CN103642597A - Method for preparing epoxy caster oil in electrochemical oxidation way - Google Patents
Method for preparing epoxy caster oil in electrochemical oxidation way Download PDFInfo
- Publication number
- CN103642597A CN103642597A CN201310640337.4A CN201310640337A CN103642597A CN 103642597 A CN103642597 A CN 103642597A CN 201310640337 A CN201310640337 A CN 201310640337A CN 103642597 A CN103642597 A CN 103642597A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- castor oil
- reaction
- viscotrol
- electrochemical oxidation
- 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.)
- Granted
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000019253 formic acid Nutrition 0.000 claims abstract description 19
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 13
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 10
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000004359 castor oil Substances 0.000 claims description 41
- 235000019438 castor oil Nutrition 0.000 claims description 41
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 38
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 22
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 22
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000749 nitanium Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 11
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000003068 static effect Effects 0.000 description 10
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 150000002924 oxiranes Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 210000000582 semen Anatomy 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000263 Rubber seed oil Polymers 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 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 description 1
- NOCWDMQAHCQAKS-UHFFFAOYSA-N 2-hydroxyoctadeca-2,4-dienoic acid Chemical compound CCCCCCCCCCCCCC=CC=C(O)C(O)=O NOCWDMQAHCQAKS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- -1 stirs Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a method for preparing epoxy caster oil in an electrochemical oxidation way. The method comprises the steps of adding caster oil and little hydrochloric acid aqueous solution into an electrolytic cell, introducing air and adding methanoic acid on a cathode, and epoxidating the unsaturated fatty acid in the caster oil by utilizing the H2O2 generated in the reduction reaction; epoxidating the unsaturated fatty acid on an anode by utilizing strong oxidants such as OH<-1>, O3 and O in the solution so as to obtain the oily epoxy caster oil. By adopting the method, the epoxidation rate is 80 to 93 percent; moreover, the equipment is simple, the energy consumption is low, the pollution is little, and the method is applicable to the industrial fields such as plastics, paint, rubber and the like.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy castor oil, concrete is a kind of method that is epoxy castor oil by Viscotrol C electrolytic oxidation by electrochemical oxidation.
Background technology
The source of unsaturated fatty acids is mainly vegetables oil, belongs to renewable resources.In recent years, the chemical utilization of reproducible unsaturated fatty acid derivative and vegetables oil has been subject to paying close attention to widely.The approach that utilizes of unsaturated fatty acids has esterification, transesterify, hydrogenation, epoxidation, isomerization, cracking etc.Wherein, epoxidized fatty acid is to be a kind ofly widely used in heat-resisting, low temperature resistant, medical packaging material as softening agent and stablizer, has good heat, light stabilization.As the additive as polyvinyl chloride, to have consistency good, and volatility is little, and transport property is little, nontoxic, almost can be for all polrvinyl chloride products.Viscotrol C is a kind of natural phant polyvalent alcohol that can be used for polyurethane production, it contains i.e. (9-thiazolinyl-1 of more unsaturated fatty acids ricinolic acid in forming, 2-hydroxy octadecadienoic acid), can generate epoxy castor oil through oxidizing reaction, epoxy castor oil has extensive use at industrial circles such as plastics, coating, rubber, the feature such as thermostability, weathering resistance that can give product fine, gets more and more people's extensive concerning.Therefore, the epoxy castor oil of R and D efficient green and epoxidation technology, to reproducible vegetables oil deep processing, walk sustainable development path, has significant economy and realistic meaning.
Sun Shangde (grain and grease, 2010,11:10～13) etc. makees catalyzer with Tai-Ace S 150, catalyzes and synthesizes epoxy Semen Maydis oil.And pass through optimization of orthogonal test reaction parameter: reaction times, temperature of reaction, formic acid consumption, hydrogen peroxide consumption and catalyzer (Tai-Ace S 150) are measured, draw optimization reaction conditions: Semen Maydis oil 30g, reaction times 9h, 50 ℃ of temperature of reaction, formic acid consumption 7mL, hydrogen peroxide consumption 35mL, addition of aluminum sulfate is 5% (in Semen Maydis oil quality).Under these processing condition, obtaining epoxidation Semen Maydis oil oxirane value is 6.3%, and transformation efficiency is 92.7%.
Goud (industrial engineering chemistry research, 2007,46:3078～3085) etc. use acidic ion exchange resin (Amberlite IR-120) is made catalyzer, by acetic acid and hydrogen peroxide original position, generates Peracetic Acid epoxidation Viscotrol C, and epoxidation productive rate has reached 90%.
Gong Jing (application chemical industry, 2011,10:1 768～1770) etc. prepares epoxy rubber seed oil with phosphoric acid does catalyst under condition of no solvent, adopts uniform design research formic acid consumption, reaction times and the impact of hydrogen peroxide consumption on oxirane value.Result shows, optimal conditions is: rubber seed oil 100g, and formic acid 12.80g, the hydrogen peroxide 50.53g that massfraction is 30%, reaction times 6h, 50～55 ℃ of temperature of reaction, product oxirane value reaches 11.68%.Rubber seed oil product color prepared by the method is shallow, steady quality.
Zhang Xueying (electrochemistry, 2000,6:324～328) etc. sets up a kind of new cathodic indirect electro-oxidation system, with VO (acac)
2oOH/ VO (acac)
2for redox medium, by catalytic cathode by O
2the H that electroreduction produces
2o
2some olefin(e) acid is carried out to indirect epoxidation as maleic acid, FUMARIC ACID TECH GRADE and butenoic acid etc.Studied the impact of the factors such as pH value, temperature, current density on reaction.Result shows, the optimum reaction condition of the indirect epoxidation reaction of negative electrode of maleic acid is: current density 1mA/cm
2; Temperature 50 C; PH 7; VO (acac)
2concentration >0.5mmol/L; By electric weight 2F/mol.
Cui Baoqiu (fine chemistry industry, 2000,10:46～48) etc.: adopt tungstate/pertungstate medium in cathodic indirect electro-oxidation, to synthesize amount of substance that suitable epoxy succinic acid obtained 70 ℃ of optimum process condition temperature of reaction, concentration of sodium tungstate 20mmol/L, reaction times 90min, pH5, material than l.0 by MALEIC ANHYDRIDE: 0.9, through liquid chromatographic detection, epoxy rate reaches 90%.
There is certain deficiency and defect in the prior art that vegetables oil is prepared epoxide, it is higher to equipment requirements, and energy consumption is larger, and cost is high, and by product is many, and environmental pollution is larger, and the productive rate of epoxide is not high.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of method that electrochemical oxidation is prepared epoxy castor oil, described in it, preparation method's step is as follows:
By Viscotrol C 40g, 3～6ml 0.1mol/L hydrochloric acid drips in electrolyzer; At negative electrode, with 2～5cm
3the oxygen-supply speed of/s passes into air continuously, adds 2～5g formic acid, the H that its reduction produces
2o
2in pH value, be 4.5～6.5, temperature is that 20～40 ℃, reaction times are that 3～5h, current density are 0.2～0.5A/cm
2under condition, the unsaturated fatty acids in Viscotrol C is carried out to epoxidation; At anode, the OH in solution
-, O
3, O strong oxidizer carries out epoxidation to Viscotrol C under above-mentioned influence factor, and reaction finishes rear separated with separating funnel, obtains oily matter epoxy castor oil.
In aforesaid method, described anode is a kind of in Pt, Pd, Ni and titanium base lead dioxide electrode; Described negative electrode is a kind of in graphite, stainless steel, Pt, Pd, Ni and titanium base lead dioxide electrode.
The method of Viscotrol C electrochemistry cyclization blown castor oil for the present invention, compared with prior art has advantages of as follows: (1) reaction is carried out in electrolyzer, and equipment is simple; (2) required H in reaction process
2o
2be to pass into air to utilize electrochemistry to generate, reduced cost; (3) technical process is simple, and investment of production is little; (4) in reaction system, formic acid can recirculation be used as redox medium, and environment is not polluted, and is a kind of eco-friendly reduction and oxidation synthetic technology; (5) reaction is easily controlled, by controlling voltage, just can control at any time reaction beginning, interrupt and stop.(6) reaction has product to generate at negative electrode and anode, has improved the productive rate of epoxy castor oil.
The present invention carries out epoxy flow measurement by GB/T 1677-2008, and the epoxy amount of the epoxy castor oil of acquisition is 0.14mol/100g～0.17mol/100g, and epoxy rate is 80～93%.
accompanying drawing explanation
Fig. 1 is the schematic diagram that in electrolyzer, electrochemical oxidation is prepared epoxy castor oil method.
Embodiment
Implement a kind of electrochemical oxidation provided by the present invention and prepare the method for epoxy castor oil, it is as follows that it implements preparation method:
First by Viscotrol C 40g, 3～6ml 0.1mol/L aqueous hydrochloric acid adds in electrolyzer, at negative electrode, with 2～5cm
3the oxygen-supply speed of/s passes into air continuously, and adds 2～5g formic acid, stirs, air bubbler is put into cathode compartment, connect power supply, electrolyzer is connected with DC stable power supply, ensure that energising is normal, in electrolyzer, it is as follows to there is epoxidised reaction equation in negative electrode:
The H that above-mentioned reduction produces
2o
2in pH value, be 4.5～6.5, temperature is that 20～40 ℃, current density are 0.2～0.5A/cm
2condition under the unsaturated fatty acids in Viscotrol C is carried out to epoxidation;
At anode, the OH in solution
-, O
3, O strong oxidizer under above-mentioned influence factor to unsaturated fatty acids ring
Oxidation, in electrolyzer, it is as follows to there is epoxidised reaction equation in anode:
After reaction 3～5h, generate oily matter epoxy castor oil, the oxirane value of gained epoxy castor oil is 0.14mol/100g～0.17mol/100g, and epoxy rate is 80～93%.
Wherein, the anode adopting is a kind of in Pt, Pd, Ni and titanium base lead dioxide electrode; The negative electrode adopting is a kind of in graphite, stainless steel, Pt, Pd, Ni and titanium base lead dioxide electrode.
The concrete a kind of electrochemical oxidation implemented of the present invention is prepared the method for epoxy castor oil, by GB/T 1677-2008, carries out epoxy flow measurement, and the epoxy amount of the epoxy castor oil of acquisition is 0.14mol/100g～0.17mol/100g, and epoxy rate is 80～93%.
Specific embodiment is as follows.
Embodiment 1
40g Viscotrol C and 3ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 2g formic acid to stir.Anode Pt electrode, negative electrode stainless steel electrode.Air bubbler is put into cathode compartment, connect power source, with 2cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.2A/cm
2.It is 20 ℃ that temperature of reaction is set, and pH value is 6.5, after reaction 3h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.145mol/100g of epoxy castor oil, epoxy rate is 80.3%.
Embodiment 2
40g Viscotrol C and 6ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 5g formic acid to stir.Titanium base lead dioxide electrode for anode, negative electrode Graphite Electrodes.Air bubbler is put into cathode compartment, connect power source, with 5cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.5A/cm
2.It is 40 ℃ that temperature of reaction is set, and pH value is 4.5, after reaction 5h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.168mol/100g of epoxy castor oil, epoxy rate is 93.3%.
Embodiment 3
40g Viscotrol C and 4ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 4g formic acid to stir.Anode Pd electrode, negative electrode Ni electrode.Air bubbler is put into cathode compartment, connect power source, with 3cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.4A/cm
2.It is 30 ℃ that temperature of reaction is set, and pH value is 6.0, after reaction 4h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.156mol/100g of epoxy castor oil, epoxy rate is 86.5%.
Embodiment 4
40g Viscotrol C and 6ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 5g formic acid to stir.Titanium base lead dioxide electrode for anode, negative electrode stainless steel electrode.Air bubbler is put into cathode compartment, connect power source, with 4cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.5A/cm
2.It is 35 ℃ that temperature of reaction is set, and pH value is 4.5, after reaction 4h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.16mol/100g of epoxy castor oil, epoxy rate is 89%.
Embodiment 5
40g Viscotrol C and 5ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 4g formic acid to stir.Anode Ni electrode, negative electrode Pd electrode.Air bubbler is put into cathode compartment, connect power source, with 3cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.2A/cm
2.It is 20 ℃ that temperature of reaction is set, and pH value is 5.0, after reaction 3h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.153mol/100g of epoxy castor oil, epoxide productive rate is 85%.
Embodiment 6
40g Viscotrol C and 4ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 3g formic acid to stir.Anode Pt electrode, titanium base lead dioxide electrode for negative electrode.Air bubbler is put into cathode compartment, connect power source, with 4cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, regulating current density is 0.2 A/cm
2.It is 40 ℃ that temperature of reaction is set, and pH value is 6.5, reacts after 5 hours, and cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.16mol/100g of epoxy castor oil, epoxide productive rate is 89%.
Embodiment 7
40g Viscotrol C and 3ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 5g formic acid to stir.Titanium base lead dioxide electrode for anode, negative electrode Pd electrode.Air bubbler is put into cathode compartment, connect power source, with 3cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.4A/cm
2.It is 25 ℃ that temperature of reaction is set, and pH value is 6.0, after reaction 4h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.15mol/100g of epoxy castor oil, epoxide productive rate is 84%.
Embodiment 8
40g Viscotrol C and 5ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 4g formic acid to stir.Anode Pt electrode, negative electrode Graphite Electrodes.Air bubbler is put into cathode compartment, connect power source, with 5cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.2A/cm
2.It is 30 ℃ that temperature of reaction is set, and pH value is 5.0, after reaction 5h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.157mol/100g of epoxy castor oil, epoxide productive rate is 87%.
Embodiment 9
40g Viscotrol C and 5ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 5g formic acid to stir.Anode Pt electrode, negative electrode Ni electrode.Air bubbler is put into cathode compartment, connect power source, with 4cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.3A/cm
2.It is 30 ℃ that temperature of reaction is set, and pH value is 5.5, after reaction 4h, cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.155mol/100g of epoxy castor oil, epoxide productive rate is 86%.
Embodiment 10
40g Viscotrol C and 5ml 0.1mol/L aqueous hydrochloric acid are added in electrolyzer, in cathode compartment, add 5g formic acid to stir.Anode Ni electrode, titanium base lead dioxide electrode for negative electrode.Air bubbler is put into cathode compartment, connect power source, with 5cm
3the logical oxygen of speed of/s.Electrolyzer is connected with DC stable power supply, ensures that energising is normal, adjusting current density is 0.5A/cm
2.It is 40 ℃ that temperature of reaction is set, and pH value is 5, reacts after 5 hours, and cathode compartment liquid is poured in beaker, and static layering, uses separating funnel separatory, obtains oily matter epoxy castor oil.The epoxy amount 0.167mol/100g of epoxy castor oil, epoxide productive rate is 92.5%.
Claims (3)
1. electrochemical oxidation is prepared a method for epoxy castor oil, it is characterized in that: described method is by Viscotrol C 40g, and 3～6ml 0.1mol/L hydrochloric acid drips in electrolyzer; At negative electrode, with 2～5cm
3the oxygen-supply speed of/s passes into air continuously, adds 2～5g formic acid, the H that its reduction produces
2o
2in pH value, be 4.5～6.5, temperature is that 20～40 ℃, reaction times are that 3～5h, current density are 0.2～0.5A/cm
2under condition, the unsaturated fatty acids in Viscotrol C is carried out to epoxidation; At anode, the OH in solution
-, O
3, O strong oxidizer carries out epoxidation to Viscotrol C under above-mentioned influence factor, and reaction finishes rear separated with separating funnel, obtains oily matter epoxy castor oil.
2. a kind of electrochemical oxidation as claimed in claim 1 is prepared the method for epoxy castor oil, it is characterized in that: described anode is a kind of in Pt, Pd, Ni and titanium base lead dioxide electrode.
3. a kind of electrochemical oxidation as claimed in claim 1 is prepared the method for epoxy castor oil, it is characterized in that: described negative electrode is a kind of in graphite, stainless steel, Pt, Pd, Ni and titanium base lead dioxide electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310640337.4A CN103642597B (en) | 2013-12-04 | 2013-12-04 | A kind of electrochemical oxidation prepares the method for epoxy castor oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310640337.4A CN103642597B (en) | 2013-12-04 | 2013-12-04 | A kind of electrochemical oxidation prepares the method for epoxy castor oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103642597A true CN103642597A (en) | 2014-03-19 |
| CN103642597B CN103642597B (en) | 2015-07-29 |
Family
ID=50247885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310640337.4A Expired - Fee Related CN103642597B (en) | 2013-12-04 | 2013-12-04 | A kind of electrochemical oxidation prepares the method for epoxy castor oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103642597B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590515A (en) * | 2016-12-15 | 2017-04-26 | 温州乐发教育科技有限公司 | Water-soluble polyurethane adhesive and preparation method thereof |
| CN110790898A (en) * | 2019-08-31 | 2020-02-14 | 王世茸 | Modified epoxy resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043338A (en) * | 1988-12-10 | 1990-06-27 | 郑发纲 | The method for preparing epoxy derivative of fatty acid |
| CN102864021A (en) * | 2012-09-26 | 2013-01-09 | 山东吉青化工有限公司 | Epoxidation vegetable oil preparation method |
-
2013
- 2013-12-04 CN CN201310640337.4A patent/CN103642597B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043338A (en) * | 1988-12-10 | 1990-06-27 | 郑发纲 | The method for preparing epoxy derivative of fatty acid |
| CN102864021A (en) * | 2012-09-26 | 2013-01-09 | 山东吉青化工有限公司 | Epoxidation vegetable oil preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 崔宝秋等: "阴极间接电氧化研究新进展", 《南都学坛(自然科学版)》, vol. 21, no. 3, 31 May 2001 (2001-05-31), pages 68 - 70 * |
| 张越等: "成对间接电氧化合成有机物研究", 《石家庄师范专科学校学报》, vol. 3, no. 2, 30 June 2001 (2001-06-30), pages 47 - 50 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590515A (en) * | 2016-12-15 | 2017-04-26 | 温州乐发教育科技有限公司 | Water-soluble polyurethane adhesive and preparation method thereof |
| CN110790898A (en) * | 2019-08-31 | 2020-02-14 | 王世茸 | Modified epoxy resin and preparation method thereof |
| CN110790898B (en) * | 2019-08-31 | 2022-03-15 | 忠信世纪电子材料(始兴)有限公司 | Modified epoxy resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103642597B (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105417536B (en) | A kind of preparation method of the adjustable graphene quantum dot of oxygen content | |
| CN105112934B (en) | A kind of preparation method of tetra-alkyl ammonium hydroxide | |
| CN105297067A (en) | Multi-room diaphragm electrolysis method and device for electroreduction of carbon dioxide into carbon monoxide | |
| CN105951117B (en) | A kind of electrolytic method of low cost production high purity of hydrogen peroxide and hydrogen | |
| CN104671361A (en) | Method for removing PPCPs micropollutants in secondary sedimentation tank wastewater | |
| CN106925314A (en) | A kind of nickel assisted cryogenic synthesizes the method for molybdenum carbide elctro-catalyst | |
| CN108892175A (en) | A kind of preparation method and electro-catalysis application having defective vanadium doping molybdenum disulfide nano flower | |
| CN108411333A (en) | A method of preparing hydrogen peroxide using the hydrophobic cathodic reduction oxygen of acetylene black | |
| CN107335433A (en) | A kind of preparation method for aoxidizing molybdenum base efficient electric catalytic hydrogen evolution catalyst | |
| CN108033522A (en) | A kind of electro-catalysis couples advanced oxidation system | |
| CN103642597B (en) | A kind of electrochemical oxidation prepares the method for epoxy castor oil | |
| CN108585044B (en) | Co-MoO with mylikes structure2Simple preparation and electrocatalysis application of nanosphere | |
| JP2019099861A (en) | Method of producing cycloalkanol and cycloalkanone | |
| CN113019380A (en) | CuO/Cu2Preparation method of O/ZnO heterojunction photoelectric catalytic material | |
| Li et al. | A new approach for epoxidation of fatty acids by a paired electrosynthesis | |
| CN103964503A (en) | Preparation method of black titanium dioxide | |
| CN205329170U (en) | Multi -chambered diaphragm electrolysis device that is carbon dioxide electroreduction carbon monoxide | |
| CN105568309B (en) | A kind of preparation method of the optoelectronic pole of photoelectrochemical cell | |
| JP2015004112A (en) | Electrolytic synthesis device | |
| CN104310671A (en) | Three-dimensional electrode electro-catalytic reactor wastewater treatment method employing intermittent power supply | |
| CN106622364A (en) | Solid phase preparation method of ionic liquid polyoxometallate nano electrocatalyst | |
| CN106048641A (en) | Process method of electrochemically preparing Fe3+ and H2 in pair | |
| CN108950647A (en) | A kind of electrochemical preparation method of boronising Nano tube array of titanium dioxide | |
| CN107746077A (en) | A kind of preparation method of flower ball-shaped silver vanadate | |
| CN107829104A (en) | A kind of method for obtaining hydrogen and biomass fuel rod simultaneously with biomass material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: BEIJING AISHIMU TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: TAIYUAN UNIV. OF TECHNOLOGY Effective date: 20150130 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 030024 TAIYUAN, SHAANXI PROVINCE TO: DONGCHENG, BEIJING |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20150130 Address after: Room 5, No. 711, Jianguo Road, 5 North Main Street, Jianguomen, Beijing, Dongcheng District Applicant after: BEIJING AISHIMU TECHNOLOGY Co.,Ltd. Address before: 030024 Yingze, Shanxi Province, Berlin District, West Street, No. 79, No. Applicant before: Taiyuan University of Technology |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201209 Address after: Room 1512, Jincheng Jianguo No.5, Jianguomen North Street, Dongcheng District, Beijing, 100005 Patentee after: Beijing Zhongke Antu Transportation Technology Co.,Ltd. Address before: Room 5, No. 711, Jianguo Road, 5 North Main Street, Jianguomen, Beijing, Dongcheng District Patentee before: BEIJING AISHIMU TECHNOLOGY Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 Termination date: 20211204 |