CN104592504A - Method for preparing light stabilizer 622 - Google Patents
Method for preparing light stabilizer 622 Download PDFInfo
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- CN104592504A CN104592504A CN201510031036.0A CN201510031036A CN104592504A CN 104592504 A CN104592504 A CN 104592504A CN 201510031036 A CN201510031036 A CN 201510031036A CN 104592504 A CN104592504 A CN 104592504A
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Abstract
The invention discloses a method for preparing a light stabilizer 622. The method comprises the following steps: under the protection of N2 and normal temperature conditions, adding succinic acid, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol (hereinafter referred to as hydroxyethyl-piperidinol) and titanate or organic bismuth-based catalyst to a reactor, in the presence or absence of a solvent, heating to reflux, carrying out heat conservation, refluxing and dehydration reaction, during the reaction, sampling, detecting by virtue of GPC until the standard is met, completing the reaction and carrying out post-processing steps, namely, cooling, adding water, stirring, filtering and desolventizing under reduced pressure to obtain the target product. According to the technical scheme disclosed by the invention, succinic acid serving as a raw material instead of dimethyl succinate and hydroxyethyl piperidol are directly subjected to esterification dehydration reaction in the presence of a catalyst to prepare the light stabilizer 622, which is free of heavy metal tin prohibited by laws at home and abroad and is in line with strict environment-friendly standards at home and abroad.
Description
Technical field
The present invention relates to a kind of preparation method of compound, be specifically related to a kind of preparation method of hindered amine light stabilizer 622.
Background technology
Photostabilizer 622 is efficient, high molecular type hindered amine as light stabilizer that first Ciba-Geigy company of Switzerland invents.
The structural formula of photostabilizer 622 is as follows:
Wherein, n=11 ~ 14.
As a kind of nontoxic industrial chemical, obtain FDA accreditation already, allow to use in polyolefine packaging material for food.In addition, photostabilizer 622 pairs of polyurethanes, polyacetal, polymeric amide, especially to nylon 11 and nylon 12, all very effective with polyester elastomer.For the application in pigments system, its result of use has exceeded ultraviolet absorbers and nickel stablizer, produces synergistic effect with ultraviolet absorbers series is used in combination.
Current industrial production photostabilizer 622, mainly uses ester-interchange method, carry out transesterification reaction and obtain, but dimethyl succinate price is obviously higher than succinic acid with hydroxyethyl piperidine alcohol with dimethyl succinate; Direct esterification is that raw material replaces dimethyl succinate and hydroxyethyl piperidine alcohol to react with succinic acid.My company scientific research personnel, in process of scientific research, finds that direct esterification Problems existing has: the first carboxylic acid can not complete reaction, and the existence of a certain amount of carboxylic acid can affect the transmittance of product, makes quality product defective; The catalyzer of the second use part kind, effectively can reduce the content of carboxylic acid, but product can be made to introduce heavy metal, as organic tin catalyzer (the domestic and international regulation of tin heavy metal is prohibited).
Summary of the invention
Technical problem to be solved by this invention is: providing a kind of is that raw material replaces dimethyl succinate with succinic acid; with hydroxyethyl piperidine alcohol direct esterification dehydration reaction under catalyst action; the obtained photostabilizer 622 meeting market quality standard-required; it is cheap that this technique has raw material; cost is lower; technique is simple, is easy to large-scale production.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of hindered amine light stabilizer 622, the steps include:
Use N
2protection; under normal temperature condition; by succinic acid, 4-hydroxyl-2; 2; 6,6-tetramethyl--1-piperidine alcohols (hereinafter referred to as hydroxyethyl piperidine alcohol) and account for the titanate ester of succinic acid quality 0.5 ~ 10% or organo-bismuth class catalyzer joins in reactor, under having solvent or solvent-free existence; be heated to reflux temperature; and being incubated reflux dewatering reaction 4 ~ 12h, in reaction process, sampling GPC detects; reaction is terminated when molecular weight reaches 3000 ~ 4000; cooling, add water stirring, filters; the postprocessing working procedures such as decompression precipitation, obtain target product.
Reaction equation is:
Described titanate ester catalyzer is Alkyl titanate, polymer supported titanate, poly-titanic acid ester, is preferably one or more mixtures formed in metatitanic acid tetra isopropyl ester, butyl titanate, tetraethyl titanate, tetrabutyl titanate, butyl (tetra) titanate, isopropyl titanate, tetraphenyl titanate, poly-tetra-n-butyl titanate, tetra-tert titanic acid ester.
Described organo-bismuth class catalyzer is one or more mixtures formed in bismuth naphthenate, Bismuth Octoate, isocaprylic acid bismuth, tin dilaurate bismuth, bismuth neodecanoate.
When react have carry out under solvent condition time, reaction solvent be in normal hexane, hexanaphthene, normal heptane, octane, nonane, decane, benzene, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene one or more formed mixtures.
Described reflux temperature is 100 DEG C ~ 200 DEG C.
The amount of substance of described succinic acid and hydroxyethyl piperidine alcohol is than being 1:1 ~ 1.5.
Photostabilizer 622 of the present invention is white or light yellow low dust powder, is dissolved in the organic solvents such as benzene, chloroform, methyl alcohol, ethanol, ether, water insoluble.Transmittance: 425nm >=95%; 500nm >=97% (10g/100mL toluene).
For the deficiency of forefathers' research, I company scientific research personnel finds through tight scientific research: first aspect, direct esterification is reacted, at the excellent catalyst that the carboxylic acid of early stage in succinic acid self of reaction is exactly direct esterification reaction, but phase carboxylic acid concentration reduces after the reaction, suitable catalyzer need be added, experiment find after the reaction the phase with titanate ester compound as catalyzer, satisfied result can be obtained; Second aspect, direct esterification is reacted, and uses organotin that product can be made inevitably to introduce Heavy Metal, Sn, if but use organo-bismuth class catalyzer, the defect of above-mentioned organic tin catalyzer can be evaded.Organic bismuth catalyst has the green safety characteristics such as low cost, easily process, hypotoxicity and low-activity, can replace plumbous mercury and the tin abolished of being made laws, to meet the export standard of European Union.
The present invention adopts direct esterification, and with titanate ester compound or organo-bismuth compounds for catalyzer, with succinic acid and hydroxyethyl piperidine alcohol for raw material, direct esterification obtains the photostabilizer 622 of higher yields.Use succinic acid to replace dimethyl succinate effectively to reduce costs, use titanate ester compound or organo-bismuth compounds to make reaction carry out more thorough for catalyzer, meet target level of product quality, and technique is simple, is easy to large-scale production.
Beneficial effect of the present invention: technical scheme disclosed in the present application is that raw material replaces dimethyl succinate with succinic acid, with hydroxyethyl piperidine alcohol direct esterification dehydration reaction under catalyst action, obtained photostabilizer 622, not containing the Heavy Metal, Sn expressly forbidden, meet harsh environmental protection standard both at home and abroad both at home and abroad.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
Embodiment 1
Be equipped with agitator, thermometer, reflux condensing tube 1000mL four-hole boiling flask in, 1mol succinic acid is added under normal temperature, 1mol hydroxyethyl piperidine alcohol, 500g trimethylbenzene, slowly reflux temperature is warming up under stirring, and after remaining on 160 ~ 185 DEG C of reflux water-dividing reaction 2h, add 3g metatitanic acid tetra isopropyl ester and continue reaction 4h (water that late phase reaction generates can not destroy Titanium series catalyst).In reaction process, sampling GPC detects, and terminates reaction when molecular weight reaches 3000 ~ 4000.
After reaction terminates, solution is cooled to 80 DEG C, add water stirring, makes titanic acid ester become titanium dioxide precipitation, then by Filtration of catalyst, then underpressure distillation removing trimethylbenzene.Remaining material is through cooling, and the transparent solid that becomes colorless is target product photostabilizer 622.This product softening temperature 55 ~ 80 DEG C, transmittance: 425nm >=95%; 500nm >=97% (10g/100mL toluene), yield is 97% (in succinic acid).
Embodiment 2
Be equipped with agitator, thermometer, reflux condensing tube 1000mL four-hole boiling flask in, 1mol succinic acid is added under normal temperature, 1.05mol hydroxyethyl piperidine alcohol, 500mL toluene and 3g tin dilaurate bismuth, be slowly warming up to reflux temperature under stirring, and after remaining on 110 ~ 135 DEG C of reflux water-dividing reaction 12h, in reaction process, sampling GPC detects, and terminates reaction when molecular weight reaches 3000 ~ 4000.
After reaction terminates, solution is cooled to room temperature, and tin dilaurate bismuth is separated out automatically, Filtration of catalyst (recyclable use again), then underpressure distillation removing solvent toluene.Remaining material is through cooling, and the transparent solid that becomes colorless is target product photostabilizer 622.This product softening temperature 55 ~ 80 DEG C, transmittance: 425nm >=95%; 500nm >=97% (10g/100mL toluene), yield is 96% (in succinic acid).
Embodiment 3
Be equipped with agitator, thermometer, reflux condensing tube 1000mL four-hole boiling flask in, 1mol succinic acid is added under normal temperature, 1.05mol hydroxyethyl piperidine alcohol, 500mL toluene and 2.4g isocaprylic acid bismuth, be slowly warming up to reflux temperature under stirring, and after remaining on 110 ~ 135 DEG C of reflux water-dividing reaction 8h, in reaction process, sampling GPC detects, and terminates reaction when molecular weight reaches 3000 ~ 4000.
After reaction terminates, solution is cooled to room temperature, and tin dilaurate bismuth is separated out automatically, Filtration of catalyst (recyclable use again), then underpressure distillation removing solvent toluene.Remaining material is through cooling, and the transparent solid that becomes colorless is target product photostabilizer 622.This product softening temperature 55 ~ 80 DEG C, transmittance: 425nm >=95%; 500nm >=97% (10g/100mL toluene), yield is 98% (in succinic acid).
Claims (7)
1. the preparation method of a photostabilizer 622; the steps include: to use N2 protection; under normal temperature condition; by succinic acid, hydroxyethyl piperidine alcohol with account for the titanate ester of succinic acid quality 0.5 ~ 10% or organo-bismuth class catalyzer joins in reactor; under having solvent or solvent-free existence; be heated to backflow; and be incubated reflux dewatering reaction 4 ~ 12h; in reaction process; sampling GPC detects, and when molecular weight reaches 3000 ~ 4000, terminates reaction; again through the postprocessing working procedures of cooling, the stirring that adds water, filtration, decompression precipitation, obtain target product.
2. the preparation method of a kind of photostabilizer 622 according to claim 1, is characterized in that: described titanate ester catalyzer is one or more mixtures formed in Alkyl titanate, polymer supported titanate, poly-titanic acid ester.
3. the preparation method of a kind of photostabilizer 622 according to claim 2, is characterized in that: described titanate ester catalyzer is one or more mixtures formed in metatitanic acid tetra isopropyl ester, butyl titanate, tetraethyl titanate, tetrabutyl titanate, butyl (tetra) titanate, isopropyl titanate, tetraphenyl titanate, poly-tetra-n-butyl titanate, tetra-tert titanic acid ester.
4. the preparation method of a kind of photostabilizer 622 according to claim 1, is characterized in that: described organo-bismuth class catalyzer is one or more mixtures formed in bismuth naphthenate, Bismuth Octoate, isocaprylic acid bismuth, tin dilaurate bismuth, bismuth neodecanoate.
5. the preparation method of a kind of photostabilizer 622 according to any one of claim 1-4, it is characterized in that: when react have carry out under solvent condition time, reaction solvent for use be in normal hexane, hexanaphthene, normal heptane, octane, nonane, decane, benzene, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene one or more formation mixtures.
6. the preparation method of a kind of photostabilizer 622 according to any one of claim 1-4, is characterized in that: the described temperature be heated to when refluxing is 100 DEG C ~ 200 DEG C.
7. the preparation method of a kind of photostabilizer 622 according to any one of claim 1-4, is characterized in that: the amount of substance of described succinic acid and hydroxyethyl piperidine alcohol is than being 1:1 ~ 1.5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131266A (en) * | 2015-09-07 | 2015-12-09 | 江苏裕兴薄膜科技股份有限公司 | Polyester copolymer with hindered amine group-containing main chain and preparation method thereof |
| CN107955144A (en) * | 2017-10-25 | 2018-04-24 | 江汉大学 | A kind of preparation method of condensation polymer type Polymeric hindered amine light stabilizer |
| CN112646152A (en) * | 2020-12-10 | 2021-04-13 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of hindered amine light stabilizer |
| CN115746284A (en) * | 2022-11-23 | 2023-03-07 | 宿迁联盛助剂有限公司 | Method for removing residual titanate catalyst in light stabilizer 622 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131266A (en) * | 2015-09-07 | 2015-12-09 | 江苏裕兴薄膜科技股份有限公司 | Polyester copolymer with hindered amine group-containing main chain and preparation method thereof |
| CN105131266B (en) * | 2015-09-07 | 2017-10-20 | 江苏裕兴薄膜科技股份有限公司 | The polyester copolymer of a kind of main chain containing hindered amine group and preparation method thereof |
| CN107955144A (en) * | 2017-10-25 | 2018-04-24 | 江汉大学 | A kind of preparation method of condensation polymer type Polymeric hindered amine light stabilizer |
| CN112646152A (en) * | 2020-12-10 | 2021-04-13 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of hindered amine light stabilizer |
| CN115746284A (en) * | 2022-11-23 | 2023-03-07 | 宿迁联盛助剂有限公司 | Method for removing residual titanate catalyst in light stabilizer 622 |
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