CN101381477B - Hindered amine light stabilizer and synthetic method thereof - Google Patents
Hindered amine light stabilizer and synthetic method thereof Download PDFInfo
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- CN101381477B CN101381477B CN2008101523383A CN200810152338A CN101381477B CN 101381477 B CN101381477 B CN 101381477B CN 2008101523383 A CN2008101523383 A CN 2008101523383A CN 200810152338 A CN200810152338 A CN 200810152338A CN 101381477 B CN101381477 B CN 101381477B
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- 150000001412 amines Chemical class 0.000 title claims abstract description 25
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 25
- 238000010189 synthetic method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- -1 diamine compound Chemical class 0.000 claims abstract description 22
- HDOWRFHMPULYOA-UHFFFAOYSA-N piperidin-4-ol Chemical compound OC1CCNCC1 HDOWRFHMPULYOA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 238000007259 addition reaction Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000001953 recrystallisation Methods 0.000 claims description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 6
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000003287 bathing Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 125000005936 piperidyl group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000004440 column chromatography Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 102000054766 genetic haplotypes Human genes 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LBLUDXKMPPLXRP-UHFFFAOYSA-N CCCCC(C(CC)(N)N)=C=O.[O] Chemical compound CCCCC(C(CC)(N)N)=C=O.[O] LBLUDXKMPPLXRP-UHFFFAOYSA-N 0.000 description 1
- LZFZMEIWBTXVFQ-UHFFFAOYSA-N CCNCCN=C=O.[O] Chemical compound CCNCCN=C=O.[O] LZFZMEIWBTXVFQ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- HDGOOWNUCOLMNZ-UHFFFAOYSA-N nitroxyl;2,2,6,6-tetramethylpiperidin-4-ol Chemical group O=N.CC1(C)CC(O)CC(C)(C)N1 HDGOOWNUCOLMNZ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Hydrogenated Pyridines (AREA)
Abstract
The invention belongs to novel hindered amine light stabilizer and a synthesizing method thereof. The method comprises the following steps: a diamine compound reacts with alpha, beta-unsaturated carboxylic ether to produce an additional product; the diamine compound and the alpha, beta-unsaturated carboxylic ether with the mol ratio of between 1:4.0 and 1:5.0 react for 4 to 48 hours at a temperature of between 0 and 70 DEG C under normal pressure to obtain an additional product; the additional product in the second step with the mol ratio of between 1:4.0 and 1:5.0 and substitutional 4-hydroxypiperidine are added to a reactor, and are subjected to oil bathing for 4 to 48 hours at a temperature of between 30 and 210 DEG C under normal temperature, with the addition of catalyst which is 0.01 to 5.0 percent against total mass of that of the reactant to make the reaction completed, the reactant is recrystallized to produce a target product. The hindered amine light stabilizer designed by the invention is obtained by using the diamine compound and the alpha, beta-unsaturated carboxylic ether as initial raw materials which are subjected to addition reaction, and carry out interchange esterification with the substitutional 4-hydroxypiperidine. The hindered amine light stabilizer has multiple hindered piperidyl, and improves the heat resistance, compatibility and extraction resistance. The method for synthesizing the hindered amine light stabilizer has the advantages of simple operation, light color of the product and good light transmittance.
Description
Technical field
The invention belongs to the design and the preparation method of photostabilizer, is novel hindered amine light stabilizer and synthetic method thereof specifically.
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 new and effective photostabilizer 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, polystyrene, urethane, its effect is the several times of traditional stablizer, and with ultraviolet absorbers and oxidation 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.
Molecular weight is lower traditional HALS (as described in the patent DE2258752), 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, high molecular becomes the development trend of HALS, and increases after the molecular weight, and except light stability was significantly improved, the HALS security also improved.Aggretion type high molecular HALS such as US20070100034, owing to contain the inflexible triazine ring in the molecule, relatively poor with the high molecular products consistency, limited its use range.Therefore, the exploitation of haplotype linear high molecular weight HALS comes into one's own all the more.
There are some researches show that two hindered amine piperidines are more more effective than single hindered amine piperidyl hindered amine as light stabilizer, major cause is that its functional group density is bigger in the hindered amine as light stabilizer of two amidos that are obstructed.Based on above consideration, we have designed and synthesized a class and have had the linear hindered amine as light stabilizer of haplotype of many hindered piperidines base, and have obtained better light stability.
Summary of the invention
The objective of the invention is to design the novel hindered amine as light stabilizer of a class, with the thermostability that increases it, resistant to extraction and with the consistency of the macromolecular material of being protected, reach better light stability.Another object of the present invention provides the preparation method of this class hindered amine as light stabilizer.
Hindered amine as light stabilizer of the present invention is characterized in that structural formula is as follows:
Wherein: R
1Be C
1～C
18Alkylidene group, C
5～C
6Cycloalkylidene, C
5～C
6The cycloalkylidene dimethylene or by the C of 1,2 or 3 Sauerstoffatom blocking-up
2～C
18Alkylidene group;
R
2, R
3Be H or C
1～C
4Alkyl;
R
5Be H, C
1-C
8Alkyl or benzyl;
R
6Be H, OH, C
1-C
18Alkyl, free radical, halogen ,-CH
2CN, C
1-C
18Alkoxyl group, C
1-C
18Hydroxy alkoxy base, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, C
2-C
18Alkynyl, C
7-C
9Phenylalkyl; Be not substituted on the phenyl or by 1,2 and 3 C
1-C
4Alkyl or aliphatic C
1-C
8Acyl substituted.
The preparation method of hindered amine as light stabilizer: it is characterized in that step is as follows:
The first step: addition reaction
With diamine compounds and α, the reaction of beta-unsaturated carboxylic acid ester generates adduct.With mol ratio is diamine compounds and the α of 1:4.0～1:5.0, and the beta-unsaturated carboxylic acid ester is at 0～70 ℃, and under the normal pressure, reaction 4～48h obtains adduct;
Second step: transesterification reaction
With mol ratio is that the first step adduct of 1:4.0～1:5.0 and the 4-hydroxy piperidine of replacement join in the reactor, adds the catalyzer of reactant total mass 0.01～5.0%, normal pressure, 30～210 ℃ of oil baths, reaction 4～48h makes to react completely, recrystallization promptly obtains target product.
Described diamine compounds molecular formula is:
H
2N-R
1-NH
2
Wherein: R
1Be C
1～C
18Alkylidene group, C
5～C
6Cycloalkylidene, C
5～C
6The cycloalkylidene dimethylene or by the C of 1,2 or 3 Sauerstoffatom blocking-up
2～C
18Alkylidene group;
Described α, beta-unsaturated carboxylic acid ester molecule formula is:
Wherein: R
2, R
3Be H or C
1～C
4Alkyl; R
4Be C
1～C
4Alkyl.
The 4-hydroxy piperidine molecular formula of described replacement is:
R
5Be H, C
1-C
8Alkyl or benzyl;
R
6Be H, OH, C
1-C
18Alkyl, free radical, halogen ,-CH
2CN, C
1-C
18Alkoxyl group, C
1-C
18Hydroxy alkoxy base, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, C
2-C
18Alkynyl, C
7-C
9Phenylalkyl; Be not substituted on the phenyl or by 1,2 and 3 C
1-C
4Alkyl or aliphatic C
1-C
8Acyl substituted.
The synthetic method of novel hindered amine light stabilizer of the present invention, wherein the first step addition reaction can be adopted following method:
With diamine compounds and α, the reaction of beta-unsaturated carboxylic acid ester generates adduct.With mol ratio is diamine compounds and the α of 1:4.0～1:5.0, and the beta-unsaturated carboxylic acid ester is at 0～70 ℃, and under the normal pressure, reaction 4～48h obtains adduct.Need add alcohol as solvent if reactant is a solid, alcohol is C
1～C
3Alkyl alcohol.
Wherein the second step transesterification reaction can adopt following method:
With mol ratio is that the first step adduct of 1:4.0～1:5.0 and the 4-hydroxy piperidine of replacement join in the reactor, adds the catalyzer of reactant total mass 0.01～5.0%, normal pressure, 30～210 ℃ of oil baths, reaction 4～48h makes to react completely, recrystallization promptly obtains target product.Also can add solvent in the system, solvent load is 1～5L/mol the first step adduct.
Solvent is sherwood oil, normal heptane, octane, benzene,toluene,xylene, hexanaphthene, tetrahydrofuran (THF) etc.
The catalyzer that the second step transesterification reaction adds is alkali metal ammonia compound, alkali metal alcoholates, alkalimetal hydride, alkali metal hydroxide, tetrabromo-isopropyl phthalate or di-n-octyltin oxide.
The second step product of transesterification reaction recrystallization solvent for use is: sherwood oil, hexanaphthene, normal heptane, octane, benzene,toluene,xylene etc.
The hindered amine as light stabilizer that the present invention is designed, with diamine compounds and α, the beta-unsaturated carboxylic acid ester is a starting raw material, through addition reaction, obtains by transesterification reaction with the 4-hydroxy piperidine that replaces again.Have many hindered piperidines base, increased thermotolerance, consistency and resistant to extraction.Its synthetic method is simple to operate, and product colour is shallow, and transmittance is good.
Reaction formula of the present invention is as follows:
Embodiment
Below in conjunction with example the present invention is described in further detail.
Example 1:
(1) in exsiccant 500mL single port flask, adds methyl acrylate (189.40g, 2.20mol), slowly drip quadrol (30.05g under the stirring at room, 0.50mol), 30min drips off, after move to 60 ℃ of oil bath reacting by heating, adopt the TLC monitoring in the reaction process, approximately 15h afterreaction liquid is formed and is no longer included obvious variation, stopped reaction, remove excessive methyl acrylate under reduced pressure, obtain faint yellow oily thing, separate obtaining pure compound N through column chromatography, N, N ', N '-tetramethyl oxygen carbonyl ethylethylenediamine, yield 85%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (202.23g, 0.50mol), 2,2,6,6-tetramethyl--4-piperidines alcohol (314.52g, 2.00mol) and the 1L octane make solvent, in reaction solution, add the 2.00g tetrabromo-isopropyl phthalate, oil bath is heated to 130 ℃, and TLC follows the tracks of reaction, and the 14h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product octane recrystallization obtains white product N, N, N ', N '-four (2,2,6,6-tetramethyl--4-piperidines) oxygen carbonyl ethylethylenediamine, yield 90%.Structural formula is:
Example 2:
(1) in exsiccant 500mL single port flask, adds ethyl propenoate (163.02g, 2.20mol) and ethanol 50mL, slowly drip hexanediamine (58.10g under the stirring at room, 0.50mol) ethanolic soln 50mL, 30min drips off, after move to 40 ℃ of oil bath reacting by heating, adopt the TLC monitoring in the reaction process, approximately 20h afterreaction liquid is formed and is no longer included obvious variation, stopped reaction, remove excessive ethyl propenoate and ethanol under reduced pressure, obtain incarnadine oily matter, separate obtaining pure compound N through column chromatography, N, N ', N '-tetramethyl oxygen carbonyl ethyl hexanediamine, yield 85%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (230.28g, 0.50mol), 1,2,2,6,6-pentamethyl--4-piperidines alcohol (338.52g, 2.00mmol) and the 0.8L normal heptane make solvent, in reaction solution, add the 24.00g Lithamide, oil bath is heated to 100 ℃, TLC follows the tracks of reaction, and the 30h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product normal heptane recrystallization promptly obtains white product N, N, N ', N '-four (1,2,2,6,6-pentamethyl--4-piperidines) oxygen carbonyl ethyl hexanediamine, yield 92%.Structural formula is:
Example 3:
(1) in exsiccant 500mL single port flask, adds M Cr (200.26g, 2.20mol) and methyl alcohol 50mL, slowly drip 1 under the stirring at room, 4-cyclohexanediamine (57.10g, 0.50mol) methanol solution 50mL, 30min drips off, after move to 60 ℃ of oil bath reacting by heating, adopt the TLC monitoring in the reaction process, approximately 15h afterreaction liquid composition no longer includes obvious variation, stopped reaction removes excessive M Cr and methyl alcohol under reduced pressure, and the column chromatography separation obtains pure compound N, N, N ', N '-tetramethyl oxygen carbonyl sec.-propyl cyclohexanediamine, yield 75%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (256.34g, 0.50mol), 1-octyloxy-2,2,6,6-tetramethyl--4-piperidines alcohol (570.94g, 2.00mmol) and 1.5L benzene make solvent, in reaction solution, add the 12.00g sodium methylate, oil bath is heated to 80 ℃, and TLC follows the tracks of reaction, and the 20h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product sherwood oil recrystallization promptly obtains white product N, N, N ', N '-four (1-octyloxy-2,2,6,6-tetramethyl--4-piperidines) oxygen carbonyl sec.-propyl cyclohexanediamine, yield 84%.Structural formula is:
Example 4:
(1) in exsiccant 500mL single port flask, adds methyl methacrylate (189.40g, 2.20mol) and methyl alcohol 50mL, slowly drip 2-(2-ammonia oxyethyl group) ethamine (52.08g under the stirring at room, 0.50mol) methanol solution 50mL, 30min drips off, after move to 70 ℃ of oil bath reacting by heating, adopt the TLC monitoring in the reaction process, approximately 10h afterreaction liquid composition no longer includes obvious variation, stopped reaction, remove excessive methyl methacrylate and methyl alcohol under reduced pressure, the column chromatography separation obtains pure compound, yield 70%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (252.31g, 0.50mol), 2,2,6,6-tetramethyl--4-piperidinol nitroxyl radical (344.48g, 2.00mol) and 1.5L toluene make solvent, in reaction solution, add the 6.00g di-n-octyltin oxide, oil bath is heated to 112 ℃, and TLC follows the tracks of reaction, and the 20h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product hexanaphthene recrystallization obtains white product, yield 90%.Structural formula is:
Example 5:
(1) (281.97g 2.20mol) with propyl alcohol 50mL, slowly drips 1 under the stirring at room to add butyl acrylate in exsiccant 500mL single port flask, 12-dodecane diamines (100.18g, 0.50mol) propanol solution 50mL, 30min drips off, after move to 50 ℃ of oil bath reacting by heating, adopt the TLC monitoring in the reaction process, approximately 15h afterreaction liquid composition no longer includes obvious variation, and stopped reaction removes excessive butyl acrylate and propyl alcohol under reduced pressure, the column chromatography separation obtains pure compound, yield 85%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (356.52g, 0.50mol), 1-benzyl-2,2,6,6-tetramethyl--4-piperidines alcohol (494.76g, 2.00mol) and 1L dimethylbenzene make solvent, in reaction solution, add the 8.00g potassium hydride KH, oil bath is heated to 145 ℃, and TLC follows the tracks of reaction, and the 14h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product toluene recrystallization obtains white product, yield 90%.Structural formula is:
Example 6:
(1) in exsiccant 500mL single port flask, adds methyl acrylate (189.40g, 2.20mol) and methyl alcohol 50mL, slowly drip 1 under the stirring at room, 18-octadecamethylene diamine (142.26g, 0.50mol) methanol solution 50mL, 30min drips off, after move to 40 ℃ of oil bath reacting by heating, adopt the TLC monitoring in the reaction process, approximately 20h afterreaction liquid composition no longer includes obvious variation, stopped reaction, remove excessive methyl acrylate and methyl alcohol under reduced pressure, the column chromatography separation obtains pure compound, receives rate 92%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (314.44g, 0.50mol), 2,2,3,6,6-pentamethyl--4-piperidines alcohol (342.56g, 2.00mol) and the 1L octane make solvent, in reaction solution, add the 4.00g tetrabromo-isopropyl phthalate, oil bath is heated to 130 ℃, TLC follows the tracks of reaction, and the 20h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product octane recrystallization, yield 87%.Structural formula is:
Example 7:
(1) in exsiccant 500mL single port flask, adds methyl acrylate (206.62g, 2.40mol) and methyl alcohol 50mL, slowly drip 1 under the stirring at room, 4-hexamethylene dimethylamine (71.12g, 0.50mol) methanol solution 80mL, 30min drips off, and adopts the TLC monitoring in the reaction process, and approximately 30h afterreaction liquid composition no longer includes obvious variation, stopped reaction, remove excessive methyl acrylate and methyl alcohol under reduced pressure, the column chromatography separation obtains pure compound, yield 95%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (243.30g, 0.50mol), 3-benzyl-2,2,6, and 6-tetramethyl--4-piperidines alcohol (519.50g, 2.10mol) and 1L cyclohexane give solvent, in reaction solution, add 5.00g potassium hydroxide, oil bath is heated to 80 ℃, and TLC follows the tracks of reaction, and the 35h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product hexanaphthene recrystallization, yield 63%.Structural formula is:
Example 8:
(1) in exsiccant 500mL single port flask, adds methyl acrylate (215.23g, 2.50mol) and methyl alcohol 50mL, slowly drip 2-{3-[3-(2-amino ethoxy)-propoxy-under the stirring at room]-propoxy-}-ethamine (110.16g, 0.50mol) methanol solution 100mL, 30min drips off, adopt the TLC monitoring in the reaction process, approximately 40h afterreaction liquid composition no longer includes obvious variation, stopped reaction, remove excessive methyl acrylate and methyl alcohol under reduced pressure, the column chromatography separation obtains pure compound, yield 84%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (282.33g, 0.50mol), 1-chloro-2,2,6,6-tetramethyl--4-piperidines alcohol (479.25g, 2.50mol) and the 1L octane make solvent, in reaction solution, add the 4.00g tetrabromo-isopropyl phthalate, oil bath is heated to 130 ℃, and TLC follows the tracks of reaction, and the 40h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product octane recrystallization, yield 80%.Structural formula is:
Example 9:
(1) in exsiccant 500mL single port flask, adds methyl acrylate (198.01g, 2.30mol) and methyl alcohol 50mL, slowly drip 1 under the stirring at room, 3-ring pentamethylene diamine (50.08g, 0.50mol) methanol solution 60mL, 30min drips off, and adopts the TLC monitoring in the reaction process, and approximately 25h afterreaction liquid composition no longer includes obvious variation, stopped reaction, remove excessive methyl acrylate and methyl alcohol under reduced pressure, the column chromatography separation obtains pure compound, yield 96%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (222.26g, 0.50mol), 1-hydroxyl-2,2,6,6-tetramethyl--4-piperidines alcohol (415.80g, 2.40mol) and the 1L octane make solvent, in reaction solution, add the 20.00g Lithamide, oil bath is heated to 130 ℃, and TLC follows the tracks of reaction, and the 18h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product toluene recrystallization, yield 88%.Structural formula is:
Example 10:
(1) in exsiccant 500mL single port flask, adds methyl acrylate (198.01g, 2.30mol) and methyl alcohol 50mL, slowly dripping 1 under the stirring at room, 3-encircles penta dimethylamine (64.11g, 0.50mol) methanol solution 70mL, 30min drips off, and adopts the TLC monitoring in the reaction process, and approximately 20h afterreaction liquid composition no longer includes obvious variation, stopped reaction, remove excessive methyl acrylate and methyl alcohol under reduced pressure, the column chromatography separation obtains pure compound, yield 92%;
(2) in the 2L four-hole bottle that water distilling apparatus is housed, add the first step adduct (236.28g, 0.50mol), 1-allyl group-2,2,6,6-tetramethyl--4-piperidines alcohol (473.57g, 2.40mol) and the 1L octane make solvent, in reaction solution, add the 5.00g potassium tert.-butoxide, oil bath is heated to 130 ℃, and TLC follows the tracks of reaction, and the 22h afterreaction finishes.Remove solvent under reduced pressure, obtain thick product.Thick product benzene recrystallization, yield 82%.Structural formula is:
Claims (8)
1. hindered amine as light stabilizer is characterized in that structural formula is as follows:
Wherein: R
1Be C
1～C
18Alkylidene group, C
5～C
6Cycloalkylidene, C
5～C
6The cycloalkylidene dimethylene or by the C of 1,2 or 3 Sauerstoffatom blocking-up
2～C
18Alkylidene group;
R
2, R
3Be H or C
1～C
4Alkyl;
R
5Be H, C
1-C
8Alkyl or benzyl;
R
6Be H, OH, C
1-C
18Alkyl, free radical, halogen ,-CH
2CN, C
1-C
18Alkoxyl group, C
1-C
18Hydroxy alkoxy base, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, C
2-C
18Alkynyl, C
7-C
9Phenylalkyl; Be not substituted on the phenyl or by 1,2 and 3 C
1-C
4Alkyl or aliphatic C
1-C
8Acyl substituted.
2. the preparation method of the hindered amine as light stabilizer of claim 1: it is characterized in that step is as follows:
The first step: addition reaction
With diamine compounds and α, the reaction of beta-unsaturated carboxylic acid ester generates adduct; With mol ratio is 1: 4.0～1: 5.0 diamine compounds and α, and the beta-unsaturated carboxylic acid ester is at 0～70 ℃, and under the normal pressure, reaction 4～48h obtains adduct;
Second step: transesterification reaction
With mol ratio is that 1: 4.0～1: 5.0 the first step adduct and the 4-hydroxy piperidine of replacement join in the reactor, adds the catalyzer of reactant total mass 0.01～5.0%, normal pressure, 30～210 ℃ of oil baths, reaction 4～48h makes to react completely, recrystallization promptly obtains target product.
3. hindered amine as light stabilizer preparation method as claimed in claim 2 is characterized by described diamine compounds structural formula and is:
H
2N-R
1-NH
2
R
1Be C
1～C
18Alkylidene group, C
5～C
6Cycloalkylidene, C
5～C
6The cycloalkylidene dimethylene or by the C of 1,2 or 3 Sauerstoffatom blocking-up
2～C
18Alkylidene group.
4. hindered amine as light stabilizer preparation method as claimed in claim 2 is characterized by described α, and beta-unsaturated carboxylic acid ester structure formula is:
Wherein: R
2, R
3Be H or C
1～C
4Alkyl; R
4Be C
1～C
4Alkyl.
5. hindered amine as light stabilizer preparation method as claimed in claim 2, the 4-hydroxy piperidine structural formula that it is characterized by described replacement is:
R
5Be H, C
1-C
8Alkyl or benzyl;
R
6Be H, OH, C
1-C
18Alkyl, free radical, halogen ,-CH
2CN, C
1-C
18Alkoxyl group, C
1-C
18Hydroxy alkoxy base, C
5-C
12Cycloalkyloxy, C
3-C
6Alkenyl, C
2-C
18Alkynyl, C
7-C
9Phenylalkyl; Be not substituted on the phenyl or by 1,2 and 3 C
1-C
4Alkyl or aliphatic C
1-C
8Acyl substituted.
6. hindered amine as light stabilizer preparation method as claimed in claim 2, it is as follows to it is characterized by the first step addition reaction:
With diamine compounds and α, the reaction of beta-unsaturated carboxylic acid ester generates adduct; With mol ratio is 1: 4.0～1: 5.0 diamine compounds and α, and the beta-unsaturated carboxylic acid ester is at 0～70 ℃, and under the normal pressure, reaction 4～48h obtains adduct, also can add C
1～C
3Alkyl alcohol as solvent.
7. hindered amine as light stabilizer preparation method as claimed in claim 2, it is as follows to it is characterized by the second step transesterification reaction:
With mol ratio is that 1: 4.0～1: 5.0 the first step adduct and the 4-hydroxy piperidine of replacement join in the reactor, the catalyzer that adds reactant total mass 0.01～5.0%, add solvent again, solvent load is 1～5L/mol the first step adduct, normal pressure, 30～210 ℃ of oil baths, reaction 4～48h, make to react completely, recrystallization promptly obtains target product; Solvent is sherwood oil, normal heptane, octane, benzene,toluene,xylene, hexanaphthene or tetrahydrofuran (THF).
8. hindered amine as light stabilizer preparation method as claimed in claim 2, the catalyzer that it is characterized by the transesterification reaction adding of second step is alkali metal ammonia compound, alkali metal alcoholates, alkalimetal hydride, alkali metal hydroxide, tetrabromo-isopropyl phthalate or di-n-octyltin oxide.
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| CN101885701B (en) * | 2010-06-28 | 2012-07-04 | 北京天罡助剂有限责任公司 | Hindered amine compound having double-hindered phenol structure for light stabilizer and preparation method thereof |
| CN102827148A (en) * | 2012-09-04 | 2012-12-19 | 中国科学院长春应用化学研究所 | Hindered amine compound and preparation method thereof |
| CN103030586A (en) * | 2012-11-09 | 2013-04-10 | 西南科技大学 | Method for preparing rubber or resin multifunctional anti-aging agent |
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| CN112126060B (en) * | 2019-06-25 | 2022-05-31 | 北京天罡助剂有限责任公司 | Polymeric high-molecular steric hindrance amine and preparation method thereof |
| CN110396060A (en) * | 2019-07-12 | 2019-11-01 | 西安工业大学 | A kind of light stabilizer and preparation method thereof containing double hindered piperidine bases |
| CN111349041A (en) * | 2020-02-25 | 2020-06-30 | 烟台大学 | High-molecular material light stabilizer with antioxidant function and preparation method 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 |
| CN115122528A (en) * | 2022-06-30 | 2022-09-30 | 安徽省天助纺织科技集团股份有限公司 | Method for manufacturing environment-friendly packaging bag by using waste textiles |
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