Summary of the invention
The object of the present invention is to provide a kind of new ultraviolet absorbers 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole].
Another object of the present invention is to provide the preparation method of a kind of above-mentioned 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole].
The structural formula of ultraviolet absorbers 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] that the present invention is new is:
The preparation method of described 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] comprises the steps:
(1) at first n-butyl mercaptan and alkali are mixed under room temperature, reaction obtains n-butyl mercaptan an alkali metal salt CH
3CH
2CH
2CH
2S
-M
+
(2) then above-mentioned n-butyl mercaptan an alkali metal salt and aprotic solvent are mixed, add 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole, be warming up to reflux temperature, reacted 10~24 hours;
(3) be cooled to room temperature again, and add acidifying, thin up is separated out precipitation, filters, and purifies, and obtains 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] at last.
In the step 1, the mol ratio of described n-butyl mercaptan and alkali is 1: 1~2, and preferred molar ratio is 1: 1.2.
In the step 1, described n-butyl mercaptan and alkali can heat after mixing slightly, make quickly to react completely.
In the step 1, described alkali can be sodium hydroxide, sodium hydride, potassium hydroxide, sodium tert-butoxide or potassium tert.-butoxide.
In the step 1, also can add the band aqua water that generates in the reaction process is taken out of.The preferred toluene of described band aqua, dimethylbenzene.
In the step 2, the mol ratio of described n-butyl mercaptan an alkali metal salt and 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole is 8~1: 1, and preferred molar ratio is 4: 1; The mol ratio of described aprotic solvent and 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole is 45~1: 1, and preferred molar ratio is 15: 1.
In the step 2, described aprotic solvent can be N-Methyl pyrrolidone or dimethyl formamide; Be preferably N-Methyl pyrrolidone.
In the step 2, described reflux temperature is 120 ℃~200 ℃, is preferably 160 ℃~190 ℃.
In the step 3, described acid can be hydrochloric acid, sulfuric acid or acetate.
In the step 3, the available petroleum ether of described precipitation.
The present invention compared with prior art has following advantage and effect:
(1) the invention provides a kind of new ultraviolet absorbers 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole];
(2) 5,5 '-two sulphur provided by the invention-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] are a kind of UVA efficiently (wavelength is between 320-400nm) UV light absorber; Can protect plastics, coating and people's skin to exempt from the infringement of this type of UV-light (UV-A, wavelength is between 320-400nm);
(3) preparation method of benzotriazole compound provided by the invention is simple, and reaction intermediate does not need to separate purifies, and productive rate can be up to 60%.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and water trap prolong, add 3.2 gram sodium hydroxide (0.08mol) and 7.25 gram n-butyl mercaptans (0.08mol).Start stirring, heating makes dissolution of sodium hydroxide slightly.Add 12.5ml toluene again, mixture heating up steams toluene to refluxing with the water (approximately 1.4ml) of taking generation out of.
Then reaction mixture is cooled to room temperature, takes down water trap, prolong then directly is connected on the flask ground.Add 30ml N-Methyl pyrrolidone (0.31mol) again in flask, 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.02mol) are heated to 186 ℃, react 18 hours.Solution is cooled to room temperature.Slowly add 7.5ml water and 7.5ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole].
5,5 '-two sulphur that present embodiment prepares-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] are the yellow powder powder.Physicochemical property is as follows:
(1) fusing point 269-270 ℃.
(2)NMR:δ1.35-1.37(s,18H),δ1.47(s,18H),δ7.39-7.40(s,2H),δ7.57-7.59(d,2H),δ7.88-7.90(d,2H),δ58.09-8.10(s,2H),δ8.21(s,2H),δ11.52(s,2H),(400MHz,CDCl
3)。
(3) FABMS:709 (M+1,7.3), 355 (6.6), 340 (10.4), 307 (4.5), 219 (5.4), 176 (5.4), 154 (40.8), 136 (36.6), 107 (17.9), 91 (23.4), 57 (100) m/z (% relative abundance).
(4) UV absorption (measuring in the chloroform) characteristic is as follows: λ
Max=364nm; ε
Max=56800.
Embodiment 2
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and prolong, add 7.25 gram n-butyl mercaptans (0.08mol), stir the 2.3 gram sodium hydrides (0.096mol) of adding down.
In reaction flask, add 30ml N-Methyl pyrrolidone (0.31mol) and 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.02mol) again, be heated to 186 ℃, reacted 18 hours.Solution is chilled to room temperature.Slowly add 9.3ml water and 9.3ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], productive rate 60%.
Physicochemical property, spectroscopic data and the UV of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] of present embodiment preparation absorbs (measuring in the chloroform) characteristic with embodiment 1.
Embodiment 3
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and prolong, add 7.25 gram n-butyl mercaptans (0.08mol), stir the 1.92 gram sodium hydrides (0.08mol) of adding down.
In reaction flask, add 30ml N-Methyl pyrrolidone (0.31mol) and 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.01mol) again, be heated to 186 ℃, reacted 18 hours.Solution is chilled to room temperature.Slowly add 7.5ml water and 7.5ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], productive rate 20%.
Physicochemical property, spectroscopic data and the UV of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] of present embodiment preparation absorbs (measuring in the chloroform) characteristic with embodiment 1.
Embodiment 4
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and prolong, add 7.25 gram n-butyl mercaptans (0.08mol).Stir and add 3.12 gram sodium hydrides (0.13mol) down.
In reaction flask, add 30ml N-Methyl pyrrolidone (0.31mol) and 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.08mol) again, be heated to 186 ℃ of reactions 18 hours.Solution is chilled to room temperature.Slowly add 12ml water and 12ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], productive rate 50%.
Physicochemical property, spectroscopic data and the UV of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] of present embodiment preparation absorbs (measuring in the chloroform) characteristic with embodiment 1.
Embodiment 5,6, Comparative Examples 1,2
The component and the consumption that provide by table 1 prepare four kinds of transparent polychloroethylene compositions.Wherein, in embodiment 5 and 6, new ultraviolet absorbers 5,5 '-two sulphur provided by the invention-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] have been added; In Comparative Examples 1 and 2, then do not add new ultraviolet absorbers provided by the invention.
Table 1 unit: gram
Component | PHR |
Embodiment 5 | Comparative Examples 1 | Embodiment 6 | Comparative Examples 2 |
Polyvinyl chloride resin (LS080s) | 100.0 | 100.0 | 100.0 | 100.0 |
Processing aid (ACR401, industrial goods) | 2.0 | 2.0 | 2.0 | 2.0 |
Calcium stearate (industrial goods) | 0.5 | 0.5 | 0.5 | 0.5 |
Three (isooctyl mercaptoacetate) antimony thermo-stabilizer (STH) | 2.0 | 2.0 | 2.0 | 2.0 |
Dimixo-octyl phthalate (industrial goods) | - | - | 40.0 | 40.0 |
5,5 '-two sulphur provided by the invention-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] | 0.2 | - | 0.2 | - |
Above-mentioned four kinds of polychloroethylene compositions are made plate, be placed on and two 40W (centre wavelength 365nm) be housed in the accelerated deterioration experimental machine of colour filter quartz burner, its stability of test under UV-light to light, a colour-change result is as follows in observation in per 24 hours:
The composition of embodiment 5 1200 hours still was little yellow transparent;
The composition of embodiment 6 720 hours still was little yellow transparent;
The composition of Comparative Examples 1 promptly became yellow in 360 hours;
The composition of Comparative Examples 2 promptly became yellow in 72 hours;
The above results shows, in adopting the stable polychloroethylene composition of mercaptan antimony organic, use new ultraviolet absorbers 5 provided by the invention, 5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] can obviously improve the anti-ultraviolet ageing stability of polychloroethylene composition.