CN103980185A - Preparation method of hindered amine light stabilizer 770 - Google Patents
Preparation method of hindered amine light stabilizer 770 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 32
- 150000001412 amines Chemical class 0.000 title claims abstract description 31
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000010992 reflux Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical compound CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229940117389 dichlorobenzene Drugs 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 20
- 230000032050 esterification Effects 0.000 abstract description 14
- 238000002834 transmittance Methods 0.000 abstract description 12
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 abstract description 10
- 150000002148 esters Chemical group 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 229940014772 dimethyl sebacate Drugs 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 0 *C1CC*CC1 Chemical compound *C1CC*CC1 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 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)
- Compositions Of Macromolecular Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of a hindered amine light stabilizer 770. According to the method, sebacic acid and tetramethylpiperidinol as reactants and an oxide and / or organic compound of the fourth main group element tin as a catalyst are subjected to a heating refluxing reaction in a solvent to obtain the hindered amine light stabilizer 770. The invention uses sebacic acid as raw material instead of dimethyl sebacate, and the sebacic acid under the effect of an appropriate catalyst performs a direct esterification dehydration reaction with tetramethylpiperidinol; and appropriate technology conditions such as an appropriate proportion of raw materials, reaction temperature adjustment and suitable solvent are employed to solve the technical problems of low esterification rate and poor light transmittance of a final product in a common direct esterification reaction, and to prepare the light stabilizer 770 product in line with the requirements of market quality standards. Compared with the ester exchange method in the prior art, the method has the advanategs of cheap raw materials, higher yield, low requirements for equipment, simple process and easiness for scale production.
Description
Technical field
The preparation method who the present invention relates to a kind of hindered amine light stabilizer 770, belongs to chemosynthesis technical field.
Background technology
Hindered amine light stabilizer (HALS) is the heat subject of polymer stabilizer field development research over nearly 20 years.Because HALS itself has unique, remarkable light-protection energy; its efficiency is 2-3 times of general traditional photostabilizer; the auxiliary agents such as while and UV light absorber, oxidation inhibitor have good synergistic effect; and do not make coloring resin; low toxicity or nontoxic, because of but a kind of tool auxiliary agent with broad prospects for development.According to statistics in 1996, world HALS year consumption Yi Zhan world photostabilizer total quantity consumed 54%, and still with annual 8% speed increment.
Photostabilizer 770 is low-molecular-weight typical products in numerous hindered amine light stabilizers, comes out in the Ciba-Geigy company of company, Switzerland altogether of Japan three the seventies.Afterwards, the cyanamide company of the U.S., Goodrich Corporation, Hirst company, Bo Ge-Time Warner, gondola ChimosMontefluos company, the Sumitomo company of Japan, and the enterprise of the country such as Czech, Russia, Germany has developed like product in succession.Because its cost is low, there is good light stability, be widely used in the polyolefine materials such as polypropylene, so far still studied and application widely.
Photostabilizer 770 is a kind of white or micro-yellow crystal pressed powder, is sebacic acid two 2,2, the trade(brand)name of 6,6-tetramethyl--4-piperidine ester, its molecular formula is C28H52N2O4, can be dissolved in the organic solvents such as benzene, chloroform, methyl alcohol, ethanol, ether, water insoluble, 81～85 DEG C of fusing points.As photostabilizer, be applicable to polypropylene, high density polyethylene(HDPE), urethane, polystyrene, ABS resin etc., its light stabilising effect is better than conventional photostabilizer at present.Industrial at present, it is carry out transesterification reaction by 2,2,6,6-tetramethyl--4-piperidine alcohols (hereinafter to be referred as piperidine alcohols) with dimethyl sebacate and make, as US5605761A, US3640928A etc. make this product from transesterify angle; China is studied a lot of of hindered amine light stabilizer, but research photostabilizer 770 is fewer, and as Zhang Zeming etc. (synthetic [J] of hindered amine light stabilizer Tinuvin-770. Hebei chemical industry, 1998. (2): 43-45) what investigate emphatically is still this kind of catalyzer that transesterification reaction is used.
The market price of dimethyl sebacate, far above the sebacic acid extracting from Viscotrol C, therefore impels people to react to prepare two 2,2,6, the 6-tetramethyl--4-piperidine esters of sebacic acid with sebacic acid and tetramethylpiperidinol direct esterification.But in prior art the technique of direct esterification can there are the following problems: the first, to be difficult to esterification complete in direct esterification reaction conventionally, has carboxyl and exist in product; The second, the carboxyl existing in product can cause the transmittance of product defective.Transmittance is defective, is unacceptable for commercially available photostabilizer 770, therefore industrially both at home and abroad adopts direct esterification route to prepare this product without bibliographical information temporarily.
Summary of the invention
In view of the defect that above-mentioned prior art exists, the object of the invention is to propose a kind of preparation method of hindered amine light stabilizer 770, can improve esterification yield and the product transmittance of esterification in preparation process.
The structural formula of preparation method's of the present invention target compound is:
Object of the present invention is achieved by the following technical programs:
A kind of preparation method of hindered amine light stabilizer 770, the method is taking sebacic acid and tetramethylpiperidinol as reactant, taking the oxide compound of the 4th main group element tin and/or organism as catalyzer, in solvent, heating reflux reaction obtains hindered amine light stabilizer 770.
Above-mentioned preparation method's reaction formula is:
In above-mentioned preparation method, the organism of the 4th main group element tin and/or oxide compound are as the catalyzer of direct esterification reaction, the esterification yield that has overcome common direct esterification reaction is on the low side, the problem that hydroxy-acid group content is high, thus the problem that direct esterification technique is difficult to the product that makes qualified transmittance solved.
In above-mentioned preparation method, preferred, the method also comprises that the hindered amine light stabilizer 770 to obtaining carries out the step of aftertreatment purifying, and described step comprises filtration, decompression precipitation, activated carbon decolorizing and crystallization.
In above-mentioned preparation method, preferred, crystallization solvent used comprises water and/or sherwood oil.
In above-mentioned preparation method, preferred, the temperature of reaction of heating reflux reaction is 110 DEG C-190 DEG C, and the reaction times is 4h-12h.
In above-mentioned preparation method, preferred, the oxide compound of described the 4th main group element tin comprises dibutyltin oxide and/or di-n-octyltin oxide.
In above-mentioned preparation method, preferred, the alkylide that the organism of described the 4th main group element tin is tin and/or alcoxylates.
In above-mentioned preparation method, preferred, the organism of described the 4th main group element tin comprises stannous octoate and/or dibutyltin dilaurate.
In above-mentioned preparation method, preferred, described solvent comprises one or more the combination in dimethylbenzene, chlorobenzene, dichlorobenzene, trimethylbenzene.
In above-mentioned preparation method, preferred, the amount of substance ratio of sebacic acid and tetramethylpiperidinol is 1: (2-2.2).
The hindered amine light stabilizer 770 that the present invention also provides a kind of above-mentioned preparation method to obtain.
The transmittance of the hindered amine light stabilizer 770 of above-mentioned gained is: 425nm >=95%; 500nm >=97% (10 grams/100 milliliters toluene).
Outstanding effect of the present invention is:
Replace dimethyl sebacate taking sebacic acid as raw material; under suitable catalyst action with tetramethylpiperidinol direct esterification dehydration reaction; adopt suitable feedstock amount of substance ratio simultaneously; adjust the temperature of reaction; the processing condition such as applicable solvent; the esterification yield that has solved common direct esterification reaction existence is low; the technological problemses such as the finished product printing opacity rate variance; make photostabilizer 770 products that conform with market quality standard-required, compared with the ester-interchange method of existing technique, raw material is more cheap; productive rate is higher; equipment requirements is low, and technique is simple, is easy to large-scale production.
Brief description of the drawings
Fig. 1 is the nuclear-magnetism H spectrogram of embodiment 1 products therefrom;
Fig. 2 is the nuclear-magnetism C spectrogram of embodiment 1 products therefrom.
Embodiment
Below by specific embodiment, method of the present invention is described, but the present invention is not limited thereto.Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1
The present embodiment provides a kind of preparation method of hindered amine light stabilizer 770, specific as follows:
In the four-hole boiling flask of 500ml that agitator, thermometer, reflux condensing tube are housed, under normal temperature, add 0.37mol (75.33g) sebacic acid, 0.76mol (120.15g) tetramethylpiperidinol, 3.88g di-n-octyltin oxide and 213.5g trimethylbenzene, under stirring, be slowly warming up to reflux temperature, and remain on 170 DEG C of-175 DEG C of reflux water-dividings reaction 4h.In reaction process, the single dibasic acid esters ratio generating by GC analytical reaction is judged reaction process, and middle control is reacted to finishing.
After reaction finishes, solution is cooled to 80 DEG C, remove by filter catalyzer, then trimethylbenzene is removed in underpressure distillation.Remaining material such as adds at heavy sherwood oil and the gac of 3.5g, is heated to 60 DEG C-70 DEG C and stir 1h, then removes by filter gac.Residual petroleum ethereal solution is cooled to 0-25 DEG C, crystallization 1h, and filtering drying obtains product, and this product is carried out to nuclear-magnetism qualification, and result as depicted in figs. 1 and 2, judges that this product is as hindered amine light stabilizer 770.This product fusing point is 82 DEG C-84 DEG C, and transmittance is: 425nm >=95%, 500nm >=97% (10 grams/100 milliliters toluene), yield is 94% (in sebacic acid).
Embodiment 2
The present embodiment provides a kind of preparation method of hindered amine light stabilizer 770, specific as follows:
In the four-hole boiling flask of 500ml that agitator, thermometer, reflux condensing tube are housed, under normal temperature, add 0.37mol (75.33g) sebacic acid, 0.76mol (120.15g) tetramethylpiperidinol, 3.88g di-n-octyltin oxide and 213.5g trimethylbenzene, under stirring, be slowly warming up to reflux temperature, and remain on 175 DEG C of reflux water-dividing reaction 6h.In reaction process, the single dibasic acid esters ratio generating by GC analytical reaction is judged reaction process, and middle control is reacted to finishing.
After reaction finishes, solution is cooled to 80 DEG C, remove by filter catalyzer, then trimethylbenzene is removed in underpressure distillation.Remaining material such as adds at heavy water and the gac of 3.5g, is heated to 60 DEG C-70 DEG C and stir 1h, then removes by filter gac.Remaining aqueous solution is cooled to 0-25 DEG C, crystallization 1h, and filtering drying obtains product hindered amine light stabilizer 770.This product fusing point is 82 DEG C-84 DEG C, transmittance: 425nm >=95%, 500nm >=97% (10 grams/100 milliliters toluene), yield is 97% (in sebacic acid).
Embodiment 3
The present embodiment provides a kind of preparation method of hindered amine light stabilizer 770, specific as follows:
In the four-hole boiling flask of 500ml that agitator, thermometer, reflux condensing tube are housed, under normal temperature, add 0.37mol (75.33g) sebacic acid, 0.76mol (120.15g) tetramethylpiperidinol, 3.88g stannous octoate and 213.5g trimethylbenzene, under stirring, be slowly warming up to reflux temperature, and remain on 170 DEG C of-175 DEG C of reflux water-dividings reaction 8h.In reaction process, the single dibasic acid esters ratio generating by GC analytical reaction is judged reaction process, and middle control is reacted to finishing.
After reaction finishes, solution is cooled to 80 DEG C, remove by filter catalyzer, then trimethylbenzene is removed in underpressure distillation.Remaining material such as adds at heavy sherwood oil and the gac of 3.5g, is heated to 60 DEG C-70 DEG C and stir 1h, then removes by filter gac.Residual petroleum ethereal solution is cooled to 0-25 DEG C, crystallization 1h, and filtering drying obtains product hindered amine light stabilizer 770.This product fusing point is 82 DEG C-84 DEG C, transmittance: 425nm >=95%, 500nm >=97% (10 grams/100 milliliters toluene), yield is 96% (in sebacic acid).
Embodiment 4
The present embodiment provides a kind of preparation method of hindered amine light stabilizer 770, specific as follows:
In the four-hole boiling flask of 500ml that agitator, thermometer, reflux condensing tube are housed, under normal temperature, add 0.37mol (75.33g) sebacic acid, 0.81mol (128.75g) tetramethylpiperidinol, 3.88g dibutyltin dilaurate and 213.5g trimethylbenzene, under stirring, be slowly warming up to reflux temperature, and remain on 170 DEG C of-175 DEG C of reflux water-dividings reaction 12h.In reaction process, the single dibasic acid esters ratio generating by GC analytical reaction is judged reaction process, and middle control is reacted to finishing.
After reaction finishes, solution is cooled to 80 DEG C, remove by filter catalyzer, then trimethylbenzene is removed in underpressure distillation.Remaining material such as adds at heavy sherwood oil and the gac of 3.5g, is heated to 60 DEG C-70 DEG C and stir 1h, then removes by filter gac.Residual petroleum ethereal solution is cooled to 0-25 DEG C, crystallization 1h, and filtering drying obtains product hindered amine light stabilizer 770.This product fusing point is 82 DEG C-84 DEG C, transmittance: 425nm >=95%, 500nm >=97% (10 grams/100 milliliters toluene), yield is 98% (in sebacic acid).
Embodiment 5
The present embodiment provides a kind of preparation method of hindered amine light stabilizer 770, specific as follows:
In the four-hole boiling flask of 500ml that agitator, thermometer, reflux condensing tube are housed, under normal temperature, add 0.37mol (75.33g) sebacic acid, 0.76mol (120.15g) tetramethylpiperidinol, the mixture of the dibutyltin dilaurate of 3.88g and stannous octoate (mass ratio 2:1), 213.5g chlorobenzene, under stirring, be slowly warming up to reflux temperature, and remain on 130 DEG C of-150 DEG C of reflux water-dividings reaction 4h.In reaction process, the single dibasic acid esters ratio generating by GC analytical reaction is judged reaction process, and middle control is reacted to finishing.
After reaction finishes, solution is cooled to 80 DEG C, remove by filter catalyzer, then chlorobenzene is removed in underpressure distillation.Remaining material such as adds at heavy sherwood oil and the gac of 3.5g, is heated to 60 DEG C-70 DEG C and stir 1h, then removes by filter gac.Residual petroleum ethereal solution is cooled to 0-25 DEG C, crystallization 1h, and filtering drying obtains product hindered amine light stabilizer 770.This product fusing point is 82 DEG C-84 DEG C, transmittance: 425nm >=95%, 500nm >=97% (10 grams/100 milliliters toluene), yield is 88% (in sebacic acid).
Embodiment 6
The present embodiment provides a kind of preparation method of hindered amine light stabilizer 770, specific as follows:
In the four-hole boiling flask of 500ml that agitator, thermometer, reflux condensing tube are housed, under normal temperature, add 0.37mol (75.33g) sebacic acid, 0.76mol (120.15g) tetramethylpiperidinol, the mixture of the di-n-octyltin oxide of 3.88g and dibutyltin dilaurate (mass ratio 3:7), 213.5g dichlorobenzene, under stirring, be slowly warming up to reflux temperature, and remain on 180 DEG C of-190 DEG C of reflux water-dividings reaction 6h.In reaction process, the single dibasic acid esters ratio generating by GC analytical reaction is judged reaction process, and middle control is reacted to finishing.
After reaction finishes, solution is cooled to 80 DEG C, remove by filter catalyzer, then dichlorobenzene is removed in underpressure distillation.Remaining material such as adds at heavy sherwood oil and the gac of 3.5g, is heated to 60 DEG C-70 DEG C and stir 1h, then removes by filter gac.Residual petroleum ethereal solution is cooled to 0-25 DEG C, crystallization 1h, and filtering drying obtains product hindered amine light stabilizer 770.This product fusing point is 82 DEG C-84 DEG C, transmittance: 425nm >=95%, 500nm >=97% (10 grams/100 milliliters toluene), yield is 95% (in sebacic acid).
Therefore, replace dimethyl sebacate taking sebacic acid as raw material, under suitable catalyst action with tetramethylpiperidinol direct esterification dehydration reaction, adopt suitable feedstock amount of substance ratio simultaneously, adjust the temperature of reaction, the processing condition such as applicable solvent, the esterification yield that has solved common direct esterification reaction existence is low, the technological problemses such as the finished product printing opacity rate variance, make photostabilizer 770 products that conform with market quality standard-required, compared with the ester-interchange method of existing technique, raw material is more cheap, productive rate is higher, equipment requirements is low, technique is simple, be easy to large-scale production.
Claims (10)
1. the preparation method of a hindered amine light stabilizer 770, the method is taking sebacic acid and tetramethylpiperidinol as reactant, taking the oxide compound of the 4th main group element tin and/or organism as catalyzer, in solvent, heating reflux reaction obtains hindered amine light stabilizer 770.
2. preparation method according to claim 1, the method also comprises that the hindered amine light stabilizer 770 to obtaining carries out the step of aftertreatment purifying, described step comprises filtration, decompression precipitation, activated carbon decolorizing and crystallization.
3. preparation method according to claim 2, is characterized in that: crystallization solvent used comprises water and/or sherwood oil.
4. preparation method according to claim 1, is characterized in that: the temperature of reaction of heating reflux reaction is 110 DEG C-190 DEG C, and the reaction times is 4h-12h.
5. preparation method according to claim 1, is characterized in that: the oxide compound of described the 4th main group element tin comprises dibutyltin oxide and/or di-n-octyltin oxide.
6. preparation method according to claim 1, is characterized in that: the alkylide that the organism of described the 4th main group element tin is tin and/or alcoxylates.
7. preparation method according to claim 6, is characterized in that: the organism of described the 4th main group element tin comprises stannous octoate and/or dibutyltin dilaurate.
8. preparation method according to claim 1, is characterized in that: described solvent comprises one or more the combination in dimethylbenzene, chlorobenzene, dichlorobenzene, trimethylbenzene.
9. preparation method according to claim 1, is characterized in that: the amount of substance ratio of sebacic acid and tetramethylpiperidinol is 1: (2-2.2).
10. the hindered amine light stabilizer 770 that the preparation method described in a claim 1-9 any one obtains.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906550A (en) * | 2016-05-23 | 2016-08-31 | 杭州欣阳三友精细化工有限公司 | Preparation method of UV770 |
| CN111849509A (en) * | 2019-04-26 | 2020-10-30 | 北京八亿时空液晶科技股份有限公司 | A kind of compound light stabilizer and its preparation method and application |
| CN114230511A (en) * | 2021-12-31 | 2022-03-25 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate |
| WO2024258749A1 (en) * | 2023-06-12 | 2024-12-19 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Chemoenzymatic synthesis of sebacic acid and dibutyl sebacate |
-
2014
- 2014-05-08 CN CN201410193843.8A patent/CN103980185A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906550A (en) * | 2016-05-23 | 2016-08-31 | 杭州欣阳三友精细化工有限公司 | Preparation method of UV770 |
| CN105906550B (en) * | 2016-05-23 | 2018-06-12 | 杭州欣阳三友精细化工有限公司 | A kind of preparation method of UV770 |
| CN111849509A (en) * | 2019-04-26 | 2020-10-30 | 北京八亿时空液晶科技股份有限公司 | A kind of compound light stabilizer and its preparation method and application |
| CN114230511A (en) * | 2021-12-31 | 2022-03-25 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate |
| CN114230511B (en) * | 2021-12-31 | 2024-01-26 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of bis (2, 6-tetramethyl-4-piperidinyl) sebacate |
| WO2024258749A1 (en) * | 2023-06-12 | 2024-12-19 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Chemoenzymatic synthesis of sebacic acid and dibutyl sebacate |
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