CN105859607B - Benzophenone-hindered amine composite light stabilizer and preparation method thereof - Google Patents
Benzophenone-hindered amine composite light stabilizer and preparation method thereof Download PDFInfo
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- CN105859607B CN105859607B CN201610210564.7A CN201610210564A CN105859607B CN 105859607 B CN105859607 B CN 105859607B CN 201610210564 A CN201610210564 A CN 201610210564A CN 105859607 B CN105859607 B CN 105859607B
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- light stabilizer
- benzophenone
- hindered amine
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- 150000001412 amines Chemical class 0.000 title claims abstract description 37
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 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
- 239000012965 benzophenone Substances 0.000 claims abstract description 9
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 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 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001914 filtration 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
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 150000003254 radicals Chemical class 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012964 benzotriazole Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 7
- 239000012634 fragment Substances 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 230000003711 photoprotective effect Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002972 Acrylic fiber Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000007788 liquid 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
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- -1 chlorine fluorine hydrocarbon Chemical class 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
- 238000007599 discharging Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 230000003902 lesion Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- CMFNMSMUKZHDEY-UHFFFAOYSA-N peroxynitrous acid Chemical compound OON=O CMFNMSMUKZHDEY-UHFFFAOYSA-N 0.000 description 1
- 230000008845 photoaging Effects 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
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009941 weaving 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
Abstract
The invention discloses a kind of benzophenone hindered amine composite light stabilizer UH 1, its structural formula is：The present invention further simultaneously discloses the preparation method of above-mentioned benzotriazole hindered amine composite light stabilizer, comprises 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 dihydroxy benaophenonels, HALS Cl progress etherification reactions are added in NaOH aqueous solutions, obtains product UH 1.The composite light stabilizer of the present invention has a variety of Photostabilised functions, the liftings to high molecular material light fastness such as absorption ultraviolet, capture free radical concurrently and has a good application prospect.
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, since a large amount of of chlorine fluorine hydrocarbon material use, atmospheric ozone layer is made to be seriously damaged, earth's surface ultraviolet
Irradiation substantially increases.Ultraviolet can carry out various lesions to the skin tape of human body, seriously affect the health of the mankind.It is meanwhile ultraviolet
Line can cause textile photooxidative degradation, destroy fibre property；Dye (face) can also be caused to expect photic faded color, change weaving
Product color and luster etc..Therefore, improve the anti-ultraviolet property of textile material and play a protective role in itself with human body to textile, become
The research hotspot in textile dyeing and finishing field in recent years.
For textile, it is the easiest, economical and effective photoprotection to carry out anti UV finishing using light stabilizer
One of method, can effectively delay light damage of the ultraviolet to textile, dyestuff and human body.Commercial application effect is preferable at present
Two kinds of light stabilizers be ultra-violet absorber (UVA) and hindered amine as light stabilizer (HALS).Ultra-violet absorber is can be high
Effect absorbs ultraviolet and the one kind for discharging the energy absorbed with the destructive less form of energy such as thermal energy, vibrational energy
Material, by its features such as long-acting, environmentally friendly, light as a kind of important light stabilizer.And hindered amine light stabilizer and purple
The mode of action of outside line stabilizer is different, it is by capturing free radical, peroxynitrite decomposition compound and the energy for transmitting excited state molecule
The number of ways such as amount are reacted to suppress photooxidation droping, are that the light of dosage maximum in current plastics and film article photoprotection is stablized
Agent.
Ultra-violet absorber can play human body and textile certain protective action, but ultraviolet by absorbing ultraviolet
Absorbent can also be subject to photochemical degradating (photooxidation, living radical effect) to cause loss failure in itself, and add hindered amine
Class light stabilizer can effectively suppress the photochemical degradating of ultra-violet absorber.
The content 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, it can
Free radical can be captured again by absorbing ultraviolet.
In order to solve the above technical problem, the present invention provides a kind of benzophenone-hindered amine composite light stabilizer, it is tied
Structure formula is：
The present invention goes back while provides the preparation method of above-mentioned Benzotriazole-hinderamine amine composite photostabilizer, including with
Lower step：
1), the chlorination reaction of pentamethvl alcohol：
1,2,2,6,6- pentamethvl alcohol are added in thionyl chloride, are heated to 60~80 DEG C, it is anti-to continue stirring
Answer 1.5~2.5h, the thionyl chloride：The molar ratio of 1,2,2,6,6- pentamethvl alcohol is 3.5~4.5:1 (preferably 4:
1)；
Absolute ethyl alcohol is added in the reaction product of gained, triethylamine is added dropwise after uniform stirring until adjusting pH to 7 ± 1,
Then ether is added, uniform stirring there is no new precipitation untill producing；Filtering, obtains filtrate respectively and filter cake (that is, precipitates
Thing)；Filter cake is washed with ether, and the cleaning solution of gained is evaporated under reduced pressure after merging with filtrate, obtains 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
1h is reacted after~45 DEG C, the HALS-Cl that step 1) obtains then is added, is continuously heating to 70~90 DEG C of 15~17h of insulation reaction；
The HALS-Cl：2,4 dihydroxyl benzophenone：The molar ratio of NaOH is 1:1:1.3~1.7 (preferably 1:1:1.5)；
After the reaction product n-hexane extraction of gained, washed successively, vacuum distillation, obtains product UH-1 (that is, hexichol
Ketone-hindered amine composite light stabilizer).
Improvement as the preparation method of the Benzotriazole-hinderamine amine composite photostabilizer of the present invention：
In the step 1), the volume ratio of absolute ethyl alcohol and ether is 1:1.
The absolute ethyl alcohol of 80~120mL of 1,2,2,6,6- pentamethvl alcohol adapteds per 0.06mol.
The reaction equation of the present invention is as follows：
Benzophenone-hindered amine composite light stabilizer of the present invention, the molecular structure of the light stabilizer is with ehter bond (- O-)
For abutment, both ends connect Benzophenone ultraviolet and absorb fragment and hindered amine light stabilizer fragment respectively.
Benzophenone-hindered amine composite light stabilizer of the present invention, its occupation mode are equal to benzophenone light stabilization
Agent.
Benzophenone-hindered amine composite light stabilizer of gained of the invention has the following advantages that：
Compared with existing commercialization light stabilizer, the Benzotriazole-hinderamine amine composite photostabilizer is ultraviolet in absorption
While line, moreover it is possible to by the amine capture free radical that is obstructed, suppress photooxidative degradation, play the role of light stabilization, substantially increase
Light stable efficiency and light resistance, and reduce the loss of light stabilizer.In addition, the Benzotriazole-hinderamine amine composite photostabilizer
There is light color, suitable for the photoprotection of colourless or light organic material.
In conclusion the present invention will have ultraviolet radiation absorption function fragment (such as benzophenone ultraviolet absorption fragment) with
Hindered amines light is stablized fragment and is introduced into same molecule, develops benzophenone-hindered amine composite light stabilizer.Such is compound
Type light stabilizer, which has concurrently, absorbs a variety of Photostabilised functions such as ultraviolet, capture free radical, to high molecular material light fastness
Lifting has a good application prospect.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the purple of benzophenone-hindered amine composite light stabilizer UH-1 and benzophenone UV-absorber UV-0
Outer absorption spectrogram；
Fig. 2 is benzophenone-hindered amine composite light stabilizer UH-1 and Benzotriazole-hinderamine amine composite photostabilizer
The UV absorption spectrogram of II.
Embodiment
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 into 100mL three-necked flasks, by 10.3g under conditions of stirring
Slowly (purpose is that control temperature is no more than 60 DEG C) is added to the 1,2,2,6,6- pentamethvls alcohol of (0.06mol) in batches
State in three-necked flask, be heated to 70 DEG C, continue stirring reaction 2h.After question response, reaction solution is transferred to 250mL
In beaker, the absolute ethyl alcohol of 100mL is added into beaker, is sufficiently stirred, three second is slowly added dropwise thereto under conditions of ice bath
Amine, until adjusting pH value of solution to neutrality, 100mL ether is added into beaker, white depositions occurs in solution, filters and use second
Ether washing filter cake carries out 90 DEG C of air-distillations twice (dosage of each ether is 50ml), after filtrate and cleaning solution are merged and is evaporated off
Solvent absolute ethyl alcohol and ether, the residual liquid in three-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 waters, 2.1g is added after being transferred in three-necked flask
(0.01mol) 2,4-DihydroxyBenzophenone, stirs to being completely dissolved, reacts 1h after being heated to 40 DEG C, and step 1) is obtained
The HALS-Cl's (1.9g, 0.01mol) arrived is added dropwise in above-mentioned solution, and 80 DEG C are warming up to after being added dropwise, is kept stirring continuation
React 16h.After question response, with n-hexane (10mL × 3) gradation extractive reaction product, merge organic phase (being located at upper strata),
Fully washed with saturated salt solution (10mL × 3), solvent hexane is evaporated off in air-distillation, and residual product is UH-1 in three-necked flask
(2.9g,0.009mol)。
Experiment 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 (n,N-Dimethylformamide) solution of mol/L, it is tested with UV-Vis spectrophotometry photometer
Ultraviolet radiation absorption intensity, the results are shown in Figure 1.
As shown in Figure 1, compound UV-0 has stronger ultraviolet absorption ability in UVA and UVB areas.In compound UV-0
Hindered amine fragment is introduced, less having lifting to molar extinction coefficient is influenced on maximum absorption wavelength of the compound in ultra-violet (UV) band
Effect.
Experiment 2：Combound itself light steady testing
With reference to the regulation of GB/T16422.2-1999, DMF solution (2 × 10 is made in compound-5Mol/L), in light aging
Artificial acceleration light aging test (xenon lamp 1000Wxl), 55 DEG C of aging the temperature inside the box are carried out in case.Aging samples after a certain period of time,
The change of light stabilizer content in its solution is tested with ultraviolet absorption spectrum instrument, the results are shown in Table 1：
Table 1
It was found from upper table 1, hindered amine fragment is introduced in compound 2,4-DihydroxyBenzophenone can improve compound certainly
The light fastness stability of body, this is because capture of the hindered amine fragment to free radical, strengthens its light stabilizer.
Test light stabilization of the 3, compound to polymeric material
With reference to the regulation of GB/T16422.2-1999, compound and acrylic fibers dissolving are made solution (acrylic fibers are molten with DMF
Concentration in liquid is 1.5g/L, and the concentration of compound in the solution is 3 × 10-3Mol/L), carry out manually adding in photo-aging box
Fast light aging test (xenon lamp 1000W), 55 DEG C of aging the temperature inside the box.Sampled after aging 12h, pre-irradiation is tested with Ubbelohde viscometer
The change of viscosity average molecular weigh afterwards, the results are shown in Table 2：
Table 2
| Compound | Pre-irradiation Mv | Mv after irradiation |
| PAN (acrylic fibers) | 43300 | 32700 |
| UV-0 | 43300 | 37450 |
| UH-1 | 43300 | 41880 |
Explanation：The compound (2,4 dihydroxyl benzophenone) of the compound of the present invention than in the prior art has more preferable
To uv stabilization of polymer barrier propterty.
Experiment 4, by ultra-violet absorber II (that is, Benzotriazole-hinderamine amine composite photostabilizer II, structural formula are as follows)
It is detected that (that is, the concentration of II and UH-1 in DMF is 2.5 × 10 according to 1 the method for experiment-5MoL/L), itself and this hair
Bright Comparative result is as described in Figure 2.
According to Fig. 2, we learn：Since benzotriazole UV absorption fragment is in the shortwave part (350- of visible region
400nm) there is certain absorption intensity, therefore such Benzotriazole-hinderamine amine composite photostabilizer apparent colour is pale yellow
Color, using limited in terms of colourless and light organic material photoprotection.And the compound light of benzophenone-hindered amine of the present invention is steady
Determine benzophenone UV in agent and absorb fragment lower, almost colourless, the application range that in visible region shortwave partially absorbs intensity
It is wider.
Finally, it should also be noted that it is listed above be only the present invention several specific embodiments.Obviously, this hair
It is bright to be not limited to above example, there can also be many deformations.Those of ordinary skill in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (3)
1. benzophenone-hindered amine composite light stabilizer, it is characterized in that structural formula is：
2. the preparation method of benzophenone as claimed in claim 1-hindered amine composite light stabilizer, it is characterized in that including
Following steps：
1), the chlorination reaction of pentamethvl alcohol：
1,2,2,6,6- pentamethvl alcohol are added in thionyl chloride, are heated to 60~80 DEG C, continue stirring reaction 1.5
~2.5h, the thionyl chloride：The molar ratio of 1,2,2,6,6- pentamethvl alcohol is 3.5~4.5:1；
Absolute ethyl alcohol is added in the reaction product of gained, triethylamine is added dropwise after uniform stirring until adjusting pH to 7 ± 1, then
Ether is added, uniform stirring there is no new precipitation untill producing；Filtering, obtains filtrate and filter cake respectively；Washed with ether
Filter cake, the cleaning solution of gained are evaporated under reduced pressure after merging with filtrate, 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
1h is reacted after DEG C, the HALS-Cl that step 1) obtains then is added, is continuously heating to 70~90 DEG C of 15~17h of insulation reaction；It is described
HALS-Cl：2,4 dihydroxyl benzophenone：The molar ratio of NaOH is 1:1:1.3~1.7；
After the reaction product n-hexane extraction of gained, washed successively, vacuum distillation, it is compound to obtain benzophenone-hindered amine
Type light stabilizer.
3. the preparation method of according to claim 2-benzophenone hindered amine composite light stabilizer, it is characterized in that：
In the step 1), the volume ratio of absolute ethyl alcohol and ether is 1:1；
The absolute ethyl alcohol of 80~120mL of 1,2,2,6,6- pentamethvl alcohol adapteds per 0.06mol.
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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 |
| 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 |
| CN110079119B (en) * | 2019-04-12 | 2020-08-18 | 杭州天马思宏数码科技有限公司 | Bisazo type sun-proof acid dye containing H acid structure 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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| JPS58159460A (en) * | 1982-03-17 | 1983-09-21 | Sumitomo Chem Co Ltd | 2,2,6,6-tetramethylpiperidine derivative and its preparation |
| DE19631244A1 (en) * | 1996-08-02 | 1998-02-12 | Clariant Gmbh | New light stabilizers based on sterically hindered amines |
| CA2427646A1 (en) * | 2000-11-03 | 2002-08-01 | Cytec Technology Corp. | Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same |
| CN101845013B (en) * | 2010-05-18 | 2012-05-23 | 北京天罡助剂有限责任公司 | Multi-hindered piperidyl-containing hindered amide compound used for light stabilizer and preparation method thereof |
| TWI513762B (en) * | 2014-04-09 | 2015-12-21 | Fdc Lees Chemical Industry Co | Stabilizers with hindered phenolic group and hindered amine, and their compositions |
| CN105040428A (en) * | 2015-08-29 | 2015-11-11 | 浙江理工大学 | Reactive light stabilizer suitable for protein fibers and preparing method thereof |
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2016
- 2016-04-05 CN CN201610210564.7A patent/CN105859607B/en not_active Expired - Fee Related
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Application publication date: 20160817 Assignee: ZHEJIANG SCI-TECH UNIVERSITY SHANGYU INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Assignor: ZHEJIANG SCI-TECH University Contract record no.: X2019330000038 Denomination of invention: Diphenyl ketone-hindered amine composite light stabilizer and preparation method thereof Granted publication date: 20180515 License type: Common License Record date: 20191108 |
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