CN117126051A - Process for preparing higher fatty alcohol (meth) acrylates - Google Patents
Process for preparing higher fatty alcohol (meth) acrylates Download PDFInfo
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- CN117126051A CN117126051A CN202210554402.0A CN202210554402A CN117126051A CN 117126051 A CN117126051 A CN 117126051A CN 202210554402 A CN202210554402 A CN 202210554402A CN 117126051 A CN117126051 A CN 117126051A
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- fatty alcohol
- higher fatty
- acrylic acid
- meth
- esterification reaction
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- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 title description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 137
- 238000005886 esterification reaction Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000000605 extraction Methods 0.000 claims abstract description 23
- -1 fatty alcohol ester Chemical class 0.000 claims abstract description 20
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004042 decolorization Methods 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000066 reactive distillation Methods 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 68
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 53
- 239000000243 solution Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 17
- 239000008346 aqueous phase Substances 0.000 description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 9
- 239000004927 clay Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 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 1
- 238000001179 sorption measurement Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical group ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of chemical industry and discloses a method for preparing (methyl) acrylic acid higher fatty alcohol ester. The method comprises the following steps: the method comprises the steps of (1) contacting higher fatty alcohol with excessive (methyl) acrylic acid for esterification reaction, leading water generated in the esterification reaction process out of an esterification reaction system along with the excessive (methyl) acrylic acid, and carrying out post-treatment after the reaction is finished to obtain a (methyl) acrylic acid higher fatty alcohol ester product; the excess (meth) acrylic acid is recovered by extraction with a hydrophobic fatty alcohol. The method can promote the esterification reaction, improve the conversion rate, does not introduce a third solvent, effectively reduces the discharge of waste liquid, is more environment-friendly, and has the advantages of low process energy consumption and low cost.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for preparing (methyl) acrylic acid higher fatty alcohol ester.
Background
The (methyl) acrylic acid higher fatty alcohol ester has active double bond, is an important fine chemical product and high polymer monomer, contains hydrophobic long chain aliphatic hydrocarbon skeleton, and its homopolymer or copolymer has the features of water resistance, flexibility, hardness and impact resistance, and is used as oil additive, adsorption resin, adhesive and internal plasticizer, and has wide application in paint, oil additive, plastic, papermaking, leather, cosmetics and other fields. The preparation of fatty alcohol (meth) acrylate generally adopts an ester interchange method, namely, methyl (meth) acrylate and higher fatty alcohol are subjected to ester interchange reaction in the presence of a catalyst, so that lower fatty alcohol is continuously removed, and the reaction is promoted; the direct esterification method of (methyl) acrylic acid can also be adopted, namely, the (methyl) acrylic acid and higher fatty alcohol are subjected to esterification reaction, and the byproduct, namely water, is required to be continuously removed in order to promote the reaction; compared with the transesterification method, the reaction temperature of the direct esterification of the (methyl) acrylic acid and the higher fatty alcohol is higher, and the reaction efficiency is higher.
The esterification reaction equilibrium conversion rate of (methyl) acrylic acid and higher fatty alcohol is low, and the byproduct water is required to be continuously removed, so that the reaction is promoted to be carried out in the forward reaction direction. Generally, a low-boiling point solvent which can form an azeotrope with water is added into a reaction system, and the removal rate of water is improved through the azeotropy of the low-boiling point solvent and the water; CN1733687a discloses a process for preparing higher fatty alcohol esters of (meth) acrylic acid, adding benzene, toluene, cyclohexane, carbon tetrachloride, chloroform, n-pentane and n-hexane as entrainer of water to the reaction system to enhance the removal of water, the molar ratio of (meth) acrylic acid to higher fatty alcohol is 0.5-5.0, preferably 1.0-2.0, and the product yield can reach 97.8%. The method has the defects that new substances are added into the reaction mixture, so that on one hand, the rectifying and purifying difficulty of a reaction system is increased, and on the other hand, the azeotropic solvent needs to be purified before being recycled to the upstream for recycling; although the solvent azeotropic method can efficiently and rapidly improve the conversion rate of the esterification reaction, the problems of secondary distillation of the solvent, process loss and the like are outstanding, the whole energy consumption and time are long, and the color of the product is poor.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for preparing (methyl) acrylic acid higher fatty alcohol ester, which can promote esterification reaction, improve conversion rate, effectively reduce waste liquid discharge, is more environment-friendly and has the advantages of lower process energy consumption and lower cost.
The inventor of the invention discovers that the increase of the amount of the higher fatty alcohol easily leads to more alcohol residues in the product and influences the quality of the product; however, by increasing the amount of (meth) acrylic acid, the reaction proceeds in the forward reaction direction remarkably effectively, and the excess (meth) acrylic acid is easily removed after the reaction is completed. In order to achieve the above object, the present invention provides a process for producing a higher fatty alcohol (meth) acrylate, comprising:
(1) The method comprises the steps of (1) contacting higher fatty alcohol with excessive (methyl) acrylic acid for esterification reaction, wherein water generated in the esterification reaction process is led out of an esterification reaction system along with the excessive (methyl) acrylic acid;
(2) Optionally, recovering (meth) acrylic acid from the mixture of water and (meth) acrylic acid extracted in step (1) by extraction with a hydrophobic higher fatty alcohol, and recycling the recovered (meth) acrylic acid for esterification in step (1);
(3) Optionally, the material containing the higher fatty alcohol (meth) acrylate produced by the esterification reaction is subjected to post-treatment to obtain the higher fatty alcohol (meth) acrylate.
The invention can obtain the following beneficial effects:
1. according to the technical scheme, excessive (methyl) acrylic acid is adopted, and byproduct water is continuously removed through azeotropy, so that the esterification reaction can be effectively promoted to proceed towards the positive reaction direction, the conversion rate is improved, and other entrainers can be not introduced. The method for recycling (methyl) acrylic acid can effectively reduce the discharge of waste liquid, is more environment-friendly, and has the advantages of low process energy consumption and low cost.
2. By adopting the method, the (methyl) acrylic acid can be extracted by adopting the higher fatty alcohol which can participate in the esterification reaction, the introduction of the azeotropic third solvent can be avoided, and the purification difficulty is reduced. Meanwhile, the polymerization inhibitor does not need to be additionally added, the process cost is further reduced, the environment is protected, and meanwhile, the extraction efficiency is higher.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the term "(meth) acrylic" refers to acrylic acid and/or methacrylic acid; the term "higher fatty alcohol (meth) acrylate" refers to higher fatty alcohol acrylate and/or higher fatty alcohol methacrylate.
The present invention provides a process for producing a higher fatty alcohol (meth) acrylate, which comprises:
(1) The method comprises the steps of (1) contacting higher fatty alcohol with excessive (methyl) acrylic acid for esterification reaction, wherein water generated in the esterification reaction process is led out of an esterification reaction system along with the excessive (methyl) acrylic acid;
(2) Optionally, recovering (meth) acrylic acid from the mixture of water and (meth) acrylic acid extracted in step (1) by extraction with a hydrophobic higher fatty alcohol, and recycling the recovered (meth) acrylic acid for esterification in step (1);
(3) Optionally, the material containing the higher fatty alcohol (meth) acrylate produced by the esterification reaction is subjected to post-treatment to obtain the higher fatty alcohol (meth) acrylate.
It will be appreciated that the esterification reaction, carboxylic acid groups and hydroxyl groups are typically reacted at a molar ratio of 1, and that an acid excess is considered when the acid is used in an amount such that the molar ratio of carboxylic acid groups to hydroxyl groups exceeds 1.
The inventor of the invention discovers in the research that compared with the traditional production mode, the method adopts excessive (methyl) acrylic acid, continuously removes byproduct-water through azeotropy, can effectively promote the esterification reaction to proceed towards the positive reaction direction, improves the conversion rate, can not introduce other entrainers, and reduces the purification difficulty. The method can effectively reduce the discharge of waste liquid and is more environment-friendly by recovering and recycling (methyl) acrylic acid. A water separator may be used to draw the produced water out of the reaction vessel with excess (meth) acrylic acid.
According to the present invention, in order to further ensure sufficient removal of water to further promote the esterification reaction and to improve the conversion, it is preferable that the initial molar ratio of (meth) acrylic acid to higher fatty alcohol in terms of hydroxyl groups is greater than 1, preferably 1.01 to 3 (for example, may be a numerical range consisting of 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.1, 1.3, 1.5, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3 and any two of the above).
According to a particularly preferred embodiment of the present invention, the esterification reaction system is free of other entrainers, including benzene, toluene, cyclohexane, carbon tetrachloride, chloroform, n-pentane, n-hexane, and the like.
According to the present invention, the higher fatty alcohol is preferably at least one of a hydrophobic fatty alcohol having 9 to 26 carbon atoms (e.g., a saturated monohydric alcohol), more preferably at least one of a hydrophobic fatty alcohol having 9 to 16 carbon atoms (e.g., a saturated monohydric alcohol). For example, at least one of (n) decanol, (n) undecanol, (n) dodecanol, and (n) tetradecanol may be used.
According to the present invention, the conditions for the esterification reaction are not particularly limited and may be those commonly used in the art. Preferably, the temperature of the esterification reaction is 70 to 140 ℃. The temperature of the esterification reaction system may be changed within a certain range, and the temperature of the esterification reaction system may be controlled within the above range.
According to the present invention, it is preferable that the time of the esterification reaction is 3 to 20 (for example, may be 3, 5, 8, 10, 12, 15, 18, 20) h.
According to the present invention, it is preferable that the esterification reaction is performed in a reactive distillation/rectification apparatus.
Wherein the esterification reaction may be performed in an inert gas such as nitrogen atmosphere, and may be performed under normal pressure.
According to the present invention, it is preferable that in the step (1), the esterification reaction is carried out in the presence of a catalyst which is at least one of sulfuric acid, sulfonic acid type, heteropolyacid and acid resin, and the catalyst is used in an amount of 0.05 to 10 (for example, may be 0.05,1,2,3,4,5,6,7,8,9, 10) wt%, more preferably 0.3 to 3 wt% based on the total weight of (meth) acrylic acid and higher fatty alcohol. The sulfonic acid may be at least one of p-toluenesulfonic acid and methanesulfonic acid. The heteropoly acid is an oxygen-containing polyacid formed by coordination and bridging of hetero atoms and multi-coordination atoms through oxygen atoms, and can be phosphotungstic acid, phosphotungstic molybdic acid, silicotungstic acid and the like. The acidic resin capable of releasing hydrogen ions may be a macroporous acidic resin or the like.
According to the present invention, it is preferable that in the step (1), the esterification reaction is carried out in the presence of at least one of a phenolic polymerization inhibitor, a quinone polymerization inhibitor, an aromatic amine polymerization inhibitor and an inorganic salt polymerization inhibitor in an amount of 0.03 to 5 (for example, may be 0.03, 0.1, 0.5, 1,2,3,4, 5% by weight, more preferably 0.03 to 0.2% by weight) based on the total weight of (meth) acrylic acid and higher aliphatic alcohol. The phenolic polymerization inhibitor can be hydroquinone, pyrogallol, p-tert-butyl catechol and the like. The quinone polymerization inhibitor can be tetrachlorobenzoquinone, 1, 4-naphthoquinone, etc. The arylamine polymerization inhibitor can be p-phenylenediamine, benzidine, diphenylamine, p- (methyl) aniline and the like. The inorganic salt polymerization inhibitor can be ferric chloride, cuprous oxide and the like.
According to the present invention, it is preferable that in step (2), the hydrophobic higher fatty alcohol is the same as or different from the higher fatty alcohol in step (1). The hydrophobic higher fatty alcohol can better extract and separate the (methyl) acrylic acid in the mixture of water and (methyl) acrylic acid.
According to the present invention, it is preferable that the hydrophobic higher fatty alcohol used for extraction is at least one of monohydric fatty alcohols having 9 to 26 carbon atoms (e.g., saturated monohydric fatty alcohols), preferably at least one of monohydric fatty alcohols having 9 to 16 carbon atoms; and is the same as the higher fatty alcohol in step (1). The (methyl) acrylic acid in the mixture of water and (methyl) acrylic acid can be better separated by adopting the higher fatty alcohol which is the same as that in the step (1), and when the separated (methyl) acrylic acid is reused in the step (1), new substances are not introduced, so that the purification difficulty is reduced, an additional polymerization inhibitor is not required, the process cost is further reduced, the environment is protected, and meanwhile, the extraction efficiency is higher.
According to the present invention, in order to further ensure sufficient extraction and separation of (meth) acrylic acid, it is preferable that the volume ratio of the hydrophobic higher fatty alcohol to the mixture used for extraction is 0.3 to 10:1, more preferably 1 to 4:1.
According to the present invention, in order to further ensure sufficient extraction and separation of (meth) acrylic acid, the extraction temperature is preferably from 0 to 90 ℃, more preferably from 20 to 60 ℃.
According to the present invention, preferably, in step (3), the post-treatment is performed by: the material containing the (meth) acrylic acid higher fatty alcohol ester is sequentially subjected to alkali washing, distillation and decolorization. By adopting the method, the (methyl) acrylic acid higher fatty alcohol ester with higher purity can be further ensured to be obtained.
According to the present invention, preferably, in step (3), the post-treatment is performed by: the post-treatment mode is as follows: alkali washing with alkali metal hydroxide solution of concentration 1-20wt% at 20-60 deg.c; then desalted water is used for treatment until the solution is neutral; then carrying out reduced pressure distillation under the vacuum degree of 5-95 kPa; and then decolorizing by using a decolorizing agent. The decolorizing agent may be a conventional choice in the art, and may be at least one of clay and diatomaceous earth, for example.
According to a particularly preferred embodiment of the invention, methacrylic acid, dodecanol, 70% by mass aqueous methanesulfonic acid and hydroquinone are added to the reaction flask in such a way that the initial molar ratio of methacrylic acid to higher fatty alcohol in terms of hydroxyl groups is 1.01 to 1.1, the amount of methanesulfonic acid being 0.36 to 0.4% by weight based on the total weight of methacrylic acid and higher fatty alcohol, and the amount of hydroquinone being 0.037 to 0.04% by weight based on the total weight of methacrylic acid and higher fatty alcohol. N is introduced into the reaction solution 2 And heating to 100 deg.c for timing the esterification reaction, controlling the reaction temperature to 100-130 deg.c, and distilling water with methacrylic acid to separate out water. After the reaction is carried out for 7.5 to 8.5 hours, unreacted methacrylic acid is distilled out under reduced pressure, alkali washing is carried out by using sodium hydroxide solution with the concentration of 1 to 20 weight percent at the temperature of 30 to 40 ℃, then desalted water is used for treatment until the reaction is neutral, reduced pressure distillation is carried out under the vacuum degree of 10 to 20kPa, and then clay is used for decolorization, thus obtaining the lauryl methacrylate.
The present invention will be described in detail by examples. In the following examples, a reactive distillation apparatus was used for the esterification reaction.
Examples 1-7 illustrate the method of esterification with excess methacrylic acid. The calculation method of the dodecanol conversion rate comprises the following steps: and detecting according to gas chromatography to obtain the residual dodecanol content in the reaction liquid, and further obtaining the conversion rate of the dodecanol and the initial dodecanol. Among them, higher fatty alcohol methacrylates are generally synthesized with high selectivity, and therefore, the reacted dodecanol is generally converted into higher fatty alcohol methacrylates. In examples 1 to 7, it was found that the liquid distilled off by the water separator was mainly water and methacrylic acid during the esterification reaction.
Example 1
Into a reaction flask, 22.38g of methacrylic acid, 38.62g of dodecanol (i.e., lauryl alcohol), 0.31g of 70 mass% aqueous methanesulfonic acid solution and 0.022g of hydroquinone were charged N 2 And heating to 100 deg.c for timing the esterification reaction, controlling the reaction temperature to 100-130 deg.c, and distilling water with methacrylic acid to separate out water. After the reaction was carried out for 8 hours, unreacted methacrylic acid was distilled off under reduced pressure, alkali washing was carried out at 25℃with a sodium hydroxide solution having a concentration of 5% by weight, then the reaction mixture was treated with desalted water to neutrality, distillation was carried out under reduced pressure at a vacuum of 10kPa, and then decolorization was carried out with clay to obtain lauryl methacrylate. The reaction solution was analyzed by gas chromatography, and the dodecanol conversion rate was 99.98%.
Example 2
Into a reaction flask, 129.14g of methacrylic acid, 186.34g of dodecanol, 1.67g of 70 mass% aqueous methanesulfonic acid solution and 0.1101g of hydroquinone were introduced N 2 And heating to 100 deg.c for timing the esterification reaction, controlling the reaction temperature to 100-140 deg.c, and distilling water with methacrylic acid to separate out water. After the reaction was carried out for 8 hours, unreacted methacrylic acid was distilled off under reduced pressure, alkali washing was carried out at 50℃with a 10% strength by weight sodium hydroxide solution, then the reaction mixture was treated with desalted water to neutrality, distillation was carried out under reduced pressure at a vacuum of 80kPa, and then decolorization was carried out with clay to obtain lauryl methacrylate. The reaction solution was analyzed by gas chromatography, and the dodecanol conversion was 99.83%.
Example 3
Into a reaction flask were charged 129.14g of methacrylic acid, 186.34g of dodecanol, 1.86g of p-toluenesulfonic acid and 0.1101g of hydroquinone, and N was introduced into the reaction mixture 2 And heating, normal pressure distillation, and heating the reaction solutionThe esterification reaction is started to be timed to 100 ℃, the reaction temperature is controlled to be 100-130 ℃, and water generated in the esterification reaction is distilled and separated along with methacrylic acid by a water separator. After the reaction was carried out for 7 hours, unreacted methacrylic acid was distilled off under reduced pressure, alkali washing was carried out at 25℃with a potassium hydroxide solution having a concentration of 5% by weight, then the reaction mixture was treated with desalted water to neutrality, distillation was carried out under reduced pressure at a vacuum of 50kPa, and then decolorization was carried out with clay to obtain lauryl methacrylate. The reaction solution was analyzed by gas chromatography, and the dodecanol conversion rate was 97.58%.
Example 4
Into a reaction flask, 25.82g of methacrylic acid, 37.27g of dodecanol, 1.86g of heteropoly acid and 0.1101g of hydroquinone were charged, and N was introduced into the reaction solution 2 And heating to 100 deg.c for timing the esterification reaction, controlling the reaction temperature to 100-130 deg.c, and distilling water with methacrylic acid to separate out water. After the reaction was carried out for 11 hours, unreacted methacrylic acid was distilled off under reduced pressure, alkali washing was carried out at 30℃with a sodium hydroxide solution having a concentration of 18% by weight, then the reaction mixture was treated with desalted water to neutrality, distillation was carried out under reduced pressure at a vacuum of 10kPa, and then decolorization was carried out with clay to obtain lauryl methacrylate. The reaction solution was analyzed by gas chromatography, and the dodecanol conversion was 98.61%.
Example 5
Into a reaction flask, 77.48g of methacrylic acid, 111.81g of dodecanol, 5g of macroporous acidic resin and 0.055g of hydroquinone were charged, and N was introduced into the reaction solution 2 And heating to 100 deg.c for timing the esterification reaction, controlling the reaction temperature to 100-122 deg.c, and distilling water with methacrylic acid to separate out water. After the reaction was carried out for 12 hours, unreacted methacrylic acid was distilled off under reduced pressure, alkali washing was carried out at 30℃with a sodium hydroxide solution having a concentration of 18% by weight, then the reaction mixture was treated with desalted water to neutrality, distillation was carried out under reduced pressure at a vacuum of 10kPa, and then decolorization was carried out with clay to obtain lauryl methacrylate. Gas chromatography detection analysis is carried out on the reaction liquid, and the dodecanol conversion rate is obtained99.78%.
Example 6
Into a reaction flask were charged 18.76g of methacrylic acid, 37.94g of dodecanol, 0.31g of 70 mass% aqueous methanesulfonic acid solution and 0.022g of hydroquinone, and N was introduced into the reaction solution 2 And heating to 100 deg.c for timing the esterification reaction, controlling the reaction temperature to 100-130 deg.c, and distilling water with methacrylic acid to separate out water. After the reaction was carried out for 8 hours, unreacted methacrylic acid was distilled off under reduced pressure, alkali washing was carried out at 30℃with a sodium hydroxide solution having a concentration of 18% by weight, then the reaction mixture was treated with desalted water to neutrality, distillation was carried out under reduced pressure at a vacuum of 10kPa, and then decolorization was carried out with clay to obtain lauryl methacrylate. The reaction solution was analyzed by gas chromatography, and the dodecanol conversion rate was 90.74%.
Example 7
Higher fatty alcohol methacrylates were prepared as in example 2, except that dodecanol was replaced with n-tetradecanol. After the reaction, the conversion of tetradecanol was 99.07%.
From the above, the method of the invention can effectively promote the esterification reaction to proceed to the positive reaction direction, and the higher fatty alcohol ester can still reach high conversion rate under the condition of no addition of the azeotropic third solvent.
Examples 8-10 illustrate the extraction of methacrylic acid from a mixture of water and methacrylic acid using a hydrophobic higher fatty alcohol. The extraction recovery rate is calculated by the following steps: and obtaining the ratio of the amount of the extracted methacrylic acid to the amount of the methacrylic acid in the initial methacrylic acid aqueous solution according to the content of the residual methacrylic acid in the aqueous phase after extraction, namely the extraction rate.
Example 8
An aqueous methacrylic acid solution was taken in an amount of 25.03g, wherein the methacrylic acid content was 2.08 mass%. Adding 75.01g of dodecanol (the volume ratio of dodecanol to methacrylic acid aqueous solution is 3.65) into methacrylic acid aqueous solution, fully mixing the mixed solution in a separating funnel at 60 ℃, standing for phase separation, and obtaining a heavy component aqueous phase and a light component organic phase after liquid separation; wherein the methacrylic acid content in the aqueous phase is 0.10 mass percent, and the total mass of the aqueous phase is 20g; the methacrylic acid content in the organic phase was 0.55 mass%. The extraction recovery rate was 96.16%.
Example 9
The aqueous methacrylic acid solution was taken to have a mass of 49.54g, and the methacrylic acid content thereof was 1.76 mass%. Adding 123.98g of dodecanol (the volume ratio of dodecanol to methacrylic acid aqueous solution is 3) into methacrylic acid aqueous solution, fully mixing the mixed solution in a separating funnel at 30 ℃, standing for phase separation, and obtaining a heavy component aqueous phase and a light component organic phase after liquid separation; wherein the methacrylic acid content in the aqueous phase is 0.05 mass percent, and the mass of the aqueous phase is 43.88g; the methacrylic acid content in the organic phase was 0.46 mass%. The extraction recovery rate was 97.58%.
Example 10
An aqueous methacrylic acid solution was taken, the mass thereof was 48.83g, and the methacrylic acid content thereof was 14.09 mass%. Adding 40.98g of dodecanol (the volume ratio of dodecanol to methacrylic acid aqueous solution is 1) into methacrylic acid aqueous solution, fully mixing the mixed solution in a separating funnel at 30 ℃, standing for phase separation, and obtaining a heavy component aqueous phase and a light component organic phase after liquid separation; wherein the methacrylic acid content in the aqueous phase is 1.47 mass percent, and the mass of the aqueous phase is 40.5g; the methacrylic acid content in the organic phase was 22.21 mass%. The extraction recovery rate was 91.35%.
As can be seen from the results of examples 8 to 10, the methacrylic acid in the mixture of water and methacrylic acid was extracted with a hydrophobic higher fatty alcohol, and the methacrylic acid in the mixture was sufficiently extracted without adding a polymerization inhibitor, as in example 9, the extraction recovery rate was as high as 97.58%, the methacrylic acid was sufficiently recovered, and the waste liquid discharge was effectively reduced. Particularly, when higher fatty alcohol which is the same as that of the esterification reaction is adopted for extraction, the extract is recycled in the esterification reaction, so that methacrylic acid is fully recycled, other substances are prevented from being introduced, and the purification difficulty is reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for preparing a higher fatty alcohol (meth) acrylate, comprising:
(1) The method comprises the steps of (1) contacting higher fatty alcohol with excessive (methyl) acrylic acid for esterification reaction, wherein water generated in the esterification reaction process is led out of an esterification reaction system along with the excessive (methyl) acrylic acid;
(2) Optionally, recovering (meth) acrylic acid from the mixture of water and (meth) acrylic acid extracted in step (1) by extraction with a hydrophobic higher fatty alcohol, and recycling the recovered (meth) acrylic acid for esterification in step (1);
(3) Optionally, the material containing the higher fatty alcohol (meth) acrylate produced by the esterification reaction is subjected to post-treatment to obtain the higher fatty alcohol (meth) acrylate.
2. The process according to claim 1, wherein in step (1), the initial molar ratio of (meth) acrylic acid to higher fatty alcohol, calculated as hydroxyl group, is greater than 1, preferably between 1.01 and 3;
and/or the higher fatty alcohol is at least one of hydrophobic fatty alcohols having 9 to 26 carbon atoms.
3. The process according to claim 1 or 2, wherein the temperature of the esterification reaction is 70-140 ℃;
and/or the esterification reaction time is 3-20 h;
and/or, the esterification reaction is carried out in a reactive distillation/rectification apparatus.
4. The process according to claim 1, wherein in step (1), the esterification reaction is carried out in the presence of a catalyst which is at least one of sulfuric acid, sulfonic acid type, heteropolyacid and acid resin and is used in an amount of 0.05 to 10% by weight based on the total weight of (meth) acrylic acid and higher fatty alcohol.
5. The method according to claim 1 or 4, wherein in the step (1), the esterification reaction is carried out in the presence of a polymerization inhibitor which is at least one of a phenolic polymerization inhibitor, a quinone polymerization inhibitor, an arylamine polymerization inhibitor and an inorganic salt polymerization inhibitor, and the amount of the polymerization inhibitor is 0.03 to 5% by weight based on the total weight of (meth) acrylic acid and higher fatty alcohol.
6. The method according to claim 1, wherein the hydrophobic higher fatty alcohol in step (2) is the same as or different from the higher fatty alcohol in step (1).
7. The process according to claim 6, wherein the hydrophobic higher fatty alcohol used for the extraction is at least one of monohydric aliphatic alcohols having 9 to 26 carbon atoms, preferably at least one of monohydric aliphatic alcohols having 9 to 16 carbon atoms; and is the same as the higher fatty alcohol in step (1);
and/or the volume ratio of the hydrophobic higher fatty alcohol to the mixture used for extraction is 0.3-10:1, preferably 1-4:1.
8. A process according to claim 6 or 7, wherein the extraction temperature is 0-90 ℃, preferably 20-60 ℃.
9. The method of claim 1, wherein in step (3), the post-processing is performed by: the material containing the (meth) acrylic acid higher fatty alcohol ester is sequentially subjected to alkali washing, distillation and decolorization.
10. The method according to claim 1 or 9, wherein in step (3), the post-treatment is performed by: alkali washing with alkali metal hydroxide solution of concentration 1-20wt% at 20-60 deg.c; then desalted water is used for treatment until the solution is neutral; then carrying out reduced pressure distillation under the vacuum degree of 5-95 kPa; and then decolorizing by using a decolorizing agent.
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