CN1460674A - Method for preparing tetraalkylammonium hydroxide - Google Patents
Method for preparing tetraalkylammonium hydroxide Download PDFInfo
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- CN1460674A CN1460674A CN 03148565 CN03148565A CN1460674A CN 1460674 A CN1460674 A CN 1460674A CN 03148565 CN03148565 CN 03148565 CN 03148565 A CN03148565 A CN 03148565A CN 1460674 A CN1460674 A CN 1460674A
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- China
- Prior art keywords
- allkylammonium
- tetraalkylammonium hydroxide
- acid tetra
- hydroxide
- tetraalkylammonium
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002798 polar solvent Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims abstract description 10
- 125000005270 trialkylamine group Chemical group 0.000 claims abstract description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkyl carbonic acid Chemical compound 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- LMASIWYRIYEBTQ-UHFFFAOYSA-M ethyl carbonate;tetraethylazanium Chemical compound CCOC([O-])=O.CC[N+](CC)(CC)CC LMASIWYRIYEBTQ-UHFFFAOYSA-M 0.000 claims description 2
- HCWMUANODLPMEO-UHFFFAOYSA-M ethyl sulfate;tetraethylazanium Chemical compound CCOS([O-])(=O)=O.CC[N+](CC)(CC)CC HCWMUANODLPMEO-UHFFFAOYSA-M 0.000 claims description 2
- YKLKUNBKAPXTEZ-UHFFFAOYSA-M methyl carbonate;tetramethylazanium Chemical compound COC([O-])=O.C[N+](C)(C)C YKLKUNBKAPXTEZ-UHFFFAOYSA-M 0.000 claims description 2
- JGJWEFUHPCKRIJ-UHFFFAOYSA-M methyl sulfate;tetramethylazanium Chemical compound C[N+](C)(C)C.COS([O-])(=O)=O JGJWEFUHPCKRIJ-UHFFFAOYSA-M 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- TXBULBYASDPNNC-UHFFFAOYSA-L tetraethylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CC[N+](CC)(CC)CC.CC[N+](CC)(CC)CC TXBULBYASDPNNC-UHFFFAOYSA-L 0.000 claims description 2
- KJFVITRRNTVAPC-UHFFFAOYSA-L tetramethylazanium;sulfate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.[O-]S([O-])(=O)=O KJFVITRRNTVAPC-UHFFFAOYSA-L 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Under the action of polar solvent said invention uses trialkylamine and dialkyl carbonate as raw material, makes them produce reaction and utilizes the control of reaction temp., reaction pressure and reaction time to obtain tetra-alkyl ammonium salt, then makes it react with alkali, through the processes of distillation and filtration, so as to obtain the invented product tetra-alkyl ammonium hydroxide.
Description
Technical field
The present invention relates to a kind of preparation method of organic bases, be specifically related in polar solvent, prepare the method for tetraalkylammonium hydroxide by alkylammonium salt and alkali reaction.
Background technology
Tetraalkylammonium hydroxide be a kind ofly be used to weave, the important fine chemical product of industries such as food, leather, wood working and plastics, polymkeric substance, plating, catalysis, also have and use widely at circuit card printing, micro-eyeglass manufacture view.
At present, the main preparation methods of tetraalkylammonium hydroxide has: the one, and electrolytic process is that raw material passes through electrolytic preparation (referring to CN1313400, US 4714530) with tetramethyl-ammonium halide, tetramethyl-volatile salt and tetramethyl-ammonium formiate.But this method facility investment big (as electrolyzer etc.), it is high that support equipment requires, so the production cost height; The 2nd, ion exchange method, it is through ion exchange resin exchange preparation (referring to " Speciality Petrochemicals " Dai Yanfeng, Liu Xiyao, Sa Xueli, 1998, (2)) with the aqueous solution of quaternary alkylammonium halides.Because be subjected to the restriction of the saturated capacity of resin, industrial scale is little.Because of needing regular regeneration, handles resin complex operation, unsuitable suitability for industrialized production simultaneously; The 3rd, the silver suboxide method, it is that quaternary alkylammonium halides and silver suboxide, water one are reacted and make.This method is because of consuming a large amount of precious metal silver, thus the production cost height, and contain in the product and be difficult for halogen ion and the silver ions removed on a small quantity, influence quality product.(referring to " Jiangxi chemical industry ", Zhang Zhongmin, Fu Jilie etc., 1996, (2))
Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of production cost low, easy and simple to handle, are suitable for the novel method of the preparation tetraalkylammonium hydroxide of suitability for industrialized production.
The method for preparing tetraalkylammonium hydroxide of the present invention is to adopt the alkaline hydrolysis reaction in polar solvent of tetraalkylammonium salt and alkali.
The tetraalkylammonium salt that the present invention adopts comprises tetraalkyl volatile salt, tetraalkyl bicarbonate of ammonia, tetraalkyl monoammonium sulfate, tetraalkyl ammonium sulfate, alkylsurfuric acid tetra-allkylammonium, alkyl carbonic acid tetra-allkylammonium, and the carbonatoms of alkyl is C
1-C
4, preferred tetramethyl-volatile salt, methyl carbonic acid tetramethyl-ammonium, tetraethyl-volatile salt, ethyl carbonate tetraethyl ammonium, tetramethyl-ammonium sulfate, methylsulfuric acid tetramethyl-ammonium, tetraethyl-ammonium sulfate, ethylsulfuric acid tetraethyl ammonium.
Alkyl carbonic acid tetra-allkylammonium that the present invention adopts or alkylsurfuric acid tetra-allkylammonium are to be raw material by trialkylamine and dialkyl carbonate or sulfuric acid dialkyl, the two mixes by certain ratio of components, and condensation makes under polar solvent, certain pressure, temperature of reaction, reaction times.
The temperature of reaction of preparation alkyl carbonic acid tetra-allkylammonium of the present invention or alkylsurfuric acid tetra-allkylammonium be 50-200 (℃), preferred temperature be 60-150 (℃), the pressure of reaction is 0.1-3 (MPa), in general, pressure and selected temperature, solvent types and consumption have substantial connection, be that the solvent consumption is few more, system pressure is high more; Temperature is high more, and pressure is big more.The pressure of the present invention's reaction preferably is controlled at 0.4-2 (MPa), can obtain the product of higher yields.
The raw material trialkylamine that the reaction of preparation alkyl carbonic acid tetra-allkylammonium of the present invention or alkylsurfuric acid tetra-allkylammonium is selected and the proportioning of dialkyl carbonate or methyl-sulfate are 2: 1-1: 2 (moles), if the ratio of trialkylamine is excessive, then superfluous in reaction system, thereby bring difficulty for the operation of subsequent technique, and contaminate environment; If the ratio of trialkylamine is too small, then dialkyl carbonate or sulfuric acid dialkyl surplus cause the loss of dialkyl carbonate or sulfuric acid dialkyl when next step reacts, and increase production cost.
The trialkylamine that the reaction of preparation alkyl carbonic acid tetra-allkylammonium of the present invention or alkylsurfuric acid tetra-allkylammonium is adopted and the reaction times of dialkyl carbonate acid esters or sulfuric acid dialkyl are 1.5-6 hour, because initial reaction stage speed is fast, exothermic phenomenon is obvious, consumption gradually along with raw material, reaction slows down, and heat release reduces gradually.In order to keep certain temperature of reaction, pressure, in reaction, can control by the consumption of constantly regulating water coolant.
The selected polar solvent of condensation reaction comprises methyl alcohol or ethanol or Virahol among the present invention, and solvent load is 1-10 a times of trialkylamine weight.
In the process of preparation tetraalkylammonium hydroxide of the present invention, the alkali that is adopted is alkali metal hydroxide or its oxide compound, for example sodium hydroxide or sodium oxide, potassium hydroxide or potassium oxide etc., and alkaline earth metal hydroxides or its oxide compound, for example calcium hydroxide or calcium oxide, hydrated barta or barium oxide etc., they and alkyl carbonic acid tetra-allkylammonium or the reaction of alkylsurfuric acid tetra-allkylammonium generate tetraalkylammonium hydroxide, the ratio of its tetraalkylammonium salt and alkali is 1: 0.5-1: 4 (moles), if adopt the oxide compound of alkali or alkaline-earth metal, then its ratio with alkylammonium salt can get by corresponding alkali calculating.
In the process of preparation tetraalkylammonium hydroxide of the present invention, temperature of reaction is 0-80 ℃, is preferably 30-50 ℃, and the reaction times is 1-10 hour.
In the process of preparation tetraalkylammonium hydroxide of the present invention, selected polar solvent comprises methyl alcohol or ethanol or Virahol or water, is preferably methyl alcohol or water, solvent load be tetraalkylammonium salt weight 1-10 doubly.
Tetraalkylammonium hydroxide preparation method of the present invention, technology is easy, and cost of material is cheap, and production cost is low, constant product quality, product yield can be higher than 95%.The tetraalkylammonium hydroxide solution of producing with method of the present invention is as phase-transfer catalyst, reached and the identical effect of other method synthetic tetraalkylammonium hydroxide, thereby make to cost an arm and a leg and the production cost of the tetraalkylammonium hydroxide of dependence on import reduces greatly, thereby be suitable for suitability for industrialized production.
Embodiment
Embodiment 1
Have whipping appts at one, in 1.5 liters the autoclave of heat riser, boost to 3.5MPa with nitrogen, not pressure release explanation device resistance to air loss is good after half an hour, add ethyl sulfate 154 grams (1.0 moles) after the release, triethylamine 101 grams (1.0 moles), ethanol 690 grams (15 moles), close the cover, start stirring, open heating unit and heat up, be warmed up to 140 ℃ and keep, 4 hours pressure 1.0MPa reaction times, cool to 1 liter of there-necked flask of room temperature discharging, add sodium hydroxide 80 grams (2.0 moles), start stirring heating and reflux, control reaction temperature is 45 ℃, reaction times is 4 hours, filter, filtrate steams part ethanol earlier, adds 500 gram water, steam ethanol (wherein having portion water to take away) when adding entry, promptly get 604 gram tetraethyl ammonium hydroxide solution, analyze to such an extent that tetraethyl ammonium hydroxide content is 23.3%, the entire reaction yield is 95.7%.
Embodiment 2
Have whipping appts at one, in 1.5 liters the autoclave of heat riser, boost to 3.5MPa with nitrogen, not pressure release explanation device resistance to air loss is good after half an hour, add diethyl carbonate 118 grams (1.0 moles) after the release, triethylamine 101 grams (1.0 moles), ethanol 690 grams (15 moles), close the cover, start stirring, open heating unit and heat up, be warmed up to 100 ℃ and keep, 4 hours pressure 1.2MPa reaction times, cool to 1 liter of there-necked flask of room temperature discharging, add sodium hydroxide 80 grams (2.0 moles), start stirring heating and reflux, control reaction temperature is 45 ℃, reaction times is 4 hours, filter, filtrate steams part ethanol earlier, adds 500 gram water, steam ethanol (wherein having portion water to take away) when adding entry, promptly get 581 gram tetraethyl ammonium hydroxide solution, analyze to such an extent that tetraethyl ammonium hydroxide content is 24.1%, the entire reaction yield is 95.3%.
Embodiment 3
Have whipping appts at one, in 1.5 liters the autoclave of heat riser, boost to 3.5MPa with nitrogen, not pressure release explanation device resistance to air loss is good after half an hour, add methylcarbonate 90 grams (1.0 moles) after the release, Trimethylamine 99 59 grams (1.0 moles), methyl alcohol 510 grams (15 moles), close the cover, start stirring, open heating unit and heat up, be warmed up to 140 ℃ and keep, 4 hours pressure 1.5MPa reaction times, cool to 1 liter of there-necked flask of room temperature discharging, the soup compound that adding calcium hydroxide and water are mixed with is calcium hydroxide solid 148 grams (2.0 moles) wherein, water 350 grams, heating edge is steamed the methyl alcohol limit and is started stirring reaction, reaction times is 8 hours, steams methyl alcohol, filters and promptly gets 355 gram tetramethyl ammonium hydroxide solutions, analyze to such an extent that hydroxide ammonium methyl content is 24.4%, the entire reaction yield is 95.2%.
Claims (20)
1, a kind of method for preparing tetraalkylammonium hydroxide is characterized in that tetraalkylammonium hydroxide is reacted in polar solvent by tetraalkylammonium salt and alkali to make.
2, the method for preparing tetraalkylammonium hydroxide according to claim 1, it is characterized in that tetraalkylammonium salt comprises tetraalkyl volatile salt, tetraalkyl bicarbonate of ammonia, tetraalkyl monoammonium sulfate, tetraalkyl ammonium sulfate, alkylsurfuric acid tetra-allkylammonium, alkyl carbonic acid tetra-allkylammonium, the carbonatoms of alkyl is C1-C4.
3, the method for preparing tetraalkylammonium hydroxide according to claim 1 and 2, it is characterized in that described tetraalkylammonium salt is the tetramethyl-volatile salt, the methyl carbonic acid tetramethyl-ammonium, the tetraethyl-volatile salt, the ethyl carbonate tetraethyl ammonium, tetramethyl-ammonium sulfate, methylsulfuric acid tetramethyl-ammonium, tetraethyl-ammonium sulfate, the ethylsulfuric acid tetraethyl ammonium.
4, according to claim 1 or the 2 or 3 described methods that prepare tetraalkylammonium hydroxide, it is characterized in that described alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium, react in polar solvent by trialkylamine and dialkyl carbonate or sulfuric acid dialkyl and make.
5. the method for preparing tetraalkylammonium hydroxide according to claim 1, it is characterized in that described alkali is alkali metal hydroxide or its oxide compound, alkaline earth metal hydroxides or its oxide compound, comprises sodium hydroxide or sodium oxide, potassium hydroxide or potassium oxide, calcium hydroxide or calcium oxide, hydrated barta or barium oxide.
6, according to claim 1 or 5 methods of stating that prepare tetraalkylammonium hydroxide, it is characterized in that described alkali is calcium hydroxide and sodium hydroxide.
7, according to claim 1 or the 4 described methods that prepare tetraalkylammonium hydroxide, the reaction pressure that it is characterized in that described preparation alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium is 0.1-3 (MPa),
8, according to claim 1 or the 4 or 7 described methods that prepare tetraalkylammonium hydroxide, the reaction pressure that it is characterized in that described preparation alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium is 0.4-2 (MPa).
9, according to claim 1 or the 4 described methods that prepare tetraalkylammonium hydroxide, the temperature of reaction that it is characterized in that described preparation alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium be 50-200 (℃).
10, according to claim 1 or the 4 or 9 described methods that prepare tetraalkylammonium hydroxide, the temperature of reaction that it is characterized in that described preparation alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium be 60-150 (℃).
11,, it is characterized in that the reaction times of described preparation alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium is 1.5-6 hour according to claim 1 or the 4 described methods that prepare tetraalkylammonium hydroxide.
12, according to claim 1 or the 4 described methods that prepare tetraalkylammonium hydroxide, it is characterized in that the described method for preparing alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium, trialkylamine is 2 with the ratio of dialkyl carbonate or sulfuric acid dialkyl: 1-1: 2 (moles).
13, according to claim 1 or the 4 or 14 described methods that prepare tetraalkylammonium hydroxide, it is characterized in that the described method for preparing alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium, selected polar solvent is methyl alcohol, ethanol, Virahol.
14, according to claim 1 or the 4 described methods that prepare tetraalkylammonium hydroxide, it is characterized in that the described method for preparing alkyl carbonic acid tetra-allkylammonium or alkylsurfuric acid tetra-allkylammonium, the consumption of polar solvent is the 1-10 (doubly) of the weight of trialkylamine.
15, the method for preparing tetraalkylammonium hydroxide according to claim 1 is characterized in that the employed polar solvent of described alkylammonium salt and alkaline reaction is methyl alcohol or ethanol or Virahol or water.
16, the method for preparing tetraalkylammonium hydroxide according to claim 1, the consumption that it is characterized in that described alkylammonium salt and the employed polar solvent of alkaline reaction are the 1-10 (doubly) of the weight of tetraalkylammonium salt.
17, the method for preparing tetraalkylammonium hydroxide according to claim 1 is characterized in that the tetraalkylammonium salt and the ratio of alkali are 1: 0.5-1: 4 (moles).
18, the method for preparing tetraalkylammonium hydroxide according to claim 1, the temperature that it is characterized in that described alkylammonium salt and alkaline reaction be 0-80 (℃).
19, the method for preparing tetraalkylammonium hydroxide according to claim 1, the temperature that it is characterized in that described alkylammonium salt and alkaline reaction be 30-50 (℃).
20, the method for preparing tetraalkylammonium hydroxide according to claim 1, the time that it is characterized in that described alkylammonium salt and alkaline reaction be 1-10 (hour).
Priority Applications (31)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03148565 CN1228310C (en) | 2003-07-04 | 2003-07-04 | Method for preparing tetraalkylammonium hydroxide |
| KR1020040051541A KR100612922B1 (en) | 2003-07-04 | 2004-07-02 | A process for producing 4-aminodiphenylamine |
| ES04738332T ES2373720T3 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR THE PRODUCTION OF 4-AMINODYPHENYLAMINE. |
| JP2006500463A JP4500302B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| CA2531074A CA2531074C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| PL04738332T PL1645555T3 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| BRPI0412101-5A BRPI0412101A (en) | 2003-07-04 | 2004-07-02 | process for the preparation of 4-aminodiphenylamine |
| CA2515238A CA2515238C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| AT04738332T ATE526305T1 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE |
| DE602004010234T DE602004010234T2 (en) | 2003-07-04 | 2004-07-02 | PROCESS FOR THE PREPARATION OF 4-AMINODIPHENYLAMINE |
| ES04738331T ES2298762T3 (en) | 2003-07-04 | 2004-07-02 | PROCESS TO PREPARE 4-AMINODYPHENYLAMINE. |
| MXPA05013788A MXPA05013788A (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine. |
| EA200501647A EA009395B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| EP04738331A EP1591438B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| EP04738332A EP1645555B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| PCT/CN2004/000733 WO2005003078A1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| PCT/CN2004/000734 WO2005003079A1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| US10/883,042 US7084302B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| US10/882,677 US7176333B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| PT04738332T PT1645555E (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| JP2006517937A JP4546958B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| EA200600052A EA009396B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| KR1020040051932A KR100612923B1 (en) | 2003-07-04 | 2004-07-05 | A process for preparing 4-aminodiphenylamine |
| US11/477,954 US7235694B2 (en) | 2003-07-04 | 2006-06-30 | Process for preparing 4-aminodiphenylamine |
| US11/757,277 US20080039657A1 (en) | 2003-07-04 | 2007-06-01 | Process for preparing 4-aminodiphenylamine |
| US11/759,901 US20070227675A1 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US11/759,897 US8293673B2 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US12/195,371 US7989662B2 (en) | 2003-07-04 | 2008-08-20 | Process for preparing 4-aminodiphenylamine |
| US12/900,459 US8486223B2 (en) | 2003-07-04 | 2010-10-07 | Falling film evaporator |
| US13/104,900 US8686188B2 (en) | 2003-07-04 | 2011-05-10 | Process for preparing 4-aminodiphenylamine |
| US13/620,588 US9029603B2 (en) | 2003-07-04 | 2012-09-14 | Process for preparing alkylated p-phenylenediamines |
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| CN 03148565 CN1228310C (en) | 2003-07-04 | 2003-07-04 | Method for preparing tetraalkylammonium hydroxide |
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| CN1228310C CN1228310C (en) | 2005-11-23 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100336796C (en) * | 2004-07-15 | 2007-09-12 | 王农跃 | Process for preparing 4-amino diphenylamine |
| CN100453525C (en) * | 2004-07-15 | 2009-01-21 | 江苏圣奥化学科技有限公司 | Process for preparing 4-amino diphenylamine |
| CN101870659A (en) * | 2010-07-20 | 2010-10-27 | 江苏扬农化工集团有限公司 | Preparation method for tetra-alkyl ammonium hydroxide and application |
| CN101992055A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method and device of continuously synthesizing tetramethyl ammonium carbonate by multi-reactors in series |
| WO2011069309A1 (en) * | 2009-12-08 | 2011-06-16 | 江苏扬农化工集团有限公司 | Di-quaternary ammonium base compound and its preparation method and use |
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| CN100336796C (en) * | 2004-07-15 | 2007-09-12 | 王农跃 | Process for preparing 4-amino diphenylamine |
| CN100453525C (en) * | 2004-07-15 | 2009-01-21 | 江苏圣奥化学科技有限公司 | Process for preparing 4-amino diphenylamine |
| CN101328128B (en) * | 2008-07-10 | 2011-07-20 | 浙江大学 | Preparation of sulfuric acid ester ion liquid |
| WO2011069309A1 (en) * | 2009-12-08 | 2011-06-16 | 江苏扬农化工集团有限公司 | Di-quaternary ammonium base compound and its preparation method and use |
| CN101870659A (en) * | 2010-07-20 | 2010-10-27 | 江苏扬农化工集团有限公司 | Preparation method for tetra-alkyl ammonium hydroxide and application |
| CN101992055A (en) * | 2010-11-03 | 2011-03-30 | 天津大学 | Method and device of continuously synthesizing tetramethyl ammonium carbonate by multi-reactors in series |
| CN101992055B (en) * | 2010-11-03 | 2013-09-11 | 天津大学 | Method and device of continuously synthesizing tetramethyl ammonium carbonate by multi-reactors in series |
| CN105209426A (en) * | 2013-03-27 | 2015-12-30 | 庄信万丰股份有限公司 | Method for preparing 1-adamantyltrimethylammonium hydroxide |
| CN107531629A (en) * | 2015-04-20 | 2018-01-02 | 庄信万丰股份有限公司 | The method of preparation structure directed agents |
| JP2018513095A (en) * | 2015-04-20 | 2018-05-24 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ | Method for preparing structure directing agents |
| US20180244618A1 (en) * | 2015-04-20 | 2018-08-30 | Johnson Matthey Public Limited Company | Method for preparing structured directing agent |
| CN113235117A (en) * | 2021-05-12 | 2021-08-10 | 肯特催化材料股份有限公司 | Production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by same |
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