CN109651136B - Method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange - Google Patents
Method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange Download PDFInfo
- Publication number
- CN109651136B CN109651136B CN201811507307.5A CN201811507307A CN109651136B CN 109651136 B CN109651136 B CN 109651136B CN 201811507307 A CN201811507307 A CN 201811507307A CN 109651136 B CN109651136 B CN 109651136B
- Authority
- CN
- China
- Prior art keywords
- trimethylolpropane
- reaction
- polymerization inhibitor
- synthesizing
- trimethylolpropane triacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 150000002148 esters Chemical group 0.000 title abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 238000010992 reflux Methods 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000005809 transesterification reaction Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 2
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- CKJMHSMEPSUICM-UHFFFAOYSA-N di-tert-butyl nitroxide Chemical compound CC(C)(C)N([O])C(C)(C)C CKJMHSMEPSUICM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims 1
- 208000005156 Dehydration Diseases 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 235000007686 potassium Nutrition 0.000 claims 1
- 239000012279 sodium borohydride Substances 0.000 claims 1
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 150000005691 triesters Chemical class 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange, belonging to the technical field of fine chemical engineering. Adding MMA or MA and TMP into a reactor, adding an acidic or basic catalyst and a polymerization inhibitor, heating to generate reflux, and continuously discharging azeotrope formed by raw material MMA or MA and byproduct methanol along with the reaction, so that the chemical equilibrium continuously moves towards the product generation direction until the reaction is finished. After the reaction is finished, removing the catalyst and the polymerization inhibitor by alkali washing or filtration, recovering the excessive MMA or MA, and decoloring to obtain the product. The invention adopts ester exchange reaction, has less side reaction, the conversion rate of trimethylolpropane reaches more than 99 percent, the recovery rate of methyl methacrylate reaches more than 98 percent, and the content of triester is more than 95 percent.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange.
Background
Trimethylolpropane trimethacrylate (short for TMPTMA) and trimethylolpropane triacrylate (short for TMPTA) are very important multifunctional acrylate monomers, and can be used as comonomers to synthesize special acrylic resin and also can be used as a cross-linking agent of rubber and plastics. Because the double bond content is high, the curing speed is high, and the formed curing film is wear-resistant and solvent-resistant, is a polyfunctional acrylate reactive diluent which is most widely applied in the field of radiation curing, and is mainly used for the aspects of paint, flexible printed matters, solder resists, photoresists, photocureable coatings, photocureable ink and the like.
At present, the methods for synthesizing TMPTMA or TMPTA mainly include a direct esterification method, an ester exchange method and an acyl chloride method.
(1) The direct esterification method comprises the following steps: methacrylic acid or acrylic acid and trimethylolpropane (TMP for short) are directly subjected to esterification reaction under the action of an acid catalyst, a polymerization inhibitor and a water-carrying agent to generate TMPTMA or TMPTA. The commonly used acidic catalysts comprise concentrated sulfuric acid, p-toluenesulfonic acid, strong acid resin and the like, and the commonly used water-carrying agents comprise cyclohexane and toluene. The reaction temperature is generally controlled to be 90-110 ℃, and the reaction time is generally 5-6 hours. After the reaction is finished, washing with alkaline water to remove the acidic catalyst, unreacted organic acid, polymerization inhibitor and the like, then recovering the water-carrying agent, and decoloring with active carbon or active clay to obtain the ester product. The method has smooth reaction, high speed and mature process, but the removal of the strong acid catalyst can not only cause the discharge of a large amount of wastewater, but also cause the generation of various byproducts, and the existence of side reactions causes poor reaction selectivity and coloring of products; the catalyst cannot be recycled and stored in the reactant, and the post-treatment needs procedures such as neutralization and water washing, so that the process route is complex, the product loss is large, a large amount of waste liquid is generated, and the environmental pollution is serious; severe corrosion of equipment, potential safety hazard and the like.
(2) Acyl chloride process
Adding thionyl chloride into a flask on a four-neck flask provided with a stirring and reflux condenser, a dropping funnel and a thermometer, adding methacrylic acid or acrylic acid into the dropping funnel, beginning dropping and stirring, gradually heating to a certain temperature after dropping, exhausting hydrogen chloride and sulfur dioxide gas under reduced pressure, then adding trimethylolpropane into a reaction system, discharging hydrogen chloride, and finishing the reaction. The main chemical reaction equation is as follows:
CH2＝CHCOOH+SOCl2→CH2＝CHCOCl+HCl↑+SO2↑
CH2＝CHCOCl+ROH→CH2＝CHCOOR+HCl↑
the process has the characteristics that no catalyst is needed to be added, the reaction can be carried out at a lower temperature, the reaction time is short, and the utilization rate of equipment is high. In the whole reaction process, the reaction temperature is low, the reaction is stable, the polymerization of raw materials and products can be effectively avoided, and the consumption of the polymerization inhibitor is low. However, harmful gases such as hydrogen chloride, sulfur dioxide and the like can be generated in the reaction process, so that the environment is seriously polluted, and no industrial case is found so far.
(3) Ester interchange method
The transesterification process is an alcoholysis reaction in which the transalkylation takes place during the reaction between an ester and an alcohol, and the boiling points of the ester and the alcohol differ, even more, to form a new ester. Transesterification is an important process for producing heavy esters (high boiling point) from light esters (low boiling point) and has wide industrial applications. But has the problems of complex subsequent treatment process, difficult solvent recovery, easy polymerization of raw materials and products, equipment corrosion and the like.
Disclosure of Invention
The purpose of the invention is as follows: in view of the problems in the prior art, the present invention aims to provide a method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification. The invention has simple process operation, less side reaction, convenient product quality control, small waste water amount, easy biodegradation and the like.
The technical scheme is as follows: in order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification comprises the following steps:
(1) adding methyl methacrylate or methyl acrylate and trimethylolpropane into a reactor, adding a catalyst and a polymerization inhibitor, and heating to generate reflux;
(2) in the reflux process, azeotrope formed by the raw material methyl methacrylate or methyl acrylate and the byproduct methanol is continuously discharged; adjusting the reflux ratio and controlling the discharge amount; the chemical equilibrium continuously moves towards the direction of product generation, the materials in the reactor are sampled and analyzed, and when the product content is more than or equal to 95 percent, the reaction is finished;
(3) and (3) cooling the materials in the reactor to 50-60 ℃, adding 50-60 ℃ washing hot water and a decolorizing agent to remove a catalyst and a polymerization inhibitor, recovering unreacted methyl methacrylate or methyl acrylate, and removing water to obtain a product trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.
Preferably, in the heating reflux process, the temperature is increased to 80-100 ℃, and air is continuously introduced into the reaction system.
Preferably, the material ratio of the synthesis reaction is as follows: 100-120 parts of trimethylolpropane, 300-400 parts of methyl methacrylate or methyl acrylate, 5-10 parts of catalyst and 2-5 parts of polymerization inhibitor.
Preferably, the control range of the reactor temperature is: when the raw material is methyl methacrylate, the temperature is 90-120 ℃, and when the raw material is methyl acrylate, the temperature is 80-110 ℃.
Preferably, the reflux ratio of the reactor is 0.5-3.
Preferably, the catalyst is one or more of a mixture of strongly basic ion exchange resin, calcium carbonate, calcium hydroxide, potassium hydroxide, aluminum oxide, lithium chloride, calcium oxide, potassium carbonate or sodium carbonate.
Preferably, the polymerization inhibitor is one or a mixture of more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, polymerization inhibitor 701, polymerization inhibitor 702, polymerization inhibitor 705, polymerization inhibitor TEMPO or di-tert-butylnitroxide radical.
Preferably, the using amount of the washing hot water is 2-3 times of the product amount, the using amount of the decolorizing agent is 5-10% of the product amount, and the washing temperature is 50-70 ℃.
Preferably, the decolorizing agent is one or more of sodium hydroxide, strong potassium oxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium thiosulfate, sodium sulfite, ferrous sulfate, stannous chloride, oxalic acid, hydroxylamine hydrochloride salt or hydroxylamine sulfate salt.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the invention adopts ester exchange reaction, has less side reaction, the conversion rate of Trimethylolpropane (TMP) reaches more than 99 percent, the recovery rate of Methyl Methacrylate (MMA) reaches more than 98 percent, and the content of triester of the product is more than 95 percent.
(2) The invention has simple process operation, less side reaction, convenient product quality control, small waste water amount, easy biodegradation and the like.
(3) The ester exchange reaction has the advantages of no need of solvent, high conversion rate, simple subsequent treatment process and the like, and is a preferred process method for producing high-boiling-point ester products.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
Synthesis of trimethylolpropane trimethacrylate (TMPTMA):
100g of trimethylolpropane, 350g of methyl methacrylate, 2g of polymerization inhibitor TEMPO, 6g of hydroquinone and 5g of mixture of calcium oxide, potassium carbonate and lithium chloride are respectively added into a reaction flask provided with a thorn-shaped fractionating column and a reflux device, heating and stirring are carried out, air is continuously introduced into the reactor, the temperature is gradually increased until reflux is generated, and the reflux ratio is controlled to be 2. And (3) as the reaction proceeds, discharging the generated methanol and methyl methacrylate from the top end of the fractionating column in the form of azeotrope, after a period of reaction, sampling from the flask for liquid chromatography analysis, wherein the detection conditions of the liquid chromatography are as follows: column C18, 4.6X 250mm, 5 μm; the volume ratio of the mobile phase methanol to the water is 30: 70; the flow rate is 1.0 mL/min; column temperature: 30 ℃; detection wavelength 254nm, sample injection amount: 10 μ L. When the product content is more than or equal to 95 percent, the reaction is finished. Cooling the flask to 50 ℃, centrifugally separating out the solid catalyst, distilling under reduced pressure at 90 ℃ and-0.09 MPa to recover excessive methyl methacrylate, dissolving 5g of hydroxylamine hydrochloride and 5g of sodium hydroxide in 500g of water, adding the solution into the flask, fully stirring for 30 minutes, transferring the solution into a separating funnel, standing, removing a water layer, and distilling under reduced pressure at 50 ℃ and-0.098 MPa to remove residual water to obtain 243g of the target product trimethylolpropane trimethacrylate with the purity of 96.01%.
Example 2
Synthesis of trimethylolpropane trimethacrylate (TMPTMA):
100g of trimethylolpropane, 350g of methyl methacrylate, 2g of polymerization inhibitor TEMPO and 6g of p-hydroxyanisole, as well as the catalyst recovered in example 1, are respectively added into a reaction flask provided with a thorn-shaped fractionating column and a reflux device, heating and stirring are carried out, air is continuously introduced into the reactor, the temperature is gradually increased until reflux is generated, and the reflux ratio is controlled to be 2. And (3) as the reaction proceeds, the generated methanol and methyl methacrylate are extracted from the top end of the fractionating column in an azeotrope form, after a period of reaction, a sample is taken from the flask for liquid chromatography analysis, and the detection conditions of the liquid chromatography are as follows: column C18, 4.6X 250mm, 5 μm; the volume ratio of the mobile phase methanol to the water is 30: 70; the flow rate is 1.0 mL/min; column temperature: 30 ℃; detection wavelength 254nm, sample injection amount: 10 μ L. When the product content is more than or equal to 95 percent, the reaction is finished. Cooling the flask to 50 ℃, centrifugally separating out the solid catalyst, recovering excessive methyl methacrylate under the conditions of 90 ℃ and-0.09 MPa under reduced pressure, dissolving 5g of sodium thiosulfate and 6g of sodium carbonate in 500g of water, adding the mixture into the flask, fully stirring for 30 minutes, transferring the mixture into a separating funnel, standing the mixture, removing a water layer, and distilling the mixture under reduced pressure under the conditions of 50 ℃ and-0.098 MPa to remove residual water to obtain 249g of the target product trimethylolpropane trimethacrylate with the purity of 95.27%.
Example 3
Synthesis procedure of trimethylolpropane triacrylate (TMPTA):
100g of trimethylolpropane, 300g of acrylate, 7052g of polymerization inhibitor, 6g of p-hydroxyanisole and 7g of mixture of potassium carbonate and lithium chloride are respectively added into a reaction flask provided with a thorn-shaped fractionating column and a reflux device, heating and stirring are carried out, air is continuously introduced into the reactor, the temperature is gradually increased until reflux is generated, and the reflux ratio is controlled to be 1.5. And (3) as the reaction proceeds, the generated methanol and methyl acrylate are extracted from the top end of the fractionating column in an azeotrope form, after a period of reaction, a sample is taken from the flask for liquid chromatography analysis, and the detection conditions of the liquid chromatography are as follows: column C18, 4.6X 250mm, 5 μm; the volume ratio of the mobile phase methanol to the water is 30: 70; the flow rate is 1.0 mL/min; column temperature: 30 ℃; detection wavelength 254nm, sample injection amount: 10 μ L. When the product content is more than or equal to 95 percent, the reaction is finished. The flask was cooled to 50 ℃, the solid catalyst was separated by centrifugation, excess methyl acrylate was recovered by distillation under reduced pressure at 90 ℃ and-0.09 MPa, 3g of sodium thiosulfate and 7g of sodium carbonate were dissolved in 500g of water and added to the flask, the mixture was stirred sufficiently for 30 minutes, the mixture was transferred to a separatory funnel and allowed to stand, after removing the water layer, residual water was removed by distillation under reduced pressure at 50 ℃ and-0.098 MPa, and 248g of the objective trimethylolpropane triacrylate having a purity of 95.27% was obtained.
Claims (8)
1. A method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification is characterized by comprising the following steps:
(1) adding methyl methacrylate or methyl acrylate and trimethylolpropane into a reactor, adding a catalyst and a polymerization inhibitor, and heating to generate reflux;
(2) in the reflux process, azeotrope formed by the raw material methyl methacrylate or methyl acrylate and the byproduct methanol is continuously discharged; adjusting the reflux ratio and controlling the discharge amount; the chemical equilibrium continuously moves towards the direction of product generation, the materials in the reactor are sampled and analyzed, and when the product content is more than or equal to 95 percent, the reaction is finished; the reflux ratio of the reactor is 0.5-3;
(3) cooling the materials in the reactor to 50-60 ℃, adding 50-60 ℃ washing hot water and a decolorizing agent to remove a catalyst and a polymerization inhibitor, recovering unreacted methyl methacrylate or methyl acrylate, and performing dehydration treatment to obtain a product trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.
2. The method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification according to claim 1, wherein the temperature is increased to 80-100 ℃ in the heating reflux process, and air is continuously introduced into the reaction system.
3. The method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification according to claim 1, wherein the material ratio of the synthesis reaction is as follows: 100-120 parts of trimethylolpropane, 300-400 parts of methyl methacrylate or methyl acrylate, 5-10 parts of catalyst and 2-5 parts of polymerization inhibitor.
4. The method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification according to claim 1, wherein the control range of the reactor temperature is as follows: when the raw material is methyl methacrylate, the temperature is 90-120 ℃, and when the raw material is methyl acrylate, the temperature is 80-110 ℃.
5. The method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification according to claim 1, wherein the catalyst is one or more of strong basic ion exchange resin, calcium carbonate, calcium hydroxide, potassium hydroxide, aluminum oxide, lithium chloride, calcium oxide, potassium carbonate or sodium carbonate.
6. The method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate according to claim 1, wherein the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, polymerization inhibitor 701, polymerization inhibitor 705, polymerization inhibitor TEMPO or di-tert-butylnitroxide radical.
7. The method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification according to claim 1, wherein the amount of the washing hot water is 2-3 times of the amount of the product, the amount of the decoloring agent is 5% -10% of the amount of the product, and the washing temperature is 50-70 ℃.
8. The method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by transesterification according to claim 1, wherein the decoloring agent is one or more of sodium hydroxide, potassium oxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium thiosulfate, sodium sulfite, ferrous sulfate, stannous chloride, oxalic acid, potassium borohydride, sodium borohydride, hydroxylamine hydrochloride or hydroxylamine sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811507307.5A CN109651136B (en) | 2018-12-10 | 2018-12-10 | Method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811507307.5A CN109651136B (en) | 2018-12-10 | 2018-12-10 | Method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109651136A CN109651136A (en) | 2019-04-19 |
| CN109651136B true CN109651136B (en) | 2021-12-14 |
Family
ID=66113973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811507307.5A Active CN109651136B (en) | 2018-12-10 | 2018-12-10 | Method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109651136B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112830793A (en) * | 2019-11-22 | 2021-05-25 | 福建臻璟新材料科技有限公司 | Preparation process for preparing high-thermal-conductivity and high-strength aluminum nitride ceramic through gel-process injection molding |
| CN111689859B (en) * | 2020-05-25 | 2023-01-24 | 江苏乾元新材料科技有限公司 | Low-shrinkage resin and preparation method and application thereof |
| CN118638008B (en) * | 2024-08-14 | 2024-12-17 | 淄博飞源化工有限公司 | Trifluoroethyl methacrylate and synthesis method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5554785A (en) * | 1993-09-03 | 1996-09-10 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification products |
| CN101337889A (en) * | 2007-07-05 | 2009-01-07 | 罗姆有限公司 | Method for preparing (methyl) acrylic ester |
| CN105837448A (en) * | 2016-03-29 | 2016-08-10 | 常州大学 | Method for synthesis of (meth)acrylate diluent |
-
2018
- 2018-12-10 CN CN201811507307.5A patent/CN109651136B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5554785A (en) * | 1993-09-03 | 1996-09-10 | Cps Chemical Company, Inc. | Organotin catalyzed transesterification products |
| CN101337889A (en) * | 2007-07-05 | 2009-01-07 | 罗姆有限公司 | Method for preparing (methyl) acrylic ester |
| CN105837448A (en) * | 2016-03-29 | 2016-08-10 | 常州大学 | Method for synthesis of (meth)acrylate diluent |
Non-Patent Citations (1)
| Title |
|---|
| 三羟甲基丙烷三(甲基)丙烯酸酯的酯交换合成工艺研究;宋国强等;《应用化工》;20140220(第02期);269-272 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109651136A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109651136B (en) | Method for synthesizing trimethylolpropane trimethacrylate and trimethylolpropane triacrylate by ester exchange | |
| CN112521283B (en) | Extraction Treatment of MMA-Methanol Mixture Containing Sodium Salt | |
| JP2529175B2 (en) | Improvement of production method of alkyl (meth) acrylate by direct esterification | |
| CN104761452B (en) | A kind of purification process of butyl acrylate coarse product | |
| JP2002511081A (en) | Method for producing dimethyl ester of unsaturated dicarboxylic anhydride | |
| Rubottom et al. | The Mcpba Oxidation of Alkyl Trimethylsilyl Ketene Acetals | |
| CN112174817A (en) | A kind of preparation technology of (meth)acrylic acid long-chain alkyl ester | |
| JP5720528B2 (en) | Method for producing acrylate and method for recovering acrylic acid | |
| CN1181039C (en) | Improved method for preparing 2-ethylhexyl acrylate | |
| CN115894229A (en) | A kind of selective synthesis process of monoethyl adipate | |
| CN104803849A (en) | Synthesizing method of acrylic fluorine-containing ester and derivatives thereof through catalyzed synthesis of solid acid | |
| CN103254073B (en) | Preparation method of high-purity (bi)pentaerythritol crylic acid non-complete esterification product | |
| CN1170401A (en) | Preparation of cinnamate sunscreen agents | |
| CN114315575B (en) | Preparation method and application of photoinitiator intermediate | |
| CN113214145B (en) | Vitamin B6 production method | |
| JPH0210137B2 (en) | ||
| CN112079714A (en) | Preparation method of 2-phenylethyl acrylate | |
| JP2686824B2 (en) | Process for producing dipentaerythritol hexaester compound | |
| JP2005194201A (en) | Process for producing 4-hydroxybutyl (meth) acrylate and production apparatus thereof | |
| CN114349618B (en) | Preparation method and application of chloro intermediate for synthesizing photoinitiator | |
| JPH09235244A (en) | Transesterification | |
| JP5018067B2 (en) | Method for producing fluorine-containing alkane esters | |
| CN112661669A (en) | Method for synthesizing N, N' -dicyclohexylcarbodiimide by microwave-assisted method | |
| CN115838327B (en) | Alkaline hydrolysis method of photoinitiator 184 | |
| KR101178238B1 (en) | Method for preparing alkylacrylate by azetropic ester reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |