CN112174817A - Preparation process of (methyl) acrylic acid long-chain alkyl ester - Google Patents
Preparation process of (methyl) acrylic acid long-chain alkyl ester Download PDFInfo
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- CN112174817A CN112174817A CN202011142233.7A CN202011142233A CN112174817A CN 112174817 A CN112174817 A CN 112174817A CN 202011142233 A CN202011142233 A CN 202011142233A CN 112174817 A CN112174817 A CN 112174817A
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- Prior art keywords
- chain alkyl
- mass
- long
- acrylic acid
- acrylate
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- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 125000005907 alkyl ester group Chemical group 0.000 title description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229950000688 phenothiazine Drugs 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000047 product Substances 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 44
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 43
- 239000003513 alkali Substances 0.000 claims description 42
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 41
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 37
- 239000003729 cation exchange resin Substances 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 claims description 11
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003456 ion exchange resin Substances 0.000 claims description 8
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229960000735 docosanol Drugs 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 description 15
- 238000004321 preservation Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 alkyl methacrylate Chemical compound 0.000 description 5
- 230000002940 repellent Effects 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004078 waterproofing 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Abstract
The invention discloses a preparation process of long-chain alkyl (meth) acrylate, which adopts a polymerization inhibitor composition with phenothiazine accounting for at least 10 percent of the total mass of the composition as a polymerization inhibitor of esterification reaction, solves the problem of self-polymerization in the post-treatment process, can also effectively control the acidity of a product, obtains a colorless or white high-purity product, and has high yield and wide product application range; and the preparation process, polymerization and reutilization of excessive (methyl) acrylic acid, not only avoids generation of a large amount of acidic waste water, but also increases comprehensive benefits.
Description
Technical Field
The invention discloses a preparation process of (methyl) acrylic acid long-chain alkyl ester, belonging to the technical field of chemical synthesis.
Background
The long-chain alkyl (meth) acrylate (including long-chain alkyl acrylate and long-chain alkyl methacrylate) is an important chemical raw material and is widely applied to plasticizers, adhesives, water-proofing agents for fiber fabrics, paper, stone and the like, lubricating oil viscosity-reducing additives, leveling agents and the like. The methods for producing long-chain alkyl (meth) acrylates include mainly transesterification and solvent transesterification.
The transesterification process is a classical process for preparing higher esters from lower esters by transesterification (alcoholysis). However, because the boiling point of the lower ester is lower, the reaction can only be carried out at a lower temperature, so that the reaction time is prolonged; the product methanol and the lower ester can also form a low-boiling-point azeotrope, take away reactants and reduce the yield; in addition, in order to prevent the occurrence of polymerization, a large amount of a polymerization inhibitor is generally used. This method is not commonly used in industry from the viewpoint of cost and post-treatment difficulty. The solvent esterification method is a synthesis method for preparing high-grade ester by directly carrying out esterification reaction, and the preparation process is relatively simple. However, toluene (forming a low azeotrope with water) is usually used as a water carrying agent, and because toluene has high toxicity, the toluene is easy to cause pollution in the production process and needs to be recycled; in addition, the solvent esterification method requires a long reflux time at a high temperature, and a large amount of polymerization inhibitor (1.0 to 1.5%) and catalyst (2.0 to 3.0%) are used in order to prevent polymerization. These all add to the cost of the solvent esterification process.
Patent CN200810018016.X discloses a process for preparing octadecyl acrylate by a melt esterification method, and excess acrylic acid and residual water are distilled out by decompression at the final stage of the reaction. The process has the advantages of high reaction rate, high reaction selectivity, short reaction time, no use of toxic azeotropic solvent, easy removal of product water, high ester yield and the like. However, in the process, a large amount of acidic waste liquid needs to be treated due to excessive acrylic acid; in addition, in order to remove the catalyst, polymerization inhibitor, etc. in the product, the crude product needs to be washed with a large amount of water, and a large amount of waste water is generated. Patent CN201210122916.5 discloses a synthesis process for preparing higher alcohol acrylate ester by a similar melt esterification method, which only replaces caustic alkali solution with weak alkali solution, but the above-mentioned defects still exist.
Patent CN201210087471.1 discloses a process for preparing a linear aliphatic alcohol ester of methacrylic acid C8-18 by vacuum dehydration under reduced pressure, wherein the process has low reaction temperature, but the yield of an esterification product is reduced because the reaction product methacrylic acid is lost simultaneously by vacuum dehydration under reduced pressure. Patent CN201310057143.1 discloses a process for preparing linear chain fatty alcohol ester of methacrylic acid C8-18 by using diluent oil as solvent, wherein the diluent oil is light lubricating oil such as 100SN, 150SN, 5# white oil and the like. However, the methacrylate synthesized by the process can only be used for preparing the lubricating oil viscosity-reducing additive with dual functions of reducing the coagulation and the turbidity.
The long-chain alkyl (meth) acrylate is often used as a raw material for a tackifier product and a water repellent product, and particularly when used as a raw material for a water repellent product, the color and acid value of the product are often strictly required. Since the color of the raw material may affect the color of the water repellent coating and thus change the original color of the substrate, which is not allowed for many substrates (such as cloth, wallpaper, leather, etc.), it is required that the long chain alkyl (meth) acrylate product used as the raw material for the water repellent is preferably colorless or white. The water-based water repellent product is usually a cationic emulsion, and if the acid value of the long-chain alkyl (meth) acrylate is too high, the stability of the emulsion is often affected, and the acid value is usually required to be less than or equal to 0.5 mgKOH/g. In addition, in the production of a long chain alkyl (meth) acrylate, the post-treatment of purification needs to be carried out at a temperature of 55 ℃ or higher for the reason of the physical properties, and the long chain alkyl (meth) acrylate is preferably a self-polymerizable material, and thus the self-polymerization tends to occur during the post-treatment.
Disclosure of Invention
The invention aims to provide a preparation process of long-chain alkyl (meth) acrylate, which can overcome the defects of the existing process, successfully solve the problem of self-polymerization in the post-treatment process, and effectively control the acidity of the product to obtain a colorless or white high-purity product.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing a long chain alkyl (meth) acrylate, comprising the steps of:
1) firstly, adding long-chain alkyl alcohol into a reaction container, properly heating to completely melt the long-chain alkyl alcohol, sequentially adding a polymerization inhibitor composition and (methyl) acrylic acid, uniformly mixing, and then adding a strong acid type acrylic acid cation exchange resin, wherein the molar ratio of the long-chain alkyl alcohol to the (methyl) acrylic acid is 1: 0.7-0.8, and phenothiazine in the polymerization inhibitor composition accounts for at least 10% of the total mass of the composition;
2) heating the mixture to 100-115 ℃, preserving heat, performing reflux reaction for 1-3 h, separating out water, and then continuing reaction for 0.5h under a reduced pressure state;
3) adding a proper amount of (methyl) acrylic acid, heating to 125-135 ℃, preserving heat, performing reflux reaction for 1-3 h, separating water, continuing to react for at least 0.5h under a reduced pressure state, and evaporating reaction product water remained in the material to generate excessive (methyl) acrylic acid, wherein the molar ratio of the long-chain alkyl alcohol to the added (methyl) acrylic acid is 1: 0.4-0.7;
4) then cooling to 100-110 ℃, and filtering to separate out ion exchange resin;
5) the filtrate is washed with alkali, and the process is as follows: firstly, adding a proper amount of water, then adding a proper amount of saturated sodium chloride solution, finally adding alkali liquor with the mass concentration of 5-25%, stirring for at least 20min, and then standing for liquid separation;
6) washing the product after alkaline washing to be neutral, and then carrying out decoloration and drying treatment to obtain a colorless or white purified product;
7) carrying out water phase polymerization reaction on the mixed solution of the excess (methyl) acrylic acid and water evaporated under reduced pressure to obtain a polymer product for water treatment;
8) neutralizing the polymer solution obtained in the step 7) with a sodium hydroxide aqueous solution until the pH value is 6-8, and obtaining a dispersing agent product for dispersing pigments and fillers.
Further, the long-chain alkyl alcohol is a straight-chain or branched-chain alcohol with 12-22 carbon atoms.
Further, the long-chain alkyl alcohol is selected from one of lauryl alcohol, stearyl alcohol and behenyl alcohol.
Further, the polymerization inhibitor composition also contains at least one of hydroquinone and cuprous chloride.
Furthermore, the dosage of the polymerization inhibitor composition is 0.3-0.6% of the mass dosage of the long-chain alkyl alcohol.
Furthermore, the ion exchange resin is sulfonic acid type cation exchange resin, and the dosage of the ion exchange resin is 0.4-1% of the mass dosage of the long-chain alkyl alcohol.
Furthermore, the crosslinking degree of the ion exchange resin is 6-10%.
Further, the alkali liquor adopts alkalescent sodium carbonate aqueous solution.
Further, the decoloring and drying treatment is carried out at a temperature of 55 to 70 ℃.
Further, the initiator adopted in the aqueous phase polymerization reaction is one of water-soluble initiators potassium persulfate, sodium persulfate and ammonium persulfate.
Further, the polymerization temperature of the aqueous phase polymerization reaction is 80-96 ℃.
The process for the preparation of long chain alkyl (meth) acrylates of the present invention employs a polymerization inhibitor composition in which phenothiazine constitutes at least 10% of the total mass of the composition. Experiments show that the polymerization inhibition effect is not ideal when only phenothiazine is adopted, the polymerization inhibition effect in the whole synthesis and post-treatment processes is obviously improved when the polymerization inhibitor composition containing phenothiazine is adopted, and the polymerization inhibition effect is better when phenothiazine accounts for 10 percent or more of the total mass of the composition. The polymerization inhibitor composition usually further contains at least one of a phenolic polymerization inhibitor such as hydroquinone and its derivatives, catechol and its derivatives, resorcinol and its derivatives, a quinone polymerization inhibitor such as tetrachlorobenzoquinone, 1, 4-naphthoquinone, p-benzoquinone, etc., and an inorganic polymerization inhibitor such as sodium sulfate, sodium sulfide, cuprous chloride, etc., preferably at least one of hydroquinone and cuprous chloride. The dosage of the polymerization inhibitor composition is more than 0.3 percent of the mass dosage of the long-chain alkyl alcohol, preferably 0.3 to 1 percent, and more preferably 0.3 to 0.6 percent.
In the preparation process of the long-chain alkyl (meth) acrylate, the (meth) acrylic acid adopts a two-step feeding method, so that the temperature shock caused by over violent reaction can be avoided, and the conversion rate of alcohol can be further improved by excessive acid after the (meth) acrylic acid is added for the second time. The amount of (meth) acrylic acid initially added is generally more than 0.85, preferably not more than 0.8, more preferably 0.7 to 0.8, mole number of the long-chain alcohol. The amount of the (methyl) acrylic acid added for the second time is at least 0.35 of the mole number of the long-chain alcohol, and if the amount of the (methyl) acrylic acid added for the second time is too low, the conversion rate of the long-chain alcohol is obviously reduced; preferably more than 0.4, more preferably 0.4-0.7, and has no effect on the improvement of the conversion rate of the long-chain alcohol after exceeding 0.7.
The long-chain alkyl alcohol is a straight-chain or branched-chain alcohol with 12-22 carbon atoms, such as lauryl alcohol (lauryl alcohol), palmityl alcohol (tetradecyl alcohol), stearyl alcohol (stearyl alcohol), behenyl alcohol and the like; of these, dodecanol, octadecanol and behenyl alcohol are preferred.
The ion exchange resin is acrylic resin, the catalytic efficiency is low when non-acrylic resin is adopted, the ideal catalytic effect can be achieved only by using higher resin dosage, and the acrylic resin with the ideal catalytic effect under the condition of low dosage is preferred from the production cost.
The ion exchange resin is sulfonic acid type cation exchange resin. The common liquid acid or solid acid catalyst needs to be removed by alkali washing and water washing after the reaction, and the water consumption for washing is large in order to completely remove the catalyst. The sulfonic acid type strong acid cation exchange resin can be separated by filtration and can be recycled; the product separated by the strong acid type cation exchange resin is neutral after being washed by a proper amount of water, and the water consumption is greatly reduced. The dosage is more than 0.3 percent of the mass dosage of the long-chain alkyl alcohol, preferably more than 0.4 percent, and more preferably 0.4 to 1 percent. When the dosage of the strong acid type cation exchange resin is less than 0.3 percent, the catalytic effect is not ideal; when the dosage is more than 0.3 percent, especially more than 0.4 percent, the catalytic effect is better. When the dosage of the strong acid type cation exchange resin exceeds 1 percent, the catalytic efficiency is not obviously improved along with the increase of the dosage of the catalyst, so the more preferable dosage is 0.4 to 1 percent.
The crosslinking degree of the ion exchange resin is preferably more than 5%, more preferably more than 6%, and when the crosslinking degree is lower, the resin is not beneficial to recycling and reusing; however, the degree of crosslinking is not so high as to affect the catalytic activity of the resin, and is preferably not more than 12%, more preferably not more than 10%.
The alkaline washing is performed by using a weak alkaline solution, such as sodium carbonate or sodium bicarbonate solution, the product is easily hydrolyzed by strong alkaline caustic soda, and the weak alkaline solution is preferably sodium carbonate aqueous solution. In addition, the sequence of addition during alkaline washing has an influence on the purity and acid value of the product. The alkaline washing sequence of the invention can control the acid value of the product within 0.4mgKOH/g, and the purity of the product is higher; on the other hand, when the alkali solution is added between the alkali washing, the acid value of the obtained product tends to be high, and is 0.5mgKOH/g or more.
The decolorization and drying processes can be carried out separately or simultaneously, and are not in sequence. The decolorization can be carried out by adsorption with activated carbon, clay or adsorbent resin. The drying can be carried out by adsorption drying with silica gel, alumina gel, molecular sieve, activated carbon, bone charcoal, mineral drying agent or activated clay or vacuum drying with vacuum low temperature drying technology. In the present invention, it is preferable that the decoloring and drying treatment is carried out at a temperature of 55 to 70 ℃ in order to achieve a good decoloring drying and subsequent separation effect.
The initiator adopted in the aqueous phase polymerization reaction is a water-soluble initiator, preferably one of potassium persulfate, sodium persulfate, ammonium persulfate and the like; the polymerization temperature is 80-96 ℃.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1) the preparation process of the (methyl) acrylic acid long-chain alkyl ester solves the problem of self-polymerization in the post-treatment process, can effectively control the acidity of the product, can obtain a colorless or white high-purity product, and has high yield and wide application range of the product;
2) according to the preparation process of the (methyl) acrylic acid long-chain alkyl ester, the catalyst can be separated and reused, so that the water consumption for washing is greatly reduced;
3) the preparation process of the long-chain alkyl (meth) acrylate has the advantages that the polymerization and the reutilization of excessive (meth) acrylic acid are realized, so that the generation of a large amount of acidic waste water is avoided, and the comprehensive benefit is increased.
Detailed Description
Example 1
Firstly, 186 parts by mass of dodecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 0.5 part by mass of hydroquinone, 0.43 part by mass of phenothiazine and 54 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.75) are sequentially added, after uniform stirring, 1 part by mass of sulfonic acid type acrylic cation exchange resin with the crosslinking degree of 8% is added, the mixture is heated to 110 ℃ and is subjected to heat preservation and reflux reaction for 1.5 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. Adding 36 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.5), heating to 130 ℃, reacting for 2 hours, separating out water, continuing to react for 1 hour under a reduced pressure state, and evaporating out the residual reaction product water and excessive acrylic acid in the materials. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 15 parts by mass of sodium carbonate alkali liquor with the mass concentration of 15%, stirring for 30min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 55 ℃ to obtain colorless and transparent lauryl acrylate. The yield in terms of dodecanol was 95.8%, the product purity was 98.87%, and the acidity was 0.2 mgKOH/g.
Example 2
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 1.35 parts by mass of hydroquinone, 0.15 part by mass of phenothiazine and 50.4 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.7) are sequentially added, after uniform stirring, 1 part by mass of sulfonic acid type acrylic acid cation exchange resin with the crosslinking degree of 8 percent is added, the mixture is heated to 100 ℃ and is subjected to heat preservation and reflux reaction for 3 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. Adding 43.2 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.6), heating to 125 ℃, reacting for 3 hours, separating out water, continuing to react for 1.5 hours in a reduced pressure state, and distilling off the residual reaction product water and excessive acrylic acid in the materials. Then the temperature is reduced to 100 ℃, and the strong acid type cation exchange resin is separated by filtration. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 25 parts by mass of saturated sodium chloride solution, finally adding 13 parts by mass of 15% sodium carbonate alkali liquor, stirring for 20min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 60 ℃ to obtain colorless and transparent octadecyl acrylate. The yield in terms of octadecanol was 95.7%, the product purity was 99.02%, and the acidity was 0.15 mgKOH/g.
Example 3
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then, 0.41 part by mass of hydroquinone, 0.4 part by mass of phenothiazine and 57.6 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.8) are sequentially added, after uniform stirring, 2.7 parts by mass of sulfonic acid type acrylic cation exchange resin with the crosslinking degree of 8 percent is added, the mixture is heated to 115 ℃ and is subjected to heat preservation and reflux reaction for 1 hour, moisture is separated out, and then, the reaction is continued for 0.5 hour under the reduced pressure state. Adding 28.8 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.4), heating to 135 ℃, reacting for 1 hour, separating water, continuing to react for 0.5 hour under a reduced pressure state, and distilling off the reaction product water and excessive acrylic acid remained in the materials. Then the temperature is reduced to 110 ℃, and the strong acid type cation exchange resin is separated by filtration. Then the filtrate is washed by alkali, and the flow is as follows: adding 30 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 10 parts by mass of 25% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 65 ℃ to obtain colorless and transparent octadecyl acrylate. The yield in terms of octadecanol was 95.9%, the product purity was 99.05%, and the acidity was 0.17 mgKOH/g.
Example 4
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 1 part by mass of hydroquinone, 0.62 part by mass of phenothiazine and 50.4 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.7) are sequentially added, after uniform stirring, 1.5 parts by mass of sulfonic acid type acrylic acid cation exchange resin with the crosslinking degree of 8 percent is added, the mixture is heated to 110 ℃ and is subjected to heat preservation and reflux reaction for 2 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. Adding 50.4 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.7), heating to 130 ℃, reacting for 2 hours, separating out water, continuing to react for 1 hour under a reduced pressure state, and distilling off the residual reaction product water and excessive acrylic acid in the materials. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 30 parts by mass of 5% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 65 ℃ to obtain colorless and transparent octadecyl acrylate. The yield in terms of octadecanol was 95.8%, the product purity was 98.92%, and the acidity was 0.12 mgKOH/g.
Example 5
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 1 part by mass of hydroquinone, 0.62 part by mass of phenothiazine and 50.4 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.7) are sequentially added, after uniform stirring, 1.5 parts by mass of sulfonic acid type acrylic acid cation exchange resin with the crosslinking degree of 6% is added, the mixture is heated to 110 ℃ and is subjected to heat preservation and reflux reaction for 2 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. Adding 50.4 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.7), heating to 130 ℃, reacting for 2 hours, separating out water, continuing to react for 1 hour under a reduced pressure state, and distilling off the residual reaction product water and excessive acrylic acid in the materials. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 30 parts by mass of 5% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 65 ℃ to obtain colorless and transparent octadecyl acrylate. The yield in terms of octadecanol was 95.9%, the product purity was 98.90%, and the acidity was 0.13 mgKOH/g.
Example 6
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 1 part by mass of hydroquinone, 0.62 part by mass of phenothiazine and 50.4 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.7) are sequentially added, after uniform stirring, 1.5 parts by mass of sulfonic acid type acrylic acid cation exchange resin with the crosslinking degree of 10 percent is added, the mixture is heated to 110 ℃ and is subjected to heat preservation and reflux reaction for 2 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. Adding 50.4 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.7), heating to 130 ℃, reacting for 2 hours, separating out water, continuing to react for 1 hour under a reduced pressure state, and distilling off the residual reaction product water and excessive acrylic acid in the materials. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 30 parts by mass of 5% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 65 ℃ to obtain colorless and transparent octadecyl acrylate. The yield in terms of octadecanol was 95.7%, the product purity was 98.94%, and the acidity was 0.11 mgKOH/g.
Example 7
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 1 part by mass of hydroquinone, 0.3 part by mass of phenothiazine and 54 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.75) are sequentially added, after uniform stirring, 1.5 parts by mass of sulfonic acid type acrylic cation exchange resin with the crosslinking degree of 8% is added, the mixture is heated to 110 ℃ and subjected to heat preservation and reflux reaction for 2 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. Adding 39.6 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.55), heating to 130 ℃, reacting for 2 hours, separating water, continuing to react for 1 hour under a reduced pressure state, and distilling off the residual reaction product water and excessive acrylic acid in the materials. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 15 parts by mass of 15% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 65 ℃ to obtain colorless and transparent octadecyl acrylate. The yield in terms of octadecanol was 96.1%, the product purity was 99.07%, and the acidity was 0.1 mgKOH/g.
Example 8
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 1 part by mass of hydroquinone, 0.3 part by mass of phenothiazine and 64.5 parts by mass of methacrylic acid (the molar ratio of the alcohol to the acid is 1: 0.75) are sequentially added, after uniform stirring, 1.5 parts by mass of sulfonic acid type acrylic cation exchange resin with the crosslinking degree of 8 percent is added, the mixture is heated to 110 ℃ and is subjected to heat preservation and reflux reaction for 2 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. 43 parts by mass of methacrylic acid (molar ratio of alkyd: 1: 0.5) are added, the temperature is raised to 130 ℃ for reaction for 2 hours, water is separated out, the reaction is continued for 1 hour under a reduced pressure state, and water and excessive acrylic acid which are remained in the materials and generated by the reaction are evaporated. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 15 parts by mass of 15% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. And (3) washing the alkali-washed product to be neutral, and decoloring and drying at 65 ℃ to obtain colorless and transparent octadecyl methacrylate. The yield in terms of octadecanol was 96.0%, the product purity was 99.01%, and the acidity was 0.12 mgKOH/g.
Example 9
Firstly, 326 parts by mass of docosyl alcohol is added into a reaction vessel, the temperature is properly raised to be completely melted, then 1 part by mass of hydroquinone, 0.3 part by mass of phenothiazine and 54 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.75) are sequentially added, after uniform stirring, 1.5 parts by mass of sulfonic acid type acrylic cation exchange resin with the crosslinking degree of 8% is added, the mixture is heated to 110 ℃ and is subjected to heat preservation and reflux reaction for 2 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. Adding 39.6 parts by mass of acrylic acid (the molar ratio of the alcohol to the acid is 1: 0.55), heating to 130 ℃, reacting for 2 hours, separating water, continuing to react for 1 hour under a reduced pressure state, and distilling off the residual reaction product water and excessive acrylic acid in the materials. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 15 parts by mass of 15% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. Washing the product after alkali washing to be neutral, and then decoloring and drying at 65 ℃ to obtain colorless and transparent acrylic acid behenyl ester. The yield in terms of behenyl alcohol was 95.8%, the product purity was 98.87%, and the acidity was 0.14 mgKOH/g.
Example 10
Firstly, 270 parts by mass of octadecyl alcohol is added into a reaction container, the temperature is properly raised to be completely melted, then 1 part by mass of cuprous chloride, 0.3 part by mass of phenothiazine and 64.5 parts by mass of methacrylic acid (the molar ratio of the alcohol to the acid is 1: 0.75) are sequentially added, after uniform stirring, 1.5 parts by mass of sulfonic acid type acrylic acid cation exchange resin with the crosslinking degree of 8% is added, the mixture is heated to 110 ℃ and is subjected to heat preservation and reflux reaction for 2 hours, moisture is separated out, and then the reaction is continued for 0.5 hour under the reduced pressure state. 43 parts by mass of methacrylic acid (molar ratio of alkyd: 1: 0.5) are added, the temperature is raised to 130 ℃ for reaction for 2 hours, water is separated out, the reaction is continued for 1 hour under a reduced pressure state, and water and excessive acrylic acid which are remained in the materials and generated by the reaction are evaporated. Then cooling to 105 ℃, and filtering to separate out the strong acid type cation exchange resin. Then the filtrate is washed by alkali, and the flow is as follows: adding 40 parts by mass of water, then adding 20 parts by mass of saturated sodium chloride solution, finally adding 15 parts by mass of 15% sodium carbonate alkali liquor, stirring for 30min, and standing for liquid separation. And (3) washing the alkali-washed product to be neutral, and decoloring and drying at 65 ℃ to obtain colorless and transparent octadecyl methacrylate. The yield in terms of octadecanol was 95.9%, the product purity was 98.92%, and the acidity was 0.11 mgKOH/g.
Example 10
The mixture of the excess acrylic acid and water distilled off under reduced pressure in examples 1 to 8 was collected, and the acrylic acid content in the mixture was analyzed to be 40.55 wt%. And (3) taking 100 parts by mass of the collected liquid, adding 0.2 part by mass of sodium sulfate, and carrying out polymerization reaction for 8 hours at 80 ℃ to obtain polyacrylic acid for water treatment.
Example 12
And (3) taking 50 parts by mass of the polyacrylic acid aqueous solution prepared in the example 9, and neutralizing the polyacrylic acid aqueous solution with a sodium hydroxide aqueous solution until the pH value is 6-8 to obtain a dispersing agent product for dispersing pigments and fillers.
Comparative example 1
Polymerization was carried out in the same manner as in example 8 except that the polymerization inhibitor was changed to 1.3 parts by mass of phenothiazine, and the temperature was raised to 130 ℃ to react for 1 hour.
Comparative example 2
The same procedure as in example 8 was repeated except that the polymerization inhibitor was replaced with 1.3 parts by mass of hydroquinone, and a part of the materials was allowed to self-polymerize during the alkali washing, resulting in a final product yield of only 71.3%.
Comparative example 3
The procedure was as in example 8 except for the alkaline washing. The specific alkali washing process is as follows: adding 15 parts by mass of 15% sodium carbonate alkali liquor, stirring for 30min, adding 20 parts by mass of saturated sodium chloride solution, and standing for liquid separation. The final product acidity was 0.45 mgKOH/g.
Comparative example 4
The procedure of example 8 was repeated, except that the sulfonic acid type acrylic cation exchange resin having a crosslinking degree of 8% was replaced with 8% sulfonic acid type styrene type cation exchange resin. The yield of the final product in terms of octadecanol was 90.2%, the product purity was 93.29%, and the acidity was 0.35 mgKOH/g. .
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple variations, equivalent substitutions or modifications based on the present invention to achieve substantially the same technical effects are within the scope of the present invention.
Claims (10)
1. A process for preparing a long chain alkyl (meth) acrylate, comprising the steps of:
1) firstly, adding long-chain alkyl alcohol into a reaction container, properly heating to completely melt the long-chain alkyl alcohol, sequentially adding a polymerization inhibitor composition and (methyl) acrylic acid, uniformly mixing, and then adding a strong acid type acrylic acid cation exchange resin, wherein the molar ratio of the long-chain alkyl alcohol to the (methyl) acrylic acid is 1: 0.7-0.8, and phenothiazine in the polymerization inhibitor composition accounts for at least 10% of the total mass of the composition;
2) heating the mixture to 100-115 ℃, preserving heat, performing reflux reaction for 1-3 h, separating out water, and then continuing reaction for 0.5h under a reduced pressure state;
3) adding a proper amount of (methyl) acrylic acid, heating to 125-135 ℃, preserving heat, performing reflux reaction for 1-3 h, separating water, continuing to react for at least 0.5h under a reduced pressure state, and evaporating reaction product water remained in the material to generate excessive (methyl) acrylic acid, wherein the molar ratio of the long-chain alkyl alcohol to the added (methyl) acrylic acid is 1: 0.4-0.7;
4) then cooling to 100-110 ℃, and filtering to separate out ion exchange resin;
5) the filtrate is washed with alkali, and the process is as follows: firstly, adding a proper amount of water, then adding a proper amount of saturated sodium chloride solution, finally adding alkali liquor with the mass concentration of 5-25%, stirring for at least 20min, and then standing for liquid separation;
6) washing the product after alkaline washing to be neutral, and then carrying out decoloration and drying treatment to obtain a colorless or white purified product;
7) carrying out water phase polymerization reaction on the mixed solution of the excess (methyl) acrylic acid and water evaporated under reduced pressure to obtain a polymer product for water treatment;
8) neutralizing the polymer solution obtained in the step 7) with a sodium hydroxide aqueous solution until the pH value is 6-8, and obtaining a dispersing agent product for dispersing pigments and fillers.
2. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the long-chain alkyl alcohol is a straight-chain or branched-chain alcohol with 12-22 carbon atoms.
3. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the long-chain alkyl alcohol is selected from one of dodecanol, octadecanol and behenyl alcohol.
4. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the polymerization inhibitor composition also contains at least one of hydroquinone and cuprous chloride.
5. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the dosage of the polymerization inhibitor composition is 0.3-0.6% of the mass dosage of the long-chain alkyl alcohol.
6. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the strong acid type cation exchange resin is sulfonic acid type cation exchange resin, and the dosage of the strong acid type cation exchange resin is 0.4-1% of the mass dosage of the long-chain alkyl alcohol.
7. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the alkali liquor is alkalescent sodium carbonate aqueous solution.
8. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the decolorization and drying treatment is carried out at a temperature of 55 ℃ to 70 ℃.
9. The process according to claim 8, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the initiator adopted in the aqueous phase polymerization reaction is one of water-soluble initiators potassium persulfate, sodium persulfate and ammonium persulfate.
10. The process according to claim 1, wherein the long chain alkyl (meth) acrylate is selected from the group consisting of: the polymerization temperature of the aqueous phase polymerization reaction is 80-96 ℃.
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| CN115197062A (en) * | 2022-08-29 | 2022-10-18 | 新乡市瑞丰新材料股份有限公司 | Acrylic acid high-carbon ester or methacrylic acid high-carbon ester and preparation method thereof |
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| 宋岩;张朝群;杨清彪;王恒国;李耀先;王莹;: "双三羟甲基丙烷丙烯酸酯的合成研究", 应用化工, no. 09, pages 1002 - 1003 * |
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| CN115057764A (en) * | 2022-06-30 | 2022-09-16 | 辽宁厚安科技有限公司 | Polymerization inhibitor for sulfur-free odorizing agent |
| CN115197062A (en) * | 2022-08-29 | 2022-10-18 | 新乡市瑞丰新材料股份有限公司 | Acrylic acid high-carbon ester or methacrylic acid high-carbon ester and preparation method thereof |
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