CN106008321B - A kind of preparation method of UV292 - Google Patents
A kind of preparation method of UV292 Download PDFInfo
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- CN106008321B CN106008321B CN201610344334.XA CN201610344334A CN106008321B CN 106008321 B CN106008321 B CN 106008321B CN 201610344334 A CN201610344334 A CN 201610344334A CN 106008321 B CN106008321 B CN 106008321B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229940014772 dimethyl sebacate Drugs 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000009413 insulation Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000000376 reactant Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 235000010891 Ptelea trifoliata Nutrition 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006902 nitrogenation reaction Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical class CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 claims abstract 2
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical class CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- -1 Piperidine alcohols Chemical class 0.000 claims 1
- 230000003111 delayed effect Effects 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- 239000004611 light stabiliser Substances 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical class CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 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
- 238000003756 stirring Methods 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
S1,2,2,6,6 tetramethylpiperidinols and dimethyl sebacate are passed through in reactor and carry out melting mixing by a kind of preparation method of UV292；S2, tetrabutyl titanate is added into reactor；S3, nitrogen, and insulation reaction are passed through into reactor；The temperature of reactant is down to 80 DEG C~85 DEG C after the completion of S4, reaction, and water and soda ash are added into reactor, continues 1~2h of insulation reaction；S5, formaldehyde or chloromethanes, and 30~45min of insulation reaction are added into reactor；S6, wait for that liquid separation while hot after the reaction was complete, filtering, washing, dehydration obtain the UV292 that purity is 98% or more.The program eliminates the step of reactant is dissolved in solvent, it is more advantageous between making reactant molecule and collides in this way, improve reaction efficiency, and also save solvent cost, and soda ash and water are added in reactor, it can ensure that reaction is in alkalescent always, and contribute to the reaction of n-butyl titanate catalyst and water, to facilitate the purification of final product.
Description
Technical field
The present invention relates to the field of chemical synthesis more particularly to a kind of preparation methods of UV292.
Background technology
Hindered amine light stabilizer becomes light stabilizer consumption market in synthetic material auxiliary agent due to its superior performance
Mainstream occupies leading position in world's light stabilizer market comsupton structure.It is ground with the basic research and application of light stabilizer
That studies carefully deepens continuously, and the application range of hindered amine light stabilizer constantly expands.Currently, the application of hindered amine light stabilizer is
Through covering in the various fields such as agricultural film, engineering plastics, fiber, high-molecular coating, artificial carpet and outdoor various plastic products.
In order to improve the performance of hindered amine light stabilizer, many enterprises have developed novel hindered amines light and stablize
Agent, such as UV292 have the preferable ability for absorbing ultraviolet light.And the preparation method of traditional UV292 is by 1,2,2,6,6-
Pentamethyl -4- hydroxy piperidines, dimethyl sebacate are dissolved in petroleum ether, and catalyst are added simultaneously, it is warming up to 110~
120 DEG C, duration of the reaction is that 2~5h washes the product of gained then by cooling down, filtering out catalyst, right later
Product is dehydrated, decolorization, to obtain pure UV292.
But need to use petroleum ether during this, and petroleum ether inherently has the characteristics that inflammable and explosive, Er Qieqi
Highly volatile, when the volume fraction of air petrochina ether reaches 1.1% or more, it is possible to explode, to give UV292
Preparation buried security risk.Therefore, also prodigious diverted via space.
Invention content
It is a kind of without solvent dissolving reactant in view of the deficiencies of the prior art, the present invention intends to provide
UV292 preparation method.
To achieve the above object, the present invention provides following technical solutions：A kind of preparation method of UV292, including it is following
Step：S1, it 2,2,6,6- tetramethylpiperidinols and dimethyl sebacate is passed through in reactor carries out melting mixing；S2, to anti-
It answers and titanium catalyst is added in device；S3, nitrogen, and insulation reaction are passed through into reactor；By the temperature of reactant after the completion of S3, reaction
Degree is down to 80 DEG C~85 DEG C, and water and soda ash are added into reactor, continues 2~4h of insulation reaction；S4, it is added into reactor
Formaldehyde or chloromethanes, and 30~45min of insulation reaction；S5, liquid separation while hot, filtering, washing and dehydration after the reaction was complete are waited for
Obtain the UV292 that purity is 98% or more.
Present invention tool has the advantage that：Due to 2,2,6,6- tetramethylpiperidinols and dimethyl sebacate in the reaction process
It is to dissolve 2,2,6,6- tetramethylpiperidinols and dimethyl sebacate instead of with petroleum ether by way of melting mixing
On the one hand mode, saves the cost input on petroleum ether in this way, on the other hand avoid because the volatilization of petroleum ether is buried
Under security risk.
And during reaction, water is added primarily to by initial reaction product and be dissolvable in water the substance of water into
The first separation of row, and the addition of soda ash can contribute to water and the positive fourth of metatitanic acid in this way with issuable acid during neutralization reaction
The reaction of ester catalyst generates titanium hydroxide precipitation, thus can be easily by initial reaction product and tetrabutyl titanate
Catalyst is detached.And the sodium ion in soda ash contributes to initial reaction product and water phase to be layered, therefore, so having
Help the purification of final product.
In addition, soda ash in acid and when will produce carbon dioxide, and the gas contributes to the object in reactor
Material is protected, and prevents it from being aoxidized.
Meanwhile chloromethanes and initial reaction product react and also will produce hydrochloric acid, such soda ash can also to hydrochloric acid into
Row neutralizes so that if reaction environment in reactor always in the case of the alkalinity, equipment can also thus be played
Protective effect extends the service life of equipment.
Preferably, 2 in reactor are passed through in S1, the molar ratio of 2,6,6- tetramethylpiperidinols and dimethyl sebacate
It is 1.7：1~2.2：1.
In the case of this kind of molar ratio, dimethyl sebacate can be with 2, and 2,6,6- tetramethylpiperidinols, which compare, to be filled
Divide ground reaction, to improve the conversion ratio of dimethyl sebacate.
Preferably, the reaction temperature of 2,2,6,6- tetramethylpiperidinols and dimethyl sebacate is maintained at 165 DEG C in S2
~180 DEG C, the reaction time controls in 4~6h.
By temperature control in the case where 165 DEG C~180 DEG C ranges can ensure normal reaction in this way, it is possible to reduce anti-
The volatilization of object and product is answered, meanwhile, the boiling point of methanol is 64.7 DEG C, is detached from reactant so being also beneficial to methanol in this way
Come, therefore, is conducive to reaction and is promoted to positive direction, to improve the conversion ratio of reactant.In addition, n-butyl titanate catalyst
Use also improve reaction rate, reduce the time of reaction.
Preferably, the reaction is every 1~2 hour, the slow release once pressure in reactor and simultaneously to reactor
Middle supplement nitrogen.
This is the methanol in order to be detached from reactant, is excluded from reactor, so as to further effective
Ground will be reacted to be promoted to positive direction, is conducive to the conversion ratio for improving reactant.
Preferably, the titanium catalyst is at least one of tetrabutyl titanate or tetraisopropyl titanate, preferably titanium
Sour N-butyl.
Carbonic acid N-butyl can react with the water generated during reactant reaction and generate precipitation, thus may be used
So that reactant reaction is carried out to positive direction to urge, improves the yield of UV292.
Preferably, the dosage of the titanium catalyst is 2%~12% of substrate in reactor.
The titanium catalyst of the quantity can be effectively facilitated reactant can be reacted completely in a relatively short period of time, from
And the waste of catalyst is greatly saved.
Preferably, the molar ratio between water and dimethyl sebacate added in S5 is 10：1~13.8:1.
Apparent lamination can be generated between reaction product and water phase final in this way, and water can also promote titanium
The hydrolysis of sour N-butyl generates titanium hydroxide precipitation, as long as therefore can be by the precipitation of generation and final by way of filtering
The reaction product n-butanol that detaches, and generated in hydrolytic process be also easier to be dissolved in water, due to water
The amount considerably beyond reactant is measured, so n-butanol can also be effectively dissolved in water, n-butanol is also just when liquid separation
As water phase is detached with final reaction product, be conducive to the purity for improving final reacting product.
Preferably, 2 in S1,2,6,6- tetramethylpiperidinols and dimethyl sebacate are mixed by magnetic agitation.
Using magnetic agitation come mixed reactant, in this way due to there is no agitating paddle to be extend into reactor from the external world, so
The possibility for reducing reactor leakage, avoids the possibility that the substance in reactor is aoxidized.
Specific implementation mode
A kind of preparation method of UV292, includes the following steps：Step 1：By 2,2,6,6- tetramethylpiperidinols and the last of the ten Heavenly stems two
Dimethyl phthalate is passed into reactor, and the temperature of reactor is then risen to 165 DEG C~180 DEG C, is opened in reactor at this time
Magnetic stirring apparatus, to 2 under molten condition, 2,6,6- tetramethylpiperidinols and dimethyl sebacate carry out uniform stirring and mix
It closes；Step 2：N-butyl titanate catalyst is added into reactor, n-butyl titanate catalyst is the amount of substrate in reactor
2%~12%；Step 3：After n-butyl titanate catalyst is added, while it being passed through nitrogen into reactor, reactor is emptied with this
In air, and 4~6h of insulation reaction, while every 1~2h, the slow release once pressure in reactor and simultaneously to reaction
Nitrogen is supplemented in device；Step 4：It waits after the completion of reacting, the temperature of reactor is reduced to 80 DEG C~85 DEG C, and into reactor
Water and soda ash is added, continues 2~4h of insulation reaction；Step 5：Wait for that step 4 after reaction, formaldehyde is added into reactor
Or chloromethanes, and 30~45min of insulation reaction；Step 6：Finally, entire liquid separation while hot, filtering, water after the reaction was complete are waited for
It washes and is dehydrated to obtain the UV292 that purity is 98% or more.
In this process, 2,2,6,6- tetramethylpiperidinols and dimethyl sebacate are mixed by way of melting,
The use for just eliminating solvent in this way is conducive to the reaction rate for improving reactant to improve intermolecular collision frequency.
And what Titanium series catalyst mainly utilized is the activity of titanium elements, so very high catalysis effect can be played to reaction
Fruit, and tetrabutyl titanate is primarily due to it has a low toxicity, the features such as capable of being dissolved in most organic matters, thus its can with 2,
2,6,6- tetramethylpiperidinols and dimethyl sebacate are adequately mixed, to improve 2,2,6,6- tetramethylpiperidinols
Catalytic effect between dimethyl sebacate.Meanwhile as " relationship of amount of substrate is to the last of the ten Heavenly stems in tetrabutyl titanate and reactor for table one
It can be obtained in the influence of the conversion ratio of acid dimethyl " when tetrabutyl titanate is the 8% of substrate, the dimethyl sebacate of 1mol
Its conversion ratio can keep balancing in 5 hours.
Table one：Influence of the content of tetrabutyl titanate to the conversion ratio of dimethyl sebacate
| Content/% of tetrabutyl titanate | 2.0 | 4.0 | 6.0 | 8.0 | 10.0 | 12.0 |
| Conversion ratio/% of dimethyl sebacate | 91.6 | 93.7 | 95.4 | 96.6 | 96.8 | 96.9 |
In addition, being passed through nitrogen primarily to excluding the air in reactor, the material in reactor is played effectively
Protective effect, it is therefore prevented that 2 evaporated from material, 2,6,6- tetramethylpiperidinols are contacted with air and that oxidation occurs is anti-
It answers, avoid the loss of material and mixes other impurities in material.
Simultaneously, within the time of certain intervals, the pressure in reactor is slowly released primarily to removing
2,2,6,6- tetramethylpiperidinols and dimethyl sebacate during the reaction caused by methanol, can thus make reaction to
Positive direction advances, to substantially increase the conversion ratio of reaction.
And when initial reaction terminates, water is added into reactor and soda ash, one side water can be with the positive fourths of metatitanic acid
Hydrolysis occurs for ester, the titanium hydroxide precipitation insoluble in initial reaction product is generated, moreover, the n-butanol generated also compares appearance
It is soluble in water, due to water amount considerably beyond reactant amount, so n-butanol can also be effectively dissolved in water,
N-butanol is also just detached with water phase with final reaction product when liquid separation, adds filtering later, so that it may with
Final reacting product is subjected to rough purification.
And the sodium ion in soda ash contributes to initial reaction product and water phase to be layered, therefore, so contributing to final
The purification of product.In addition, soda ash in acid and when will produce carbon dioxide, and the gas contributes to in reactor
Material is protected, and prevents it from being aoxidized.Meanwhile chloromethanes reacts with initial reaction product and also will produce hydrochloric acid, in this way
Soda ash can also neutralize hydrochloric acid so that if reaction environment in reactor always in the case of the alkalinity, in this way
It can also just play a protective role to equipment, extend the service life of equipment.
Embodiment 1,
A kind of preparation method of hindered amine light stabilizer, by the 2,2,6 of the raw material dimethyl sebacate of 10mol and 17mol,
6- tetramethylpiperidinols are added in reactor, are warming up to 165 DEG C~180 DEG C, are opened magnetic stirring apparatus and are stirred, and add
Enter mole and be 8% tetrabutyl titanate of substrate, while being passed through nitrogen, the air in emptying reactor, insulation reaction 4h, and
Every the pressure in 2 hours releasing reactors and nitrogen is filled at this point, the conversion ratio of dimethyl sebacate is 94.3%, and dibasic acid esters contains
Amount is 70.5%, is cooled to 80 DEG C~85 DEG C later, and the water of 100mol~138mol is added, while adding soda ash and keeping reactor
Interior solution ph is 9~10, continues insulation reaction 2h, but after the elementary reaction, and 21.8mol chlorine is added into reactor
Methane, insulation reaction 30min, later by liquid separation while hot, while hot filter, wash and dehydration etc. operations, until purity be 98.3%
UV292, yield 96.3%.
Embodiment 2,
A kind of preparation method of hindered amine light stabilizer, by the 2,2,6 of the raw material dimethyl sebacate of 10mol and 22mol,
6- tetramethylpiperidinols are added in reactor, are warming up to 165 DEG C~180 DEG C, are opened magnetic stirring apparatus and are stirred, and add
Enter mole and be 8% tetrabutyl titanate of substrate, while being passed through nitrogen, the air in emptying reactor, insulation reaction 6h, and
Every the pressure in 1 hour releasing reactor and it is filled with nitrogen, at this point, the conversion ratio of dimethyl sebacate is 96.7%, dibasic acid esters contains
Amount is 74.7%, is cooled to 80 DEG C~85 DEG C later, and the water of 100mol~138mol is added, while adding soda ash and keeping reactor
Interior solution ph is 9~10, continues insulation reaction 4h, but after the elementary reaction, and 21.8mol chlorine is added into reactor
Methane, insulation reaction 45min, later by liquid separation while hot, while hot filter, wash and dehydration etc. operations, until purity be 99.1%
UV292, yield 97.4%.
Embodiment 3,
A kind of preparation method of hindered amine light stabilizer, by the 2,2,6 of the raw material dimethyl sebacate of 10mol and 17mol,
6- tetramethylpiperidinols are added in reactor, are warming up to 165 DEG C~180 DEG C, are opened magnetic stirring apparatus and are stirred, and add
Enter mole and be 8% tetrabutyl titanate of substrate, while being passed through nitrogen, the air in emptying reactor, insulation reaction 5h, and
Every the pressure in 1 hour releasing reactor and it is filled with nitrogen, at this point, the conversion ratio of dimethyl sebacate is 95.6%, dibasic acid esters contains
Amount is 73.4%, is cooled to 80 DEG C~85 DEG C later, and the water of 100mol~138mol is added, while adding soda ash and keeping reactor
Interior solution ph is 9~10, continues insulation reaction 3h, but after the elementary reaction, and 40mol first is added into reactor
Aldehyde, insulation reaction 40min are filtered by liquid separation while hot, while hot, are washed and the operations such as dehydration, later until purity is 98.6%
UV292, yield 96.7%.
Embodiment 4,
A kind of preparation method of hindered amine light stabilizer, by the 2,2,6 of the raw material dimethyl sebacate of 10mol and 22mol,
6- tetramethylpiperidinols are added in reactor, are warming up to 165 DEG C~180 DEG C, are opened magnetic stirring apparatus and are stirred, and add
Enter mole and be 8% tetrabutyl titanate of substrate, while being passed through nitrogen, the air in emptying reactor, insulation reaction 5h, often
Every the pressure in 1.5 hours releasing reactors and it is filled with nitrogen, after waiting for initial reaction, the conversion ratio of dimethyl sebacate is
94.8%, dibasic acid esters content is 72.1%, is cooled to 80 DEG C~85 DEG C later, and the water of 100mol~138mol is added, while being added pure
It is 9~10 that alkali, which keeps the solution ph in reactor, continues insulation reaction 3h, but after the elementary reaction, into reactor
Be added 40mol formaldehyde, insulation reaction 40min, later by liquid separation while hot, while hot filter, wash and dehydration etc. operations, Deng Daochun
Degree is 98.6% UV292, yield 95.6%.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of UV292, includes the following steps：
S1, it 2,2,6,6- tetramethylpiperidinols and dimethyl sebacate is passed through in reactor carries out melting mixing, 2,2,6,6-
The molar ratio of tetramethylpiperidinol and dimethyl sebacate is 1.7：1~2.2：1；
S2, titanium catalyst is added into reactor；
S3, nitrogen, and insulation reaction are passed through into reactor；
The temperature of reactant is down to 80 DEG C~85 DEG C after the completion of S4, reaction, and water and soda ash are added into reactor, after continuation of insurance
Temperature 2~4h of reaction, the molar ratio between water and dimethyl sebacate are 10：1~13.8：1；
S5, formaldehyde or chloromethanes, and 30~45min of insulation reaction are added into reactor；
S6, wait for that liquid separation while hot, filtering, washing and dehydration obtain the UV292 that purity is 98% or more after the reaction was complete.
2. the preparation method of UV292 according to claim 1 a kind of, it is characterised in that：2,2,6,6- tetramethyls piperazine in S3
The reaction temperature of pyridine alcohol and dimethyl sebacate is maintained at 165 DEG C~180 DEG C, and the reaction time controls in 4~6h.
3. the preparation method of UV292 according to claim 2 a kind of, it is characterised in that:The reaction was delayed every 1~2 hour
On The Drug Release once the pressure in reactor and supplements nitrogen into reactor simultaneously.
4. the preparation method of UV292 according to claim 3 a kind of, it is characterised in that：The titanium catalyst be metatitanic acid just
At least one of butyl ester or tetraisopropyl titanate.
5. the preparation method of UV292 according to claim 4 a kind of, it is characterised in that：The dosage of the titanium catalyst is
The 2%~12% of substrate mole in reactor.
6. the preparation method of UV292 according to claim 1 a kind of, it is characterised in that：2,2,6,6- tetramethyls in S1
Piperidine alcohols and dimethyl sebacate are mixed by magnetic agitation.
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