CN107674017B - Synthesis method of light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol - Google Patents
Synthesis method of light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol Download PDFInfo
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- CN107674017B CN107674017B CN201711015303.0A CN201711015303A CN107674017B CN 107674017 B CN107674017 B CN 107674017B CN 201711015303 A CN201711015303 A CN 201711015303A CN 107674017 B CN107674017 B CN 107674017B
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- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 33
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 23
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 18
- 238000007031 hydroxymethylation reaction Methods 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011949 solid catalyst Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005292 vacuum distillation Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- GGZVRPWBJOPSIC-UHFFFAOYSA-N 1-(hydroxymethyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1CO GGZVRPWBJOPSIC-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000007865 diluting Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical compound CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- NIZBFFOETCKGBI-UHFFFAOYSA-N 1-hydroxy-2,2,3,3,4-pentamethylpiperidine Chemical compound CC1CCN(O)C(C)(C)C1(C)C NIZBFFOETCKGBI-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000011987 methylation Effects 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000006824 Eschweiler-Clarke methylation reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
The invention provides a method for synthesizing a light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol, and particularly relates to the technical field of light stabilizer preparation, wherein the method comprises two steps of reaction, wherein in the first step, 2,2,6, 6-tetramethyl-4-piperidinol and paraformaldehyde are mixed and added into a solvent according to a certain proportion, the mixture is stirred for a certain time at a certain reaction temperature under normal pressure, so that the 2,2,6, 6-tetramethyl-4-piperidinol is completely reacted, and then the mixture is cooled to room temperature, and excessive paraformaldehyde is removed by filtration to obtain a hydroxymethylation product; and secondly, filling the reduced solid catalyst into a fixed bed reactor, adding a solvent into the reaction solution, continuously introducing the reaction solution into the fixed bed reactor at a certain feeding speed, introducing hydrogen, heating, continuously flowing out from the lower end of the fixed bed reactor, and cooling, separating gas from liquid, filtering the liquid, evaporating the filtrate to remove the solvent and purifying the reaction solution to obtain the target product. The method has the advantages of simple preparation, economy, environmental protection, high product quality and high yield, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of light stabilizer preparation, and particularly relates to a synthetic method of a light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol.
Background
Hindered Amine Light Stabilizer (HALS) is an organic polymer material assistant with excellent light and thermal stability, and the polymer additive has good compatibility with most polymers and excellent light stability, so that the HALS is one of hot spots of research and development of light stabilizers at home and abroad, 1,2,2,6, 6-pentamethyl-4-piperidinol is a main intermediate for synthesizing the hindered amine light stabilizer, and the demand for the pentamethyl piperidinol is gradually increased along with the continuous development of the application field of the hindered amine light stabilizer.
At present, the methods for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol which are publicly reported in the world are generally methylation of 2,2,6, 6-tetramethyl-4-piperidinol by various means. US3364220(A), EP0837057(A1), WO2004072035(A1) and the like disclose a process for nitrogen methylation utilizing the Eschweiler-Clarke reaction, tetramethylpiperidinol is reacted with formaldehyde in the presence of formic acid, which acts as a reducing agent and is converted to CO2The method is a current common industrial production method, can achieve higher yield and higher product quality, but uses a large amount of acid and alkali in the reaction and post-treatment processes, so that a large amount of waste water is generated in the production process, and the environment is seriously polluted, then CN105820108(A) discloses a method for preparing pentamethylpiperidinol by tetramethylpiperidinol by a formaldehyde hydrogenation method, although the method avoids the use of formic acid, a noble metal catalyst is used, so that the production cost is increased, the conversion rate cannot reach 100%, and because the boiling points of the tetramethylpiperidinol and the pentamethylpiperidinol are close, the product quality is highIn addition, CN101198604(A) discloses a method for methylation by using methyl iodide, but the price of methyl iodide is higher, which greatly increases the production cost, and an equivalent of alkali is required to quench the reaction in the reaction, so that a certain amount of waste water is generated, and the environmental pollution is caused.
Therefore, a synthesis method of 1,2,2,6, 6-pentamethyl-4-piperidinol, which is a light stabilizer intermediate, is simple to prepare, economic and environment-friendly, high in product quality and yield and suitable for industrial production, is urgently needed.
Disclosure of Invention
The invention aims to solve the problems of high production cost, low product quality, environmental pollution and the like in the existing preparation process of 1,2,2,6, 6-pentamethyl-4-piperidinol, and provides a synthetic method of light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol, which has the advantages of simple preparation, economy, environmental protection, high product quality, high yield and suitability for industrial production.
The invention provides the following technical scheme:
a method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
Mixing 2,2,6, 6-tetramethyl-4-piperidinol and paraformaldehyde according to a certain proportion, adding into a solvent, stirring for a certain time at a certain reaction temperature under normal pressure to ensure that the 2,2,6, 6-tetramethyl-4-piperidinol is completely reacted, cooling to room temperature, and filtering to remove excessive paraformaldehyde to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol;
the structural formula of the 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol is as follows:
the second step is that: catalytic hydrogenolysis reaction
Filling a reduced solid catalyst into a fixed bed reactor, adding a solvent into reaction liquid after the hydroxymethylation reaction to ensure that the concentration of a hydroxymethylation product reaches 20-40%, continuously introducing the reaction liquid into the fixed bed reactor at a certain feeding speed, introducing hydrogen, heating, continuously flowing out from the lower end of the fixed bed reactor, cooling the flowing-out reaction liquid, carrying out gas-liquid separation, filtering the liquid, evaporating the solvent from filtrate, and purifying to obtain the target product 1,2,2,6, 6-pentamethyl-4-piperidinol.
The structural formula of the 1,2,2,6, 6-pentamethyl-4-piperidinol is as follows:
preferably, the molar ratio of the 2,2,6, 6-tetramethyl-4-piperidinol to the formaldehyde in the first-step reaction is 1: 1.2-1: 3.
Preferably, the solvent in the first-step reaction and the second-step reaction is at least one of methanol, ethanol, isopropanol and toluene.
Preferably, the reaction temperature in the first step of reaction is 50-110 ℃, and the reaction time is 4-16 hours.
Preferably, the reaction temperature in the first step of reaction is 70-110 ℃, and the reaction time is 6-12 hours.
Preferably, the reduced solid catalyst in the second-step reaction is gamma-Al2O3The preparation method of the reduction type solid catalyst comprises the steps of dissolving nitrate of metal, impregnating, drying and roasting to obtain an oxidation type solid catalyst, and reducing the oxidation type solid catalyst in a hydrogen atmosphere.
The expression method of the catalyst consists of supported metal and a carrier, and the lower subscript of the metal is the mass percentage content of the metal in the prepared catalyst. With Cu30Cr5/γ-Al2O3For example, the preparation method comprises the following steps: 22.73g of Cu (NO)3)2·3H2O、7.69g Cr(NO3)3·9H2Dissolving O in 200mL of deionized water to prepare a nitrate solution. 13.08g of Na2CO3Dissolved in 200mL of deionized water to prepareA precipitating agent. Then, under the condition of rapid mechanical stirring in a 70 ℃ water bath, simultaneously dropwise adding a nitrate solution and a precipitator into a beaker filled with 200mL of deionized water, maintaining the pH value between 7 and 8, aging for 1h after complete precipitation, filtering, washing a filter cake with the deionized water until no nitrate ions exist, and drying the filter cake for 6h at 110 ℃. And crushing the filter cake, mixing the crushed filter cake with 15.58g of pseudo-boehmite and 30mL of 2% dilute nitric acid, fully stirring and grinding, extruding the mixture into strips by using a self-made strip extruder, fully drying the strips in a drying oven at 110 ℃, and slowly heating the strips to 500 ℃ in a muffle furnace for roasting for 4 hours. Before use, cutting the catalyst into 3-5 mm length, and reducing with hydrogen at 150 ℃ for 4h to obtain the required catalyst.
Preferably, the loading amount of the active component in the second step of reaction is 15-30%.
Preferably, the feeding speed in the second step of reaction is 0.2-1.0 mL/min, the hydrogen pressure is 2.0-6.0 MPa, and the reaction temperature is 80-200 ℃.
Preferably, the feeding speed in the second step of reaction is 0.4-0.6 mL/min, the hydrogen pressure is 2.0-4.0 MPa, and the reaction temperature is 80-120 ℃.
Preferably, the purification method in the second step of reaction is vacuum distillation, and the distilled solvent can be recycled.
The invention has the beneficial effects that:
1. the invention provides a method for preparing 1,2,2,6, 6-pentamethyl-4-piperidinol by a two-step method for making up the defects of the prior art, which comprises the steps of completely reacting 2,2,6, 6-tetramethyl-4-piperidinol to generate 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol, and then carrying out catalytic hydrogenolysis to obtain a high-quality product 1,2,2,6, 6-pentamethyl-4-piperidinol.
2. The invention avoids the problem that the tetramethylpiperidinol can not be completely converted in the traditional method through step-by-step reaction, and the obtained product has high quality and high yield.
3. The invention uses cheap reduction type solid catalyst in the reaction process, has simple preparation, economy and environmental protection, and high selectivity and activity, and is suitable for industrial production.
Detailed Description
Example 1
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
157.25g of 2,2,6, 6-tetramethyl-4-piperidinol, 45.04g of paraformaldehyde and 400mL of ethanol were put into a 1L four-necked flask, stirred and reacted at 80 ℃ for 10 hours, the reaction was monitored by gas phase to be complete, the 2,2,6, 6-tetramethyl-4-piperidinol was cooled to room temperature, and excess paraformaldehyde was removed by filtration to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Ni30/γ-Al2O3Loading into a fixed bed reactor, wherein the inner diameter of the reactor is 14mm, the length of the tube is 650mm, diluting the reaction solution obtained in the previous step by adding 400mL of ethanol, continuously introducing into the fixed bed reactor at a feeding speed of 0.6mL/min, introducing hydrogen, heating to ensure that the pressure of the hydrogen in the fixed bed reactor is 4.0MPa and the temperature is 100 ℃, continuously flowing out of the reaction solution from the lower end of the fixed bed reactor, cooling, carrying out gas-liquid separation and liquid filtration on the flowing-out reaction solution, analyzing the filtrate by using a gas chromatography to obtain the yield of 98.34%, and carrying out vacuum distillation to obtain the pure 1,2,2,6, 6-pentamethyl-4-piperidinol.
Example 2
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
157.25g of 2,2,6, 6-tetramethyl-4-piperidinol, 90.09g of paraformaldehyde and 400mL of methanol were put into a 1L four-necked flask, stirred and reacted at 50 ℃ for 16 hours, the reaction was monitored by gas phase to be complete, the 2,2,6, 6-tetramethyl-4-piperidinol was cooled to room temperature, and excess paraformaldehyde was removed by filtration to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Ni30/γ-Al2O3Loading into a fixed bed reactor with inner diameter of 14mm and tube length of 650mm, continuously introducing the reaction solution obtained in the above step into the fixed bed reactor at a feeding speed of 0.4mL/min,introducing hydrogen, heating to make the pressure of hydrogen in the fixed bed reactor be 2.0MPa and the temperature be 80 deg.C, continuously making the reaction liquor flow out from lower end of the fixed bed reactor, cooling the flowed reaction liquor, gas-liquid separating, filtering liquor, analyzing filtrate by gas chromatography to obtain yield of 97.76%, vacuum distilling to obtain pure 1,2,2,6, 6-pentamethyl-4-piperidinol.
Example 3
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
125.80g of 2,2,6, 6-tetramethyl-4-piperidinol, 28.83g of paraformaldehyde and 200mL of toluene were put into a 1L four-necked flask, stirred and reacted at 110 ℃ for 8 hours, the reaction was monitored by gas phase for completion of the reaction of 2,2,6, 6-tetramethyl-4-piperidinol, cooled to room temperature, and excess paraformaldehyde was removed by filtration to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Cu30Cr5/γ-Al2O3Loading into a fixed bed reactor, wherein the inner diameter of the reactor is 14mm, the length of the tube is 650mm, diluting the reaction solution obtained in the previous step by adding 20mL of toluene, continuously introducing into the fixed bed reactor at a feeding speed of 0.2mL/min, introducing hydrogen, heating to ensure that the pressure of the hydrogen in the fixed bed reactor is 3.0MPa and the temperature is 150 ℃, continuously flowing out of the reaction solution from the lower end of the fixed bed reactor, cooling, carrying out gas-liquid separation and liquid filtration on the flowing-out reaction solution, analyzing the filtrate by using a gas chromatography to obtain the yield of 96.97%, and carrying out vacuum distillation to obtain the pure 1,2,2,6, 6-pentamethyl-4-piperidinol.
Example 4
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
125.80g of 2,2,6, 6-tetramethyl-4-piperidinol, 48.05g of paraformaldehyde, 200mL of ethanol and 200mL of isopropanol are added into a 1L four-necked flask, stirred and reacted at 80 ℃ for 6 hours, the gas phase is monitored that the 2,2,6, 6-tetramethyl-4-piperidinol has completely reacted, the temperature is cooled to room temperature, and the excessive paraformaldehyde is removed by filtration to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Cu40/γ-Al2O3Loading into a fixed bed reactor, wherein the inner diameter of the reactor is 14mm, the length of the tube is 650mm, diluting the reaction solution obtained in the previous step by adding 200mL of ethanol, continuously introducing into the fixed bed reactor at a feeding speed of 1.0mL/min, introducing hydrogen, heating to ensure that the pressure of the hydrogen in the fixed bed reactor is 6.0MPa and the temperature is 120 ℃, continuously flowing out the reaction solution from the lower end of the fixed bed reactor, cooling, carrying out gas-liquid separation and liquid filtration on the flowing-out reaction solution, analyzing the filtrate by using a gas chromatography to obtain the yield of 97.41 percent, and carrying out vacuum distillation to obtain the pure 1,2,2,6, 6-pentamethyl-4-piperidinol.
Example 5
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
157.25g of 2,2,6, 6-tetramethyl-4-piperidinol, 39.04g of paraformaldehyde and 400mL of isopropanol were put into a 1L four-necked flask, stirred and reacted at 70 ℃ for 12 hours, the gas phase was monitored that 2,2,6, 6-tetramethyl-4-piperidinol had reacted completely, cooled to room temperature, and excess paraformaldehyde was removed by filtration to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Ni15/γ-Al2O3Loading into a fixed bed reactor, wherein the inner diameter of the reactor is 14mm, the length of the tube is 650mm, diluting the reaction solution obtained in the previous step with 200mL of isopropanol, continuously introducing into the fixed bed reactor at a feeding speed of 0.5mL/min, introducing hydrogen, heating to ensure that the pressure of the hydrogen in the fixed bed reactor is 4.0MPa and the temperature is 90 ℃, continuously flowing out of the reaction solution from the lower end of the fixed bed reactor, cooling, carrying out gas-liquid separation and liquid filtration on the flowing-out reaction solution, analyzing the filtrate by using a gas chromatography to obtain the yield of 97.24%, and carrying out vacuum distillation to obtain the pure 1,2,2,6, 6-pentamethyl-4-piperidinol.
Example 6
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
157.25g of 2,2,6, 6-tetramethyl-4-piperidinol, 60.06g of paraformaldehyde and 400mL of toluene were put into a 1L four-necked flask, stirred at 100 ℃ for 4 hours, monitored by gas phase that 2,2,6, 6-tetramethyl-4-piperidinol had reacted completely, cooled to room temperature, and filtered to remove excess paraformaldehyde to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Ni10/γ-Al2O3Loading into a fixed bed reactor, wherein the inner diameter of the reactor is 14mm, the length of the tube is 650mm, continuously introducing the reaction liquid obtained in the previous step into the fixed bed reactor at a feeding speed of 0.3mL/min, introducing hydrogen, heating to ensure that the pressure of the hydrogen in the fixed bed reactor is 3.0MPa and the temperature is 200 ℃, continuously flowing out of the lower end of the fixed bed reactor, cooling the flowing reaction liquid, performing gas-liquid separation and liquid filtration, analyzing the filtrate by using gas chromatography to obtain the yield of 96.69%, and performing vacuum distillation to obtain the pure 1,2,2,6, 6-pentamethyl-4-piperidinol.
Example 7
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
125.80g of 2,2,6, 6-tetramethyl-4-piperidinol, 36.03g of paraformaldehyde and 300mL of ethanol were put into a 1L four-necked flask, stirred and reacted at 75 ℃ for 12 hours, the reaction was monitored by gas phase for completion of the reaction of 2,2,6, 6-tetramethyl-4-piperidinol, cooled to room temperature, and excess paraformaldehyde was removed by filtration to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Ni30Cr5/γ-Al2O3Loading into fixed bed reactor with inner diameter of 14mm and length of 650mm, diluting the reaction solution with 100mL isopropanol, continuously introducing into fixed bed reactor at feeding speed of 0.6mL/min, introducing hydrogen, heating to make hydrogen pressure in fixed bed reactorThe reaction liquid continuously flows out from the lower end of the fixed bed reactor at the temperature of 110 ℃ under the pressure of 3.0MPa, the flowing reaction liquid is cooled, separated from gas and liquid, filtered, analyzed by gas chromatography, the yield of the filtrate is 97.81 percent, and the pure product of the 1,2,2,6, 6-pentamethyl-4-piperidinol is obtained after vacuum distillation.
Example 8
A method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol comprises the following two steps:
the first step is as follows: hydroxymethylation reaction
125.80g of 2,2,6, 6-tetramethyl-4-piperidinol, 43.24g of paraformaldehyde and 300mL of isopropanol were put into a 1L four-necked flask, stirred and reacted at 85 ℃ for 7 hours, the 2,2,6, 6-tetramethyl-4-piperidinol was monitored by gas phase to be reacted completely, cooled to room temperature, and excess paraformaldehyde was removed by filtration to obtain 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol.
The second step is that: catalytic hydrogenolysis reaction
Mixing Cu20/γ-Al2O3Loading into a fixed bed reactor, wherein the inner diameter of the reactor is 14mm, the length of the tube is 650mm, diluting the reaction solution obtained in the previous step by adding 100mL of ethanol, continuously introducing into the fixed bed reactor at a feeding speed of 0.5mL/min, introducing hydrogen, heating to ensure that the pressure of the hydrogen in the fixed bed reactor is 3.5MPa and the temperature is 130 ℃, continuously flowing out of the reaction solution from the lower end of the fixed bed reactor, cooling, carrying out gas-liquid separation and liquid filtration on the flowing-out reaction solution, analyzing the filtrate by using a gas chromatography to obtain the yield of 96.82%, and carrying out vacuum distillation to obtain the pure 1,2,2,6, 6-pentamethyl-4-piperidinol.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The synthesis method of the light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol is characterized by comprising the following two steps of reactions:
the first step is as follows: hydroxymethylation reaction
Mixing 2,2,6, 6-tetramethyl-4-piperidinol and paraformaldehyde according to a certain proportion, adding into a solvent, stirring for a certain time at a certain reaction temperature under normal pressure to ensure that the 2,2,6, 6-tetramethyl-4-piperidinol is completely reacted, cooling to room temperature, and filtering to remove excessive paraformaldehyde to obtain a hydroxymethylation product, namely 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinemethanol;
the second step is that: catalytic hydrogenolysis reaction
Loading a reduced solid catalyst into a fixed bed reactor, adding a solvent into reaction liquid after the hydroxymethylation reaction, continuously introducing the reaction liquid into the fixed bed reactor at a certain feeding speed after the concentration of a hydroxymethylation product reaches 20-40%, introducing hydrogen, heating, continuously flowing out from the lower end of the fixed bed reactor, cooling the flowing-out reaction liquid, carrying out gas-liquid separation, filtering the liquid, evaporating the solvent from filtrate, and purifying to obtain a target product 1,2,2,6, 6-pentamethyl-4-piperidinol;
the reduction type solid catalyst in the second step reaction is gamma-Al2O3The preparation method of the reduction type solid catalyst comprises the steps of dissolving nitrate of metal, impregnating, drying and roasting to obtain an oxidation type solid catalyst, and reducing the oxidation type solid catalyst in a hydrogen atmosphere;
the feeding speed in the second step of reaction is 0.2-1.0 mL/min, the hydrogen pressure is 2.0-6.0 MPa, and the reaction temperature is 80-200 ℃.
2. The method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol as an intermediate of a light stabilizer according to claim 1, wherein the molar ratio of 2,2,6, 6-tetramethyl-4-piperidinol to paraformaldehyde in the first reaction step is 1: 1.2-1: 3.
3. The method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol, which is an intermediate of a light stabilizer, according to claim 1, characterized in that the solvent in the first-step reaction and the second-step reaction is at least one of methanol, ethanol, isopropanol and toluene.
4. The method for synthesizing the light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol according to claim 1, wherein the reaction temperature in the first step is 50-110 ℃ and the reaction time is 4-16 hours.
5. The method for synthesizing the light stabilizer intermediate 1,2,2,6, 6-pentamethyl-4-piperidinol according to claim 4, wherein the reaction temperature in the first step is 70-110 ℃ and the reaction time is 6-12 hours.
6. The method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol as an intermediate of a light stabilizer according to claim 1, wherein the feeding speed in the second reaction step is 0.4-0.6 mL/min, the hydrogen pressure is 2.0-4.0 MPa, and the reaction temperature is 80-120 ℃.
7. The method for synthesizing 1,2,2,6, 6-pentamethyl-4-piperidinol, which is an intermediate of a light stabilizer, according to claim 1, wherein the purification method in the second reaction step is vacuum distillation.
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| US3974127A (en) * | 1973-09-17 | 1976-08-10 | E. I. Du Pont De Nemours And Company | Alkylene oxide condensates of tetramethylpiperidine alcohols or glycols |
| US20070015802A1 (en) * | 2002-07-08 | 2007-01-18 | Nicholas Piramal India Limited | Inhibitors of cyclin dependent kinases and their use |
| CN104130161A (en) * | 2014-07-14 | 2014-11-05 | 烟台恒迪克能源科技有限公司 | Synthetic method of carbonic diamide di(methylamino valerate) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3974127A (en) * | 1973-09-17 | 1976-08-10 | E. I. Du Pont De Nemours And Company | Alkylene oxide condensates of tetramethylpiperidine alcohols or glycols |
| US20070015802A1 (en) * | 2002-07-08 | 2007-01-18 | Nicholas Piramal India Limited | Inhibitors of cyclin dependent kinases and their use |
| CN104130161A (en) * | 2014-07-14 | 2014-11-05 | 烟台恒迪克能源科技有限公司 | Synthetic method of carbonic diamide di(methylamino valerate) |
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