CN106008321A - UV292 preparing method - Google Patents
UV292 preparing method Download PDFInfo
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- CN106008321A CN106008321A CN201610344334.XA CN201610344334A CN106008321A CN 106008321 A CN106008321 A CN 106008321A CN 201610344334 A CN201610344334 A CN 201610344334A CN 106008321 A CN106008321 A CN 106008321A
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- 238000000034 method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229940014772 dimethyl sebacate Drugs 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000009413 insulation Methods 0.000 claims abstract description 24
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000000376 reactant Substances 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical compound CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006902 nitrogenation reaction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 238000005406 washing Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 abstract 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 229940050176 methyl chloride Drugs 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000004611 light stabiliser Substances 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- -1 separatory when Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000002699 waste material Substances 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)
- Catalysts (AREA)
Abstract
A UV 292 preparing method comprises the steps of S1, adding 2,2,6,6,-tetramethyl piperidine and dimethyl sebacate into a reactor to be molten and mixed; S2, adding tetrabutyl titanate into the reactor; S3, introducing nitrogen into the reactor and carrying out thermal-insulation reaction; S4, cooling a temperature of reactant to 80 DEG C to 85 DEG C after reaction is finished, adding water and sodium carbonate into the reactor and continuously carrying out thermal-insulation reaction for 1-2h; S5, adding methanol or methyl chloride into the reactor and carrying out thermal-insulation reaction for 30-45min; S6, separating liquid, filtering, washing and dewatering to obtain UV292 with the purity as 98% or above before cooling after the reaction is completely finished. The UV292 preparing method avoids a step of dissolving the reactant into solvent, so that collision between molecules of the reactant is facilitated, and the reacting efficiency is improved. Furthermore, the cost of the solvent is also saved, the reaction is always in alkalescence is guaranteed, reaction between the tetrabutyl titanate catalyst and water is facilitated, and purification of final products is facilitated.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to the preparation method of a kind of UV292.
Background technology
Hindered amine light stabilizer, due to its superior performance, becomes the main flow of light stabilizer consumption market in synthetic material auxiliary agent, occupies leading position in world's light stabilizer market comsupton structure.Along with the basic research of light stabilizer and deepening continuously of applied research, the range of application of hindered amine light stabilizer constantly expands.At present, the application of hindered amine light stabilizer is already covered by the various fields such as agricultural film, engineering plastics, fiber, high-molecular coating, artificial carpet and outdoor various plastics.
In order to improve the performance of hindered amine light stabilizer, many enterprises have developed novel hindered amine light stabilizer, and such as UV292, it has the ability preferably absorbing ultraviolet.And the preparation method of traditional UV292 is by 1,2,2,6,6-pentamethyl-4-hydroxy piperidine, dimethyl sebacate dissolve in petroleum ether, and it is simultaneously introduced catalyst, and it being warming up to 110～120 DEG C, duration of the reaction is 2～5h, then by cooling, filter catalyst, the product of gained is washed, afterwards product is dehydrated, desolventing technology, thus obtain pure UV292.
But need during this to use petroleum ether, and petroleum ether inherently has an inflammable and explosive feature, and its highly volatile, when in air, the volume fraction of petroleum ether reaches more than 1.1%, it is possible to explode, thus has buried potential safety hazard to the preparation of UV292.Therefore, also have the biggest diverted via space.
Summary of the invention
The deficiency existed for prior art, it is an object of the invention to provide the preparation method of a kind of UV292 without using solvent to dissolve reactant.
For achieving the above object, the technical scheme is that the preparation method of a kind of UV292, comprise the following steps: S1, by 2,2,6,6-tetramethylpiperidinols and dimethyl sebacate are passed through in reactor and carry out melting mixing；S2, in reactor add titanium catalyst；S3, in reactor, it is passed through nitrogen, and insulation reaction；S3, reacted after the temperature of reactant is down to 80 DEG C～85 DEG C, and in reactor, add water and soda, continue insulation reaction 2～4h；S4, in reactor, add formaldehyde or chloromethanes, and insulation reaction 30～45min；S5, question response be fully completed after while hot separatory, filter, wash and be dehydrated and obtain the UV292 that purity is more than 98%.
The present invention has an advantage that in this course of reaction due to 2,2,6,6-tetramethylpiperidinol and dimethyl sebacate are to instead of to dissolve 2 with petroleum ether by the way of melting mixing, 2,6,6-tetramethylpiperidinols and the mode of dimethyl sebacate, so on the one hand, save the cost on petroleum ether to put into, on the other hand avoid because the potential safety hazard buried of the volatilization of petroleum ether.
And during reaction, add water primarily to initial reaction product and the material being dissolvable in water water are separated for the first time, and the addition of soda can neutralize issuable acid in course of reaction, so contribute to water and the reaction of tetrabutyl titanate catalyst, generation titanium hydroxide precipitates, and thus can initial reaction product and tetrabutyl titanate catalyst be separated easily.And the sodium ion in soda contributes to initial reaction product and aqueous phase is layered, therefore, so contributing to the purification of end product.
It addition, soda can produce carbon dioxide with acid neutralizing when, and this gas contributes to protecting the material in reactor, prevents it oxidized.
Simultaneously; chloromethanes and initial reaction product react and also can produce hydrochloric acid, and hydrochloric acid can also be neutralized by such soda so that if the reaction environment in reactor all the time be in alkalescence in the case of; thus equipment can also be played a protective role, extend the service life of equipment.
As preferably, being passed through 2 in reactor in S1, the mol ratio of 2,6,6-tetramethylpiperidinols and dimethyl sebacate is 1.7:1～2.2:1.
In the case of this kind of mol ratio, dimethyl sebacate can be with 2, and 2,6,6-tetramethylpiperidinols occur more fully to react, thus improve the conversion ratio of dimethyl sebacate.
As preferably, in S2, the reaction temperature of 2,2,6,6-tetramethylpiperidinols and dimethyl sebacate is maintained at 165 DEG C～180 DEG C, and the response time controls 4～6h.
Temperature is controlled 165 DEG C～180 DEG C of scopes, in the case of so can ensure that normal reaction, the volatilization of reactant and product can be reduced, simultaneously, the boiling point of methanol is 64.7 DEG C, spins off, therefore so being so also beneficial to methanol from reactant, be conducive to reaction to advance to positive direction, thus improve the conversion ratio of reactant.It addition, the use of tetrabutyl titanate catalyst also improves reaction rate, decrease the time of reaction.
As preferably, this reaction, every 1～2 hour, slowly discharges the pressure in reactor and supplements nitrogen simultaneously in reactor.
This is the methanol in order to will spin off from reactant, gets rid of from reactor, such that it is able to effectively further reaction advanced to positive direction, is conducive to improving the conversion ratio of reactant.
As preferably, described titanium catalyst is at least one in tetrabutyl titanate or tetraisopropyl titanate, preferably tetrabutyl titanate.
Carbonic acid N-butyl can react with the water of generation during reactant reaction and generate precipitation, thus can urge and make reactant reaction carry out to positive direction, improve the productivity of UV292.
As preferably, the consumption of described titanium catalyst is 2%～12% of substrate in reactor.
The titanium catalyst of this quantity can be effectively facilitated reactant and can react completely in the short period of time, thus is greatly saved the waste of catalyst.
As preferably, the mol ratio between water and dimethyl sebacate added in S5 is 10:1～13.8:1.
Obvious lamination can be produced between the most final product and aqueous phase, and water can also promote that the hydrolysis of tetrabutyl titanate generates titanium hydroxide precipitation, as long as therefore just the precipitation generated and final product can be separated by the way of filtration, and the n-butyl alcohol produced in hydrolytic process is also easier to be dissolved in water, owing to the amount of water is considerably beyond the amount of reactant, so n-butyl alcohol can also be effectively dissolved in water, separatory when, n-butyl alcohol the most just separates along with aqueous phase there occurs with final product, be conducive to improving the purity of final reacting product.
As preferably, 2 in S1,2,6,6-tetramethylpiperidinols and dimethyl sebacate are to be mixed by magnetic agitation.
Magnetic agitation is utilized to carry out mixed reactant, so owing to not having stirring paddle to extend into reactor from the external world, so reducing the probability of reactor leakage, it is to avoid the probability that material in reactor is oxidized.
Detailed description of the invention
A kind of preparation method of UV292, comprise the following steps: step one: by 2,2,6,6-tetramethylpiperidinols and dimethyl sebacate are passed in reactor, then the temperature of reactor is risen to 165 DEG C～180 DEG C, now open the magnetic stirring apparatus in reactor, to 2,2 under molten condition, 6,6-tetramethylpiperidinols and dimethyl sebacate carry out uniform stirring mixing；Step 2: adding tetrabutyl titanate catalyst in reactor, tetrabutyl titanate catalyst is 2%～12% of the amount of substrate in reactor；Step 3: adding after tetrabutyl titanate catalyst, be passed through nitrogen simultaneously in reactor, emptying the air in reactor, and insulation reaction 4～6h with this, simultaneously every 1～2h, slowly discharges the pressure in reactor and supplements nitrogen simultaneously in reactor；Step 4: after question response completes, is reduced to 80 DEG C～85 DEG C by the temperature of reactor, and adds water and soda in reactor, continues insulation reaction 2～4h；Step 5: after the reaction of step 4 terminates, adds formaldehyde or chloromethanes, and insulation reaction 30～45min in reactor；Step 6: last, after whole reaction is fully completed while hot separatory, filter, wash and be dehydrated and obtain the UV292 that purity is more than 98%.
In this process, by the way of melted, mix 2,2,6,6-tetramethylpiperidinol and dimethyl sebacates, the most just eliminate the use of solvent, thus improve intermolecular collision frequency, be conducive to improving the reaction rate of reactant.
And Titanium series catalyst mainly utilizes is the activity of titanium elements, so reaction can be played the highest catalytic effect, and tetrabutyl titanate is primarily due to it has low toxicity, can be dissolved in the features such as most Organic substances, so they can be with 2,2,6,6-tetramethylpiperidinols and dimethyl sebacate sufficiently mix, thus improve 2, catalytic effect between 2,6,6-tetramethylpiperidinols and dimethyl sebacate.Meanwhile, as drawn in table one " tetrabutyl titanate and the relation of the amount of substrate impact on the conversion ratio of dimethyl sebacate in reactor ", when 8% that tetrabutyl titanate is substrate, the dimethyl sebacate of 1mol its conversion ratio in 5 hours just can keep balancing.
Table one: the content of the tetrabutyl titanate impact on the conversion ratio of dimethyl sebacate
| Content/the % of tetrabutyl titanate | 2.0 | 4.0 | 6.0 | 8.0 | 10.0 | 12.0 |
| Conversion ratio/the % of dimethyl sebacate | 91.6 | 93.7 | 95.4 | 96.6 | 96.8 | 96.9 |
Additionally; it is passed through nitrogen primarily to the air got rid of in reactor; material in reactor is served the effect of being effectively protected; prevent 2 evaporated from material; 2; 6,6-tetramethylpiperidinols and air contact and there is oxidation reaction, it is to avoid the loss of material and mix other impurity in material.
Simultaneously, within the time of certain intervals, discharge the pressure in reactor slowly primarily to remove 2,2,6,6-tetramethylpiperidinol and dimethyl sebacate be produced methanol in course of reaction, reaction thus can be made to advance to positive direction, thus substantially increase the conversion ratio of reaction.
And initial reaction terminates when, water and soda is added in reactor, on the one hand water can be with tetrabutyl titanate generation hydrolysis, generate the titanium hydroxide precipitation insoluble in initial reaction product, and, the n-butyl alcohol produced also is easier to be dissolved in water, owing to the amount of water is considerably beyond the amount of reactant, so n-butyl alcohol can also be effectively dissolved in water, separatory when, n-butyl alcohol the most just separates along with aqueous phase there occurs with final product, add filtration afterwards, it is possible to final reacting product is carried out purification substantially.
And the sodium ion in soda contributes to initial reaction product and aqueous phase is layered, therefore, so contributing to the purification of end product.It addition, soda can produce carbon dioxide with acid neutralizing when, and this gas contributes to protecting the material in reactor, prevents it oxidized.Simultaneously; chloromethanes and initial reaction product react and also can produce hydrochloric acid, and hydrochloric acid can also be neutralized by such soda so that if the reaction environment in reactor all the time be in alkalescence in the case of; thus equipment can also be played a protective role, extend the service life of equipment.
Embodiment 1,
nullA kind of preparation method of hindered amine as light stabilizer，By the raw material dimethyl sebacate and the 2 of 17mol of 10mol,2,6,6-tetramethylpiperidinol joins in reactor，It is warming up to 165 DEG C～180 DEG C，Unlatching magnetic stirring apparatus is stirred，And add the tetrabutyl titanate of mole is substrate 8%，It is passed through nitrogen simultaneously，Air in emptying reactor，Insulation reaction 4h,And pressure in 2 hours releasing reactors be filled with nitrogen now，The conversion ratio of dimethyl sebacate is 94.3%,Dibasic acid esters content is 70.5%，It is cooled to 80 DEG C～85 DEG C afterwards，Add the water of 100mol～138mol，The solution ph simultaneously added in soda holding reactor is 9～10，Continue insulation reaction 2h,But after this elementary reaction terminates，21.8mol chloromethanes is added in reactor，Insulation reaction 30min，Afterwards by separatory while hot、Filtered while hot、The operation such as washing and dehydration，By the time purity is the UV292 of 98.3%，Yield is 96.3%.
Embodiment 2,
nullA kind of preparation method of hindered amine as light stabilizer，By the raw material dimethyl sebacate and the 2 of 22mol of 10mol,2,6,6-tetramethylpiperidinol joins in reactor，It is warming up to 165 DEG C～180 DEG C，Unlatching magnetic stirring apparatus is stirred，And add the tetrabutyl titanate of mole is substrate 8%，It is passed through nitrogen simultaneously，Air in emptying reactor，Insulation reaction 6h,And pressure in 1 hour releasing reactor be filled with nitrogen，Now，The conversion ratio of dimethyl sebacate is 96.7%,Dibasic acid esters content is 74.7%，It is cooled to 80 DEG C～85 DEG C afterwards，Add the water of 100mol～138mol，The solution ph simultaneously added in soda holding reactor is 9～10，Continue insulation reaction 4h,But after this elementary reaction terminates，21.8mol chloromethanes is added in reactor，Insulation reaction 45min，Afterwards by separatory while hot、Filtered while hot、The operation such as washing and dehydration，By the time purity is the UV292 of 99.1%，Yield is 97.4%.
Embodiment 3,
nullA kind of preparation method of hindered amine as light stabilizer，By the raw material dimethyl sebacate and the 2 of 17mol of 10mol,2,6,6-tetramethylpiperidinol joins in reactor，It is warming up to 165 DEG C～180 DEG C，Unlatching magnetic stirring apparatus is stirred，And add the tetrabutyl titanate of mole is substrate 8%，It is passed through nitrogen simultaneously，Air in emptying reactor，Insulation reaction 5h,And pressure in 1 hour releasing reactor be filled with nitrogen，Now，The conversion ratio of dimethyl sebacate is 95.6%,Dibasic acid esters content is 73.4%，It is cooled to 80 DEG C～85 DEG C afterwards，Add the water of 100mol～138mol，The solution ph simultaneously added in soda holding reactor is 9～10，Continue insulation reaction 3h,But after this elementary reaction terminates，40mol formaldehyde is added in reactor，Insulation reaction 40min，Afterwards by separatory while hot、Filtered while hot、The operation such as washing and dehydration，By the time purity is the UV292 of 98.6%，Yield is 96.7%.
Embodiment 4,
nullA kind of preparation method of hindered amine as light stabilizer，By the raw material dimethyl sebacate and the 2 of 22mol of 10mol,2,6,6-tetramethylpiperidinol joins in reactor，It is warming up to 165 DEG C～180 DEG C，Unlatching magnetic stirring apparatus is stirred，And add the tetrabutyl titanate of mole is substrate 8%，It is passed through nitrogen simultaneously，Air in emptying reactor，Insulation reaction 5h，Pressure in 1.5 hours releasing reactors is also filled with nitrogen，After initial reaction terminates，The conversion ratio of dimethyl sebacate is 94.8%,Dibasic acid esters content is 72.1%，It is cooled to 80 DEG C～85 DEG C afterwards，Add the water of 100mol～138mol，The solution ph simultaneously added in soda holding reactor is 9～10，Continue insulation reaction 3h,But after this elementary reaction terminates，40mol formaldehyde is added in reactor，Insulation reaction 40min，Afterwards by separatory while hot、Filtered while hot、The operation such as washing and dehydration，By the time purity is the UV292 of 98.6%，Yield is 95.6%.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-described embodiment, and all technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that, for those skilled in the art, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (8)
1. a preparation method of UV292, comprises the following steps:
S1,2,2,6,6-tetramethylpiperidinol and dimethyl sebacate are passed through in reactor carry out melting mixing；
S2, in reactor add titanium catalyst；
S3, in reactor, it is passed through nitrogen, and insulation reaction；
S4, reacted after the temperature of reactant is down to 80 DEG C～85 DEG C, and in reactor, add water and soda, continue insulation reaction 2～4h；
S5, in reactor, add formaldehyde or chloromethanes, and insulation reaction 30～45min；
S6, question response be fully completed after while hot separatory, filter, wash and be dehydrated and obtain the UV292 that purity is more than 98%.
The preparation method of a kind of UV292 the most according to claim 1, it is characterised in that: being passed through 2 in reactor in S1, the mol ratio of 2,6,6-tetramethylpiperidinols and dimethyl sebacate is 1.7:1～2.2:1.
The preparation method of a kind of UV292 the most according to claim 2, it is characterised in that: in S2, the reaction temperature of 2,2,6,6-tetramethylpiperidinols and dimethyl sebacate is maintained at 165 DEG C～180 DEG C, and the response time controls 4～6h.
The preparation method of a kind of UV292 the most according to claim 3, it is characterised in that: this reaction, every 1～2 hour, slowly discharges the pressure in reactor and supplements nitrogen simultaneously in reactor.
The preparation method of a kind of UV292 the most according to claim 4, it is characterised in that: described titanium catalyst is at least one in tetrabutyl titanate or tetraisopropyl titanate, preferably tetrabutyl titanate.
The preparation method of a kind of UV292 the most according to claim 5, it is characterised in that: the consumption of described titanium catalyst is 2%～12% of substrate in reactor.
The preparation method of a kind of UV292 the most according to claim 1, it is characterised in that: the mol ratio between water and dimethyl sebacate added in S5 is 10:1～13.8:1.
The preparation method of a kind of UV292 the most according to claim 1, it is characterised in that: 2 in S1,2,6,6-tetramethylpiperidinols and dimethyl sebacate are mixed by magnetic agitation.
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| CN110655488A (en) * | 2018-06-29 | 2020-01-07 | 江苏紫奇化工科技有限公司 | Method for catalytically synthesizing light stabilizer LS-770 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0837057A1 (en) * | 1996-10-17 | 1998-04-22 | Mitsui Chemicals, Inc. | Method of preparation of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine |
| CN101712772A (en) * | 2009-10-10 | 2010-05-26 | 南通惠康国际企业有限公司 | Light stabilizer and production method thereof |
| CN103319398A (en) * | 2013-05-20 | 2013-09-25 | 启东金美化学有限公司 | Preparation method of hindered amine light stabilizer |
-
2016
- 2016-05-23 CN CN201610344334.XA patent/CN106008321B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0837057A1 (en) * | 1996-10-17 | 1998-04-22 | Mitsui Chemicals, Inc. | Method of preparation of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine |
| CN101712772A (en) * | 2009-10-10 | 2010-05-26 | 南通惠康国际企业有限公司 | Light stabilizer and production method thereof |
| CN103319398A (en) * | 2013-05-20 | 2013-09-25 | 启东金美化学有限公司 | Preparation method of hindered amine light stabilizer |
Non-Patent Citations (3)
| Title |
|---|
| 刘军生: "受阻胺类光稳定剂Tinuvin765 的合成工艺研究", 《广州化工》 * |
| 刘欣等: "1,2,2,6,6 五甲基哌啶醇的合成", 《河北师范大学学报(自然科学版)》 * |
| 邓义等: "癸二酸二甲酯与1,2,2,6,6-五甲基哌啶醇的酯交换反应", 《石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655488A (en) * | 2018-06-29 | 2020-01-07 | 江苏紫奇化工科技有限公司 | Method for catalytically synthesizing light stabilizer LS-770 |
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