CN101845013B - Multi-hindered piperidyl-containing hindered amide compound used for light stabilizer and preparation method thereof - Google Patents
Multi-hindered piperidyl-containing hindered amide compound used for light stabilizer and preparation method thereof Download PDFInfo
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- YBWODHHWEALNHC-UHFFFAOYSA-N CC(C)(C1)N(Cc2ccccc2)C(C)(C)CC1OC(CCC(CCC(OC1CC(C)(C)N(Cc2ccccc2)C(C)(C)C1)=O)(C(OC1CC(C)(C)N(Cc2ccccc2)C(C)(C)C1)=O)C(OC1CC(C)(C)N(Cc2ccccc2)C(C)(C)C1)=O)=O Chemical compound CC(C)(C1)N(Cc2ccccc2)C(C)(C)CC1OC(CCC(CCC(OC1CC(C)(C)N(Cc2ccccc2)C(C)(C)C1)=O)(C(OC1CC(C)(C)N(Cc2ccccc2)C(C)(C)C1)=O)C(OC1CC(C)(C)N(Cc2ccccc2)C(C)(C)C1)=O)=O YBWODHHWEALNHC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a multi-hindered piperidyl-containing hindered amide compound used for a light stabilizer, which is represented by a general formula (I). The hindered amide compound of the invention is provided with a plurality of hindered piperidyls; and therefore, heat resistance, compatibility and extraction resistance are enhanced when the hindered amide compound is used as the light stabilizer. The invention also discloses a preparation method for the multi-hindered piperidyl-containing hindered amide compound used for the light stabilizer. In the general formula described in the specification, R1 and R2 are Hs or alkyls of C1 to C4; R4 is an H, an alkyl of C1 to C8, or a phenmethyl; and R5 is the H, an oxygen radical, -OH, -Cl, -CH2CN, the alkyl of C1 to C8, an alkoxyl of C1 to C8, a hydroxyl-substituted alkoxyl of C1 to C8, a cycloalkyloxy of C5 to C12, an alkenyl of C3 to C6, or a phenyl-substituted alkyl of C1 to C3.
Description
Technical field
The present invention relates to a kind of hindered amine compound and preparation method thereof, relate in particular to a kind of hindered amine compound that contains many hindered piperidines base that is used for photostabilizer and preparation method thereof.
Background technology
Photostabilizer is to suppress or slow down owing to photooxidation makes macromolecular material the auxiliary agent of degraded takes place.Therefore, the adding of photostabilizer can effectively improve fast light, the oxygen aging performance of macromolecular material, prolongs outdoor work-ing life.
Hindered amine light stabilizer (HALS) is the efficiency light stablizer of excellent property.Develop rapidly along with macromolecular material; Especially increasing to the outdoor goods scope of application, relate to nearly all macromolecular material Application Areas, be specially adapted to macromolecular materials such as polyolefine, PS, urethane; Its effect is the several times of traditional stablizer; And with ultraviolet absorbers and inhibitor good synergy is arranged, and replace traditional photostabilizer to become the main flow of consumption gradually, accounted for the over half of world's photostabilizer consumption at present.
The general molecular weight of traditional HALS, functional group density are lower, in the bigger goods of specific surface areas such as some fibre, owing to the lower relative deficiency that causes aspects such as anti-migration, anti-volatilization and resistant to extraction of its molecular weight.
Therefore, that need a family macromolecule amount and hindered amine compound that is used for photostabilizer that functional group density increases and the method for preparing this photostabilizer simply, at low cost.
Summary of the invention
An object of the present invention is to provide a kind of hindered amine compound that contains many hindered piperidines base that is used for photostabilizer.
Another object of the present invention provides the preparation method of the hindered amine compound that contains many hindered piperidines base that is used for photostabilizer.
Hindered amine compound of the present invention is represented by general formula (I):
Wherein: R
1, R
2Be H or C
1-C
4Alkyl;
R
4Be H, C
1-C
8Alkyl or benzyl;
R
5For H, O radical (O) ,-OH ,-Cl ,-CH
2CN, C
1-C
8Alkyl, C
1-C
8Alkoxyl group, by the substituted C of hydroxyl
1-C
8Alkoxyl group, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, by the substituted C of phenyl
1-C
3Alkyl.
In more particular embodiment of the present invention, R
1, R
2Be H, CH
3, CH
3CH
2R
4Be H, CH
3Or benzyl; R
5For H, O radical ,-OH ,-Cl, CH
3, octyloxy, propenyl, by the substituted methyl of phenyl.
The preparation method who is used for the hindered amine compound that contains many hindered piperidines base of photostabilizer provided by the invention comprises step:
(a) with diester malonate and the α that is represented by formula (III) by formula (II) expression, the beta-unsaturated carboxylic acid ester is a starting raw material, in the presence of addition reaction catalyst, in solvent, obtains the adduct by formula (IV) expression through addition reaction,
Its Chinese style (II) is:
R
3Be C
1-C
4Alkyl;
Formula (III) is:
R wherein
1, R
2Be H or C
1-C
4Alkyl; R
3Be C
1-C
4Alkyl;
Formula (IV) does
R wherein
1, R
2Be H or C
1-C
4Alkyl; R
3Be C
1-C
4Alkyl;
And
(b) with said adduct and the substituted 4-hydroxy piperidine of representing by formula V under catalyzer, under the situation of further adding solvent, carry out transesterification reaction and obtain the described hindered amine compound of formula (I),
Formula V does
R wherein
4Be H, C
1-C
8Alkyl or benzyl;
R
5For H, O oxyradical ,-OH ,-Cl ,-CH
2CN, C
1-C
8Alkyl, C
1-C
8Alkoxyl group, by the substituted C of hydroxyl
1-C
8Alkoxyl group, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, by the substituted C of phenyl
1-C
3Alkyl.
In more particular embodiment of the present invention, the method comprising the steps of:
(a) mol ratio is 1: 2.0-1: 2.4 diester malonate (like methyl-malonate, ethyl malonate etc.) and α; The beta-unsaturated carboxylic acid ester is in the presence of the catalyzer of the 1.0%-5.0% of reactant total mass; Add solvent and react, at 0 ℃-80 ℃, under the normal pressure; Reacted 4-48 hour, and obtained adduct;
(b) mol ratio is 1: 4.0-1: 4.8 the first step adduct and substituted 4-hydroxy piperidine are in the presence of the catalyzer of the 0.01%-5.0% of reactant total mass; Add solvent, normal pressure, 60 ℃-210 ℃ of temperature of reaction; Reacted 4-48 hour; Make to react completely, recrystallization promptly obtains title product.
Solvent in the step (a) can adopt MeOH, EtOH, H
2O, MeCN, THF, C
6H
6Deng.
Catalyzer in the step (a) can adopt alkali metal hydroxide, alkalimetal hydride, alkali metal alcoholates, alkali metal amino compound, alkaline carbonate etc., and basic metal comprises lithium, sodium, potassium etc.Wherein preferred NaOMe, KOH (adding Tetrabutyl amonium bromide during use), K
2CO
3(adding Tetrabutyl amonium bromide during use), LiNH
2, NaB (OMe)
4Deng.
Solvent in the step (b) is sherwood oil, normal heptane, octane, benzene,toluene,xylene, hexanaphthene, THF etc., and solvent load is the adduct in the step (a) of 1-5L/mol.
Catalyzer in the step (b) is alkali metal hydroxide, alkalimetal hydride, alkali metal alcoholates, alkali metal amino compound, tetrabromo-isopropyl phthalate or di-n-octyltin oxide etc., and basic metal comprises lithium, sodium, potassium etc.Wherein preferred LiNH
2, NaOMe, NaOH, KH, Ti [OCH (CH
3)
2]
4Or (C
8H
17)
2SnO etc.
Product of transesterification reaction recrystallization solvent for use is in the step (b): sherwood oil, hexanaphthene, normal heptane, octane, benzene,toluene,xylene etc.
Hindered amine compound provided by the invention has many hindered piperidines base, has therefore increased its functional group density, can increase thermotolerance, consistency and resistant to extraction when it is used as photostabilizer.The hindered amine compound that contains many hindered piperidines base that is used for photostabilizer of the present invention is after the manufacturing of adding polymkeric substance to, and resulting macromolecular material product colour is shallow, and transmittance is good.
Preparing method provided by the invention, by product is few, and technology is simple, and cost is low.
Reaction formula of the present invention is following:
Embodiment
Through can understanding aforementioned content better with reference to each following embodiment, each embodiment is contemplated to be exemplary and does not expect to limit scope of the present invention.
Embodiment 1:
(1) in exsiccant 500mL single port flask, adds methyl-malonate (66.05g; 0.50mol) and the methanol solution of 29% sodium methylate (20.49g, 0.11mol), slow dropwise addition of acrylic acid methyl esters (90.39g under 15 ℃ of-20 ℃ of stirrings; 1.05mol), dripped off in 30 minutes.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 15 hours afterreaction liquid is formed and is no longer included obvious variation, stopped reaction is poured reaction solution among the 1M HCl into, separatory, water layer use extracted with diethyl ether, merging organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2,2-dimethoxycarbonyl ethyl methyl-malonate, yield 86.55%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add 2, and 2-dimethoxycarbonyl ethyl methyl-malonate (152.15g, 0.50mol), 1; 2,2,6; 6-pentamethyl--4-piperidines alcohol (359.73g, 2.10mol) and the 1L octane make solvent, in reaction solution, add the 2.56g tetrabromo-isopropyl phthalate; Be heated to 130 ℃, TLC follows the tracks of reaction, and afterreaction finished in 14 hours.Underpressure distillation obtains thick product.Thick product is used the octane recrystallization, obtains white product, yield 83.76%.Structural formula is:
Embodiment 2:
(1) in exsiccant 500mL single port flask, adds ethyl malonate (80.09g; 0.50mol), the saturated aqueous solution of Pottasium Hydroxide (6.16g, 0.11mol) and 100mL ethanol, slow dropwise addition of acrylic acid ethyl ester (110.13g under 15～20 ℃ of stirrings; 1.10mol), dripped off in 30 minutes.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 17 hours afterreaction liquid is formed and is no longer included obvious variation, stopped reaction is poured reaction solution among the 1M HCl into, separatory, water layer use extracted with diethyl ether, merging organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2,2-diethoxy carbonyl ethyl malonic acid diethylester, yield 87.20%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add 2, and 2-diethoxy carbonyl ethyl malonic acid diethylester (180.20g, 0.50mol), 2; 2,6,6-tetramethyl--4-piperidines alcohol (322.36g; 2.05mol) and the 1L octane make solvent, in reaction solution, add the 2.65g tetrabromo-isopropyl phthalate, be heated to 130 ℃; TLC follows the tracks of reaction, and afterreaction finished in 14 hours.Underpressure distillation obtains thick product.Thick product is used the octane recrystallization, obtains white product, yield 82.75%.Structural formula is:
Embodiment 3:
(1) in exsiccant 500mL single port flask, adds methyl-malonate (66.06g; 0.50mol), salt of wormwood (69.10g; 0.50mol), Tetrabutyl amonium bromide (1.84g, 0.005mol) and 200mL benzene, slow dropwise addition of acrylic acid ethyl ester (110.13g under 15～20 ℃ of stirrings; 1.10mol), dripped off in 30 minutes.After move to 80 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 10 hours afterreaction liquid is formed and is no longer included obvious variation; Stopped reaction is reduced to room temperature, filters; Concentrating under reduced pressure gets product 2,2-diethoxy carbonyl ethyl malonic acid dimethyl ester, yield 84.50%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add 2, and 2-diethoxy carbonyl ethyl malonic acid dimethyl ester (166.18g, 0.50mol), 1-octyloxy-2; 2,6,6-tetramethyl--4-piperidines alcohol (613.76g; 2.15mol) and 1L sherwood oil (60～90 ℃ of boiling ranges) make solvent, in reaction solution, add the 23.40g Lithamide, be heated to 85 ℃; TLC follows the tracks of reaction, and afterreaction finished in 30 hours.Underpressure distillation obtains thick product.Thick product is used the sherwood oil recrystallization, obtains white product, yield 80.17%.Structural formula is:
Embodiment 4:
(1) in exsiccant 500mL single port flask, add the propanedioic acid di-n-propyl ester (94.11g, 0.50mol), (2.76g, 0.12mol) and 200mL methyl alcohol, 15～20 ℃ of stirrings slowly drip M Crs down, and (120.14g 1.20mol), dripped off Lithamide in 30 minutes.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 11 hours afterreaction liquid is formed and is no longer included obvious variation; Stopped reaction is poured reaction solution in the 100mL zero(ppm) water into separatory; Water layer is used extracted with diethyl ether, merges organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2,2-two (1-methyl-2-methoxycarbonyl) ethyl malonic acid di-n-propyl ester, yield 78.50%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add 2, and 2-two (1-methyl-2-methoxycarbonyl) ethyl malonic acid di-n-propyl ester (194.23g, 0.50mol), 1-chloro-2; 2,6,6-tetramethyl--4-piperidines alcohol (431.33g; 2.25mol) and 1.5L benzene make solvent, in reaction solution, add the 19.30g sodium methylate, be heated to 80 ℃; TLC follows the tracks of reaction, and afterreaction finished in 37 hours.Underpressure distillation obtains thick product.Thick product is used the hexanaphthene recrystallization, obtains white product, yield 72.36%.Structural formula is:
Embodiment 5:
(1) in exsiccant 500mL single port flask, adds propanedioic acid di-n-butyl (108.14g; 0.50mol) tetramethoxy boron sodium (18.95g, 0.12mol) and 200mL methyl alcohol, 15～20 ℃ of stirrings slowly drip TEB 3K (115.14g down; 1.15mol), dripped off in 30 minutes.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 20 hours afterreaction liquid is formed and is no longer included obvious variation, stopped reaction is poured reaction solution among the 1M HCl into, separatory, water layer use extracted with diethyl ether, merging organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2,2-two (2-methyl-2-methoxycarbonyl) ethyl malonic acid di-n-butyl, yield 75.22%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add 2, and 2-two (1-methyl-2-methoxycarbonyl) ethyl malonic acid di-n-butyl (208.26g, 0.50mol), 1-propenyl-2; 2,6,6-tetramethyl--4-piperidines alcohol (359.73g; 2.10mol) and 0.8L cyclohexane give solvent, in reaction solution, add the 20.16g di-n-octyltin oxide, be heated to 80 ℃; TLC follows the tracks of reaction, and afterreaction finished in 40 hours.Remove solvent under reduced pressure, obtain thick product.Thick product is used the hexanaphthene recrystallization, obtains white product, yield 70.07%.Structural formula is:
Embodiment 6:
(1) in exsiccant 500mL single port flask, adds propanedioic acid di-n-propyl ester (94.11g; 0.50mol), sodium hydride (2.40g, 0.10mol) and the 200mL THF, the positive butyl ester (134.58g of slow dropwise addition of acrylic acid under 15～20 ℃ of stirrings; 1.05mol), dripped off in 30 minutes.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 17 hours afterreaction liquid is formed and is no longer included obvious variation; Stopped reaction is poured reaction solution in the 100mL zero(ppm) water into separatory; Water layer is used extracted with diethyl ether, merges organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2,2-two positive butoxy carbonyl ethyl malonic acid di-n-propyl esters, yield 70.70%.
(2) in the 2L four-hole bottle, add 2, and 2-two positive butoxy carbonyl ethyl malonic acid di-n-propyl esters (222.28g, 0.50mol), 1-oxyradical-2; 2,6,6-tetramethyl--4-piperidines alcohol (378.93g; 2.20mol) and 1L toluene make solvent, in reaction solution, add the 15.03g potassium hydride KH, be heated to 110 ℃; TLC follows the tracks of reaction, and afterreaction finished in 35 hours.Underpressure distillation gets thick product.Thick product is used the octane recrystallization, gets product, yield 61.30%.Structural formula is:
Embodiment 7:
(1) in exsiccant 500mL single port flask, add NSC 406716 (94.11g, 0.50mol), (2.53g, 0.11mol) and 200mL methyl alcohol, (125.55g 1.10mol), dripped off slow dropwise addition of acrylic acid n-propyl under 15～20 ℃ of stirrings Lithamide in 30 minutes.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 11 hours afterreaction liquid is formed and is no longer included obvious variation; Stopped reaction is poured reaction solution in the 100mL zero(ppm) water into separatory; Water layer is used extracted with diethyl ether, merges organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2, the 2-two positive third oxygen carbonyl ethyl malonic acid diisopropyl esters, yield 81.00%.
(2) in the 2L four-hole bottle, add 2, and the 2-two positive third oxygen carbonyl ethyl malonic acid diisopropyl esters (208.26g, 0.50mol), 1-benzyl-2; 2,6,6-tetramethyl--4-piperidines alcohol (519.50g; 2.10mol) and the 1L normal heptane make solvent, in reaction solution, add 36.39g sodium hydroxide, be heated to 100 ℃; TLC follows the tracks of reaction, and afterreaction finished in 27 hours.Remove solvent under reduced pressure, obtain thick product.Thick product is used the octane recrystallization, gets product, yield 69.05%.Structural formula is:
Embodiment 8:
(1) in exsiccant 500mL single port flask, adds methyl-malonate (66.06g; 0.50mol), salt of wormwood (69.10g; 0.50mol), Tetrabutyl amonium bromide (1.84g, 0.005mol) and 200mL benzene, 15～20 ℃ of stirrings slowly drip n propyl methacrylate (147.40g down; 1.15mol), dripped off in 30 minutes.After move to 80 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 18 hours afterreaction liquid is formed and is no longer included obvious variation; Stopped reaction; Reduce to room temperature, filter, concentrating under reduced pressure gets product 2; 2-two (the positive third oxygen carbonyl of 2-methyl-2-) ethyl malonic acid dimethyl ester, yield 64.90%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add 2, and the 2-two positive third oxygen carbonyl ethyl malonic acid dimethyl esters (194.23g, 0.50mol), 2; 2,3,6; 6-pentamethyl--4-piperidines alcohol (322.36g, 2.05mol) and 0.8L YLENE make solvent, in reaction solution, add the 15.50g tetra isopropyl titanate; Be heated to 140 ℃, TLC follows the tracks of reaction, and afterreaction finished in 25 hours.Underpressure distillation obtains thick product.Thick product is used the sherwood oil recrystallization, obtains white product, yield 71.15%.Structural formula is:
Embodiment 9:
(1) (80.09g, 0.50mol) (2.53g, 0.11mol) and 200mL methyl alcohol, 15～20 ℃ of stirrings slowly drip Jia Jibingxisuanyizhis down, and (115.14g 1.15mol), dripped off Lithamide in 30 minutes in exsiccant 500mL single port flask, to add ethyl malonate.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 15 hours afterreaction liquid is formed and is no longer included obvious variation; Stopped reaction is poured reaction solution in the 100mL zero(ppm) water into separatory; Water layer is used extracted with diethyl ether, merges organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2,2-two (2-methyl-2-ethoxycarbonyl) ethyl malonic acid diethylester, yield 72.00%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add two adducts (194.23g, 0.50mol), 2,2; 6,6-tetramethyl--3-benzyl-4-piperidines alcohol (566.65g, 2.30mol) and the 0.8L octane make solvent; In reaction solution, add the 22.83g di-n-octyltin oxide; Be heated to 130 ℃, TLC follows the tracks of reaction, and afterreaction finished in 30 hours.Underpressure distillation obtains thick product.Thick product is used the hexanaphthene recrystallization, yield 62.95%.Structural formula is:
Embodiment 10:
(1) in exsiccant 500mL single port flask, adds methyl-malonate (66.05g; 0.50mol) and the methanol solution of 29% sodium methylate (22.34g, 0.12mol), 15～20 ℃ of stirrings slowly drip ethylacrylic acid methyl esters (132.26g down; 1.15mol), dripped off in 30 minutes.After move to 60 ℃ oil bath reacting by heating, adopt the TLC monitoring in the reaction process, about 17 hours afterreaction liquid is formed and is no longer included obvious variation, stopped reaction is poured reaction solution among the 1M HCl into, separatory, water layer use extracted with diethyl ether, merging organic layer, anhydrous MgSO
4Drying is filtered, and concentrating under reduced pressure gets product 2,2-two (2-ethyl-2-methoxycarbonyl) ethyl malonic acid dimethyl ester, yield 79.20%.
(2) in the 2L four-hole bottle that the azeotropic dehydration device is housed, add two adducts (180.20g, 0.50mol), 2,2; 6,6-tetramethyl--1,4-dihydroxyl piperidines (372.49g; 2.15mol) and the 1L normal heptane make solvent, in reaction solution, add the 16.58g Lithamide, be heated to 100 ℃; TLC follows the tracks of reaction, and afterreaction finished in 20 hours.Underpressure distillation obtains thick product.Thick product is used the normal heptane recrystallization, yield 77.55%.Structural formula is:
With PE is sample, adds the compound or other auxiliary agents that make among above-mentioned each embodiment respectively, like haplotype low molecular weight hindered amine photostabilizer Tinuvin 770, and promptly two (2,2,6,6-tetramethyl--4-piperidyl) sebates; Polymerized hindered amine light stabilizer Tinuvin 622; Aggretion type high molecular weight hindered amine light stabilizer Chimassorb 944 from Ciba-Geigy company; The Irganox B215 of the compound of antioxidant 1010 and inhibitor 168.
PE sample to such preparation has carried out oxidation induction period test and fluorescent ultraviolet lamp burn-in test, and the result is presented at (each compound number is corresponding to the embodiment of corresponding numbering) in table 1 and the table 2 respectively.
The oxidation induction period test: this test is carried out on DSC 200PC apparatus for thermal analysis, connects oxygen and nitrogen, opens the flow that the gas shifter is regulated two kinds of gases respectively, makes it all to reach (50 ± 5) ml/min, switches to nitrogen then.The opening aluminum dish that will fill (15 ± 0.5) mg sample places on the sample supporting rack of thermal analyzer, is warming up to (200 ± 0.1) ℃ with the speed of 20 ℃/min, and makes this homo(io)thermism, the opening entry heating curve.After keeping constant temperature 5min, switch to oxygen rapidly.When recording oxidation heat liberation termination test when reaching peak on the heating curve.
The fluorescent ultraviolet lamp burn-in test: this test is to carry out according to the requirement of GB/T 16422.1-2006, and it adopts UV-A365 fluorescent ultraviolet lamp irradiation sample, power of lamp tube 300W, fluorescent tube length 1200mm, ultraviolet wavelength 260nm～360nm.The sample exposure is in completely in the irradiation range, on sample end 260mm scope and the fluorescent tube arrangement plane limit in the 50mm scope, and 60 ℃ of irradiation temperatures.The every irradiation of sample 2h spray zero(ppm) water is in sample surfaces 2h.Shine sampling and testing stretch function behind the certain hour respectively, calculate elongation at break and extension at break retention rate.
Table 1 has added the oxidation induction period test result of the PE sample of different auxiliary agents
| Sample | Compound 1 | Compound 3 | Compound 6 | Compound 8 | Tinuvin 770 | Chimassor b?944 | Tinuvin 622 | Irganox B215 |
| Oxidation induction period (min) | 24.71 | 33.12 | 48.10 | 22.52 | 10.58 | 20.90 | 13.40 | 26.80 |
Table 2 has added the fluorescent ultraviolet lamp ageing test result of the PE sample of different auxiliary agents
| Sample | Compound 1 | Compound 3 | Compound 6 | Compound 8 | Tinuvin?770 | Chimassorb?944 |
| The extension at break retention rate (%, PE) | ?53 | ?62 | ?67 | 49 | 49 | 40 |
Can find out that from the result of table 1 compound 1,3,6 and 8 oxidation induction period are apparently higher than the sample that has added polymerized hindered amine light stabilizer Chimassorb 944 and Tinuvin 622.Compound 3 and 6 oxidation induction period are higher than inhibitor Irganox B215 commonly used.It is thus clear that in the PE material, the antioxidant effect that we design the synthetic hindered amine as light stabilizer is higher than inhibitor Irganox B215.
Can intuitively find out the effect of photostabilizer from the data of table 2 to material.When illumination after 10 hours, compound 1,3,6 and 8 extension at break retention rate numerical value are respectively 53%, 62%, 67% and 49%.
Can learn through above analysis; The hindered amine compound that contains many hindered piperidines base of the present invention can make the performance of PE material be able to good maintenance as photostabilizer; And be superior to traditional polymerized hindered amine light stabilizer Chimassorb 944 and haplotype hindered amine as light stabilizer Tinuvin 770, thereby play the effect in work-ing life of better prolongation material.Because our power of the fluorescent ultraviolet lamp selected for use is 300W, is higher than GB/T 16422 desired 40W, thus sample in the fluorescence climate box except that receiving the photoaging effect, the thermal ageing effect is also clearly.But under identical test conditions, the hindered amine compound that contains many hindered piperidines base of the present invention shows better performance when being used as photostabilizer.
Claims (8)
1. hindered amine compound that contains many hindered piperidines base that is used for photostabilizer, it is represented by general formula (I):
Wherein
R
1, R
2Be H or C
1-C
4Alkyl;
R
4Be H, C
1-C
8Alkyl or benzyl;
R
5For H, O radical ,-OH ,-Cl ,-CH
2CN, C
1-C
8Alkyl, C
1-C
8Alkoxyl group, by the substituted C of hydroxyl
1-C
8Alkoxyl group, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, by the substituted C of phenyl
1-C
3Alkyl.
2. hindered amine compound as claimed in claim 1, wherein R
1, R
2Be H, CH
3, CH
3CH
2R
4Be H, CH
3Or benzyl; R
5For H, O radical ,-OH ,-Cl, CH
3, octyloxy, propenyl, by the substituted methyl of phenyl.
3. hindered amine compound as claimed in claim 1, wherein R
1, R
2, R
4And R
5All be H.
4. one kind prepares the method that is used for the hindered amine compound that contains many hindered piperidines base of photostabilizer as claimed in claim 1, and wherein said method comprises step:
(a) with diester malonate and the α that representes by formula (III) by formula (II) expression; The beta-unsaturated carboxylic acid ester is a starting raw material; In the presence of addition reaction catalyst; In solvent, obtain the adduct by formula (IV) expression through addition reaction, the described catalyzer of this step is selected from alkali metal hydroxide, alkalimetal hydride, alkali metal alcoholates, alkali metal amino compound, alkaline carbonate and NaB (OCH
3)
4, said basic metal is lithium, sodium or potassium,
Its Chinese style (II) is:
R wherein
3Be C
1-C
4Alkyl;
Formula (III) is:
R wherein
1, R
2Be H or C
1-C
4Alkyl; R
3Be C
1-C
4Alkyl;
Formula (IV) does
R wherein
1, R
2Be H or C
1-C
4Alkyl; R
3Be C
1-C
4Alkyl; And
(b) with said adduct and the substituted 4-hydroxy piperidine of representing by formula V in the presence of catalyzer; Further adding under the situation of solvent; Carry out transesterification reaction and obtain the described hindered amine compound of formula (I); The described catalyzer of this step is selected from alkali metal ammonia compound, alkali metal alcoholates, alkalimetal hydride, alkali metal hydroxide, tetrabromo-isopropyl phthalate and di-n-octyltin oxide, and said basic metal is lithium, sodium or potassium
Formula V is:
R wherein
4Be H, C
1-C
8Alkyl or benzyl;
R
5For H, O oxyradical ,-OH ,-Cl ,-CH
2CN, C
1-C
8Alkyl, C
1-C
8Alkoxyl group, by the substituted C of hydroxyl
1-C
8Alkoxyl group, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, by the substituted C of phenyl
1-C
3Alkyl.
5. method as claimed in claim 4, wherein said diester malonate and said α, the mol ratio of beta-unsaturated carboxylic acid ester is 1: 2.0-1: 2.4; The mol ratio of said adduct and said substituted 4-hydroxy piperidine is 1: 4.0-1: 4.8.
6. method as claimed in claim 4, wherein in said step (a), said solvent is selected from CH
3OH, H
2O, CH
3CN and THF.
7. method as claimed in claim 4, wherein in said step (a), said catalyzer is selected from NaOCH
3, KOH, K
2CO
3, LiNH
2And NaB (OCH
3)
4
8. method as claimed in claim 4, wherein in said step (b), said solvent is selected from sherwood oil, normal heptane, octane, benzene,toluene,xylene, hexanaphthene and THF.
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| CN105859607B (en) * | 2016-04-05 | 2018-05-15 | 浙江理工大学 | Benzophenone-hindered amine composite light stabilizer and preparation method thereof |
| CN111393355A (en) * | 2020-04-13 | 2020-07-10 | 宿迁联盛科技股份有限公司 | Preparation method of novel efficient end group hindered amine light stabilizer |
| CN112175233B (en) * | 2020-10-15 | 2022-01-04 | 宿迁联盛科技股份有限公司 | Hindered amine light stabilizer and preparation method and application thereof |
| CN116333523A (en) * | 2021-12-17 | 2023-06-27 | 天津利安隆新材料股份有限公司 | Dendritic N-alkoxy hindered amine light stabilizer, preparation method and application thereof |
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| US4556714A (en) * | 1983-01-24 | 1985-12-03 | Ciba-Geigy Corporation | N-(Polyalkylpiperidinyl)-carbamates of polyols |
| US5180830A (en) * | 1991-04-24 | 1993-01-19 | Himont Incorporated | Process for preparing hindered amine light stabilizers |
| IT1264945B1 (en) * | 1993-07-16 | 1996-10-17 | Ciba Geigy Spa | PIPERIDINE COMPOUNDS SUITABLE FOR USE AS STABILIZERS FOR ORGANIC MATERIALS |
| CN1219534A (en) * | 1997-12-12 | 1999-06-16 | 中国科学院化学研究所 | Preparation method for polymerized hindered amine light stabilizer monomer |
| CN101168527A (en) * | 2007-11-16 | 2008-04-30 | 中国科学院新疆理化技术研究所 | Undecane to pentadecane dicarboxylic acid di(2,2,6,6-tetramethylpiperidinyl)ester and use thereof |
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