CN1280297C - Organosilicon modified cinnamate as reactive ultraviolet ray absorbent and its prepn and application - Google Patents
Organosilicon modified cinnamate as reactive ultraviolet ray absorbent and its prepn and application Download PDFInfo
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- CN1280297C CN1280297C CN 03106946 CN03106946A CN1280297C CN 1280297 C CN1280297 C CN 1280297C CN 03106946 CN03106946 CN 03106946 CN 03106946 A CN03106946 A CN 03106946A CN 1280297 C CN1280297 C CN 1280297C
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Abstract
The present invention relates to an ultraviolet absorbent of the type of reactive organoslicon modified cinnamate, a preparing method thereof, and the application thereof in the preparation of organosiloxane polymers and composite anti-ultraviolet materials. The general formula of the ultraviolet absorbent of the type of reactive organoslicon modified cinnamate is disclosed in the specification.
Description
Technical field
The present invention relates to organic-silicon-modified cinnamate derivative UV light absorber of a kind of response type and preparation method thereof and the application in preparation organosiloxane polymer and compound ultraviolet ray-resistant material.
Background technology
A spot of ultraviolet ray can help human body to synthesize the necessary vitamins D of skeleton development, simultaneously, ultraviolet ray has also brought many harm to the mankind, it mainly comprises skin, eyes, immunity system to the injury of human body, can cause that skin shines red, tanned, sunburn, skin aging, produce wrinkle, destroy immunity system, cause skin carcinoma, cause cataract etc.Along with the further expansion in antarctic ozone cavity, ozonosphere is weakened absorption and the scattering process of UV, the mankind, animal, plant are accepted the UV irradiation dose to be increased greatly.According to relevant report, the every minimizing 1% of ozone content, uitraviolet intensity increases by 2%, and skin carcinoma patient will increase by 3%.For fear of the negative impact that ultraviolet ray brings to the mankind, in recent years, research work synthetic about UV light absorber and that use is very active.Laurate compounds, particularly Methoxycinnamate compounds are important UV light absorber.According to statistics, as the makeup sun-screening agent, p-methoxycinnamic acid monooctyl ester 1997 is the highest sun-screening agent of frequency of utilization in the China and the U.S., it also ranks among the best in Europe, the p-methoxycinnamic acid monooctyl ester can effectively absorb the ultraviolet ray of 280nm-320nm, assimilated efficiency is higher, and is low to skin irritation.But, cinnamate derivative as the brilliant shortcoming of making up with sun-screening agent be water-fast, perspiration resistance is poor, service efficiency is low, and cost is higher.
At field of textiles, because existing cinnamate derivative compound molecular weight is little and fabric fibre avidity is poor, a little less than fastness, not water-fast washing used few;
In macromolecular material industry, existing laurate compounds is during as UV light absorber, because its consistency is poor, overflows poor effect easily.
Summary of the invention
The object of the present invention is to provide and a kind ofly can be used for handling inorganic and organic polymer material surface and give its anti-ultraviolet function, also can be used as the organic-silicon-modified cinnamate derivative UV light absorber of the monomeric response type of anti-ultraviolet function of organosilicon polymer.
Another object of the present invention is to provide the preparation method of the organic-silicon-modified cinnamate derivative UV light absorber of a kind of this response type.
Further purpose of the present invention is to provide the application of the organic-silicon-modified cinnamate derivative UV light absorber of a kind of response type of the present invention in the preparation organosiloxane polymer.
Another object of the present invention also is to provide the water miscible liquid of the organic-silicon-modified laurate of a kind of response type of the present invention or water-alcohol solution to can be used as the ultraviolet radiation absorption component of the sun-proof component of makeup, rubber, plastics and as the application in the compound ultraviolet ray-resistant material of the ultraviolet radiation absorption component of coating in preparation.
In order to achieve the above object, technical program of the present invention lies in having adopted the organic-silicon-modified cinnamate derivative UV light absorber of a kind of response type, its general formula is as follows:
In the formula: R
1-C
1-4Alkoxyl group, chlorine or dimethylin;
R
2-C
1-4Alkoxyl group, chlorine or dimethylin;
R
3-C
1-4Alkyl;
R
4-C
1-4Alkyl;
The positive integer of n-value between 1-18;
A=0,1 or 2, b=1,2 or 3, and a+b=3.
Simultaneously, technical program of the present invention also lies in providing the preparation method of the organic-silicon-modified cinnamate derivative UV light absorber of a kind of response type, may further comprise the steps:
(1) sodium salt or sylvite and the silver salt or the lead salt of preparation cinnamic acid derivative
A, with in sodium alkoxide or the potassium alcoholate and cinnamic acid derivative, generate the sodium salt or the sylvite of cinnamic acid derivative; Or
B, cinnamic acid derivative is dissolved in the dilute alkaline soln, regulates pH to neutral, add Silver Nitrate or lead nitrate, generate the silver salt or the lead salt precipitation of corresponding cinnamic acid with diluted acid; Or
C, with in the dilute solution of sodium hydroxide or potassium hydroxide, yellow soda ash or salt of wormwood and cinnamic acid derivative, generate the sylvite or the sodium salt of cinnamic acid derivative;
(2) sodium salt of the cinnamic acid derivative that makes in the step (1) or sylvite and silver salt or lead salt are dissolved in or are suspended in boiling point in 100-180 ℃ organic solvent;
(3) in the reaction system of step (2), add the haloalkyl siloxanes, reacted 4-20 hour down, can make the organic-silicon-modified laurate of response type at 100-160 ℃.
The general formula of described cinnamic acid derivative is:
R
1-C
1-4Alkoxyl group, chlorine or dimethylin;
R
2-C
1-4Alkoxyl group, chlorine or dimethylin.
Described organic solvent can be in benzene, toluene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, N, dinethylformamide, methyl-sulphoxide or 1, the 4-dioxane any.
The general formula of described haloalkyl siloxanes is:
X(CH
2)nSi(R
3)a(OR
4)b
In the formula: X-Cl, Br or I;
R
3-C
1-4Alkyl;
R
4-C
1-4Alkyl;
The positive integer of n-value between 1-18;
A=0,1 or 2, b=1,2 or 3, and a+b=3.
Another technical scheme of the present invention also is to provide the organic-silicon-modified cinnamate derivative UV light absorber of a kind of response type to can be used as application in the organosiloxane polymer of the sun-proof component of used for cosmetic, the sun-proof finishing composition of textiles and polymer materials ultraviolet protection coating in preparation.
The application of the organic-silicon-modified cinnamate derivative UV light absorber of response type in the compound ultraviolet ray-resistant material of preparation.
Because the organic-silicon-modified cinnamate derivative UV light absorber of response type of the present invention contains reactive group, can be used for handling inorganic or organic polymer material is surperficial, and give its anti-ultraviolet function, also can be used as the organosiloxane polymer that the organopolysiloxane of the anti-ultraviolet function monomer of organosilicon polymer and siliceous hydroxyl or ring dimethyl siloxane or the preparation of organoalkoxysilane (as: tetramethoxy-silicane, trimethoxymethylsila,e etc.) polyreaction have the ultraviolet radiation absorption function.This organosiloxane polymer can be used as the sun-proof component of used for cosmetic, also as the sun-proof finishing composition of textiles, and can also be as ultraviolet radiation absorption component and glass, pottery and the polymer materials ultraviolet protection coating of coating.
It is one through 100-180 ℃ of dry solidification that response type of the present invention organic-silicon-modified cinnamate derivative UV light absorber water miscible liquid or water-alcohol solution adopt spray method to handle inorganic oxide powder (as titanium dioxide, zinc oxide, lime carbonate, talcum powder, silicon-dioxide etc.), make the compound ultraviolet ray-resistant material of siloxanes bonding cinnamate derivative UV light absorber, this compound ultraviolet ray-resistant material can be used as the sun-proof component of makeup, the ultraviolet radiation absorption component that also can be used as rubber, plastics can also be as the ultraviolet radiation absorption component of coating.
Utilize response type of the present invention organic-silicon-modified cinnamate derivative UV light absorber water miscible liquid or hydrolysis alcohol solution, adopt spray method or pickling process to handle glasswork, ceramic, plastics, surface of natural fibers, after the processing that is heating and curing, can make it all possess anti-ultraviolet function.
Embodiment
Embodiment 1
In the four-necked bottle that electric mixer, thermometer, water distilling apparatus, dropping funnel are housed, add p-methoxycinnamic acid potassium 21.6g (0.1mol), N, dinethylformamide 60g, heated and stirred is dissolved it fully.Add γ-r-chloropropyl trimethoxyl silane 21.8g (0.11mol), be warming up to 130 ℃, make water distilling apparatus into reflux, reacted 10 hours.Cooling, standing over night, suction filtration.Filtrate is under nitrogen protection, and the water pump underpressure distillation is reclaimed solvent N, dinethylformamide.
Cooling, scavenge oil pump.189-191 ℃/50Pa cut is collected in underpressure distillation under nitrogen protection.Get 3-trimethoxy silicon propyl group p-methoxycinnamic acid ester 24.5g, yield 72.1%.
IR (liquid-film method): 3060 (γ=
C-H, phenyl ring); 2944,2840 (γ
C-H-CH
2-,-CH
3); 1710 (γ
C=O); 1635 (γ
C=C, two keys); 1605,1576,1513 (γ
C=C, phenyl ring); 1253 (γ
COO); 1167 (γ
Si-CH2); 1086 (γ
Si-o-c).
1H?NMR(CDCl
3)δ，ppm：7.662-7.622(1H，d，J＝16Hz)；7.488-7.466(2H，d，J＝8.8Hz)；6.916-6.894(2H，d，J＝8.8Hz)6.330-6.290(1H，d，J＝16Hz)4.185-4.152(2H，t，J＝13.2Hz)；3.838(3H，s)；3.579(9H，s)；1.841-1.799(2H，m)；0.747-0.705(2H，m)。
13C-NMR(CDCl
3)δ，ppm：：167.3(C
7)；161.4(C
1)；144.3(C
5)；129.7(C
3，C
3)；127.2(C
4)；115.7(C
6)；114.3(C
2，C
2)；66.30(C
8)；55.36(OCH
3)；50.58(C
11)；22.20(C
9)；5.421(C
10)。
Chemical structural formula is:
Embodiment 2
Chloro-cinnamic acid 18.3g (0.1mol) between in the four-necked bottle that electric mixer, thermometer, water distilling apparatus, dropping funnel are housed, adding, N, dinethylformamide 45.0g, heated and stirred is dissolved it fully.Slowly add 30% industrial methanol sodium methanol solution 18.0g (0.1mol), add γ-r-chloropropyl trimethoxyl silane 21.8g (0.11mol), reclaim methyl alcohol under the heated and stirred, be warming up to 110 ℃.Make water distilling apparatus into reflux, 110 ℃ of temperature controls reacted 20 hours.Cooling, standing over night.Suction filtration, filtrate are under nitrogen protection, and 48-50 ℃ of cut 35g (N, dinethylformamide) under the 730mmHg collected in the water pump underpressure distillation, and under this pressure, oil bath is warming up to 180 ℃, and not seeing has cut to distillate.Cooling, scavenge oil pump.Underpressure distillation under nitrogen protection is collected 169-172 ℃/80Pa cut 3-trimethoxy silicon propyl group m-chloro laurate 18.4g, yield 53.4%.
IR (liquid-film method): 3080 (γ=
C-H, phenyl ring); 2944,2841 (γ
C-H,-CH
2-,-CH
3); 1716 (γ
C=O); 1641 (γ
C=C, two keys); 1595,1566,1474 (γ
C=C, phenyl ring); 1201 (γ
COO); 1176 (γ
Si-CH2-); 1087 (γ
Si-O-C).
1H?NMR(CDCl
3)δ，ppm：7.631-7.591(1H，d，J＝16Hz)；7.509(1H，m)；7.401-7.319(3H，m)；6.458-6.418(1H，d，J＝16Hz)；4.202-4.168(2H，t，J＝6.8Hz )；3.590(9H，s)；1.863-1.804(2H，m)；0.743-0.701(2H，m)。
13C-NMR(CDCl
3)δ，ppm：166.6(C
7)；143.0(C
5)；136.3(C
4)；134.9(C
2)；130.1(C
1，C
3)；127.8(C
2’)；126.2(C
3’)；119.7(C
6)；66.65(C
8)；50.7(C
11)；22.15(C
9)；5.426(C
10)。
Chemical structural formula is:
Embodiment 3
In the four-necked bottle that electric mixer, thermometer, reflux, dropping funnel are housed, add 2,3-dimethoxy-cinnamic acid 10.4g (0.05mol), N, dinethylformamide 20g, be heated to 50 ℃ under stirring, be dissolved into clear solution, slowly add 30% industrial methanol sodium methanol solution 9g (0.05mol).Steam methyl alcohol under the heated and stirred, make water distilling apparatus into reflux, be warming up to 160 ℃, add γ-r-chloropropyl trimethoxyl silane 10.9g (0.055mol), reaction is 10 hours under this temperature.Cooling, standing over night is divided into two-layer.Suction filtration, filtrate are under nitrogen protection, and 48-50 ℃ of cut 15.0g (N, dinethylformamide) under the 730mmHg collected in the water pump underpressure distillation, and under this pressure, oil bath is warming up to 180 ℃, and not seeing has cut to distillate.
Cooling, scavenge oil pump.Underpressure distillation under nitrogen protection is collected 162-164 ℃/60Pa cut 3-trimethoxy silicon propyl group 2,3-dimethoxy-cinnamic acid ester 12.9g.Yield 69.8%.
IR (liquid-film method): 3080 (γ=
C-H, phenyl ring); 2943,2840 (γ C-H ,-CH
2-,-CH
3); 1713 (γ
C=O); 1635 (γ
C=C, two keys); 1579,1479 (γ
C=C, phenyl ring); 1224 (γ
COO); 1168 (γ
Si-CH2); 1087 (γ
Si-o-c).
1H?NMR(CDCl
3)δ，ppm：8.021-8.017(1H，d，J＝16.4Hz)；7.164-7.142(1H，d，J＝8Hz)；7.079-7.039(1H，t，J＝8Hz)；6.512-6.466(1H，d，J＝16.4Hz)；4.202-4.168(2H，t，J＝13.6Hz)；3.388(3H，s)；3.386(3H，s)；3.579(9H，s)；1.869-1.810(2H，m)；0.752-0.710(2H，m)。
13C-NMR(CDCl
3)δ，ppm：167.2(C
7)；153.2(C
2)；148.5(C
3)；139.4(C
5)；128.7(C
4)；124.2(C
1)；119.3(C
2’，C
3’)；113.9(C
6)；66.42(C
8)；61.31(OCH
3)；55.90(OCH
3)；50.80(C
11)；22.16(C
9)；5.368(C
10)。
Chemical structural formula is:
Embodiment 4
In the four-necked bottle that electric mixer, thermometer, water distilling apparatus, dropping funnel are housed, add dimethylin styracin 15.28g (0.08mol), N, dinethylformamide 80g, heated and stirred is dissolved it fully.Slowly add 30% industrial methanol sodium methanol solution 14.4g (0.08mol), solution becomes harder block, add γ-r-chloropropyl trimethoxyl silane 17.46g (0.088mol), heated and stirred steams methyl alcohol, continue to be warming up to 134-136 ℃, make water distilling apparatus into reflux, reacted 10 hours.Cooling, standing over night, suction filtration, filtrate is under nitrogen protection, and the water pump underpressure distillation is reclaimed solvent N, dinethylformamide.
Cooling, scavenge oil pump carries out underpressure distillation, collects 205-210 ℃/50Pa cut, gets 3-trimethoxy silicon propyl group to dimethylin laurate 23.4g.Yield 82.7%.
IR (liquid-film method): 3030 (γ=
C-H, phenyl ring); 2944,2840 (γ
C-H,-CH
2-,-CH
3); 1702 (γ
C=O, carbonyl); 1630 (γ
C=C, two keys); 1601,1527 (γ
C=C, phenyl ring); 1222 (γ
COO); 1157 (γ
Si-CH2); 1085 (γ
Si-o-c).
1H?NMR(CDCl
3)δ，ppm：7.638-7.598(1H，d，J＝16Hz)；7.428-7.406(2H，d，J＝8.8Hz)；6.686-6.664(2H，d，J＝8.8Hz)；6.241-6.202(1H，d，J＝16Hz)；4.170-4.136(2H，t，J＝6.8Hz)；3.585(9H，s)；3.014(6H，s)；1.835-1.793(2H，m)；0.749-0.707(2H，m)。
13C-NMR(CDCl
3)δ，ppm：167.9(C
7)；151.7(C
1)；145.1(C
5)；129.7(C
3，C
3’)；122.5(C
4)；112.7(C
6)；111.9(C
2，C
2’)；66.09(C
8)；50.61(C
11)；40.22(N(CH
3)
2)；22.25(C
9)；5.340(C
10)。
Chemical structural formula is:
Embodiment 5
Have in the 100ml reaction flask of stirring and temperature regulating device one, add the compound 3-trimethoxy silicon propyl group p-methoxycinnamic acid ester 7.8g of embodiment 1 gained, octamethylcyclotetrasiloxane 23.7g, stirring mixes it.Slowly add by palmityl trimethyl ammonium chloride 3g the aqueous solution that polyoxyethylene nonylphenol ether 0.5g and deionized water 63g form.Mixture is emulsified into emulsion in advance, adds 5% potassium hydroxide aqueous solution 2g then.Stir also and be heated to 80 ℃, letex polymerization is 48 hours under this temperature, a solid content is 33.82% the organic siloxane emulsion with ultraviolet radiation absorption function, can be used as the sun-proof component and the anti-ultraviolet ray finishing of textiles agent of makeup.
Embodiment 6
With methyltrimethoxy silane 20.3g, acetate 0.06g, the colloid silica 16.7g of 30% solid content adds a reaction vessel.Stirred 16 hours under the room temperature.The compound 3-trimethoxy silicon propyl group p-methoxycinnamic acid ester 2.9g that adds Virahol 38g and embodiment 1 gained.Stir under the room temperature and got the silicone resin colloidal sol with ultraviolet radiation absorption function in 48 hours, can be used as the uvioresistant supercoat of timber, metal and plastics.
Claims (7)
1, the organic-silicon-modified cinnamate derivative UV light absorber of a kind of response type, its general formula is as follows:
In the formula: R
1One C
1-4Alkoxyl group, chlorine or dimethylin;
R
2One C
1-4Alkoxyl group, chlorine or dimethylin;
R
3One C
1-4Alkyl;
R
4One C
1-4Alkyl;
The positive integer of n one value between 1-18;
A=0,1 or 2, b=1,2 or 3, and a+b=3.
2, the preparation method of the organic-silicon-modified cinnamate derivative UV light absorber of a kind of response type as claimed in claim 1 may further comprise the steps:
(1) sodium salt or sylvite and the silver salt or the lead salt of preparation cinnamic acid derivative
A, with in sodium alkoxide or the potassium alcoholate and cinnamic acid derivative, generate the sodium salt or the sylvite of cinnamic acid derivative; Or
B, cinnamic acid derivative is dissolved in the dilute alkaline soln, regulates pH to neutral, add Silver Nitrate or lead nitrate, generate the silver salt or the lead salt precipitation of corresponding cinnamic acid with diluted acid; Or
C, with in the dilute solution of sodium hydroxide or potassium hydroxide, yellow soda ash or salt of wormwood and cinnamic acid derivative, generate the sylvite or the sodium salt of cinnamic acid derivative;
(2) sodium salt of the cinnamic acid derivative that makes in the step (1) or sylvite and silver salt or lead salt are dissolved in or are suspended in boiling point in 100-180 ℃ organic solvent;
(3) in the reaction system of step (2), add the haloalkyl siloxanes, reacted 4-20 hour down, can make the organic-silicon-modified laurate of response type at 100-160 ℃.
3, according to the preparation method of the organic-silicon-modified cinnamate derivative UV light absorber of the described response type of claim 2, it is characterized in that: the general formula of described cinnamic acid derivative is:
R
1-C
1-4Alkoxyl group, chlorine or dimethylin;
R
2-C
1-4Alkoxyl group, chlorine or dimethylin.
4, the preparation method of the organic-silicon-modified cinnamate derivative UV light absorber of response type according to claim 2 is characterized in that: described organic solvent can be in benzene, toluene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, N, dinethylformamide, methyl-sulphoxide or 1,4 one dioxane any.
5, the organic-silicon-modified cinnamate derivative UV light absorber of response type according to claim 2 preparation method, it is characterized in that: the general formula of described haloalkyl siloxanes is:
X(CH
2)nSi(R
3)a(OR
4)b
In the formula: X one C1, Br or I;
R
3One C
1-4Alkyl;
R
4One C
1-4Alkyl;
The positive integer of n one value between 1-18;
A=0,1 or 2, b=1,2 or 3, and a+b=3.
6, the organic-silicon-modified cinnamate derivative UV light absorber of response type as claimed in claim 1 or 2 can be used as application in the organosiloxane polymer of the sun-proof component of used for cosmetic, the sun-proof finishing composition of textiles and polymer materials ultraviolet protection coating in preparation.
7, the application of the organic-silicon-modified cinnamate derivative UV light absorber of response type as claimed in claim 1 or 2 in the compound ultraviolet ray-resistant material of preparation.
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|---|---|---|---|
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|---|---|---|---|
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| CN102488632B (en) * | 2011-12-26 | 2015-02-11 | 上海应用技术学院 | Polysiloxane composite particles of chemical sun-screening agent formed by coated camphor derivative and preparation method thereof |
| CN102488630B (en) * | 2011-12-26 | 2015-03-18 | 上海应用技术学院 | Polysiloxane composite particle cladding chemical sun-screening agent formed by p-methoxycinnamic acid esters and preparation method thereof |
| CN102488631B (en) * | 2011-12-26 | 2015-03-18 | 上海应用技术学院 | Polysiloxane composite particles of chemical sun-screening agent formed with coated methane derivative, and preparation method thereof |
| CN102488625B (en) * | 2011-12-26 | 2015-02-11 | 上海应用技术学院 | Benzophenone-type chemical sun-screening agent-coated polysiloxane composite particle and preparation method thereof |
| CN102552067B (en) * | 2011-12-26 | 2014-01-01 | 上海应用技术学院 | Polysiloxane composite particle coated with sunscreen chemical formed by esters of ortho-aminobenzoic acid and derivatives thereof and preparation method of same |
| CN107298905A (en) * | 2017-08-23 | 2017-10-27 | 重庆索利特涂料有限公司 | Texture coating of energy-saving corrosion-resisting and preparation method thereof |
| CN112708096B (en) * | 2020-12-14 | 2022-07-12 | 淮安凯悦科技开发有限公司 | Multifunctional foaming water-based resin and preparation method thereof |
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