stirring condition, keeping the temperature at 72 ℃ for reaction for 3 hours, then starting to collect reaction products out of the reaction products to a filler rectifying tower for separation, controlling the tower top temperature of the rectifying tower to be about 62.5 ℃ (the azeotropic temperature of methanol-methyl acrylate) and collecting tower top liquid; the tower bottom liquid circulates to the reaction tower kettle and is continuously brought to the rectifying tower through the supplemented methanol for separation, the reaction is stopped when the material reflux temperature in the reaction tower kettle is reduced to about 65 ℃, the total 10 hours of external recovery circulation are recorded, and the total methanol supplementation amount in the reaction system in batches is 559 Kg.
Through detection and calculation: 454.34Kg of alcoholic methyl acrylate was collected from the rectification column, wherein Gas Chromatography (GC) detected: the contents of methyl acrylate and methanol in the mixed system are 47.979% and 52.009% respectively, and the moisture content detected by a micro-water meter is 0.04%; the total esterification rate was 99.37% based on the amount of acrylic acid charged.
EXAMPLE 4 use of alcoholic methyl acrylates
The methanol-methyl acrylate mixture (m) taken out from the top of the rectifying column in each of the above examples 1 was distilled off from the bottom of the rectifying columnAlcohol(s)：mEsters52.3: 47.3) and 2-phosphonic acid dimethyl dimethylester succinate according to the mass ratio of 1:1.4, controlling the reaction temperature to be less than 10 ℃, and carrying out double bond addition reaction under the action of catalyst sodium methoxide. And (3) stopping the reaction when the content of the methyl acrylate in the reaction system is less than 0.2 percent through gas phase controlled monitoring to obtain the 2-phosphonic acid dimethylesterate-1, 2, 4-trimethyl butyrate.
Claims (9)
1. The method for synthesizing the alcohol-containing methyl acrylate is characterized by comprising the following steps:
(1) adding acrylic acid and methanol into a mixing kettle, adding a polymerization inhibitor and a catalyst, and fully stirring to uniformly mix the acrylic acid and the methanol;
(2) transferring the uniformly mixed material in the step (1) into a reaction kettle, heating and raising the temperature under the stirring condition, and then carrying out heat preservation reaction;
(3) controlling the temperature to be 65-70 ℃, extracting outside the system to a rectifying tower for separation, and simultaneously adding methanol into the reaction system until the reflux temperature of materials in the kettle of the reaction tower is reduced to 65 ℃, and stopping the cyclic rectification reaction.
2. The method according to claim 1, wherein the mass ratio of the acrylic acid to the methanol in the kettle in the step (1) is 1: 0.44-1.33.
3. The method according to claim 1, wherein the polymerization inhibitor in step (1) is any one or a combination of p-hydroxyanisole or hydroquinone; the amount of the acrylic acid is 0.1-1.0% by mass.
4. The method of claim 1, wherein the catalyst in step (1) is one or more of concentrated sulfuric acid, a strongly acidic cationic resin, or a molecular sieve; the amount of the catalyst accounts for 6-15% of the mass of the acrylic acid in the kettle.
5. The method according to claim 1, wherein the temperature for the heat preservation reaction in the step (2) is 70-75 ℃.
6. The method according to claim 1, wherein the heat preservation reaction time in the step (2) is 1 to 5 hours.
7. The method according to claim 1, wherein methanol is supplemented in a batch manner in the step (3), and the mass ratio of the supplemented total amount to the acrylic acid is 3-8: 1.
8. the method as claimed in claim 1, wherein the mixed material extracted from step (3) enters a packed rectifying tower, and an azeotrope containing methanol and methyl acrylate is extracted from the top of the tower, wherein the mass ratio of methanol to methyl acrylate is mMethanol：mAcrylic acid methyl ester=52 to 56: 43-48; the tower bottom liquid circulates to the reaction kettle and is continuously brought to the rectifying tower for separation through the supplemented methanol, and meanwhile, the samples are sampled and the esterification reaction process is monitored through the gas chromatography until the esterification rate of the acrylic acid is more than 99.5 percent.
9. The method of claim 1, wherein said alcoholic methyl acrylate is used in the synthesis of 2-phosphonodimethylesteryl-1, 2, 4-butanetricarboxylate.
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