CN109678790A - A kind of response type hindered amine light stabilizer and preparation method thereof - Google Patents
A kind of response type hindered amine light stabilizer and preparation method thereof Download PDFInfo
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- CN109678790A CN109678790A CN201910103589.0A CN201910103589A CN109678790A CN 109678790 A CN109678790 A CN 109678790A CN 201910103589 A CN201910103589 A CN 201910103589A CN 109678790 A CN109678790 A CN 109678790A
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- light stabilizer
- hindered amine
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- response type
- amine light
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
Abstract
The present invention relates to a kind of response type hindered amine light stabilizers and preparation method thereof, and tetramethylpiperidinol and its derivative are dissolved in solvent, and polymerization inhibitor and α is added, beta-unsaturated carboxylic acid ester, and precipitation is washed, light stabilizer is obtained after progress esterification under the action of catalyst；The product purity of a kind of response type hindered amine light stabilizer disclosed by the invention and preparation method thereof, simple process, mild condition, production is high, and yield is 90% or more.Its synthetic method is easy to operate, and product colour is shallow, and light transmittance is good.
Description
Technical field
The present invention relates to a kind of response type hindered amine light stabilizers and preparation method thereof, belong to light stabilizer synthesis field.
Background technique
Hindered amine light stabilizer (HALS) has unique, brilliant photoprotection performance, therefore by domestic and international industry
The extensive concern on boundary.Hindered amine light stabilizer is the piperidine derivative with space steric effect, wherein containing alkyl or alkane
Oxygroup connects the auxiliary group of hindered piperidine base.Since auxiliary base and substituent group are there are many different type, multiplicity is presented in kind
Change.For example, functionalization hindered amine is that bonding has UV absorption, thermal oxidation resistance, peroxide in hindered amine light stabilizer
The group of the functions such as decomposition is accomplished one multi-purpose.Low alkalinity hindered amine solves traditional hindered amine and halogen resin, acid tree
The problem of the synergistic stability effect difference of rouge.Reactive group is had in response type the structure of hindered amine, and it is steady to improve hindered amines light
Determine the dispersion performance and light stablizing effect of agent in the polymer.Common hindered amine light stabilizer has HALS-770 in the market,
HALS-944, HALS-622 etc., HALS-770 are a kind of low molecular weight light stabilizers currently used more, are added to matrix
A most important problem is exactly to be easier to migrate after resin, influences the use of product.HALS-944, HALS-622 are subsequent
The light stabilizer for the polymerism high molecular weight developed, effectively improves the migration problem of light stabilizer, but 944,622
To equipment, temperature, pressure, more stringent requirements are proposed for polymerization.The hindered amine light stabilizer of response type also compares currently on the market
It is few, it is in the pilot plant test stage mostly, and the purity of product is not high.
Summary of the invention
The purpose of the present invention is to provide a kind of easy preparation, technique is relatively easy, hindered amine light stabilizer of function admirable
The preparation method of agent has reactive group in response type the structure of hindered amine, is bonded in polymer preparation, process poly-
It closes on owner's chain, forms the permanent light stabilising polymer with the amine functional group that is obstructed, overcome previous addition type hindered amine light
Stabilizer as physical migration or volatilization caused by mass loss.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of response type hindered amine light stabilizer, the structural formula of the light stabilizer such as Formulas I:
Wherein: R1 H, the alkyl of C1-C18, oxygen radical, C1-C18 alkoxy；
R2For the alkyl of H, C1-C4.
As an improvement of the present invention, the preparation method includes the following steps: Formula II intermediate being dissolved in solvent
In, polymerization inhibitor and formula III intermediate is added, and wash precipitation after progress esterification under the action of catalyst, obtains light and stablize
Agent Formulas I,
Wherein, the alkoxy of R1 H, the alkyl of C1-C18, oxygen radical, C1-C18；
R2For the alkyl of H, C1-C4；
R3For the alkyl of H, C1-C4.
A kind of response type hindered amine light stabilizer prepared by the present invention has the carbon-carbon double bond of response type, is allowed in polymer
Preparation and processing in be bonded or be grafted on main polymer chain with formed the persistent optical with the amine functional group that is obstructed stablize it is poly-
Close object.Previous addition type HALS is overcome as physical migration or volatilization and caused by stabilizer lose, improve
The dispersibility and photostability of HALS in the polymer.Especially suitable for polyethylene, polypropylene, polystyrene and ABS, improve
The phenomenon that small molecule light stabilizer is easily moved out.
As an improvement of the present invention, the molar ratio of Formula II intermediate and formula III intermediate is 1: 0.5-4.
As an improvement of the present invention, the solvent is petroleum ether, normal heptane, normal octane, n-hexane, hexamethylene, first
Any one in benzene or dimethylbenzene.
As an improvement of the present invention, the polymerization inhibitor is phenol, hydroquinone, p-hydroxyanisole or 2,4- diformazan
Any one in base -6- tert-butyl phenol.
As an improvement of the present invention, the quality sum and solvent quality of the Formula II intermediate and formula III intermediate
Ratio be 1: 0.5-4.
As an improvement of the present invention, the polymerization inhibitor quality is the 0.01-2% of weight among formula III.
As an improvement of the present invention, the catalyst quality is the 0.1-5.0% of weight among Formula II.
As an improvement of the present invention, the catalyst is sodium methoxide, sodium ethoxide, butyl titanate, four isopropyl of metatitanic acid
Any one in ester or tetrabutyl titanate.
As an improvement of the present invention, the temperature of the esterification is 80-130 DEG C, reaction time 2-10 hour.
Due to using the above technology, the present invention compared with the prior art, is had the advantage that as follows:
The invention discloses a kind of response type hindered amine light stabilizer and preparation method thereof, present invention piperidinol derivatives
With α, beta-unsaturated carboxylic acid ester is Material synthesis hindered amine light stabilizer, and reaction condition is mild, is not necessarily to high temperature and pressure, separating-purifying
Process is simple, and the reaction time is short, and product yield is high, reaches 90% or more, and less energy consumption is at low cost, is to realize industrialized production
Comparatively ideal technique.Meanwhile light stabilizer steric hindrance of the invention is smaller, compares the light stabilizer with phenyl ring, carbon-carbon double bond
It is easier to be bonded on main polymer chain, enhances compatibility between the two, greatly reduce physical migration or volatilization and make
At mass loss.
A kind of response type hindered amine light stabilizer disclosed by the invention and preparation method thereof, simple process, mild condition are raw
The product purity of production is high, and yield is 90% or more.Its synthetic method is easy to operate, and product colour is shallow, and light transmittance is good.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated.
Embodiment 1:
In the four-hole boiling flask equipped with thermometer, 1,2,2,6,6- tetramethylpiperidinol 103g, methyl methacrylate is added
Ester 72g, p-hydroxyanisole 1g, sodium methoxide 2.0g are dissolved in the petroleum ether solvent of 300g, load onto condenser pipe, start stirring
Device, when being warming up to 100 DEG C, reaction time 5h.Washing precipitation is carried out after esterification to exist to get target product yield
95%.
Embodiment 2:
In the four-hole boiling flask equipped with thermometer, 2,2,6,6- tetramethylpiperidinol 157g, ethyl methacrylate is added
170g, 2,4- dimethyl -6- tert-butyl phenol 2g, butyl titanate 2.5g are dissolved in the xylene solvent of 300g, load onto cold
Solidifying pipe, starts blender, when being warming up to 90 DEG C, reaction time 7h.Washing precipitation is carried out after esterification to get target production
Object, yield is 90%.
Embodiment 3:
In the four-hole boiling flask equipped with thermometer, 1,2,2,6,6- pentamethvl alcohol 103g, ethyl acrylate is added
200g, hydroquinone 1g, tetraisopropyl titanate 1.5g are dissolved in the normal heptane solvent of 300g, load onto condenser pipe, start stirring
Device, when being warming up to 115 DEG C, reaction time 5h.Washing precipitation is carried out after esterification to get target product, yield exists
96%.
Embodiment 4:
In the four-hole boiling flask equipped with thermometer, 1- oxygroup -2,2,6,6- tetramethylpiperidinol 172g, metering system is added
Sour 130g, tetrabutyl titanate 1.0g, is dissolved in the cyclohexane solvent of 300g, loads onto condenser pipe, starts blender, is warming up to
At 110 DEG C, reaction time 10h.Washing precipitation is carried out after esterification to get target product, yield is 90%.
Above-described embodiment is only the preferred technical solution of the present invention, and is not construed as limitation of the invention, the present invention
Protection scope should with claim record technical solution, including claim record technical solution in technical characteristic etc.
It is protection scope with alternative, i.e., equivalent replacement within this range is improved, also within protection scope of the present invention.
Claims (10)
1. a kind of response type hindered amine light stabilizer, it is characterised in that: the structural formula of the light stabilizer such as Formulas I:
Wherein: R1 H, the alkyl of C1-C18, oxygen radical, C1-C18 alkoxy；
R2For the alkyl of H, C1-C4.
2. a kind of preparation method of response type hindered amine light stabilizer according to claim 1, which is characterized in that including such as
Lower step: Formula II intermediate is dissolved in solvent, polymerization inhibitor and formula III intermediate is added, and carry out under the action of catalyst
After esterification, precipitation is washed, light stabilizer Formulas I is obtained,
Wherein, the alkoxy of R1 H, the alkyl of C1-C18, oxygen radical, C1-C18；
R2For the alkyl of H, C1-C4；
R3For the alkyl of H, C1-C4.
3. a kind of preparation method of response type hindered amine light stabilizer according to claim 2, it is characterised in that: the formula
The molar ratio of II intermediate and formula III intermediate is 1: 0.5-4.
4. a kind of preparation method of response type hindered amine light stabilizer according to claim 2, it is characterised in that: described molten
Agent is any one in petroleum ether, normal heptane, normal octane, n-hexane, hexamethylene, toluene or dimethylbenzene.
5. a kind of preparation method of response type hindered amine light stabilizer according to claim 2, it is characterised in that: the resistance
Poly- agent is phenol, hydroquinone, p-hydroxyanisole or 2, any one in 4- dimethyl -6- tert-butyl phenol.
6. a kind of preparation method of response type hindered amine light stabilizer according to claim 2, it is characterised in that: the formula
The ratio of the quality sum and solvent quality of II intermediate and formula III intermediate is 1: 0.5-4.
7. a kind of preparation method of response type hindered amine light stabilizer according to claim 2, it is characterised in that: the resistance
Poly- agent quality is the 0.01-2% of weight among formula III.
8. a kind of preparation method of response type hindered amine light stabilizer according to claim 2, it is characterised in that: described to urge
Agent quality is the 0.1-5.0% of weight among Formula II.
9. a kind of preparation method of response type hindered amine light stabilizer according to claim 8, it is characterised in that: described to urge
Agent is any one in sodium methoxide, sodium ethoxide, butyl titanate, tetraisopropyl titanate or tetrabutyl titanate.
10. a kind of preparation method of response type hindered amine light stabilizer according to claim 2, it is characterised in that: described
The temperature of esterification is 80-130 DEG C, reaction time 2-10 hour.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357807A (en) * | 2019-06-13 | 2019-10-22 | 宿迁联盛科技股份有限公司 | A kind of preparation method of novel hindered amine light stabilizer |
| CN110484052A (en) * | 2019-07-29 | 2019-11-22 | 宿迁联盛科技股份有限公司 | A kind of dedicated anti-aging auxiliary agent of acrylic coating and preparation method thereof |
| CN112047875A (en) * | 2020-08-21 | 2020-12-08 | 宿迁市振兴化工有限公司 | Light stabilizer and synthesis process thereof |
| CN112175233A (en) * | 2020-10-15 | 2021-01-05 | 宿迁联盛科技股份有限公司 | Hindered amine light stabilizer and preparation method and application thereof |
| CN112195712A (en) * | 2020-08-14 | 2021-01-08 | 江苏固迈新材料技术有限公司 | Colored anti-skidding road surface |
| CN112646152A (en) * | 2020-12-10 | 2021-04-13 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of hindered amine light stabilizer |
| CN112961101A (en) * | 2021-03-05 | 2021-06-15 | 宿迁联盛科技股份有限公司 | Novel hindered amine light stabilizer and preparation method and application thereof |
| CN113024447A (en) * | 2021-03-11 | 2021-06-25 | 宿迁联盛科技股份有限公司 | Preparation method of 2,2,6, 6-tetramethyl piperidine nitroxide free radical-4-yl acetate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357807A (en) * | 2019-06-13 | 2019-10-22 | 宿迁联盛科技股份有限公司 | A kind of preparation method of novel hindered amine light stabilizer |
| CN110484052A (en) * | 2019-07-29 | 2019-11-22 | 宿迁联盛科技股份有限公司 | A kind of dedicated anti-aging auxiliary agent of acrylic coating and preparation method thereof |
| CN112195712A (en) * | 2020-08-14 | 2021-01-08 | 江苏固迈新材料技术有限公司 | Colored anti-skidding road surface |
| CN112047875A (en) * | 2020-08-21 | 2020-12-08 | 宿迁市振兴化工有限公司 | Light stabilizer and synthesis process thereof |
| CN112175233A (en) * | 2020-10-15 | 2021-01-05 | 宿迁联盛科技股份有限公司 | Hindered amine light stabilizer and preparation method and application thereof |
| 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 |
| CN112646152A (en) * | 2020-12-10 | 2021-04-13 | 利安隆凯亚(河北)新材料有限公司 | Preparation method of hindered amine light stabilizer |
| CN112961101A (en) * | 2021-03-05 | 2021-06-15 | 宿迁联盛科技股份有限公司 | Novel hindered amine light stabilizer and preparation method and application thereof |
| CN113024447A (en) * | 2021-03-11 | 2021-06-25 | 宿迁联盛科技股份有限公司 | Preparation method of 2,2,6, 6-tetramethyl piperidine nitroxide free radical-4-yl acetate |
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Application publication date: 20190426 |