CN108178731A - One kettle way prepares the green synthesis method of AMP-95 - Google Patents
One kettle way prepares the green synthesis method of AMP-95 Download PDFInfo
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- CN108178731A CN108178731A CN201810052336.0A CN201810052336A CN108178731A CN 108178731 A CN108178731 A CN 108178731A CN 201810052336 A CN201810052336 A CN 201810052336A CN 108178731 A CN108178731 A CN 108178731A
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- propyl alcohol
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- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000000243 solution Substances 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000047 product Substances 0.000 claims abstract description 26
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical class CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 2
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical class CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 16
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- -1 alkyl butyrate Chemical compound 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007530 organic bases Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the green synthesis methods that a kind of one kettle way prepares AMP 95, include the following steps：S1, in alcoholic solution, acetone, hydrogen peroxide and ammonia generate 2 nitropropanes under the catalytic action of catalyst；The not purified direct and formaldehyde under alkaline condition of reaction solution or polyformaldehyde reaction generate 2 nitro, 2 methyl, 1 propyl alcohol in S2, the S1 steps；The not purified direct hydrogenation of reaction product obtains 2 amino of product, 2 methyl, 1 propyl alcohol (AMP 95) in S3, the S2 steps, reaches more than 99.5% through rectifying purity.Raw material of the present invention is cheap and easy to get, and reaction step is simple, and environmental pollution is small, at low cost, and yield is high, and product is easily purified, and is suitble to industrialized production.
Description
Technical field
The present invention relates to the technical field that is synthetically prepared of fine chemical product, specially a kind of one kettle way prepares AMP-95's
Green synthesis method.
Background technology
2-amino-2-methyl-1-propanol is referred to as AMP-95, water-miscible for white crystals or colourless viscous liquid,
Dissolve in ethyl alcohol.AMP-95 is a kind of multifunction additive being widely known by the people, be widely used in coating and printing ink, metal working fluid,
In the industries such as personal nursing and medicine intermediate.AMP-95 causes it to have higher pH as a kind of primary amine, high pKa value
Value, simultaneously as it is organic base, it is relatively milder, there is preferable compatibility with a variety of lotions, to the other performance of product
It influences smaller.Compared with other organic bases such as ammonium hydroxide, trimethylamine and triethylamine, the stability of AMP-95 is good, is not easy xanthochromia,
Small toxicity simultaneously, and it is not volatile, the smell of system can be reduced, reduces corrosion and flash rusting, belongs to the conditioning agent of environment-friendly type.At present
All using AMP-95TM, as pH adjusting agent and formulation optimization auxiliary agent, AMP-95TM helps them to ten big coatings enterprises before the whole world
The performance of product is improved, while reduces cost.In the Coating Market of China, AMP-95TM is also coating material production producer
First choice, the market coverage of AMP-95TM are more than 80%.Domestic well-known coating material production producer is since the 1990s
It is used till today using the product, stability and the superiority of AMP-95TM get the consistent favorable comment of client.
The synthetic method of existing 2-amino-2-methyl-1-propanol has very much, and United States Patent (USP) US20110224460 is with 2-
Nitropropane and formalin react generation 2- nitros -2- methyl-1s-propyl alcohol, then carry out under metalNicatalyst plus hydrogen
Reaction, isolated 2-amino-2-methyl-1-propanol.This method cost of material is high, dangerous big, is not easy storage transport, production
The shortcomings such as equipment investment is big, and product purity is low.Chinese patent CN1810767 is existed using isopropanol with sodium nitrite, paraformaldehyde
It reacts at 0-25 DEG C, 2- nitros -2- methyl-1s-propyl alcohol is obtained, then catalytic hydrogenation obtains using extraction, washing and distillation
Product.This method synthesis condition is complicated, and the reaction time is long, and post-processing difficulty is big.Chinese patent CN1911899 discloses one and leads to
The Ritter processes for crossing isobutene prepare the preparation method of 2-amino-2-methyl-1-propanol.This method reaction raw materials type is more,
Preparation process is complicated, and yield is relatively low, yield 50-70%.Chinese patent CN201310152527 describes different with alpha-amido
The alcoholic solution of alkyl butyrate occurs hydrogenolysis reducing with hydrogen in the presence of metallic catalyst and reacts, and a step obtains 2- amino -2-
The method of methyl-1-propyl alcohol, this method cost of material is higher, and complex steps cause serious pollution to the environment, low yield, and product is not easy
Purification is not suitable for industrialized production.
Invention content
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides the green synthesis method that a kind of one kettle way prepares AMP-95, solutions
The method cost of material for having determined traditional is higher, and complex steps cause serious pollution to the environment, low yield, and product is not easily purified, and is not suitable for
The problem of industrialized production.
(2) technical solution
To achieve the above object, the present invention provides following technical solution：
A kind of one kettle way prepares the green synthesis method of AMP-95, includes the following steps：
S1, in alcoholic solution, acetone, hydrogen peroxide and ammonia generate 2- nitropropanes under the catalytic action of catalyst；
Wherein, the required condition of 2- nitropropanes is prepared in the S1 steps is：In certain temperature range and time
Under range, the catalyst is stephanoporate framework metal hybrid catalyst, its skeleton of stephanoporate framework metal hybrid catalyst is mainly
Silicon, oxygen and hybridized metal, wherein hybridized metal are titanium, zirconium, vanadium and molybdenum one kind or combination of two, silicon and hybridized metal atom
Than being 20~100：1, and hydridization bimetallic molar ratio is 1:20~1:100；The catalyst be configured as ZSM-5, MCM-41,
SBA-15 and its one of micropore-mesopore composite construction and mesopore-macropore composite construction, the wherein dosage of catalyst are total for material
The 0.001~10% of amount；
The not purified direct and formaldehyde under alkaline condition of reaction solution or polyformaldehyde reaction generation in S2, the S1 steps
2- nitros -2- methyl-1s-propyl alcohol；
Wherein, 2- nitros -2- methyl-1s-required condition of propyl alcohol is prepared in the S2 steps is：In certain temperature
Under scope and time range, alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, bicarbonate
One or more of sodium, saleratus, dimethylamine, triethylamine, diethylamine, pyridine and ammonium hydroxide, the dosage of alkali is 2- nitros third
The 0.001-2 of alkane quality；
The not purified direct hydrogenation of reaction product obtains product 2-amino-2-methyl-1-propanol in S3, the S2 steps
(AMP-95), reach more than 99.5% through rectifying purity；
Wherein, 2- nitros -2- methyl-1s-propyl alcohol Hydrogenation is for the required conditions of AMP-95 in the S3 steps：
Under certain temperature range, time range and under hydrogenation pressure range, hydrogenation catalyst is palladium carbon or Raney's nickel, hydrogenation catalyst
Dosage is the 0.001-30% of 2- nitros -2- methyl-1s-propyl alcohol.
Preferably, in the S1 steps, hydrogen peroxide and acetone molar ratio are 0.1:1~5:1, acetone and ammonia molar ratio are 1:
0.01~1:3, and range of reaction temperature is 20-120 DEG C, and reaction time range is 0.5-5h.
Preferably, in the S1 steps, alcoholic solution is water or methanol, ethyl alcohol, n-butanol, isobutanol, propyl alcohol, isopropanol,
The tert-butyl alcohol, ethylene glycol and propylene glycol one or more of.
Preferably, it is 10-120 DEG C that required temperature range is reacted in the S2 steps, and reacts the required time
Ranging from 0.5-12h, and the molar ratio of formaldehyde or paraformaldehyde and 2- nitropropanes is 1:1-5:1.
Preferably, hydrogenation pressure ranging from 0.1-10MPa in the S3 steps, range of reaction temperature are 10-120 DEG C, and
Reaction time range is 0.5-10h.
(3) advantageous effect
The present invention provides the green synthesis methods that a kind of one kettle way prepares AMP-95, have following advantageous effect：
(1), raw material of the present invention is cheap and easy to get, and reaction step is simple, and environmental pollution is small, at low cost, and yield is high, and product is easy
Purification is suitble to industrialized production.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
The present invention provides a kind of technical solution：
A kind of one kettle way prepares the green synthesis method of AMP-95, includes the following steps：
S1, in alcoholic solution, acetone, hydrogen peroxide and ammonia generate 2- nitropropanes under the catalytic action of catalyst；
Wherein, the required condition of 2- nitropropanes is prepared in S1 steps is：Range of reaction temperature is 20-120 DEG C, and anti-
Ranging from 0.5-5h between seasonable, catalyst are stephanoporate framework metal hybrid catalyst, its bone of stephanoporate framework metal hybrid catalyst
Frame is mainly silicon, oxygen and hybridized metal, and wherein hybridized metal is one kind or combination of two of titanium, zirconium, vanadium and molybdenum, silicon and hydridization gold
The ratio for belonging to atom is 20~100：1, and hydridization bimetallic molar ratio is 1:20~1:100；The catalyst be configured as ZSM-5,
MCM-41, SBA-15 and its one of micropore-mesopore composite construction and mesopore-macropore composite construction, the dosage of wherein catalyst are
The 0.001~10% of material total amount, hydrogen peroxide and acetone molar ratio are 0.1:1~5:1, acetone and ammonia molar ratio are 1:0.01~
1:3, among alcoholic solution is water or methanol, ethyl alcohol, n-butanol, isobutanol, propyl alcohol, isopropanol, the tert-butyl alcohol, ethylene glycol and propylene glycol
One or more；
The not purified direct and formaldehyde under alkaline condition of reaction solution or polyformaldehyde reaction generation 2- nitre in S2, S1 step
Base -2- methyl-1s-propyl alcohol；
Wherein, 2- nitros -2- methyl-1s-required condition of propyl alcohol is prepared in S2 steps is：React required temperature
Ranging from 10-120 DEG C, and required time range is reacted for 0.5-12h, alkali is sodium hydroxide, potassium hydroxide, hydroxide
In calcium, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, dimethylamine, triethylamine, diethylamine, pyridine and ammonium hydroxide
One or more, the dosage of alkali is the 0.001-2 of 2- nitropropane quality, and formaldehyde or paraformaldehyde and 2- nitropropanes
Molar ratio is 1:1-5:1；
The not purified direct hydrogenation of reaction product obtains product 2-amino-2-methyl-1-propanol (AMP- in S3, S2 step
95), reach more than 99.5% through rectifying purity；
Wherein, 2- nitros -2- methyl-1s-propyl alcohol Hydrogenation is for the required conditions of AMP-95 in S3 steps：Add hydrogen pressure
Power ranging from 0.1-10MPa, range of reaction temperature is 10-120 DEG C, and reaction time range is 0.5-10h, and hydrogenation catalyst is
Palladium carbon or Raney's nickel, hydrogenation catalyst dosage are the 0.001-30% of 2- nitros -2- methyl-1s-propyl alcohol.
And the catalyst used in the present invention is miscellaneous for the stephanoporate framework metal referred in Patent No. ZL201510866441.4
Change catalyst.
Embodiment one
By catalyst 10g (Ti-V-ZSM-5), acetone 58.08g, ammonium hydroxide 20g are added in 400ml methanol, are warming up to 70
DEG C, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained to react 1h at 65-75 DEG C, obtain 2- nitros third after being added dropwise
Alkane reaction solution；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, formaldehyde (40% aqueous solution) is added dropwise, drip with
The reaction was continued afterwards 3h, obtains 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in autoclave, adds in Raney's nickel 14g,
75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-amino -1- propyl alcohol crude products, rectifying obtains product
(AMP-95)44.6g。
Embodiment two
By catalyst 10g (Zr-V-SBA-15), acetone 58.08g, ammonium hydroxide 20g are added in 400ml methanol, are warming up to 70
DEG C, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained to react 2h at 65-75 DEG C, obtain 2- nitros third after being added dropwise
Alkane reaction solution；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, formaldehyde (40% aqueous solution) is added dropwise, drip with
The reaction was continued afterwards 3h, obtains 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in autoclave, adds in Raney's nickel 14g,
75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-amino -1- propyl alcohol crude products, rectifying obtains product
(AMP-95)53.4g。
Embodiment three
By catalyst 10g (Zr-Mo-MCM-41), acetone 58.08g, ammonium hydroxide 20g are added in 400ml methanol, are warming up to
70 DEG C, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained to react 1h at 65-75 DEG C, obtain 2- nitros after being added dropwise
Propane reaction solution；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, formaldehyde (40% aqueous solution) is added dropwise, drips
The reaction was continued 3h later, obtains 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in autoclave, adds in Raney's nickel
14g, 75 DEG C, reaction pressure 3MPa of reaction temperature react 4h, obtain 2- methyl-2-amino -1- propyl alcohol crude products, rectifying is produced
Product (AMP-95) 50.9g.
Example IV
By catalyst 10g (titanium zirconium doped meso-porous-macropore composite catalyst), acetone 58.08g, ammonium hydroxide 20g is added to
In 400ml methanol, 70 DEG C are warming up to, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained after being added dropwise in 65-75
DEG C, 1h is reacted, obtains 2- nitropropane reaction solutions；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, first is added dropwise
Aldehyde (40% aqueous solution), the reaction was continued after dripping 3h obtain 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in
In autoclave, Raney's nickel 14g is added in, 75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-aminos -1-
Propyl alcohol crude product, rectifying obtain product (AMP-95) 57.5g.
Embodiment five
By catalyst 10g (titanium zirconium doped meso-porous-macropore composite catalyst), acetone 58.08g, ammonium hydroxide 20g is added to
In 400ml methanol, 70 DEG C are warming up to, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained after being added dropwise in 65-75
DEG C, 1h is reacted, obtains 2- nitropropane reaction solutions；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, adds in batches
Enter paraformaldehyde 20g, the reaction was continued 3h obtains 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in autoclave, is added
Enter Raney's nickel 14g, 75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-amino -1- propyl alcohol crude products, essence
It evaporates to obtain product (AMP-95) 55.9g.
Embodiment six
By catalyst 10g (titanium zirconium doped meso-porous-macropore composite catalyst), acetone 58.08g, ammonium hydroxide 10g is added to
In 400ml methanol, 70 DEG C are warming up to, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained after being added dropwise in 65-75
DEG C, 1h is reacted, obtains 2- nitropropane reaction solutions；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, adds in batches
Enter paraformaldehyde 20g, the reaction was continued 3h obtains 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in autoclave, is added
Enter Raney's nickel 14g, 75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-amino -1- propyl alcohol crude products, essence
It evaporates to obtain product (AMP-95) 40.6g.
Embodiment seven
By catalyst 10g (titanium zirconium doped meso-porous-macropore composite catalyst), acetone 58.08g, ammonium hydroxide 20g is added to
It in 400ml methanol, heats up 50 DEG C, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained after being added dropwise at 50-60 DEG C,
2h is reacted, obtains 2- nitropropane reaction solutions；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, is added portionwise more
Polyformaldehyde 20g, the reaction was continued after dripping 4h, obtain 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in into high pressure
In kettle, Raney's nickel 14g is added in, 75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-amino -1- propyl alcohol
Crude product, rectifying obtain product (AMP-95) 50.1g.
Embodiment eight
By catalyst 20g (titanium zirconium doped meso-porous-macropore composite catalyst), acetone 58.08g, ammonium hydroxide 20g is added to
It in 400ml methanol, heats up 70 DEG C, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained after being added dropwise at 65-75 DEG C,
1h is reacted, obtains 2- nitropropane reaction solutions；Filtering adds in 5g sodium hydroxides to reaction solution, is warming up to 35 DEG C, is added portionwise more
Polyformaldehyde 20g, the reaction was continued after dripping 4h, obtain 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in into high pressure
In kettle, Raney's nickel 14g is added in, 75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-amino -1- propyl alcohol
Crude product, rectifying obtain product (AMP-95) 59.1g.
Embodiment nine
By catalyst 20g (titanium zirconium doped meso-porous-macropore composite catalyst), acetone 58.08g, ammonia 20g is added to 400ml
It in methanol, heats up 70 DEG C, hydrogen peroxide (35%) 226.7g is slowly added dropwise, temperature is maintained after being added dropwise at 65-75 DEG C, reaction
1h obtains 2- nitropropane reaction solutions；Filtering adds in 10g sodium hydroxides to reaction solution, is warming up to 55 DEG C, poly is added portionwise
Formaldehyde 20g, the reaction was continued after dripping 2h, obtain 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in into autoclave
In, Raney's nickel 14g is added in, 75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, it is thick to obtain 2- methyl-2-amino -1- propyl alcohol
Product, rectifying obtain product (AMP-95) 53.6g.
Embodiment ten
By catalyst 20g (titanium zirconium doped meso-porous-macropore composite catalyst), acetone 58.08g, ammonium hydroxide 20g is added to
It in 400ml methanol, heats up 70 DEG C, hydrogen peroxide (35%) 326.7g is slowly added dropwise, temperature is maintained after being added dropwise at 65-75 DEG C,
1h is reacted, obtains 2- nitropropane reaction solutions；Filtering adds in 10g sodium hydroxides to reaction solution, is warming up to 55 DEG C, is added portionwise
Paraformaldehyde 20g, the reaction was continued after dripping 2h, obtain 2- methyl -2- nitros-propyl alcohol reaction solution；Reaction solution is added in high
It presses in kettle, adds in Raney's nickel 14g, 75 DEG C, reaction pressure 3MPa of reaction temperature reacts 4h, obtains 2- methyl-2-aminos -1- third
Alcohol crude product, rectifying obtain product (AMP-95) 54.9g.
It can to sum up obtain, raw material of the present invention is cheap and easy to get, and reaction step is simple, and environmental pollution is small, at low cost, and yield is high,
Product is easily purified, and is suitble to industrialized production.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of one kettle way prepares the green synthesis method of AMP-95, which is characterized in that includes the following steps：
S1, in alcoholic solution, acetone, hydrogen peroxide and ammonia generate 2- nitropropanes under the catalytic action of catalyst；
Wherein, the required condition of 2- nitropropanes is prepared in the S1 steps is：In certain temperature range and time range
Under, the catalyst is stephanoporate framework metal hybrid catalyst, its skeleton of stephanoporate framework metal hybrid catalyst is mainly silicon, oxygen
And hybridized metal, wherein hybridized metal be titanium, zirconium, vanadium and molybdenum one kind or combination of two, the ratio of silicon and hybridized metal atom is
20~100：1, and hydridization bimetallic molar ratio is 1:20~1:100；The catalyst is configured as ZSM-5, MCM-41, SBA-
15 and its one of micropore-mesopore composite construction and mesopore-macropore composite construction, the wherein dosage of catalyst is material total amount
0.001~10%；
The not purified direct and formaldehyde under alkaline condition of reaction solution or polyformaldehyde reaction generation 2- nitre in S2, the S1 steps
Base -2- methyl-1s-propyl alcohol；
Wherein, 2- nitros -2- methyl-1s-required condition of propyl alcohol is prepared in the S2 steps is：In certain temperature range
Under time range, alkali for sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate,
One or more of saleratus, dimethylamine, triethylamine, diethylamine, pyridine and ammonium hydroxide, the dosage of alkali is 2- nitropropane matter
The 0.001-2 of amount；
The not purified direct hydrogenation of reaction product obtains product 2-amino-2-methyl-1-propanol (AMP- in S3, the S2 steps
95), reach more than 99.5% through rectifying purity；
Wherein, 2- nitros -2- methyl-1s-propyl alcohol Hydrogenation is for the required conditions of AMP-95 in the S3 steps：Certain
Temperature range, under time range and under hydrogenation pressure range, hydrogenation catalyst is palladium carbon or Raney's nickel, hydrogenation catalyst dosage
0.001-30% for 2- nitros -2- methyl-1s-propyl alcohol.
2. one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S1 steps
In, hydrogen peroxide and acetone molar ratio are 0.1:1~5:1, acetone and ammonia molar ratio are 1:0.01~1:3, and range of reaction temperature
It it is 20-120 DEG C, and reaction time range is 0.5-5h.
3. a kind of one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S1
In step, alcoholic solution is water or methanol, ethyl alcohol, n-butanol, isobutanol, propyl alcohol, isopropanol, the tert-butyl alcohol, ethylene glycol and propylene glycol
One or more of.
4. one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S2 steps
The middle required temperature range of reaction is 10-120 DEG C, and reacts required time range for 0.5-12h, and formaldehyde or poly
The molar ratio of formaldehyde and 2- nitropropanes is 1:1-5:1.
5. one kettle way according to claim 1 prepares the green synthesis method of AMP-95, it is characterised in that：The S3 steps
Middle hydrogenation pressure ranging from 0.1-10MPa, range of reaction temperature are 10-120 DEG C, and reaction time range is 0.5-10h.
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| CN110172029A (en) * | 2019-06-28 | 2019-08-27 | 南京红宝丽醇胺化学有限公司 | A kind of method of continuous synthesis 2-amino-2-methyl-1-propanol |
| CN114105788A (en) * | 2021-11-29 | 2022-03-01 | 河北旭阳能源有限公司 | Method for preparing 2-amino-2-methyl-1-propanol with high selectivity |
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