CN103012843A - Benzotriazole-hindered amine composite photostabilizer and preparation method thereof - Google Patents
Benzotriazole-hindered amine composite photostabilizer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Benzotriazole-hinderamine amine composite photostabilizer, structural formulas are as follows:
; R1 is H, CH3, C2H5, OCH3, OC2H5, Cl or Br, and R2 is
Or
, R3 is alkyl, alkoxy or alkanoyl, R4 H, alkyl, alkoxy or alkanoyl. The present invention further simultaneously discloses the preparation method of above-mentioned Benzotriazole-hinderamine amine composite photostabilizer, including diazo-coupling reaction, reduction ring-closure reaction, acyl chloride reaction and alcoholization or aminating reaction, to obtain Benzotriazole-hinderamine amine composite photostabilizer.
Description
Technical field
The present invention relates to a kind of benzotriazole-hindered amine composite light stabilizer and preparation method thereof.
Background technology
In recent years, because a large amount of uses of chlorine fluorine hydrocarbon material are seriously damaged atmospheric ozone layer, earth's surface ultraviolet irradiation amount obviously increases.Ultraviolet ray can bring various pathologies to the skin of human body, has a strong impact on human health.Simultaneously, ultraviolet ray can cause the textiles photo-oxidative degradation, destroys material property; Can also cause and dye photic variable color, the change textiles color and luster etc. of taking off of (face) material.Therefore, improve the anti-ultraviolet property of textile materials and textiles itself and human body are played a protective role, become the in recent years study hotspot in textile dyeing and finishing field.
For textiles, using photostabilizer to carry out anti UV finishing is one of the easiest, economic, effective photo-protection method, can effectively delay ultraviolet ray to the light loss evil of textiles, dyestuff and human body.Present commercial application effect preferably two kinds of photostabilizers is UV light absorber (UVA) and hindered amine as light stabilizer (HALS).UV light absorber be can efficient absorption ultraviolet ray and a class material that the energy that absorbs is discharged with the less form of energy of destructiveness such as heat energy, vibrational energy, the characteristics such as, environmental protection long-acting by means of it, light color become the important photostabilizer of a class.And hindered amine light stabilizer is different from the mode of action of ultra-violet stabilizer, it is to suppress the photooxidation droping reaction by the number of ways such as energy of catching free radical, decompose hydroperoxide and transmission excited state molecule, is the photostabilizer of consumption maximum in present plastics and the film article photo-protection.
UV light absorber can play certain protective effect to human body and textiles by absorbing ultraviolet, but UV light absorber itself also can be subject to photochemical degradation (photoxidation, living radical effect) and cause loss failure, and adds the photochemical degradation that hindered amine light stabilizer just can the establishment UV light absorber.Therefore, will have ultraviolet radiation absorption function fragment and hindered amines light and stablize the fragment introducing with in a part, develop benzotriazole-hindered amine composite light stabilizer.Such composite light stabilizer has absorbing ultraviolet concurrently, catches the multiple light stabilization functions such as free radical, and the lifting of macromolecular material light fastness is had a good application prospect.
The people such as the Shao Yuchang of Dalian Chemical Research ﹠. Design Inst. once synthesized a series of benzotriazole light stabilizers that contain the structure of hindered amine, such photostabilizer with the carboxylate group as abutment, two ends have connected respectively benzotriazole ultraviolet absorption fragment and hindered amine light is stablized fragment, have good light stability.But its carboxylicesters abutment acid and alkali-resistance stability is not good, and the material protection aspect is subject to easily the impact of the environmental problem such as acid rain and causes this composite light stabilizer hydrolysis to be run off out of doors, reduces the persistence of light stabilization protective performance.
The people such as the Shao Yuchang of Dalian Chemical Research ﹠. Design Inst. have synthesized a series of benzotriazole light stabilizers that contain the structure of hindered amine, are shown below:
Wherein: X=H or C1; R=H or CH
3
Reference: Shao Yuchang is left loud and clear. contain the synthetic and sign [J] of the benzotriazole light stabilizer of the structure of hindered amine. fine chemistry industry 2007,24 (12): 1163-1167.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of benzotriazole-hindered amine composite light stabilizer, and it can catch free radical again by absorbing ultraviolet.
In order to solve the problems of the technologies described above, the invention provides a kind of benzotriazole-hindered amine composite light stabilizer, its structural formula is:
R
1Be H, CH3, C2H5, OCH3, OC2H5, Cl or Br,
R
2For
Or
,
R
3Be alkyl, alkoxyl group or alkyloyl, R
4Be H, alkyl, alkoxyl group or alkyloyl.
As the improvement of benzotriazole of the present invention-hindered amine composite light stabilizer, its structural formula is:
The present invention also provides the preparation method of above-mentioned benzotriazole-hindered amine composite light stabilizer simultaneously, specifically may further comprise the steps:
1), diazo-coupling reaction:
Adopt diazotisation methods that o-Nitraniline or derivatives thereof (being o-Nitraniline or ortho-nitrophenyl sulfonamide derivatives) is prepared into its diazonium salt solution, coupled reaction occurs in diazonium salt solution and p-hydroxybenzenyl sulfonate in 0 ~ 5 ℃, pH value are 8 ~ 10 solution system, get adjacent nitro-azo dyestuff intermediate; The mol ratio of diazonium salt and p-hydroxybenzenyl sulfonate is that 1:0.9 ~ 1.1(is preferably 1:1); The temperature of coupled reaction is 0 ~ 5 ℃, and the time is that 1.5 ~ 2.5h(is preferably 2h);
2), reduction ring-closure reaction:
The adjacent nitro-azo dyestuff intermediate that step 1) is obtained reduces in the solution system of thiourea peroxide and sodium hydroxide, gets the intermediate benzotriazole UV absorbers; The mol ratio of adjacent nitro-azo dyestuff intermediate and thiourea peroxide, sodium hydroxide is 1:4 ~ 6:8 ~ 14;
. the temperature of reduction reaction is 70 ~ 90 ℃, and the time is 2.5 ~ 3.5h;
3), acyl chloride reaction:
With step 2) the intermediate benzotriazole UV absorbers that obtains and sulfur oxychloride as catalyzer, carry out acyl chloride reaction with DMF (DMF), gets chloride product intermediate; The mol ratio of intermediate benzotriazole UV absorbers and sulfur oxychloride is 1:25 ~ 30; The mol ratio of DMF and benzotriazole UV absorbers is 1:3 ~ 6;
The temperature of acyl chloride reaction is 50 ~ 70 ℃, and the time is 1.5 ~ 2.5h;
4), alcoholization or aminating reaction:
The chloride product intermediate that step 3) is obtained is dissolved in the acetone, does acid binding agent with salt of wormwood, reacts with hindered amine light stabilizer, gets benzotriazole-hindered amine composite light stabilizer; The mol ratio of described chloride product intermediate and salt of wormwood, hindered amine as light stabilizer is 1:1 ~ 2:1 ~ 2;
Temperature of reaction is room temperature (being generally 10 ~ 30 ℃), and the time is 0.5 ~ 1.5h.
Benzotriazole of the present invention-hindered amine composite light stabilizer, the molecular structure of this photostabilizer are take sulfuryl amine group as abutment, and two ends connect respectively benzotriazole ultraviolet and absorb fragment and hindered amine light stabilizer fragment.
Benzotriazole of the present invention-hindered amine composite light stabilizer, its use-pattern is equal to benzotriazole light stabilizer.
The benzotriazole of gained of the present invention-hindered amine composite light stabilizer has following advantage:
Compare with existing commercialization photostabilizer, such benzotriazole-hindered amine composite light stabilizer is in absorbing ultraviolet, can also catch free radical by hindered amine, suppress photo-oxidative degradation, play the stable effect of light, greatly improve Light stable efficiency and photostabilization, and reduced the loss of photostabilizer.Compare with the composite light stabilizer of Shao Yuchang exploitation, its acid and alkali-resistance stability is better, and is stronger to the light stabilization protective ability of macromolecular material.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the ultraviolet radiation absorption intensity contrast figure of Compound I, II and I ', III.
Embodiment
The preparation method of embodiment 1, a kind of benzotriazole-hindered amine composite light stabilizer, carry out following steps successively:
1), the diazotization reaction of p-chloro-o-nitroaniline:
The p-chloro-o-nitroaniline of 0.3mol is added in the mixed solution of the concentrated hydrochloric acid (hydrochloric acid of mass concentration 〉=35%) of 1.2mol and 20ml water composition, stir 1h, 0 ~ 5 ℃ of lower sodium nitrite in aqueous solution 50ml that drips 6.6mol/L, 1h adds, and insulation reaction 2h, behind the arrival reaction end (being after stopping in the reaction times), thereby add urea and remove excessive nitrous acid, terminal point detects with starch potassium iodide paper, when test paper is apparent in 3 seconds when not becoming rapidly blue, show not contained nitrous acid in the reaction product.Filter, get settled solution; This settled solution is the solution that contains the p-chloro-o-nitroaniline diazonium salt.
2), the coupled reaction of p-chloro-o-nitroaniline diazonium salt and p-hydroxybenzenyl sulfonate:
The p-hydroxybenzenyl sulfonate of 0.3mol is dissolved in the NaOH of the 100ml aqueous solution (1mol/L) water, get coupling solution.Under 0 ~ 5 ℃, whole solution that contains the p-chloro-o-nitroaniline diazonium salt of step 1) gained is added drop-wise in the coupling solution, about 1h adds, and continues reaction 2h in 0 ~ 5 ℃, drip and reaction process in, all with the pH value to 9 of powdered sodium carbonate conditioned reaction system.Can utilize and ooze the circle method is carried out reaction end to the reaction solution of gained detection (being whether detection reaction is fully finished).
When oozing of reaction solution generates without coloring matter after circle oozes the circle contact with diazo liquid (that is, containing the solution of p-chloro-o-nitroaniline diazonium salt), illustrate that the coupling component reaction is complete in the reaction solution; After the oozing circle and coupling solution and ooze circle and contact of reaction solution, without coloring matter generation, illustrate that diazo component reacts complete in the reaction solution.
Behind the above-mentioned reaction 2h, coupling component and diazo component all react complete in the reaction solution.The product of gained, direct filtration, pickling (hydrochloric acid soln of 5mol/L concentration washes twice, and each consumption is about 10-20ml), oven dry (80 ℃) namely get coupling product (namely to the adjacent nitro-azo dyestuff intermediate of chlorine) to constant weight.Its structural formula is:
3), the reduction reaction of coupling product
Adding above-mentioned steps 2 in the 250mL there-necked flask) bolarious coupling product (namely to the adjacent nitro-azo dyestuff intermediate of the chlorine) 6.46g (0.02mo l) for preparing and get, deionized water 160mL, sodium hydroxide 8.80g(0.22mol), stir, be heated to 80 ℃, minute 5 crowdes of adding thiourea peroxide 10.80g(0.1mol in 5min), reactant becomes yellow by garnet.Behind the insulation reaction 3h, in the frozen water with reactant impouring 150ml, stir, take hydrochloric acid soln (concentration is as 5mol/L) neutralization (to pH as 7), suction filtration, washing (twice, each 10-20ml), after drying, obtain the intermediate benzotriazole UV absorbers.Its structural formula is:
4), the sulfonating chlorinating of intermediate benzotriazole UV absorbers
Under the stirring at room, to the intermediate benzotriazole UV absorbers 2.91 g(0.01 mol that are arranged in flask) and the mixed solution of sulfur oxychloride (20 mL) drip DMF(0.2 mL).Then with mixture heating up to 60 ℃ insulation reaction 2 h.Sulfur oxychloride is reclaimed in underpressure distillation, residue is cooled to room temperature, then pour in the mixture of ice and water (150 mL), with remaining a small amount of solid in a small amount of (about 5ml) acetone rinse flask, together pour in the mixture of ice and water, leave standstill rear suction filtration, and be neutral with ice cold water washing leaching cake to filtrate, with filter cake vacuum-drying, get the sulfonating chlorinating product.The structural formula of this sulfonating chlorinating product is:
5), benzotriazole-hindered amine composite light stabilizer is synthetic
In 100 mL there-necked flasks, add sulfonating chlorinating product 1.55 g(0.005mol) and 25mL acetone, in mixed solution, add 0.70g K under constantly stirring
2CO
3With 1,2,2,6 of 0.86g, 6-pentamethyl-piperidine alcohols (0.01 mol).Reaction distilling off solvent acetone after 1 hour under the room temperature, with residuum with 100mL 10%(mass concentration) dilute hydrochloric acid fully wash after, the mixed solution filtration under diminished pressure washes filter cake with water till the filtrate neutrality, must product after the drying, its structural formula is as follows:
Embodiment 2, the stable preparation method of the compound light of a kind of benzotriazole-hindered amine, carry out following steps successively:
1), the diazotization reaction of o-Nitraniline
The o-Nitraniline of 0.3mol is added in the mixed solution of the concentrated hydrochloric acid (hydrochloric acid of mass concentration 〉=35%) of 1.2mol and 20ml water composition, stir 0.5h, 0 ~ 5 ℃ of lower sodium nitrite in aqueous solution 50ml that drips 6.6mol/L, 1h adds, and insulation reaction 2.5h, (being after stopping in the reaction times) removes excessive nitrite thereby add urea behind the arrival reaction end; Terminal point detects with starch potassium iodide paper; When test paper is apparent in 3 seconds when not becoming rapidly blue, show not contained nitrous acid in the reaction product.Filter, get settled solution; This settled solution is final, must contain the solution of o-Nitraniline diazonium salt.
2), the coupled reaction of the diazonium salt of o-Nitraniline and p-hydroxybenzenyl sulfonate
The p-hydroxybenzenyl sulfonate of 0.3mol is dissolved in the NaOH of the 100ml aqueous solution (1mol/L) water, get coupling solution.Under 0 ~ 5 ℃, whole solution that contains the o-Nitraniline diazonium salt of step 1) gained is added drop-wise in the coupling solution, about 1h adds, and continues reaction 2h in 0 ~ 5 ℃, drip and reaction process in, all with the pH value to 8.5 of powdered sodium carbonate conditioned reaction system.Can utilize and ooze the circle method is carried out reaction end to the reaction solution of gained detection (being whether detection reaction is fully finished).
When oozing of reaction solution generates without coloring matter after circle oozes the circle contact with diazo liquid (that is, containing the solution of o-Nitraniline diazonium salt), illustrate that the coupling component reaction is complete in the reaction solution; After the oozing circle and coupling solution and ooze circle and contact of reaction solution, without coloring matter generation, illustrate that diazo component reacts complete in the reaction solution.
Behind the above-mentioned reaction 2h, coupling component and diazo component all react complete in the reaction solution.The product of gained, direct filtration, pickling (hydrochloric acid soln of 5mol/L concentration washes twice, and each consumption is about 10-20ml), oven dry (80 ℃) namely gets coupling product (being adjacent nitro-azo dyestuff intermediate) to constant weight.Its structural formula is:
3), the reduction reaction of coupling product
Adding above-mentioned steps 2 in the 250mL there-necked flask) bolarious coupling product (the being adjacent nitro-azo dyestuff intermediate) 6.46g (0.02mo l) for preparing and get, deionized water 160mL, sodium hydroxide 8.80g(0.22mol), stir, be heated to 80 ℃, minute 3 crowdes of adding thiourea peroxide 10.80g(0.1mol in 5min), reactant becomes yellow by garnet.Behind the insulation reaction 3h, in the frozen water with reactant impouring 150ml, stir, take hydrochloric acid soln (concentration is as 5mol/L) neutralization (to pH as 7), suction filtration, washing, after drying, obtain the intermediate benzotriazole UV absorbers, its structural formula is:
4), the sulfonating chlorinating of intermediate benzotriazole UV absorbers
Under the stirring at room, to the intermediate benzotriazole UV absorbers 2.91 g(0.01 mol that are arranged in flask) and the mixed solution of sulfur oxychloride (20 mL) drip DMF(0.2 mL).Then with mixture heating up to 60 ℃ insulation reaction 2 h.Sulfur oxychloride is reclaimed in underpressure distillation, residue is cooled to room temperature, then pour in the mixture of ice and water (150 mL), with remaining a small amount of solid in a small amount of acetone (about 5ml) rinse flask, together pour in the frozen water, leave standstill rear suction filtration, and be neutral with ice cold water washing leaching cake to filtrate, filter cake vacuum-drying is got the sulfonating chlorinating product.Its structural formula is:
5), benzotriazole-hindered amine composite light stabilizer is synthetic
In 100 mL there-necked flasks, add sulfonating chlorinating product 1.55 g(0.005mol) and 25mL acetone, in mixed solution, add 0.7g K under constantly stirring
2CO
34-amino-2,2,6,6-tetramethylpiperidine (0.01 mol) with 1.56g.Reaction distilling off solvent acetone after 1 hour under the room temperature, with residuum with 100mL 10%(mass concentration) dilute hydrochloric acid fully wash after, the mixed solution filtration under diminished pressure washes filter cake with water till the filtrate neutrality, must product after the drying, its structural formula is as follows:
Compound I, II and I ', III are mixed with 2 * 10
-5The DMF(N of mol/L, dinethylformamide) solution, test its ultraviolet radiation absorption intensity with the ultraviolet-visible light spectrophotometer, the result is as shown in Figure 1.
As shown in Figure 1, Compound I, I ', II and III have stronger ultraviolet absorption ability at UVA and UVB district.In Compound I and I ', introduce the hindered amine fragment, little on uv-absorbing wavelength and the molar extinction coefficient impact of compound.
Contrast experiment 1, existing compound is IV and V at present.
Test 1: compound self light steady testing
With reference to the regulation of GB/T16422.2-1999, compound is made DMF solution (2*10
-5Mol/L), in photo-aging box, carry out artificial acceleration light aging test (xenon lamp 1000 Wxl), 55 ℃ of aging the temperature inside the box.Take a sample behind the aging certain hour, test the variation of photostabilizer content in its solution with the ultra-violet absorption spectrum instrument, the result is as shown in table 1:
Table 1
From upper table 1 as can be known, introduce the light fastness stability that the hindered amine fragment can improve compound in Compound I and I ', this is because the hindered amine fragment to the catching of free radical, strengthens its photostabilizer.Contrast II, III and IV, V find that Compound I I of the present invention and III have higher light fastness stability than compound IV of the prior art and V.
Experiment 2, compound are to the light stabilization of polymer materials
With reference to the regulation of GB/T16422.2-1999, (concentration of acrylic fibers in solution is 1.5g/L, and the concentration of compound in solution is 3*10 with DMF solution to be made in the dissolving of compound and acrylic fibers
-3Mol/L), in photo-aging box, carry out artificial acceleration light aging test (xenon lamp 1000W), 55 ℃ of aging the temperature inside the box.Take a sample behind the aging 12h, with the variation of viscosity-average molecular weight behind the Ubbelohde viscometer test pre-irradiation, the result is as shown in table 2:
Table 2
| Compound | Pre-irradiation Mv | Mv after the irradiation |
| The PAN(acrylic fibers) | 43300 | 32700 |
| I | 43300 | 34200 |
| I’ | 43300 | 35300 |
| II | 43300 | 40100 |
| III | 43300 | 39800 |
| IV | 43300 | 37900 |
| V | 43300 | 38600 |
Illustrate: Compound I I of the present invention and III have better light stability than compound IV of the prior art and V.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (3)
1. benzotriazole-hindered amine composite light stabilizer is characterized in that structural formula is:
Described R
1Be H, CH3, C2H5, OCH3, OC2H5, Cl or Br,
R
2For
Or
,
R
3Be alkyl, alkoxyl group or alkyloyl, R
4Be H, alkyl, alkoxyl group or alkyloyl.
2. benzotriazole according to claim 1-hindered amine composite light stabilizer is characterized in that structural formula is:
3. the preparation method of benzotriazole as claimed in claim 1 or 2-hindered amine composite light stabilizer may further comprise the steps:
1), diazo-coupling reaction:
Adopt diazotisation methods that the o-Nitraniline or derivatives thereof is prepared into its diazonium salt solution, coupled reaction occurs in described diazonium salt solution and p-hydroxybenzenyl sulfonate in 0 ~ 5 ℃, pH value are 8 ~ 10 solution system, get adjacent nitro-azo dyestuff intermediate; The mol ratio of described diazonium salt and p-hydroxybenzenyl sulfonate is 1:0.9 ~ 1.1; The temperature of coupled reaction is 0 ~ 5 ℃, and the time is 1.5 ~ 2.5h;
2), reduction ring-closure reaction:
The adjacent nitro-azo dyestuff intermediate that step 1) is obtained reduces in the solution system of thiourea peroxide and sodium hydroxide, gets the intermediate benzotriazole UV absorbers; The mol ratio of described adjacent nitro-azo dyestuff intermediate and thiourea peroxide, sodium hydroxide is 1:4 ~ 6:8 ~ 14;
The temperature of reduction reaction is 70 ~ 90 ℃, and the time is 2.5 ~ 3.5h;
3), acyl chloride reaction:
With step 2) the intermediate benzotriazole UV absorbers that obtains and sulfur oxychloride as catalyzer, carry out acyl chloride reaction with DMF, gets chloride product intermediate; The mol ratio of described intermediate benzotriazole UV absorbers and sulfur oxychloride is 1:25 ~ 30; The mol ratio of DMF and benzotriazole UV absorbers is 1:3 ~ 6;
The temperature of acyl chloride reaction is 50 ~ 70 ℃, and the time is 1.5 ~ 2.5h;
4), alcoholization or aminating reaction:
The chloride product intermediate that step 3) is obtained is dissolved in the acetone, does acid binding agent with salt of wormwood, reacts with hindered amine light stabilizer, gets benzotriazole-hindered amine composite light stabilizer; The mol ratio of described chloride product intermediate and salt of wormwood, hindered amine as light stabilizer is 1:1 ~ 2:1 ~ 2;
Temperature of reaction is room temperature, and the time is 0.5 ~ 1.5h.
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| CN105040428A (en) * | 2015-08-29 | 2015-11-11 | 浙江理工大学 | Reactive light stabilizer suitable for protein fibers and preparing method thereof |
| CN105712981A (en) * | 2016-04-15 | 2016-06-29 | 佛山市聚成生化技术研发有限公司 | Hindered-amine light stabilizing agent and synthesizing method thereof |
| CN105801561A (en) * | 2016-04-15 | 2016-07-27 | 佛山市聚成生化技术研发有限公司 | Novel hindered amine light stabilizer and synthesis method thereof |
| CN111087705A (en) * | 2020-03-09 | 2020-05-01 | 深圳汉唐材料有限责任公司 | Foaming composition, foaming material, preparation method and application thereof |
| CN111205510A (en) * | 2020-02-13 | 2020-05-29 | 西安工业大学 | Dual-functional ultraviolet absorbent and preparation method thereof |
| CN115947719A (en) * | 2022-12-07 | 2023-04-11 | 宿迁市振兴化工有限公司 | Tetramethyl piperidine derivative light stabilizer and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040428A (en) * | 2015-08-29 | 2015-11-11 | 浙江理工大学 | Reactive light stabilizer suitable for protein fibers and preparing method thereof |
| CN105712981A (en) * | 2016-04-15 | 2016-06-29 | 佛山市聚成生化技术研发有限公司 | Hindered-amine light stabilizing agent and synthesizing method thereof |
| CN105801561A (en) * | 2016-04-15 | 2016-07-27 | 佛山市聚成生化技术研发有限公司 | Novel hindered amine light stabilizer and synthesis method thereof |
| CN105712981B (en) * | 2016-04-15 | 2018-06-19 | 双键化工（泰兴）有限公司 | A kind of hindered amine light stabilizer and its synthetic method |
| CN111205510A (en) * | 2020-02-13 | 2020-05-29 | 西安工业大学 | Dual-functional ultraviolet absorbent and preparation method thereof |
| CN111087705A (en) * | 2020-03-09 | 2020-05-01 | 深圳汉唐材料有限责任公司 | Foaming composition, foaming material, preparation method and application thereof |
| CN111087705B (en) * | 2020-03-09 | 2023-02-03 | 深圳汉唐材料有限责任公司 | Foaming composition, foaming material, preparation method and application thereof |
| CN115947719A (en) * | 2022-12-07 | 2023-04-11 | 宿迁市振兴化工有限公司 | Tetramethyl piperidine derivative light stabilizer and preparation method thereof |
| CN115947719B (en) * | 2022-12-07 | 2024-02-20 | 宿迁市振兴化工有限公司 | Tetramethyl piperidine derivative light stabilizer and preparation method thereof |
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| CN103012843B (en) | 2014-04-16 |
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