CN102488632B - Polysiloxane composite particles of chemical sun-screening agent formed by coated camphor derivative and preparation method thereof - Google Patents
Polysiloxane composite particles of chemical sun-screening agent formed by coated camphor derivative and preparation method thereof Download PDFInfo
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- CN102488632B CN102488632B CN201110439910.6A CN201110439910A CN102488632B CN 102488632 B CN102488632 B CN 102488632B CN 201110439910 A CN201110439910 A CN 201110439910A CN 102488632 B CN102488632 B CN 102488632B
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Abstract
The invention discloses polysiloxane composite particles of a chemical sun-screening agent formed by coated camphor derivative. The polysiloxane composite particles are prepared by the following steps of: firstly uniformly dispersing a chemical sun-screening agent, an emulsifier, grease and a co-emulsifier which are formed by an oil phase component camphor derivative; homogenizing water and simultaneously adding the oil phase component, Homogenizing, stirring, and cooling to room temperature so as to prepare a nano-emulsion of the sun-screening agent formed by the coated camphor derivative; preparing an organosilicon monomer hydrolysate solution, mixing the organosilicon monomer hydrolysate solution with the nano-emulsion of the chemical sun-screening agent formed by the coated camphor derivative, adjusting pH to 7.5-13.5, controlling the reaction temperature within 0-100DEG C, stirring at the agitation speed of 10-1000 r/min for 0.1-24 hours so as to obtain a fluid suspension of the polysiloxane composite particles of the chemical sun-screening agent formed by the coated camphor derivative, followed by washing, centrifugation, drying and the like to obtain the nano-polysiloxane composite particles of the chemical sun-screening agent formed by the coated camphor derivative.
Description
Technical field
The present invention relates to a kind of coated chemical sun polysiloxane composite particles, more particularly relate to polysiloxane composite particles of the chemical sun that a kind of coated camphor derivative is formed and preparation method thereof.
Background technology
Chemical sun mainly refers to the organic compound with the ultraviolet radiation that can be absorbed with injury effect, is commonly referred to chemical ultraviolet absorbent., UV(ultraviolet different according to the wave band of protection radiation) absorbent can be divided into UVA(life ultraviolet) and UVB(open air ultraviolet) two kinds of absorbent.Chemically structure can be divided into para-amino benzoic acid and esters, salicylic acid esters and derivant thereof, o-aminobenzoa class, benzophenone and derivant, p-methoxycinnamic acid class, methane derivative and camphor derivative etc.Be applied to chemical sun in cosmetics due to its photo-labile and the zest to skin, can produce certain side effect, belong at European Union's part sunscreen and limit the use of raw material, part sunscreen then belongs to forbidding raw material.Meanwhile, general sunscreen only has anti-sunlight function in a kind of wavelength band of UVA or UVB wave band.
Camphor derivative Camphora class is UVB section absorbent, and its general structure is:
In structural formula:
α-(2-oxoborn-3 subunit)-Toluene-2,4-diisocyanate-sulfonic acid: R
1=H, R
2=SO
3h; λ
max=296nm
3-(4-methylbenzilidene)-camphane-2-ketone: R
1=H, R
2=CH
3; λ
max=300nm
3-benzal camphane-2-ketone: R
1=H, R
2=H; λ
max=290nm
These UV absorbent are usually used in tanned goods America and Europe, their storage-stables, not chafe, and without photosensitization, toxicity is little, and its stability and chemical inertness are also better, but skin to absorb this thing ability weak.
Organosilicon microsphere is that organosilane monomers carries out polyreaction under certain conditions and obtains.The characteristics such as organosilicon microsphere has that hardness is high, fusing point is high, wear-resisting, lubricious, nontoxic, tasteless, transparent, gloss, and Stability Analysis of Structures, environmental friendliness, is therefore widely used as filler and the modifier of rubber, plastics, cosmetics, coating etc.In recent years, the research and development of organosilicon microsphere are one of focuses of organosilicon material research.
Current domestic disclosed relevant core-shell type polysiloxane composite particles, but there is not yet the Silicone particles of the chemical sun that openly coated camphor derivative is formed, difference of the present invention is mainly first to form the nanoemulsions comprising the chemical sun that camphor derivative is formed, and carries out siloxanes hydrolysis more afterwards, polycondensation forms coated shell; And the nano polysilicon oxygen alkane compound particle stable performance of the chemical sun that the distinctive stability of Silicone particles makes prepared coated camphor derivative be formed, in application system, substantially increase the stability of the chemical sun that camphor derivative is formed.
Summary of the invention
An object of the present invention is the chemical sun polysiloxane composite particles in order to provide a kind of coated camphor derivative to be formed.
Two of object of the present invention is to provide the preparation method of the polysiloxane composite particles of the chemical sun that above-mentioned a kind of coated camphor derivative is formed.
Technical scheme of the present invention
A polysiloxane composite particles for the chemical sun that coated camphor derivative is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that camphor derivative is formed, is comprised
The described nanoemulsions comprising the chemical sun that camphor derivative is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 0.1 ~ 10%
Emulsifying agent 0.1 ~ 20%
Oils and fats 0.1 ~ 10%
Help Emulsion 0.1 ~ 20%
Surplus is water;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that camphor derivative is formed is as follows:
First chemical sun camphor derivative formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, then while homogenizing water, the chemical sun that camphor derivative is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, homogenizing process control rate is 10000 ~ 50000r/min, time is 0.1 ~ 30min, after homogenizing, stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that camphor derivative is formed, it is 10 ~ 1000r/min that above-mentioned whipping process controls mixing speed,
The chemical sun that described sunscreen is formed for camphor derivative;
Described camphor derivative is 4-Methylbenzylidene subunit Camphora, polyacrylamide methyl benzylidene camphor, Camphora benzene prick one or more mixture formed in ammonium methyl sulphate, Terephthalidene Dicamphor Sulfonic Acid and benzylidene camphor sulfonic acid;
Wherein said anion surfactant is fatty alcohol carboxylate, and its structural formula is C
nh
2n+1cOOM, wherein n is generally 11 ~ 17, M is Na, K or NH
3;
Described non-ionic surface active agent is fatty alcohol-polyoxyethylene ether series, and its structural formula is:
wherein fatty alcohol carbon number n is between 7 ~ 19, and in polyoxyethylene, oxygen ethylene number m is between 3 ~ 20;
Described oils and fats be mineral grease, natural origin Vegetable oil lipoprotein, natural origin animal oil and synthetic ester oil one or more rich mixture;
Described mineral grease is white oil, vaseline, microwax or montan wax;
Described natural origin Vegetable oil lipoprotein is candlenut oil, Oleum Hippophae, water Bulbus Allii mustard oil, cameline oil, grape-pip oil, Flos Rosae Multiflorae fruit oil, Flos Inulae oil, aloe, Herba Passiflorae Caeruleae caul-fat, Fructus Mangifera Indicae kernel oil, cocoa butter, mother-in-law sieve's fat, mowrah fat, Adeps Bovis seu Bubali resin, Brazil wax, candelilla wax, haze tallow or aromatic wax;
Described natural origin animal oil is water leopard oil, shark liver oil, horse fat, exquisite Adeps Cervi, spermaceti or Cera Flava;
Described synthetic ester oil is lanolin derivative series, as lanonol, Pilus Caprae seu Ovis fatty acid, wool oil, pure lanocerin, pancreas lanoline, Wool wax alcohols,ethoxylated, PULLRONIC F68 wool oil, hydrogenated lanolin, polyethylene glycol hydrogenated lanoline, polyoxyethylene Pilus Caprae seu Ovis alcohol ether or lanolin fatty acid isopropyl ester;
Described co-emulsifier is monohydric alcohol or polyhydric alcohol, and wherein the molecular formula of monohydric alcohol is C
nh
2n+1oH, wherein n is between 1 ~ 12; Polyhydric alcohol is ethylene glycol, 1,2-PD, 1,3-PD, 1, one or more mixed alcohols formed in 3 butanediols, propylene carbonate and glycerol;
(2), the preparation of organic silicon monomer hydrolysising product solution
Organosilicon is added in the mixture of water and/or organic solvent, then under acid or alkali effect, control pH be 1 ~ 6 or pH 7.5 ~ 11.5 to be hydrolyzed reaction, hydrolysis time, at 0.1 ~ 10h, is preferably 3.5 ~ 5h, temperature 1 ~ 100 DEG C, be preferably 10 ~ 25 DEG C, mixing speed 10 ~ 1000r/min, is preferably 70 ~ 120r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
Described organosilyl addition calculates i.e. organosilicon in mass ratio: the mixture of water and/or organic solvent is 1 ~ 50:100;
Described organosilicon is organosiloxane, and its structural formula is R
1nSiX
(4-n);
Wherein R
1that representative is selected from replacement or the unsubstituted univalent perssad having a C atom to be connected directly between alkyl on Si atom or alkenylphenyl, n is the integer of 0 ~ 3, X is hydrolysising group, is hydroxyl, hydrogen, alkoxyl, halogen group, carboxyl, amino or siloxy;
As n > 1, each R1 group can be identical or different;
And as (4-n) > 1, each X group can be identical or different;
Described acid is one or more mixed acid in citric acid, acetic acid, oxalic acid, tartaric acid, hydrochloric acid, phosphoric acid, carbonic acid and sulfurous acid;
Described alkali is one or more mixed bases in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine and triethylamine;
Said organic solvent is methanol, ethanol, ethylene glycol, propanol, isopropyl alcohol, butanols, isobutanol, propylene carbonate, glycerol, Methanamide, N, one or more mixture in N-dimethyl acetylamide, DMF, acetone, oxolane, dimethylsulfone, ethyl acetate, pyridine and acetonitrile;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated camphor derivative
The organic silicon monomer hydrolysising product solution obtain step (2) and the nanoemulsions comprising the chemical sun that camphor derivative is formed of step (1) gained calculate in mass ratio, namely the nanoemulsions of the chemical sun that camphor derivative is formed is comprised: organic silicon monomer hydrolysising product solution is that 0.1:99.9 ~ 50:50 mixes, then the suspension that polycondensation reaction obtains the polysiloxane composite particles of the chemical sun formed containing coated camphor derivative is carried out under regulating with alkaline matter the condition that pH is 7.5 ~ 13.5, it is 0 DEG C ~ 100 DEG C that polycondensation process controls reaction temperature, be preferably 10 ~ 25 DEG C, speed of agitator is 10 ~ 1000r/min, be preferably 100 ~ 150r/min, time is 0.1 ~ 24h, be preferably 5h,
By the suspension water, the ethanol circulation cleaning that contain the polysiloxane composite particles of the chemical sun that coated camphor derivative is formed of gained after polycondensation reaction completes, and centrifugal, filter, control centrifugal rotational speed 10000 ~ 15000 r/min, filtration time 10 ~ 100min, filter cake dry 5 ~ 10h at 100 ~ 200 DEG C of gained, the solids finally obtained are the polysiloxane composite particles of the chemical sun that coated camphor derivative is formed;
Wherein said alkaline matter is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine or triethylamine.
The polysiloxane composite particles of the chemical sun that a kind of coated camphor derivative of the present invention is formed, is suitable for being applied in the chemical sunscreen product that camphor derivative formed, as the articles for use such as sun care preparations, sun-screening umbrella.
In addition, in order to avoid the permeability of chemical sun on skin that camphor derivative is formed, the particle diameter of lipid particles is not easily too little, the particle diameter of the polysiloxane composite particles of the chemical sun formed by the coated camphor derivative of gained of the present invention between 80nm ~ 500nm, preferred 100nm ~ 300nm.
Beneficial effect of the present invention
The polysiloxane composite particles of the chemical sun that a kind of coated camphor derivative of the present invention is formed, comprise the nanoemulsions of the chemical sun that camphor derivative is formed owing to first being formed in preparation process, carry out siloxanes hydrolysis more afterwards, polycondensation forms coated shell; The polysiloxane composite particles performance of the chemical sun that the distinctive stability of such Silicone particles makes prepared coated camphor derivative be formed is more stable, substantially increases the stability of the chemical sun that camphor derivative is formed in application system.
And the polysiloxane composite particles of chemical sun that a kind of coated camphor derivative of the present invention is formed, that the chemical sun formed by camphor derivative is coated in Silicone particles, thus avoid and contact with the direct of skin, greatly reduce chemical sun that camphor derivative formed to the zest of skin.Good sun-proof result can be embodied.
In addition, the polysiloxane composite particles of the chemical sun that a kind of coated camphor derivative of the present invention is formed, owing to being comprise the nanoemulsions of the chemical sun that camphor derivative is formed, organosilicon as raw material, therefore preparation method is easy, and productive rate is high, there is industrial production prospect.
Detailed description of the invention
Below by embodiment, the present invention is set forth further, but do not limit the present invention.
embodiment 1
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that 4-Methylbenzylidene subunit Camphora is formed, is comprised
The described nanoemulsions comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 5%
Emulsifying agent 5%
Oils and fats 5%
Help Emulsion 5%
Surplus is water;
The chemical sun that described sunscreen is formed for 4-Methylbenzylidene subunit Camphora, the product that ISP International Specialty Products company limited produces;
Described emulsifying agent is fatty alcohol-polyoxyethylene ether (21EO), and CRODA(standing grain is large) Chemical Co., Ltd. produce emulsifying agent for cosmetics;
Described oils and fats is Adeps Bovis seu Bubali resin, BASF(BASF) Chemical Co., Ltd. produce oils and fats used for cosmetic;
Described co-emulsifier is the grade product of propylene glycol, traditional Chinese medicines group;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed is as follows:
First the chemical sun, emulsifying agent, the oils and fats that 4-Methylbenzylidene subunit Camphora are formed and help being uniformly mixed of Emulsion, the chemical sun that 4-Methylbenzylidene subunit Camphora is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion and water to be heated to 60 ~ 80 DEG C respectively; The chemical sun while homogenizing water, 4-Methylbenzylidene subunit Camphora formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, homogenizing process control rate is 10000r/min, time is 3min, stir the nanoemulsions being cooled to room temperature and must comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed after homogenizing, it is 100r/min that above-mentioned whipping process controls mixing speed;
(2), the preparation of organic silicon monomer hydrolysising product solution
8g trimethylmethoxysilane is placed in 92g water and alcohol mixeding liquid, water: ethanol is 1:99, with hydrochloric acid solution by pH regulator to 3.0 ~ 4.0, be hydrolyzed reaction, hydrolysis time is 5h, temperature 20 DEG C, mixing speed 100r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated 4-Methylbenzylidene subunit Camphora
PH is regulated to be 7.5 ~ 8.5 with ammonia after organic silicon monomer hydrolysising product solution 70g step (2) obtained mixes with the nanoemulsions 30g comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed of step (1) gained, control temperature is 20 DEG C, mixing speed is 100 r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated 4-Methylbenzylidene subunit Camphora after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed obtained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 10h at 100 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated 4-Methylbenzylidene subunit Camphora of 11.6g is formed, its particle diameter is 0.8 μm.
The sun-proof performance of the polysiloxane composite particles of the chemical sun formed with the coated 4-Methylbenzylidene subunit Camphora of ultraviolet spectrophotometry to above-mentioned gained measures, this mensuration adopts the evaluation methodology-ultraviolet spectrophotometry of GB QB/T2410-98 sun-proof performances to measure, and the present invention's spectrophotometric used is counted Shanghai precision scientific instrument company and manufactured 759 ultraviolet spectrophotometers.Determination step is as follows:
(1), by the breathable adhesive tape that 3M company produces be cut into lcm × 4cm size, be pasted onto quartz colorimetric utensil printing opacity and survey on the surface;
(2), switch on power, preheating spectrophotometer, setting UVB district determined wavelength is 280nm, 290nm, 300nm, 310nm and 320nm, and UVA district determined wavelength is 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm and 400nm;
(3), by the quartz colorimetric utensil posting adhesive tape sample arm and reference light paths is placed in, adjustment instrument zero;
(4), get powder sample prepared by 1g, be scattered in water, obtain the dispersion liquid that mass concentration is 10%, accurately take dispersion liquid 8mg(error 0.2mg), by sample uniform application on quartz colorimetric utensil 3M adhesive tape, claim five Duplicate Samples;
(5), the article colorimetric ware prepared is placed in room temperature under, dry 30min;
(6), by testing sample cuvette be placed in sample arm, another quartz cell posting adhesive tape is placed in reference light paths, measures the ultraviolet light absorption angle value of 280nm ~ 400nm district setting wavelength respectively, then measured value is asked arithmetic mean of instantaneous value ā;
Sequentially determining five parallel sample ā 1 ~ ā 5, ask arithmetic mean of instantaneous value, are exactly the ultraviolet light absorption angle value ā sample of sample, the results are shown in following table 1:
the sun-proof capacity measurement data of polysiloxane composite particles of the chemical sun that table 1, coated 4-Methylbenzylidene subunit Camphora are formed
| Sequence number | Wavelength | Absorbance (ā) |
| 1 | 280.00nm | 0.705A |
| 2 | 290.00nm | 1.211A |
| 3 | 300.00nm | 1.310A |
| 4 | 310.00nm | 1.340A |
| 5 | 320.00nm | 1.283A |
| 6 | 330.00nm | 1.224A |
| 7 | 340.00nm | 0.883A |
| 8 | 350.00nm | 0.761A |
| 9 | 360.00nm | 0.813A |
| 10 | 370.00nm | 0.797A |
| 11 | 380.00nm | 0.854A |
| 12 | 390.00nm | 0.798A |
| 13 | 400.00nm | 0.886A |
(test condition: slit: 2.00 nm wavelength numbers: 13)
Can find out there is good absorbability between wavelength 290nm ~ 330nm from the result table, can illustrate that the polysiloxane composite particles of the chemical sun that the coated 4-Methylbenzylidene subunit Camphora of gained of the present invention is formed has certain anti-sunlight function.
embodiment 2
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated Terephthalidene Dicamphor Sulfonic Acid is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed, is comprised
The described nanoemulsions comprising the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 0.1%
Emulsifying agent 0.1%
Oils and fats 0.1%
Help Emulsion 0.1%
Surplus is water;
The chemical sun that described sunscreen is formed for Terephthalidene Dicamphor Sulfonic Acid, BASF(BASF) product produced of Chemical Co., Ltd.;
Described emulsifying agent is fatty alcohol-polyoxyethylene ether (2EO), and CRODA(standing grain is large) Chemical Co., Ltd. produce emulsifying agent for cosmetics;
Described oils and fats is white oil, the product that Hangzhou Refinery is produced;
Described co-emulsifier is the grade product of glycerol, traditional Chinese medicines group;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed is as follows:
First chemical sun Terephthalidene Dicamphor Sulfonic Acid formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion and water to be heated to 60 ~ 80 DEG C respectively; The chemical sun while homogenizing water, Terephthalidene Dicamphor Sulfonic Acid formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, homogenizing process control rate is 10000r/min, time is 3min, stir the nanoemulsions being cooled to room temperature and must comprising the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed after homogenizing, it is 100r/min that above-mentioned whipping process controls mixing speed;
(2), the preparation of organic silicon monomer hydrolysising product solution
3g trimethylmethoxysilane is placed in 97g water and alcohol mixeding liquid, water: ethanol is 25:75, with hydrochloric acid solution by pH regulator to 4.0 ~ 5.0, be hydrolyzed reaction, hydrolysis time is 4.5h, temperature 10 DEG C, mixing speed 90r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated Terephthalidene Dicamphor Sulfonic Acid
PH is regulated to be 8.5 ~ 9.5 with ammonia after organic silicon monomer hydrolysising product solution 50g step (2) obtained mixes with the nanoemulsions 50g comprising the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed of step (1) gained, control temperature is 10 DEG C, mixing speed is 150r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated Terephthalidene Dicamphor Sulfonic Acid after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated Terephthalidene Dicamphor Sulfonic Acid is formed obtained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 8h at 150 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated Terephthalidene Dicamphor Sulfonic Acid of 1.7g is formed, its particle diameter is 0.7 μm.
embodiment 3
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that 4-Methylbenzylidene subunit Camphora is formed, is comprised
The described nanoemulsions comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 10%
Emulsifying agent 20%
Oils and fats 10%
Help Emulsion 20%
Surplus is water;
The chemical sun that described sunscreen is formed for 4-Methylbenzylidene subunit Camphora, the product that ISP International Specialty Products company limited produces;
Described emulsifying agent is fatty alcohol-polyoxyethylene ether (25EO), BASF(BASF) Chemical Co., Ltd. produce emulsifying agent for cosmetics;
Described oils and fats is lanonol, the raw material used for cosmetic that Jiangyin Xing Peng Chemical Co., Ltd. produces;
Described co-emulsifier is the grade product of isopropyl alcohol, traditional Chinese medicines group;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed is as follows:
First the chemical sun, emulsifying agent, the oils and fats that 4-Methylbenzylidene subunit Camphora are formed and help being uniformly mixed of Emulsion, the chemical sun that 4-Methylbenzylidene subunit Camphora is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion and water to be heated to 80 ~ 90 DEG C respectively; The chemical sun while homogenizing water, 4-Methylbenzylidene subunit Camphora formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, homogenizing process control rate is 50000r/min, time is 2min, stir the nanoemulsions being cooled to room temperature and must comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed after homogenizing, it is 150r/min that above-mentioned whipping process controls mixing speed;
(2), the preparation of organic silicon monomer hydrolysising product solution
15g trimethylmethoxysilane is placed in 85g water and alcohol mixeding liquid, water: ethanol is 50:50, with hydrochloric acid solution by pH regulator to 3.0 ~ 4.0, be hydrolyzed reaction, hydrolysis time is 3.5h, temperature 25 DEG C, mixing speed 110r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated 4-Methylbenzylidene subunit Camphora
The organic silicon monomer hydrolysising product solution 90g that step (2) is obtained and step (1) comprise the chemical sun that 4-Methylbenzylidene subunit Camphora is formed nanoemulsions 10g mix after regulate pH to be 7.5 ~ 8.5 with ammonia, control temperature is 15 DEG C, mixing speed is 100r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated 4-Methylbenzylidene subunit Camphora after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed obtained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 5h at 200 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated 4-Methylbenzylidene subunit Camphora of 19.5g is formed, its particle diameter is 0.9 μm.
embodiment 4
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that 4-Methylbenzylidene subunit Camphora is formed, is comprised
With embodiment 1;
(2), the preparation of organic silicon monomer hydrolysising product solution
8g phenyl triethoxysilane is placed in 92g water and alcohol mixeding liquid, water: ethanol is 1:99, with hydrochloric acid solution by pH regulator to 3.5 ~ 4.5, be hydrolyzed reaction, hydrolysis time is 3.0h, temperature 10 DEG C, mixing speed 120r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated 4-Methylbenzylidene subunit Camphora
PH is regulated to be 7.5 ~ 8.5 with ammonia after organic silicon monomer hydrolysising product solution 70g step (2) obtained mixes with the nanoemulsions 30g comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed of step (1) gained, control temperature is 25 DEG C, mixing speed is 100 r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated 4-Methylbenzylidene subunit Camphora after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed obtained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 10h at 100 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated 4-Methylbenzylidene subunit Camphora of 11.6g is formed, its particle diameter is 0.8 μm.
embodiment 5
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated Terephthalidene Dicamphor Sulfonic Acid is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed, is comprised
With embodiment 2.
(2), the preparation of organic silicon monomer hydrolysising product solution
3g phenyl trichlorosilane is placed in 97g water and alcohol mixeding liquid, water: ethanol is 25:75, with hydrochloric acid solution by pH regulator to 3.0 ~ 4.0, be hydrolyzed reaction, and hydrolysis time is 2.5h, temperature 15 DEG C, mixing speed 80r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated Terephthalidene Dicamphor Sulfonic Acid
PH is regulated to be 8.5 ~ 9.5 with ammonia after organic silicon monomer hydrolysising product solution 50g step (2) obtained mixes with the nanoemulsions 50g comprising the chemical sun that Terephthalidene Dicamphor Sulfonic Acid is formed of step (1) gained, control temperature is 10 DEG C, mixing speed is 150r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated Terephthalidene Dicamphor Sulfonic Acid after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated Terephthalidene Dicamphor Sulfonic Acid is formed obtained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 8h at 150 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated Terephthalidene Dicamphor Sulfonic Acid of 1.7g is formed, its particle diameter is 0.7 μm.
embodiment 6
A nano polysilicon oxygen alkane compound particle for the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that 4-Methylbenzylidene subunit Camphora is formed, is comprised
With embodiment 3;
(2), the preparation of organic silicon monomer hydrolysising product solution
15g dimethyldichlorosilane is placed in 85g water and alcohol mixeding liquid, water: ethanol is 50:50, with hydrochloric acid solution by pH regulator to 3.0 ~ 4.0, be hydrolyzed reaction, hydrolysis time is 4.0h, temperature 10 DEG C, mixing speed 70r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3) preparation of the suspension of the nano polysilicon oxygen alkane compound particle of the chemical sun, formed containing coated 4-Methylbenzylidene subunit Camphora
PH is regulated to be 7.5 ~ 8.5 with ammonia after organic silicon monomer hydrolysising product solution 90g step (2) obtained mixes with the nanoemulsions 10g comprising the chemical sun that 4-Methylbenzylidene subunit Camphora is formed of step (1) gained, control temperature is 25 DEG C, mixing speed is 100r/min, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated 4-Methylbenzylidene subunit Camphora after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated 4-Methylbenzylidene subunit Camphora is formed obtained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 5h at 200 DEG C, obtain the polysiloxane composite particles of the chemical sun that the nano level coated 4-Methylbenzylidene subunit Camphora of 19.5g is formed, its particle diameter is 0.9 μm.
Foregoing be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (6)
1. the polysiloxane composite particles of chemical sun that formed of coated camphor derivative, is characterized in that preparing by the following method:
(1) preparation of the nanoemulsions of the chemical sun that camphor derivative is formed, is comprised
The described nanoemulsions comprising the chemical sun that camphor derivative is formed is calculated by mass percentage, its raw material composition and content as follows:
Sunscreen 0.1 ~ 10%
Emulsifying agent 0.1 ~ 20%
Oils and fats 0.1 ~ 10%
Help Emulsion 0.1 ~ 20%
Surplus is water;
The chemical sun that described sunscreen is formed for camphor derivative;
Described camphor derivative is 4-Methylbenzylidene subunit Camphora, polyacrylamide methyl benzylidene camphor, Camphora benzene prick one or more mixture formed in ammonium methyl sulphate, Terephthalidene Dicamphor Sulfonic Acid and benzylidene camphor sulfonic acid;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that camphor derivative is formed is as follows:
First chemical sun camphor derivative formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, then while homogenizing water, the chemical sun that camphor derivative is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, continue homogenizing, homogenizing process control rate is 10000 ~ 50000r/min, time is 0.1 ~ 30min, after homogenizing, stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that camphor derivative is formed, it is 10 ~ 1000r/min that above-mentioned whipping process controls mixing speed,
Described emulsifying agent is anion surfactant or non-ionic surface active agent;
Wherein said anion surfactant is fatty alcohol carboxylate, and its structural formula is C
nh
2n+1cOOM, wherein n is 11 ~ 17, M is Na, K or NH
3;
Described non-ionic surface active agent is fatty alcohol-polyoxyethylene ether series, and its structural formula is:
wherein fatty alcohol carbon number n is between 7 ~ 19, and in polyoxyethylene, oxygen ethylene number m is between 3 ~ 20;
Described oils and fats be mineral grease, natural origin Vegetable oil lipoprotein, natural origin animal oil and synthetic ester oil one or more rich mixture;
Described mineral grease is white oil, vaseline, microwax or montan wax;
Described natural origin Vegetable oil lipoprotein is candlenut oil, Oleum Hippophae, water Bulbus Allii mustard oil, cameline oil, grape-pip oil, Flos Rosae Multiflorae fruit oil, Flos Inulae oil, aloe, Herba Passiflorae Caeruleae caul-fat, Fructus Mangifera Indicae kernel oil, cocoa butter, mother-in-law sieve's fat, mowrah fat, Adeps Bovis seu Bubali resin, Brazil wax, candelilla wax, haze tallow or aromatic wax;
Described natural origin animal oil is water leopard oil, shark liver oil, horse fat, spermaceti or Cera Flava;
Described synthetic ester oil is lanonol, Pilus Caprae seu Ovis fatty acid, wool oil, pure lanocerin, pancreas lanoline, Wool wax alcohols,ethoxylated, PULLRONIC F68 wool oil, hydrogenated lanolin, polyethylene glycol hydrogenated lanoline, polyoxyethylene Pilus Caprae seu Ovis alcohol ether or lanolin fatty acid isopropyl ester;
Described co-emulsifier is monohydric alcohol or polyhydric alcohol, and wherein the molecular formula of monohydric alcohol is C
nh
2n+1oH, wherein n is between 1 ~ 12; Polyhydric alcohol is ethylene glycol, 1,2-PD, 1,3-PD, 1, one or more mixed alcohols formed in 3 butanediols, propylene carbonate and glycerol;
(2), the preparation of organic silicon monomer hydrolysising product solution
Organosilicon is added in the mixture of water and/or organic solvent, then under acid or alkali effect, control pH be 1 ~ 6 or pH 7.5 ~ 11.5 to be hydrolyzed reaction, hydrolysis time was at 0.1 ~ 10 hour, temperature 1 ~ 100 DEG C, mixing speed 10 ~ 1000r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
Described organosilyl addition calculates i.e. organosilicon in mass ratio: the mixture of water and/or organic solvent is 1 ~ 50:100;
Described organosilicon is organosiloxane, and its structural formula is R
1nSiX
(4-n);
Wherein R
1that representative is selected from replacement or the unsubstituted univalent perssad having a C atom to be connected directly between alkyl on Si atom or alkenylphenyl, n is the integer of 0 ~ 3, X is hydrolysising group, is hydroxyl, hydrogen, alkoxyl, halogen group, carboxyl, amino or siloxy;
As n > 1, each R1 group can be identical or different;
And as (4-n) > 1, each X group can be identical or different;
Said organic solvent is methanol, ethanol, ethylene glycol, propanol, isopropyl alcohol, butanols, isobutanol, propylene carbonate, glycerol, Methanamide, N, the mixture of one or more compositions in N-dimethyl acetylamide, DMF, acetone, oxolane, dimethylsulfone, ethyl acetate, pyridine and acetonitrile;
(3) preparation of the suspension of the polysiloxane composite particles of the chemical sun, formed containing coated camphor derivative
The organic silicon monomer hydrolysising product solution obtain step (2) and the nanoemulsions comprising the chemical sun that camphor derivative is formed of step (1) gained calculate in mass ratio, namely the nanoemulsions of the chemical sun that camphor derivative is formed is comprised: organic silicon monomer hydrolysising product solution is that 0.1:99.9 ~ 50:50 mixes, then the suspension that polycondensation reaction obtains the polysiloxane composite particles of the chemical sun formed containing coated camphor derivative is carried out under regulating with alkaline matter the condition that pH is 7.5 ~ 13.5, it is 0 DEG C ~ 100 DEG C that polycondensation process controls reaction temperature, speed of agitator is 10 ~ 1000r/min, time is 0.1 ~ 24h,
By the suspension water, the ethanol circulation cleaning that contain the polysiloxane composite particles of the chemical sun that coated camphor derivative is formed of gained after polycondensation reaction completes, and centrifugal, filtration, the filter cake of gained is dry at 100 ~ 200 DEG C, and the solids finally obtained are the polysiloxane composite particles of the chemical sun that coated camphor derivative is formed.
2. the polysiloxane composite particles of chemical sun that formed of a kind of coated camphor derivative as claimed in claim 1, is characterized in that the organosilan described in step in preparation process (2) is trimethylmethoxysilane, trimethylethoxysilane, trimethyl silanol, tri-phenyl chloride, trim,ethylchlorosilane, dimethyldichlorosilane, diethyl dichlorosilane, Methylethyl dichlorosilane, dimethyl chloride methoxy silane, diphenyl dichlorosilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, aminomethyl phenyl dimethoxysilane, methyltrimethylsilane, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, hexyl trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, vinyltrimethoxy silane, VTES, methyl allyl acyloxypropyl trimethoxysilane, methyl trichlorosilane, phenyl trichlorosilane, tetramethoxy-silicane, tetraethoxysilane, one or more organosilane mixtures formed in four butoxy silanes and tetrachloro silicane.
3. the polysiloxane composite particles of chemical sun that formed of a kind of coated camphor derivative as claimed in claim 1, is characterized in that:
Acid described in step (2) is citric acid, one or more mixture formed in acetic acid, oxalic acid, tartaric acid, hydrochloric acid, phosphoric acid, carbonic acid and sulfurous acid;
Alkali described in step (2) is the mixture of one or more compositions in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine and triethylamine.
4. the polysiloxane composite particles of chemical sun that formed of a kind of coated camphor derivative as claimed in claim 1, is characterized in that the alkaline matter of step (3) is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, ethamine, diethylamine or triethylamine.
5. a kind of coated camphor derivative as described in as arbitrary in Claims 1 to 4 the polysiloxane composite particles of chemical sun that formed, it is characterized in that:
The hydrolysis preferred control time described in step (2) is 3.5 ~ 5h, and temperature is 10 ~ 25 DEG C, and mixing speed is 70 ~ 120r/min;
Polycondensation reaction preferred process reaction temperature described in step (3) is 10 ~ 25 DEG C, and speed of agitator is 100 ~ 150r/min, and the time is 5h.
6. a kind of coated camphor derivative as described in as arbitrary in Claims 1 to 4 the polysiloxane composite particles of chemical sun that formed, it is characterized in that the particle diameter of the polysiloxane composite particles of the chemical sun that described a kind of coated camphor derivative is formed is preferably 100nm ~ 300nm.
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Citations (4)
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|---|---|---|---|---|
| WO1998035649A1 (en) * | 1997-02-17 | 1998-08-20 | L'oreal | Sunscreen composition comprising a solid elastomeric organopolysiloxane |
| CN1506367A (en) * | 2002-12-06 | 2004-06-23 | 河南省科学院同位素研究所 | Organosilicon modified cinnamate as reactive ultraviolet ray absorbent and its prepn and application |
| CN101589997A (en) * | 2009-06-25 | 2009-12-02 | 上海应用技术学院 | A kind of UVB ultra light sun block lotion and preparation method thereof |
| CN101849891A (en) * | 2008-12-04 | 2010-10-06 | 国际香料和香精公司 | The microcapsule that contains active component |
-
2011
- 2011-12-26 CN CN201110439910.6A patent/CN102488632B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998035649A1 (en) * | 1997-02-17 | 1998-08-20 | L'oreal | Sunscreen composition comprising a solid elastomeric organopolysiloxane |
| CN1506367A (en) * | 2002-12-06 | 2004-06-23 | 河南省科学院同位素研究所 | Organosilicon modified cinnamate as reactive ultraviolet ray absorbent and its prepn and application |
| CN101849891A (en) * | 2008-12-04 | 2010-10-06 | 国际香料和香精公司 | The microcapsule that contains active component |
| CN101589997A (en) * | 2009-06-25 | 2009-12-02 | 上海应用技术学院 | A kind of UVB ultra light sun block lotion and preparation method thereof |
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| Title |
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| 我国防晒剂发展概况;赵玥等;《日用化学品科学》;20101231;第33卷(第12期);第14-16页 * |
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