CN105859607A - Diphenyl ketone-hindered amine composite light stabilizer and preparation method thereof - Google Patents
Diphenyl ketone-hindered amine composite light stabilizer and preparation method thereof Download PDFInfo
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- CN105859607A CN105859607A CN201610210564.7A CN201610210564A CN105859607A CN 105859607 A CN105859607 A CN 105859607A CN 201610210564 A CN201610210564 A CN 201610210564A CN 105859607 A CN105859607 A CN 105859607A
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- light stabilizer
- amine composite
- reaction
- hals
- hindered amine
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- 150000001412 amines Chemical class 0.000 title claims abstract description 35
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 235000010290 biphenyl Nutrition 0.000 title 1
- 239000004305 biphenyl Substances 0.000 title 1
- 125000006267 biphenyl group Chemical group 0.000 title 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 9
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 4
- 238000006266 etherification reaction Methods 0.000 claims abstract description 4
- 239000013067 intermediate product Substances 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 8
- 239000012965 benzophenone Substances 0.000 description 8
- 239000004753 textile Substances 0.000 description 8
- 239000012634 fragment Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003711 photoprotective effect Effects 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 206010051246 Photodermatosis Diseases 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008845 photoaging Effects 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- -1 chlorine fluorine hydrocarbon Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- CMFNMSMUKZHDEY-UHFFFAOYSA-N peroxynitrous acid Chemical compound OON=O CMFNMSMUKZHDEY-UHFFFAOYSA-N 0.000 description 1
- 230000008832 photodamage Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- 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
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
-
- 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
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of benzophenone-hindered amine composite light stabilizer UH-1, structural formulas are as follows:
The present invention further simultaneously discloses the preparation method of above-mentioned Benzotriazole-hinderamine amine composite photostabilizer, comprising the following steps: 1,2,2,6,6- pentamethvl alcohol are added in thionyl chloride and carry out chlorination reaction, obtain chlorinating intermediate product HALS-Cl; 2,4-DihydroxyBenzophenone, HALS-Cl progress etherification reaction are added in NaOH aqueous solution, obtains product UH-1. Composite light stabilizer of the invention, which has both, absorbs a variety of Photostabilised functions such as ultraviolet light, capture free radical, has a good application prospect to the promotion of high molecular material light fastness.
Description
Technical field
The present invention relates to a kind of benzophenone-hindered amine composite light stabilizer and preparation method thereof.
Background technology
In recent years, due to a large amount of uses of chlorine fluorine hydrocarbon material, atmospheric ozone layer is made to be seriously damaged, earth's surface ultraviolet irradiation
Amount substantially increases.Ultraviolet brings various pathological changes can to the skin of human body, has a strong impact on the health of the mankind.Meanwhile, ultraviolet energy
Enough cause textile photooxidative degradation, destroy fibre property；Dye (face) can also be caused to expect photic faded color, change textile
Color and luster etc..Therefore, improve the anti-ultraviolet property of textile material and textile itself and human body are played a protective role, becoming near
The study hotspot in textile dyeing and finishing field over Nian.
For textile, using light stabilizer to carry out anti UV finishing is photoprotection method the easiest, economic, effective
One of, it is possible to effectively delay the ultraviolet light damage to textile, dyestuff and human body.Commercial application effect preferable two at present
Planting light stabilizer is UV absorbent (UVA) and hindered amine as light stabilizer (HALS).UV absorbent is can be efficient
Absorb ultraviolet the class material discharged by the energy absorbed with the destructive less form of energy such as heat energy, vibrational energy,
The features such as, environmental protection long-acting by it, light color become the light stabilizer that a class is important.And hindered amine light stabilizer is steady with ultraviolet
The model of action determining agent is different, and it is multiple by capture free radical, peroxynitrite decomposition compound and the energy transmitting excited state molecule etc.
Approach suppresses photooxidation droping to react, and is the light stabilizer that in current plastics and film article photoprotection, consumption is maximum.
Human body and textile can be played certain protective action by absorbing ultraviolet by UV absorbent, but UV absorbent
Itself also can be caused loss failure by photochemical degradating (photooxidation, living radical effect), and it is steady to add hindered amines light
Determine agent and just can effectively suppress the photochemical degradating of UV absorbent.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of benzophenone-hindered amine composite light stabilizer, and it can absorb ultraviolet
Line can capture again free radical.
In order to solve above-mentioned technical problem, the present invention provides a kind of benzophenone-hindered amine composite light stabilizer, and its structural formula is:
The present invention provides the preparation method of above-mentioned Benzotriazole-hinderamine amine composite photostabilizer the most simultaneously, comprises the following steps:
1), the chlorination reaction of pentamethvl alcohol:
In thionyl chloride, add 1,2,2,6,6-pentamethvl alcohol, be heated to 60～80 DEG C, continue stirring reaction 1.5～2.5
H, described thionyl chloride: the mol ratio of 1,2,2,6,6-pentamethvl alcohol is 3.5～4.5:1 (preferably 4:1)；
In the product of gained, add dehydrated alcohol, drip triethylamine after uniform stirring until regulation pH to 7 ± 1, then add
Entering ether, uniform stirring is till no longer having new precipitation to produce；Filter, obtain filtrate and filter cake (that is, precipitate) respectively；
Washing filter cake with ether, the cleaning mixture of gained carries out decompression distillation with filtrate after merging, obtain chlorinating intermediate product HALS-Cl；
2), etherification reaction:
Weigh NaOH to be dissolved in deionized water, add 2,4-DihydroxyBenzophenone and stir to being completely dissolved, be warming up to 35～45 DEG C
Rear reaction 1h, is subsequently adding step 1) HALS-Cl that obtains, it is continuously heating to 70～90 DEG C of insulation reaction 15～17h；Institute
The mol ratio stating HALS-Cl:2,4-dihydroxy benaophenonel: NaOH is 1:1:1.3～1.7 (preferably 1:1:1.5)；
After the product n-hexane extraction of gained, the most scrubbed, decompression distillation, obtain product UH-1 (i.e.,
Benzophenone-hindered amine composite light stabilizer).
The improvement of preparation method as the Benzotriazole-hinderamine amine composite photostabilizer of the present invention:
Described step 1) in, dehydrated alcohol is 1:1 with the volume ratio of ether.
The dehydrated alcohol of the 1,2,2,6,6-pentamethvl alcohol adapted 80～120mL of every 0.06mol.
The reaction equation of the present invention is as follows:
The benzophenone of the present invention-hindered amine composite light stabilizer, the molecular structure of this light stabilizer with ehter bond (-O-) as bridge
Base, two ends connect Benzophenone ultraviolet respectively and absorb fragment and hindered amine light stabilizer fragment.
The benzophenone of the present invention-hindered amine composite light stabilizer, its occupation mode is equal to benzophoenone light stabiliziers.
The benzophenone of gained of the present invention-hindered amine composite light stabilizer has the advantage that
Compared with existing commercialization light stabilizer, this Benzotriazole-hinderamine amine composite photostabilizer is absorbing the same of ultraviolet
Time, moreover it is possible to capture free radical by hindered amine, suppress photooxidative degradation, play the effect that light is stable, substantially increase light stable
Efficiency and light resistance, and reduce the loss of light stabilizer.Additionally, this Benzotriazole-hinderamine amine composite photostabilizer has light color
Advantage, it is adaptable to the colourless or photoprotection of light organic material.
In sum, the present invention will have ultra-violet absorption function fragment (as benzophenone ultraviolet absorbs fragment) and be obstructed
Amine light is stablized fragment and is introduced with in a part, develops benzophenone-hindered amine composite light stabilizer.Such compound light is steady
Determining agent and have the multiple Photostabilised function such as absorption ultraviolet, capture free radical concurrently, the lifting to macromolecular material light fastness has
Good application prospect.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
Fig. 1 is the ultraviolet suction of benzophenone-hindered amine composite light stabilizer UH-1 and benzophenone UV-absorber UV-0
Receive spectrogram；
Fig. 2 is benzophenone-hindered amine composite light stabilizer UH-1 and Benzotriazole-hinderamine amine composite photostabilizer II
Uv absorption spectrogram.
Detailed description of the invention
The preparation method of embodiment 1, benzophenone-hindered amine composite light stabilizer, follows the steps below successively:
1), the chlorination reaction of pentamethvl alcohol:
The thionyl chloride of 17.4mL (0.24mol) is added, by 10.3g under conditions of stirring in 100mL there-necked flask
(0.06mol) 1,2,2,6,6-pentamethvl alcohol the most slowly (purpose is to control temperature less than 60 DEG C) joins
State in there-necked flask, be heated to 70 DEG C, continue stirring reaction 2h.After question response terminates, reaction solution is transferred to 250
In mL beaker, in beaker, add the dehydrated alcohol of 100mL, be sufficiently stirred for, drip the most wherein under conditions of ice bath
Triethylamine, until regulation pH value of solution is to neutral, adds 100mL ether in beaker, occurs white depositions, mistake in solution
Filter also washs filter cake twice (consumption of each ether is 50ml) with ether, often carries out 90 DEG C after filtrate and cleaning mixture being merged
Pressure distillation is evaporated off solvent dehydrated alcohol and ether, and the residual liquid in there-necked flask is chlorinating intermediate product HALS-Cl 11.3g
(0.05mol)。
2), etherification reaction:
Weigh 0.6g (0.015mol) NaOH to be dissolved in 30mL deionized water, after being transferred in there-necked flask, add 2.1g
(0.01mol) 2,4-DihydroxyBenzophenone, stirring, to being completely dissolved, reacts 1h, by step 1 after being heated to 40 DEG C)
The dropping to of the HALS-Cl (1.9g, 0.01mol) obtained, in above-mentioned solution, is warming up to 80 DEG C after dropping, keep stirring
Mix continuation reaction 16h.After question response terminates, with normal hexane (10mL × 3) extractive reaction product by several times, merge organic facies (position
In upper strata), fully to wash with saturated aqueous common salt (10mL × 3), air-distillation is evaporated off solvent hexane, remaining in there-necked flask
Product is UH-1 (2.9g, 0.009mol).
Test 1, by benzophenone UV-absorber UV-0 (i.e. 2,4 dihydroxyl benzophenone (UV-0)), product UH-1
It is configured to 2.5 × 10-5DMF (DMF) solution of mol/L, tests it with UV-Vis spectrophotometry photometer
Ultra-violet absorption intensity, result is as shown in Figure 1.
As shown in Figure 1, compound UV-0 has stronger ultraviolet absorption ability in UVA and UVB district.At compound UV-0
Middle introducing hindered amine fragment, not quite has lifting to molar extinction coefficient to the compound maximum absorption wavelength impact in ultra-violet (UV) band
Effect.
Experiment 2: compound self light steady testing
With reference to the regulation of GB/T16422.2 1999, compound is made DMF solution (2 × 10-5Mol/L), in photo-aging box
Carry out artificial acceleration light aging test (xenon lamp 1000Wxl), aging the temperature inside the box 55 DEG C.Sample after aging certain time, with purple
Outer absorption spectrometer tests the change of light stabilizer content in its solution, and result is as shown in table 1:
Table 1
Knowable to upper table 1, compound 2,4-DihydroxyBenzophenone introduces hindered amine fragment and can improve the fast light of compound self
Stability, this is due to the capture to free radical of the hindered amine fragment so that it is light stabilizer strengthens.
Experiment 3, the compound light stabilization to polymeric material
With reference to the regulation of GB/T16422.2 1999, with DMF compound and acrylon dissolved and to make solution (acrylon are in the solution
Concentration is 1.5g/L, and compound concentration in the solution is 3 × 10-3Mol/L), photo-aging box carries out artificial acceleration photoaging
Test (xenon lamp 1000W), aging the temperature inside the box 55 DEG C.Sample after aging 12h, divide equally with viscous after Ubbelohde viscometer test pre-irradiation
The change of son amount, result is as shown in table 2:
Table 2
| Compound | Pre-irradiation Mv | Mv after irradiation |
| PAN (acrylon) | 43300 | 32700 |
| UV-0 | 43300 | 37450 |
| UH-1 | 43300 | 41880 |
Illustrate: the compound of the present invention has preferably to poly-than compound of the prior art (2,4 dihydroxyl benzophenone)
The Photostabilised barrier propterty of compound.
Experiment 4, by UV absorbent II (that is, Benzotriazole-hinderamine amine composite photostabilizer II, structural formula is as follows) according to
Method described in experiment 1 carries out detecting that (that is, II and UH-1 concentration in DMF is 2.5 × 10-5MoL/L), itself and the present invention
Comparative result as described in Figure 2.
According to Fig. 2, we learn: owing to benzotriazole uv absorption fragment is in the shortwave part (350-400nm) of visible region
Having certain absorption intensity, therefore such Benzotriazole-hinderamine amine composite photostabilizer apparent colour is light yellow, colourless
And light color organic material photoprotection aspect application is limited.And the hexichol in the benzophenone of the present invention-hindered amine composite light stabilizer
It is lower that ketone uv absorption fragment partially absorbs intensity at visible region shortwave, and almost colourless, range of application is wider.
Finally, in addition it is also necessary to be only several specific embodiments of the present invention it is noted that listed above.Obviously, the present invention is not
It is limited to above example, it is also possible to have many deformation.Those of ordinary skill in the art directly can lead from present disclosure
The all deformation gone out or associate, are all considered as protection scope of the present invention.
Claims (3)
1. benzophenone-hindered amine composite light stabilizer, is characterized in that structural formula is:
2. the preparation method of Benzotriazole-hinderamine amine composite photostabilizer as claimed in claim 1, is characterized in that including following
Step:
1), the chlorination reaction of pentamethvl alcohol:
In thionyl chloride, add 1,2,2,6,6-pentamethvl alcohol, be heated to 60～80 DEG C, continue stirring reaction 1.5～2.5
H, described thionyl chloride: the mol ratio of 1,2,2,6,6-pentamethvl alcohol is 3.5～4.5:1；
In the product of gained, add dehydrated alcohol, drip triethylamine after uniform stirring until regulation pH to 7 ± 1, then add
Entering ether, uniform stirring is till no longer having new precipitation to produce；Filter, obtain filtrate and filter cake respectively；With ether washing filter
Cake, the cleaning mixture of gained carries out decompression distillation, obtains chlorinating intermediate product HALS-Cl after merging with filtrate；
2), etherification reaction:
Weigh NaOH to be dissolved in deionized water, add 2,4-DihydroxyBenzophenone and stir to being completely dissolved, be warming up to 35～45 DEG C
Rear reaction 1h, is subsequently adding step 1) HALS-Cl that obtains, it is continuously heating to 70～90 DEG C of insulation reaction 15～17h；Institute
The mol ratio stating HALS-Cl:2,4-dihydroxy benaophenonel: NaOH is 1:1:1.3～1.7；
After the product n-hexane extraction of gained, the most scrubbed, decompression distillation, obtain product UH-1.
The preparation method of Benzotriazole-hinderamine amine composite photostabilizer the most according to claim 2, is characterized in that:
Described step 1) in, dehydrated alcohol is 1:1 with the volume ratio of ether.
The dehydrated alcohol of the 1,2,2,6,6-pentamethvl alcohol adapted 80～120mL of every 0.06mol.
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| CN201610210564.7A CN105859607B (en) | 2016-04-05 | 2016-04-05 | Benzophenone-hindered amine composite light stabilizer and preparation method thereof |
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| CN201610210564.7A CN105859607B (en) | 2016-04-05 | 2016-04-05 | Benzophenone-hindered amine composite light stabilizer and preparation method thereof |
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| CN108824080A (en) * | 2018-07-05 | 2018-11-16 | 朱文杰 | A kind of preparation method of the stabilizer for fluorescer |
| CN109369957A (en) * | 2018-11-20 | 2019-02-22 | 华南理工大学 | It is a kind of to have both UV absorption and fire-retardant difunctional phosphorus flame retardant and preparation and application |
| CN109439016A (en) * | 2018-10-19 | 2019-03-08 | 绍兴金美珂化工有限公司 | A kind of sun-proof acid dyes of red and preparation method thereof |
| CN110079119A (en) * | 2019-04-12 | 2019-08-02 | 江苏吉华化工有限公司 | Sun-proof acid dyes of the structure bis-azo type of acid containing H and preparation method thereof |
| CN111253620A (en) * | 2020-04-09 | 2020-06-09 | 福州大学 | Ultraviolet light and oxygen aging resistant composite light stabilizer and preparation method thereof |
| US11417857B2 (en) | 2018-01-24 | 2022-08-16 | Samsung Display Co., Ltd. | Heterocyclic compound and electronic apparatus |
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|---|---|---|---|---|
| JPS58159460A (en) * | 1982-03-17 | 1983-09-21 | Sumitomo Chem Co Ltd | 2,2,6,6-tetramethylpiperidine derivative and its preparation |
| CN1173493A (en) * | 1996-08-02 | 1998-02-18 | 赫彻斯特股份公司 | Novel light stabilizers based on sterically hindered amines |
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| US11417857B2 (en) | 2018-01-24 | 2022-08-16 | Samsung Display Co., Ltd. | Heterocyclic compound and electronic apparatus |
| CN108824080A (en) * | 2018-07-05 | 2018-11-16 | 朱文杰 | A kind of preparation method of the stabilizer for fluorescer |
| CN109439016A (en) * | 2018-10-19 | 2019-03-08 | 绍兴金美珂化工有限公司 | A kind of sun-proof acid dyes of red and preparation method thereof |
| CN109439016B (en) * | 2018-10-19 | 2020-04-07 | 绍兴金美珂化工有限公司 | Red sun-proof acid dye and preparation method thereof |
| CN109369957A (en) * | 2018-11-20 | 2019-02-22 | 华南理工大学 | It is a kind of to have both UV absorption and fire-retardant difunctional phosphorus flame retardant and preparation and application |
| CN110079119A (en) * | 2019-04-12 | 2019-08-02 | 江苏吉华化工有限公司 | Sun-proof acid dyes of the structure bis-azo type of acid containing H and preparation method thereof |
| CN111253620A (en) * | 2020-04-09 | 2020-06-09 | 福州大学 | Ultraviolet light and oxygen aging resistant composite light stabilizer and preparation method thereof |
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