CN105153121B - hindered amine light stabilizer and its synthetic method - Google Patents
hindered amine light stabilizer and its synthetic method Download PDFInfo
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- CN105153121B CN105153121B CN201510676723.8A CN201510676723A CN105153121B CN 105153121 B CN105153121 B CN 105153121B CN 201510676723 A CN201510676723 A CN 201510676723A CN 105153121 B CN105153121 B CN 105153121B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
Abstract
The invention discloses a kind of low alkalinity hindered amine light stabilizers, and structure is shown in formula I, have excellent stablizing effect, and compatibility is good, resistant to extraction, has a wide range of application, preparation method includes：Intermediate is obtained by the reaction in N (2,2,6,6 tetramethyl, 4 piperidyl) amine and Cyanuric Chloride；Intermediate and N, bis- [the N (2 of N ', 2,6,6 tetramethyl, 4 piperidyl)] 1,6 hexamethylene diamines are by being obtained by the reaction polymer, and target product further is obtained by the reaction with hexamethylene under hydroperoxides and catalyst action, this method has the advantages that easy to operate, product yield is high, narrow molecular weight distribution
Description
Technical field：
The present invention relates to polymeric material fields, more particularly to a kind of hindered amine light stabilizer and preparation method thereof.
Background technology：
With the continuous improvement of human life quality and production technology level, high molecular material has been widely applied to people
The every field of class social life.But high molecular material is during processing, storage and use, its is physical for generally existing
The phenomenon that matter, chemical property and mechanical property can gradually be deteriorated.Such as the turning to be yellow of plastics, embrittlement and cracking；Rubber it is tacky, hard
Change, cracking and decreasing insulating.Phenomena such as discoloration of fibre, colour fading, strength reduction, fracture.These phenomenons are referred to as
The aging or degradation of high molecular material.Cause the factor of macromolecule material aging very much, wherein with oxygen, light and heat influence most
It is notable.So in order to prevent or delaying its aging, extend its service life, people are usually by some changes with specific function
Auxiliary agent is learned to be added in high molecular material.Wherein, light stabilizer, which is exactly one kind, can intervene high molecular material photoinduction degradation product
It is also one of most important high molecular material additive that the compound of Physicochemical process, which is the most frequently used,.
The kind of light stabilizer includes mainly benzophenone, benzotriazole, triazine-based ultraviolet absorbent, nickel at present
Salt excited state quenchers and hindered amine light stabilizer.Wherein, hindered amine light stabilizer because its excellent light stablizing effect by
It is to study most active a kind of light stabilizer over nearly two, 30 years both at home and abroad to extensive concern.Although this kind of light stabilizer is opened
The ratio of hair is later, but quickly grows.Hindered amine light stabilizer has accounted for 60% or so in the light stabilizer of foreign applications at present.
At home, hindered amine light stabilizer proportion higher, about 80% or so.
Although the hindered amine light stabilizer kind light stability of early stage is excellent, most of there are average relative molecular mass
The shortcomings of low, alkaline high.The hindered amine light stabilizer greatest drawback of low molecular weight is that resistant to extraction, use are not easy damage in the process
It loses；And alkalinity height keeps its difficult and acid additive compounds, and can not be applied in the acidic environments such as polyvinyl chloride, coating.So new
The developing trend of type hindered amine light stabilizer mainly under the premise of improving or not losing its light stability, improves product
Relative molecular weight reduces its alkalinity.
Patent CN102827148A provides a kind of hindered amine compound, using blocking group on GW-944 piperidine rings
Amino protected, then utilize necleophilic reaction leading-in end alkenyl group.When light stabilizer as high molecular polymer, by
It technology can be grafted on macromolecular chain via radiation in the end alkenyl group containing unsaturated bond, form carbon-carbon bond, therefore
Hindered amine compound not readily dissolves precipitation, photostability enhancing.
Patent CN104725361A discloses light stabilizer 3346 and preparation method thereof, light stabilizer 3346 be aggretion type by
Amine light stabilizer is hindered, the protection of the coloured or colourless polyolefin articles more demanding to weatherability is especially effective, and special applicable
In agricultural film, fiber and moulding article etc., in addition to fabulous photostability, with the fabulous compatibility of resin, color it is shallow, it is nontoxic and
Outside the features such as high-temperature volatile is low, also there is good hot oxygen barrier propterty.
The hindered amine light stabilizer disclosed in above-mentioned patent still has the higher problem of alkalinity, limits it and is set with acidity
The synergistic stability effect of fat, halogen containing flame-retardant and phenolic antioxidant.
To overcome the deficiencies of existing technologies, the present invention provides a kind of piperidines system N- alkoxies to replace hindered amine light stabilizer
And preparation method thereof.
Invention content：
A purpose of the invention is to provide a kind of hindered amine light stabilizer, solves hindered amine light stabilizer in the prior art
The high defect of alkalinity, the hindered amine light stabilizer is applied widely, and has good smooth stablizing effect.
The present invention, which a further object is, provides a kind of preparation method of hindered amine light stabilizer, easy to operate, makes to be prepared into
The product yield arrived is high, narrow molecular weight distribution.
Thus, one aspect of the present invention provides a kind of hindered amine light stabilizer, and structure is shown in formula I：
N is 2-10 in Formulas I；
R in Formulas I1The alkynyl of the naphthenic base of alkyl, C3-C6, the alkenyl of C2-C6, C2-C6 selected from C1-C6, it is preferred that
R1Selected from methyl, ethyl, propyl, butyl, it is furthermore preferred that R1Selected from butyl.
In the specific implementation mode of the present invention, the hindered amine light stabilizer, structure is as shown in formula IV：
Another aspect of the present invention provides a kind of preparation method of hindered amine light stabilizer, includes the following steps：
(1) N- (2,2,6,6- tetramethyl -4- piperidyls) amine and Cyanuric Chloride are obtained by the reaction at -50-20 DEG C such as Formula II
Intermediate；
(2) Formula II intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines of N '-occur poly-
It closes reaction and generates such as formula III polymer；
(3) formula III polymer is obtained by the reaction under hydroperoxides and catalyst action with hexamethylene generation N- alkoxides
Formulas I hindered amine light stabilizer；
Wherein, n 2-10；
R1The alkynyl of the naphthenic base of alkyl, C3-C6, the alkenyl of C2-C6, C2-C6 selected from C1-C6, it is preferred that R1It is selected from
Methyl, ethyl, propyl, butyl, it is furthermore preferred that R1Selected from butyl.
In the specific embodiment of the present invention, the N- (2,2,6,6- tetramethyl -4- piperidyls) amine is selected from
N- (2,2,6,6- tetramethyl -4- piperidyls) n-butylamine.
In the specific embodiment of the present invention, the Formula II intermediate is：
In the specific embodiment of the present invention, the formula III polymer is
The step of preparation method of hindered amine light stabilizer of the present invention (1) includes：N- (2,2,6,6- tetramethyls-
4- piperidyls) amine and Cyanuric Chloride addition in molar ratio 1: 1-3, alkali is added, 1-12h is reacted at -50-20 DEG C and obtains Formula II
Intermediate.Preferably, N- (2,2,6,6- tetramethyl -4- piperidyls) amine and Cyanuric Chloride addition are 1: 1-2 in molar ratio, more
Preferably 1: 1-1.5；Reaction temperature is preferably -20-10 DEG C, more preferably -10-10 DEG C；Reaction dissolvent is acetone, two
The combination of one or more of chloromethanes, toluene, dimethylbenzene or tetrahydrofuran；Reaction dissolvent addition by N- (2,2,
6,6- tetramethyl -4- piperidyls) amine is calculated as 1-5L/mol；The alkali is selected from the carbonic acid of the hydroxide of alkali metal, alkali metal
Salt, the hydroxide of alkaline-earth metal, the carbonate of alkaline-earth metal, organic amine, pyridine, it is preferred that the alkali be selected from NaOH,
KOH、Na2CO3、 K2CO3, triethylamine, pyridine；The alkali addition is rubbed with N- (2,2,6,6- tetramethyl -4- piperidyls) amine
You are than being 1-1.5: 1.
The step of preparation method of hindered amine light stabilizer of the present invention (2) includes：Formula II intermediate and N, N '-are bis-
[N- (2,2,6,6- tetramethyl -4- piperidyls)] -1,6- hexamethylene diamines addition is in molar ratio 1.5-5: 1, is stirred at 30-60 DEG C
After mixing 1-2h, alkali is added, 3-12h is reacted at 50-100 DEG C and obtains formula III polymer.Preferably, Formula II intermediate and N,
Bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines additions of N '-are 2-4: 1 in molar ratio, more preferably
It is 2-3: 1；The alkali is selected from the hydroxide of alkali metal, the carbonate of alkali metal, the hydroxide of alkaline-earth metal, alkaline earth gold
Carbonate, organic amine, the pyridine of category, it is preferred that the alkali is selected from NaOH, KOH, Na2CO3、K2CO3, triethylamine, pyridine；Instead
It is the combination of one or more of toluene, chlorobenzene, dimethylbenzene, dichloro-benzenes and mesitylene to answer solvent；Reaction dissolvent
Addition presses N, and bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines of N '-are calculated as 1-5L/mol.
The step of preparation method of hindered amine light stabilizer of the present invention (3) includes：Formula III polymer is in hydrogen peroxide
5-12h is reacted with hexamethylene under compound and catalyst action and obtain Formulas I hindered amine light stabilizer, wherein the catalyst is selected from
The combination of one or more of molybdenum trioxide, vanadium pentoxide, chromium trioxide, tungstic acid and manganese dioxide.Preferably,
Reaction temperature is 0-100 DEG C, it is furthermore preferred that reaction temperature is 50-80 DEG C；The hydroperoxides are selected from tert-butyl hydroperoxide
Hydrogen, Peracetic acid and/or hydrogen peroxide；Mole of the hindered amine piperidine structure unit of the hydroperoxides addition and addition
Than being 1-6: 1, more preferably 2-5: 1；The molar ratio of the hindered amine piperidine structure unit of the catalyst charge and addition
It is 0.001-1: 1, more preferably 0.02-0.2: 1.
In the specific embodiment of the present invention, the preparation method reaction equation of the hindered amine light stabilizer is：
Hindered amine light stabilizer excellent effect of the present invention, compatibility is good, resistant to extraction, has a wide range of application；This hair simultaneously
The preparation method of the hindered amine light stabilizer of bright offer has the advantages that easy to operate, product yield is high, narrow molecular weight distribution.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, and following embodiment is descriptive, is not limit
Qualitatively, protection scope of the present invention cannot be limited with this.
Embodiment 1
18.4g Cyanuric Chlorides are dissolved in 300mL acetone, after being cooled to 0 DEG C, sequentially add 21.2g N- (2,2,6,6- tetra-
Methyl -4- piperidyls) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyls) n-butylamine is 1:
And 13.8g K 1)2CO3, 1h, filtering are stirred, filtrate water washs, and organic phase is concentrated to give intermediate.
Intermediate is dissolved in 100mL chlorobenzenes, bis- [N- (2,2,6, the 6- tetramethyl -4- piperidines of 16.2g N, N '-are added
Base)] -1,6- hexamethylene diamines (intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines mole of N ' -
Than for 2: 1), after reacting on 30 DEG C of stirring 2h, 13.8g K are added2CO3, 12h then is stirred in 50 DEG C, is cooled to room temperature, is filtered, filter
Liquid is washed with water, and organic phase is concentrated to give polymer.
It dissolves a polymer in 150mL hexamethylenes, 70% tert-butyl hydroperoxide of 51.5g and 0.9g tungstic acids is added,
12h is stirred in 50 DEG C, is cooled to room temperature, is filtered, excessive saturation NaHSO is added to filtrate3Solution stirs, separation, and organic phase is dense
Contracting obtains target product, yield 87%.
1H NMR (300MHz, CDCl3) δ=0.62-0.65 (N (CH2)3-CH3)；0.84-0.99(N(CH2)2-CH2-)；
1.12 (C-CH3)；1.24-1.76(-CH2-)；2.12-2.23(N-CH-)；2.30-2.39(O-CH-)；3.01-3.15(N-
CH2-)。
MS：M/z=2547,1458,908,680,419,364,283.
Embodiment 2
22.1g Cyanuric Chlorides are dissolved in 300mL dichloromethane, after being cooled to 0 DEG C, sequentially add 21.2gN- (2,2,6,6-
Tetramethyl -4- piperidyls) (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyls) n-butylamine is n-butylamine
1.2: 1) and 84g 10wt%KOH aqueous solutions, stirring 9h remove water phase, and organic phase is concentrated to give intermediate.
Intermediate is dissolved in 300mL toluene, bis- [N- (2,2,6, the 6- tetramethyl -4- piperidines of 12.9g N, N '-are added
Base)] -1,6- hexamethylene diamines (intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines mole of N ' -
Than for 2.5: 1), after reacting on 30 DEG C of stirring 2h, 5.6g potassium hydroxide is added, then stirs 9h in 80 DEG C, is cooled to room temperature, mistake
Filter, filtrate water washing, organic phase are concentrated to give polymer.
It dissolves a polymer in 100mL hexamethylenes, 35% Peracetic acid of 117.3g and 3.6g chromium trioxides is added, in 50
DEG C stirring 12h, is cooled to room temperature, filters, excessive saturation NaHSO is added to filtrate3Solution stirs, and separation, organic phase is concentrated to give
To target product, yield 85%.
1H NMR (300MHz, CDCl3) δ=0.62-0.65 (N (CH2)3-CH3)；0.84-0.99(N(CH2)2-CH2-)；
1.12 (C-CH3)；1.24-1.76(-CH2-)；2.12-2.23(N-CH-)；2.30-2.39(O-CH-)；3.01-3.15(N-
CH2-)。
Embodiment 3
18.4g Cyanuric Chlorides are dissolved in 400mL toluene, after being cooled to 0 DEG C, sequentially add 21.2g N- (2,2,6,6- tetra-
Methyl -4- piperidyls) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyls) n-butylamine is 1:
1) and 7.9g pyridines, stirring 1h, organic phase are concentrated to give intermediate.
Intermediate is dissolved in 100mL toluene, bis- [N- (2,2,6, the 6- tetramethyl -4- piperidines of 16.2g N, N '-are added
Base)] -1,6- hexamethylene diamines (intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines mole of N ' -
Than for 2: 1), after reacting on 30 DEG C of stirring 2h, 7.9g pyridines are added, then stir 12h in 50 DEG C, be cooled to room temperature, reaction solution is used
Water washing, organic phase are concentrated to give polymer.
It dissolves a polymer in 150mL hexamethylenes, 70% tert-butyl hydroperoxide of 60.7g and 1.9g manganese dioxide is added,
5h is stirred in 80 DEG C, is cooled to room temperature, is filtered, excessive saturation NaHSO is added to filtrate3Solution stirs, separation, and organic phase is dense
Contracting obtains target product, yield 92%.
Embodiment 4
18.4g Cyanuric Chlorides are dissolved in 100mL toluene, after being cooled to 10 DEG C, sequentially add 21.2g N- (2,2,6,6- tetra-
Methyl -4- piperidyls) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyls) n-butylamine is 1:
1) and 40 g 10wt%NaOH aqueous solutions, stirring 1h remove water phase, and organic phase is concentrated to give intermediate.
Intermediate is dissolved in 100mL dimethylbenzene, bis- [N- (2,2,6, the 6- tetramethyl -4- piperidines of 16.2g N, N '-are added
Base)] -1,6- hexamethylene diamines (intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines mole of N ' -
Than for 2: 1), after reacting on 30 DEG C of stirring 2h, 4.0g sodium hydroxides are added, then stirs 12h in 50 DEG C, is cooled to room temperature, react
Liquid is washed with water, and organic phase is concentrated to give polymer.
It dissolves a polymer in 100mL hexamethylenes, 70% tert-butyl hydroperoxide of 51.5g and 0.9g molybdenum trioxides is added,
12h is stirred in 50 DEG C, is cooled to room temperature, is filtered, excessive saturation NaHSO is added to filtrate3Solution stirs, separation, and organic phase is dense
Contracting obtains target product, yield 87%.
Embodiment 5
18.4g Cyanuric Chlorides are dissolved in 400mL toluene, after being cooled to 0 DEG C, sequentially add 21.2g N- (2,2,6,6- tetra-
Methyl -4- piperidyls) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyls) n-butylamine is 1:
And 10.6g Na 1)2CO3, 1h, filtering are stirred, filtrate is washed, and organic phase is concentrated to give intermediate.
Intermediate is dissolved in 100mL mesitylene, bis- [N- (2,2,6, the 6- tetramethyl -4- piperazines of 16.2g N, N '-are added
Piperidinyl)] -1,6- hexamethylene diamines (intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines mole of N ' -
Than for 2: 1), after reacting on 30 DEG C of stirring 2h, 10.6g Na are added2CO3, 12h then is stirred in 50 DEG C, is cooled to room temperature, is filtered,
Filtrate water washs, and organic phase is concentrated to give polymer.
It dissolves a polymer in 150mL hexamethylenes, 70% tert-butyl hydroperoxide of 53.8g and 1.9g tungstic acids is added,
6h is stirred in 80 DEG C, is cooled to room temperature, is filtered, excessive saturation NaHSO is added to filtrate3Solution stirs, separation, and organic phase is dense
Contracting obtains target product, yield 89%.
Embodiment 6
27.6g Cyanuric Chlorides are dissolved in 500mL dimethylbenzene, after being cooled to -10 DEG C, sequentially add 21.2g N- (2,2,6,
6- tetramethyl -4- piperidyls) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl 4- piperidyls) n-butylamine
It is 1.5: 1) and 40g 10wt%NaOH aqueous solutions, stirring 12h remove water phase, and organic phase is concentrated to give intermediate.
Intermediate is dissolved in 500mL dimethylbenzene, 10.8gN, bis- [N- (2,2,6, the 6- tetramethyl -4- piperidines of N '-are added
Base)] -1,6- hexamethylene diamines (intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines mole of N ' -
Than for 3: 1), after reacting on 60 DEG C of stirring 1h, 4.0g sodium hydroxides are added, then stirs 3h in 100 DEG C, is cooled to room temperature, react
Liquid is washed with water, and organic phase is concentrated to give polymer.
It dissolves a polymer in 150mL hexamethylenes, 30% hydrogen peroxide of 94.4g and 1.5g vanadic anhydrides is added, in 70 DEG C
9h is stirred, room temperature is cooled to, is filtered, excessive saturation NaHSO is added to filtrate3Solution stirs, and separation, organic phase is concentrated to give
Target product, yield 76%.
Embodiment 7
18.4g Cyanuric Chlorides are dissolved in 400mL tetrahydrofurans, after being cooled to 0 DEG C, sequentially add 21.2g N- (2,2,6,
6- tetramethyl -4- piperidyls) n-butylamine (molar ratio of Cyanuric Chloride and N- (2,2,6,6- tetramethyl -4- piperidyls) n-butylamine
It is 1: 1) and 10.1g triethylamines, stirring 1h, organic phase are concentrated to give intermediate.
Intermediate is dissolved in 100mL dichloro-benzenes, bis- [N- (2,2,6, the 6- tetramethyl -4- piperidines of 16.2g N, N '-are added
Base)] -1,6- hexamethylene diamines (intermediate and N, bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1, the 6- hexamethylene diamines mole of N ' -
Than for 2: 1), after reacting on 30 DEG C of stirring 2h, 10.1g triethylamines are added, then stirs 12h in 50 DEG C, is cooled to room temperature, reaction solution
It is washed with water, organic phase is concentrated to give polymer.
It dissolves a polymer in 150mL hexamethylenes, 70% tert-butyl hydroperoxide of 51.5g and 1.7g manganese dioxide is added,
8h is stirred in 60 DEG C, is cooled to room temperature, is filtered, excessive saturation NaHSO is added to filtrate3Solution stirs, separation, and organic phase is dense
Contracting obtains target product, yield 90%.
Embodiment 8
(1) oxidation induction period is tested
Respectively using PP and PE as sample, in ratio addition compound or other auxiliary agents in table 1.Tinuvin770 is haplotype
Low molecular weight hindered amine light stabilizer, i.e., bis- (2,2,6,6- tetramethyl -4- piperidyls) sebacates；Tinuvin622 is polymerization
Type hindered amine light stabilizer；Chimassorb944 is the aggretion type high molecular weight hindered amine light stabilizer of Ciba-Geigy companies；
IrganoxB215 is the compound of antioxidant 1010 and antioxidant 168；1 product of embodiment is what embodiment 1 was prepared
Compound.
Oxidation induction period test has been carried out as sample using the PP and PE that are prepared in table 1, has as a result seen table 2-3 respectively.
Oxidation induction period is tested：The test carries out on DSC200PC apparatus for thermal analysis, connects oxygen and nitrogen, beats
The flow that gas switching device adjusts two kinds of gas respectively is opened, is allowed to reach (50 ± 5) mL/min, then switches to nitrogen.
The opening aluminum dish that (15+0.5) mg samples will be filled is placed on the sample support of thermal analyzer, is heated up with the rate of 20 DEG C/min
To (200 ± 0.1) DEG C, and keep the temperature constant, start recording heating curve.After keeping constant temperature 5min, oxygen is switched to rapidly.When
Termination test when oxidation heat liberation reaches maximum value is recorded on heating curve.
1 sample of table forms
The oxidation induction period of table 2PP samples
The oxidation induction period of table 3PE samples
As can be seen from Table 2 in PP samples, the effect of the product of embodiment 1, which is better than, is added to low molecular weight hindered amine
The sample of light stabilizer Tinuvin770.As can be seen from Table 3, using PE as base material, the antioxidant effect of the product of embodiment 1 is big
In anti-oxidant Irganox B215.And be added to polymerized hindered amine light stabilizer Chimassorb944 and Tinuvin622
Sample compare, the effect of hindered amine light stabilizer of the present invention is more prominent.
(2) fluorescent ultraviolet lamp burn-in test
Using PE as sample, in ratio addition compound or other auxiliary agents in table 4.Wherein 1 product of embodiment is made for embodiment 1
Standby obtained compound.
Fluorescent ultraviolet lamp burn-in test has been carried out as sample using the PE being prepared in table 4, has as a result seen table 5-8 respectively.
Fluorescent ultraviolet lamp burn-in test：The test is carried out according to the requirement of GB/T16422.1-2006, and UV- is used
A365 fluorescent ultraviolet light irradiation samples, power of lamp tube 300W, fluorescent tube length 1200mm, ultraviolet wavelength 260-360nm.Sample is sudden and violent
Show up in complete irradiation range, in face sample end 260mm ranges and fluorescent tube arrangement plane side within the scope of 50mm, irradiation
Temperature 60 C.Sample often irradiates 2h and steams distilled water in sample surfaces 2h.Sampling and testing stretch function after a certain period of time is irradiated respectively,
Calculate elongation at break and extension at break retention rate.
4 sample of table forms
Mechanical property under 5 pure PE illumination of table
Mechanical property under table 6PE+0.5%Chimassorb944 illumination
Mechanical property under table 7PE+0.5%Tinuvin770 illumination
Mechanical property under 1 color light of table 8PE+0.5% embodiments
By experimental result it is known that light stabilizer of the present invention can enable the performance of PE and PP materials very
Good holding, and it is better than traditional polymerized hindered amine light stabilizer Chimassorb944 and haplotype hindered amine light stabilizer
Tinuvin770, to play the role of more preferably extending the materials'use service life.
This specification illustrates the present invention above in conjunction with specific embodiment, it should be appreciated that these describe and explain
It releases and is intended merely to more fully understand the present invention, without constituting any restriction to the present invention.Those skilled in the art are reading
The specific implementation mode of the present invention can be carried out after present specification necessary change without departing from the spirit of the present invention and
Range.Protection scope of the present invention is limited by the accompanying claims, and covers the equivalents of claim.
Claims (4)
1. a kind of hindered amine light stabilizer, which is characterized in that the structural formula of the light stabilizer such as Formulas I：
N is 2-10 in formula,
R1For butyl.
2. the preparation method of hindered amine light stabilizer described in claim 1, which is characterized in that include the following steps：
(1) N- (2,2,6,6- tetramethyl -4- piperidyls) amine and Cyanuric Chloride are obtained by the reaction at -50-20 DEG C as among formula II
Body；
(2) polymerization occurs for II intermediate of formula and bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)] -1,6- hexamethylene diamines of N, N '-anti-
It should generate such as III polymer of formula；
(3) III polymer of formula under hydroperoxides and catalyst action with hexamethylene occur N- alkoxides be obtained by the reaction formula I by
Hinder amine light stabilizer；
Wherein, n 2-10；
R1For butyl；
The step (1) includes：
N- (2,2,6,6- tetramethyl -4- piperidyls) amine and Cyanuric Chloride addition are 1 in molar ratio:Alkali is added, anti-in 1-3
It answers and reacts 1-12h at -50-20 DEG C of temperature, obtain II intermediate of formula；
The step (2) includes：
- 1,6- hexamethylene diamines addition is in molar ratio by II intermediate of formula and N, N '-bis- [N- (2,2,6,6- tetramethyl -4- piperidyls)]
For 1.5-5:1, after stirring 1-2h at 30-60 DEG C, alkali is added, reacts 3-12h at 50-100 DEG C, obtains III polymer of formula；
The step (3) includes：III polymer of formula reacts 5-12h with hexamethylene under hydroperoxides and catalyst action and obtains
To I hindered amine light stabilizer of formula；The wherein described catalyst be selected from molybdenum trioxide, vanadium pentoxide, chromium trioxide, tungstic acid and
The combination of one or more of manganese dioxide；The hydroperoxides are selected from tert-butyl hydroperoxide, Peracetic acid
And/or hydrogen peroxide；The molar ratio of the hindered amine piperidine structure unit of the hydroperoxides addition and addition is 1-6:1；
The molar ratio of the hindered amine piperidine structure unit of the catalyst charge and addition is 0.001-1:1.
3. the preparation method of the hindered amine light stabilizer described in claim 2, which is characterized in that in step (1)：
The reaction temperature is -10-10 DEG C；Reaction dissolvent is in acetone, dichloromethane, toluene, dimethylbenzene and tetrahydrofuran
A combination of one or more；The alkali is selected from the hydroxide of alkali metal, the carbonate of alkali metal, alkaline-earth metal
The combination of one or more of hydroxide, the carbonate of alkaline-earth metal, organic amine and pyridine.
4. the preparation method of the hindered amine light stabilizer described in claim 2, which is characterized in that in step (2)：The alkali choosing
From the hydroxide of alkali metal, the carbonate of alkali metal, the hydroxide of alkaline-earth metal, the carbonate of alkaline-earth metal, organic amine
With the combination of one or more of pyridine；Reaction dissolvent is in toluene, chlorobenzene, dimethylbenzene, dichloro-benzenes and mesitylene
A combination of one or more.
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