CN105693641A - Preparation method of triazine ultraviolet absorbent - Google Patents
Preparation method of triazine ultraviolet absorbent Download PDFInfo
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- CN105693641A CN105693641A CN201511019160.1A CN201511019160A CN105693641A CN 105693641 A CN105693641 A CN 105693641A CN 201511019160 A CN201511019160 A CN 201511019160A CN 105693641 A CN105693641 A CN 105693641A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title description 8
- 230000002745 absorbent Effects 0.000 title description 6
- 239000002250 absorbent Substances 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002879 Lewis base Substances 0.000 claims abstract description 5
- 150000007527 lewis bases Chemical class 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- 229940049706 benzodiazepine Drugs 0.000 claims description 11
- 150000001557 benzodiazepines Chemical class 0.000 claims description 11
- -1 lauryl diglycidyl ether Chemical compound 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 208000035126 Facies Diseases 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract 4
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 abstract 2
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 abstract 1
- FROCQMFXPIROOK-UHFFFAOYSA-N 4-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]benzene-1,3-diol Chemical compound CC1=CC(C)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(O)=CC=2)O)=N1 FROCQMFXPIROOK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000037029 cross reaction Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 2- [4- [ 2-hydroxy-3-dodecyloxypropyl ] oxy-2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine shown as a formula (I), which comprises the following steps: 4- [4, 6-di (2, 4-xylyl) -1,3, 5-triazine-2-yl ] -1, 3-benzenediol (benzenediol for short) and dodecyl glycidyl ether are used as raw materials, Lewis base is used as a catalyst, and the reaction is carried out in water/organic solvent at the temperature of 70-120 ℃; the solvent can be one or a mixture of toluene, xylene, N-Dimethylformamide (DMF), butanone and the like. The reaction process comprises two steps: (1) weighing a certain amount of benzenediol, dissolving the benzenediol into a preferable solvent, and reacting the benzenediol with Lewis base in an equal molar ratio to generate an intermediate (II); (2) after reacting for a period of time, dissolving excessive dodecyl glycidyl ether in a corresponding solvent, slowly dripping into the solution, continuing reflux reaction for a certain time, washing with water, and then distilling under reduced pressure to obtain the target product (I).
Description
Technical field
The preparation method that the present invention relates to double; two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazine of a kind of 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-。
Background technology
Along with the fast development of macromolecular material, the research and development of its auxiliary agent enjoy favor。Triazine-based ultraviolet absorbent, because of the feature such as its high efficiency, high temperature resistant, lighter color, the compatibility be good, has good development prospect as novel light stabilizer。Although the number of 2,4,6 upper substituted hydroxies is more many in triazine, absorbing ultraviolet ability more strong, but hydroxy number is more many, uv absorption scope red shift degree is more big, and absorption portion visible ray, and after causing interpolation, macromolecule material product turns to be yellow。Conventional triazines as light stabilizer has triazine-5, triazine-425, UV-1164, UV-1577 etc.。The preparation of many this triaryl-1,3,5-triazines compounds and application are referred to the patent of invention of following publication number: US6306939B1, CN1478083A, US3118837 etc.。
On the other hand, investigation finds not much lower by the compound of etherificate than a hydroxyl by the triazine parent compound of etherificate dissolubility in dibutyl phthalate, it is the alkoxyl with branched hydroxy group by phenolic hydroxyl group etherificate, can significantly strengthen the compatibility (referring to the Sui Zhaode light stabilizer write and the application technology first edition, 197-214 page) of product and macromolecule product。
Coating, as the series products in macromolecular material, has the character of oneself uniqueness, is film forming matter (resin), pigment, solvent and additive, organic solvent or water the thick liquid being configured to。Described coating and compositions thereof are possibly together with other compositionss, but be not limited to the compositionss such as solvent, dyestuff, plasticiser, stabilizer, it is possible to composition example see the industrial chemistry encyclopaedia the 5th edition of Ullmann., A18 rolls up, 429-471 page, is incorporated herein by reference。Triazine uv absorber described in this patent can be used for these coating and compositions thereof, and carries out aging resistance experiment test with Du Li automobile varnish。
Summary of the invention
The present invention relates to a kind of triazine-based ultraviolet absorbent shown in formula I, double; two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazines of its chemistry 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl] by name-4,6-:
UV-absorber products of the present invention mainly has industrial paint and the automobile coating of superior performance and life requirement。This absorbent is a kind of with the UV absorbers of other component no cross reactions in system, the coating system that special exploitation solidifies for amine catalysis or metal catalytic, has the better compatibility with coating。Through the process in later stage, this product is usable in water miscible coating。
Harmful substance in complex steps, the uneconomical environmental protection of catalyst, production waste water is there is more for prior art, the present invention provides a kind of 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl) 1,3, the preparation method of 5-triazine, have technique simple, easy to operate, without advantages such as Litter pollutions。
The technical solution used in the present invention is:
The preparation method of a kind of double; two (2,4-3,5-dimethylphenyl)-1,3,5-triazines of 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-, specifically comprises the following steps that
(1). weigh a certain amount of Benzodiazepines and be added in there-necked flask, then there-necked flask is placed in thermostatical oil bath；
(2). add appropriate solvent, after a certain amount of catalyst, heat and stir, after reaction 1h, obtain intermediate；
(3). after lauryl diglycidyl ether is dissolved to coordinative solvent, drop to above-mentioned solution, continue reaction 24-48h；
(4). after reaction terminates, washing, separatory, target product is steamed to obtain in rotation。
Compared with prior art, advantages of the present invention and having the active effect that
1, the present invention adopts one pot of two-step method, simple and easy to do；First step Benzodiazepines and lewis base react and generate the phenolate with excellent nucleophilicity；Epoxide ring on the orientable attack glycidyl ether of second step phenolate, carries out ring-opening reaction。The method, without processing intermediate product, reduces the generation of operating procedure and the three wastes, and solvent and catalyst can realize recycling, simple to operate, saves cost。
2, product of the present invention is as a kind of UV absorbent, there is molecular weight higher, heat, light etc. are stable, there is the ultra-violet absorption usefulness of excellence, molecular structure is unique, all there is the good compatibility with the base material of opposed polarity, can be applicable to have in superior performance and the different industrial paint of life requirement, automobile coating and other type coatings。
Accompanying drawing illustrates:
Fig. 1 is the synthetic route of double; two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazine of 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-。
Fig. 2 is double; two (2,4-3,5-dimethylphenyl) the 1,3,5-triazine product of 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-1HNRM spectrogram。The chemical shift ownership of main peaks: 13.3ppm is hydrogen bond displacement in polyhydroxylated molecule, and 6.5ppm is hydrogen chemical shifts on phenolic hydroxyl group。8.4ppm is the chemical shift of the aromatic ring hydrogen near triazine ring, and 2.32ppm is substituent methyl on aromatic ring, CH between hydroxyl and alkyl ether2On H chemical shift at 3-3.5ppm etc.。
Fig. 3 is the uv absorption spectrogram of this product。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, and following example are explanation of the invention and protection scope of the present invention is not limited to following example。
Embodiment 1
Weigh 1.98g Benzodiazepines (5.39mmol) and be added in 250mL there-necked flask, then there-necked flask is placed in thermostatical oil bath。Add 70mL dimethylbenzene, open heating and stirring, be subsequently adding identical equivalent NaOH (be first dissolved in 10mL deionized water by NaOH, and add the quaternary ammonium salt of 0.1 times of equivalent), be warming up to 70 DEG C。Reaction 1h, is dissolved in 30mL dimethylbenzene by 1.67mL lauryl diglycidyl ether (6.2mmol) and is added drop-wise in above-mentioned solution, reacts 24h at 70 DEG C。Catalyst is removed after terminating by reaction by the method washed, and rotary evaporation removes solvent, uses chromatographic column separating-purifying, obtains corresponding product。
Embodiment 2
According to embodiment 1, weigh 1.98g Benzodiazepines (5.39mmol) and be added in 250mL there-necked flask, then there-necked flask is placed in thermostatical oil bath。Add 70mL dimethylbenzene, open heating and stirring, be subsequently adding identical equivalent KOH (be first dissolved in 10mL deionized water by KOH, and add the quaternary ammonium salt of 0.1 times of equivalent), after being warming up to 110 DEG C。After reaction 1h, 2.17mL lauryl diglycidyl ether (8.08mmol) is dissolved in 30mL dimethylbenzene and is added drop-wise in above-mentioned solution, at 110 DEG C, react 24h。Catalyst is removed after terminating by reaction by the method washed, and rotary evaporation removes solvent, uses chromatographic column separating-purifying, obtains corresponding product。
Embodiment 3
According to embodiment 1, weigh 1.98g Benzodiazepines (5.39mmol) and be added in 250mL there-necked flask, then there-necked flask is put in thermostatical oil bath。Add 70mL dimethylbenzene, open heating and stirring, be subsequently adding identical equivalent LiOH (be first dissolved in 10mL deionized water by LiOH, and add the quaternary ammonium salt of 0.1 times of equivalent), after being warming up to 100 DEG C。After reaction 1h, 1.67mL lauryl diglycidyl ether (6.2mmol) is dissolved in the dimethylbenzene of 30mL and is added drop-wise in above-mentioned solution, at 100 DEG C, react 48h。Catalyst is removed after terminating by reaction by the method washed, and rotary evaporation removes solvent, uses chromatographic column separating-purifying, obtains corresponding product。
Embodiment 4
According to embodiment 1, weigh 1.98g Benzodiazepines (5.39mmol) and be added in 250mL there-necked flask, then there-necked flask is placed in thermostatical oil bath。Adding 70mL toluene, open heating and stirring, the inorganic base KOH being subsequently adding identical equivalent is catalyst (is first dissolved in 10mL deionized water by KOH, and adds the quaternary ammonium salt of 0.1 times of equivalent), after being warming up to 90 DEG C。After reaction 1h, 1.67mL lauryl diglycidyl ether (6.2mmol) is dissolved in 30mL dimethylbenzene and is added drop-wise in above-mentioned solution, at 90 DEG C, react 36h。Catalyst is removed after terminating by reaction by the method washed, and rotary evaporation removes solvent, uses chromatographic column separating-purifying, obtains corresponding product。
Embodiment 5
According to embodiment 1, weigh 1.98g Benzodiazepines (5.39mmol) and be added in 250mL there-necked flask, then there-necked flask is placed in thermostatical oil bath。Add 70mL butanone, open heating and stirring, be subsequently adding the inorganic base NaOH (be first dissolved in 10mL deionized water by NaOH, and add the quaternary ammonium salt of 0.1 times of equivalent) of identical equivalent, after being warming up to 80 DEG C。After reaction a period of time, by 1.67mL lauryl diglycidyl ether (6.2mmol) dissolved dilution in 30mL butanone, it is added drop-wise in above-mentioned solution, at 80 DEG C, reacts 24h。Catalyst is removed after terminating by reaction by the method washed, and rotary evaporation removes solvent, uses chromatographic column separating-purifying, obtains corresponding product。
Embodiment 6
According to embodiment 1, weigh 1.98g Benzodiazepines (5.39mmol) and be added in 250mL there-necked flask, then there-necked flask is placed in thermostatical oil bath。Adding 70mLDMF, open heating and stirring, the NaOH being subsequently adding identical equivalent makees catalyst (be first dissolved in 10mL deionized water by NaOH, and add the quaternary ammonium salt of 0.1 times of equivalent), after being warming up to 110 DEG C。After reaction a period of time, by 1.67mL lauryl diglycidyl ether (6.2mmol) dissolved dilution in 30mL dimethylbenzene, it is added drop-wise in above-mentioned solution, at 110 DEG C, reacts 48h。Catalyst is removed after terminating by reaction by the method washed, and rotary evaporation removes solvent, uses chromatographic column separating-purifying, obtains corresponding product。
Embodiment 7
Prepared by above-described embodiment 6 after products therefrom and other type light stabilizers (being provided by rising star's chemistry) and DuxoneDX42 automobile varnish (being provided by Du Pont's paint) mix homogeneously, with reference to standard GB/T/T1727-92, carry out sample preparation；Sample preparation is accelerated senile experiment with reference to international standard ISO4892-3 after completing；Experiment carries out performance comparison after terminating。
Above-mentioned comparing result shows, the ageing resistace of product of the present invention is better than other kinds of UV absorbent。
Claims (8)
1. double; two (2, the 4-3,5-dimethylphenyl)-1 of 2-[4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-, 3, the preparation method of 5-triazine, its structural formula is as shown in (I), it is characterised in that described method comprises the steps:
(1). weigh a certain amount of Benzodiazepines and be added in there-necked flask, then there-necked flask is placed in thermostatical oil bath；
(2). add appropriate solvent, after a certain amount of catalyst, heat and stir, after reaction 1h, obtain intermediate (II)；
(3). after lauryl diglycidyl ether is dissolved to coordinative solvent, drop to above-mentioned solution, continue reaction 24-48h；
(4). after reaction terminates, washing, separatory, target product (I) is steamed to obtain in rotation。
2. 2-according to claim 1 [4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl)-1,3, the preparation method of 5-triazine, it is characterized in that: described solvent can be toluene, dimethylbenzene, DMF (DMF), butanone。
3. 2-according to claim 1 [4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl)-1,3, the preparation method of 5-triazine, it is characterised in that: the catalyst that reactions steps (2) adopts is lewis base LiOH, NaOH, KOH。
4. 2-according to claim 3 [4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl)-1,3, the preparation method of 5-triazine, it is characterised in that: the mole dosage of lewis base and Benzodiazepines mole dosage relation are 1:1。
5. 2-according to claim 3 [4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl)-1,3, the preparation method of 5-triazine, it is characterised in that: used catalyst is first dissolved in deionized water, is joined by alkali liquor in above-mentioned reactant liquor, this solvent adds appropriate quaternary ammonium salt, promotes the reaction of organic facies/aqueous phase。
6. 2-according to claim 1 [4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl)-1,3, the preparation method of 5-triazine, it is characterised in that: the molar ratio of described step (3) Benzodiazepines and lauryl diglycidyl ether is 1:1.15～1.5。
7. 2-according to claim 1 [4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl)-1,3, the preparation method of 5-triazine, it is characterized in that: after reacting completely, the solvent that rotary evaporation obtains can serve as the solvent of a new batch reaction, it is achieved solvent is applied mechanically。
8. 2-according to claim 1 [4-[2-hydroxyl-3-dodecyloxy propyl group] oxygen base-2-hydroxy phenyl]-4,6-double; two (2,4-3,5-dimethylphenyl)-1,3, the preparation method of 5-triazine, it is characterized in that: the reaction temperature that the course of reaction of lauryl diglycidyl ether and intermediate adopts is 70-120 DEG C, and the response time is 24-48h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019160.1A CN105693641A (en) | 2015-12-29 | 2015-12-29 | Preparation method of triazine ultraviolet absorbent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511019160.1A CN105693641A (en) | 2015-12-29 | 2015-12-29 | Preparation method of triazine ultraviolet absorbent |
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| CN105693641A true CN105693641A (en) | 2016-06-22 |
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| CN107805224A (en) * | 2017-11-15 | 2018-03-16 | 利安隆（中卫）新材料有限公司 | The method for preparing the mixing Long carbon chain triazine uv absorber containing ehter bond |
| CN111094464A (en) * | 2017-09-26 | 2020-05-01 | 株式会社Kcc | Ultraviolet-curable coating composition |
| CN113214173A (en) * | 2021-04-27 | 2021-08-06 | 烟台新特路新材料科技有限公司 | Multifunctional triazine ultraviolet absorbent with thioether antioxidant structure and preparation method thereof |
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| CN106565619A (en) * | 2016-11-10 | 2017-04-19 | 中昊(大连)化工研究设计院有限公司 | Method for refining 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-s-triazine |
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| CN113214173A (en) * | 2021-04-27 | 2021-08-06 | 烟台新特路新材料科技有限公司 | Multifunctional triazine ultraviolet absorbent with thioether antioxidant structure and preparation method thereof |
| CN113214173B (en) * | 2021-04-27 | 2022-08-02 | 烟台新特路新材料科技有限公司 | Multifunctional triazine ultraviolet absorbent with thioether antioxidant structure and preparation method thereof |
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