CN102488630B - Polysiloxane composite particle cladding chemical sun-screening agent formed by p-methoxycinnamic acid esters and preparation method thereof - Google Patents
Polysiloxane composite particle cladding chemical sun-screening agent formed by p-methoxycinnamic acid esters and preparation method thereof Download PDFInfo
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- CN102488630B CN102488630B CN201110439596.1A CN201110439596A CN102488630B CN 102488630 B CN102488630 B CN 102488630B CN 201110439596 A CN201110439596 A CN 201110439596A CN 102488630 B CN102488630 B CN 102488630B
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Abstract
The invention discloses a polysiloxane composite particle cladding a chemical sun-screening agent formed by p-methoxycinnamic acid esters. A preparation method for the composite particle comprises the following steps: uniformly dispersing the oil-phase components, i.e., the chemical sun-screening agent formed by p-methoxycinnamic acid esters, an emulsifying agent, grease and an auxiliary emulsifying agent; adding the oil-phase components while homogenizing water, carrying out homogeneous stirring and cooling an obtained mixture to room temperature so as to obtain nanometer emulsion containing the chemical sun-screening agent formed by p-methoxycinnamic acid esters; preparing a solution of hydrolysates of organosilicon monomers, mixing the solution with the nanometer emulsion containing the chemical sun-screening agent formed by p-methoxycinnamic acid esters, adjusting the pH value of an obtained mixture to be 7.5 to 13.5, controlling temperature to be 0 to 100 DEG C, a rotating speed to be 10 to 1000 r/min and rotating time to be 0.1 to 24 h so as to obtain a fluid suspension of polysiloxane composite particles cladding the chemical sun-screening agent formed by p-methoxycinnamic acid esters and carrying out washing, centrifugation, drying and the like on the fluid suspension so as to obtain a final product.
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 p-methoxycinnamic acid esters 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.
P-methoxycinnamic acid esters is the good absorption agent in UVB district, and it is respond well.Very prevailing in Europe, as the product methyl cinnamic acid monooctyl ester (CTFA names as octyl methoxycinnamate) of American I SP and Dutch DSM N. V., its commodity are called Parsol MCX, molecular formula C
18h
26o
3, be the UV absorbent that UVB district is good, λ max is 310nm, is pale yellow lightweight oily liquids, boiling point 198 ~ 200 DEG C, and freezing point-25 DEG C, in formic acid, maxima solubility is l0%.
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 p-methoxycinnamic acid esters is formed, difference of the present invention is mainly first to form the nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters is formed, and carries out siloxanes hydrolysis more afterwards, polycondensation forms coated shell; And the polysiloxane composite particles stable performance of the chemical sun that the distinctive stability of Silicone particles makes prepared coated p-methoxycinnamic acid esters be formed, in application system, substantially increase the stability of the chemical sun that p-methoxycinnamic acid esters is formed.
Summary of the invention
An object of the present invention is the polysiloxane composite particles in order to the chemical sun providing a kind of coated p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters is formed.
Technical scheme of the present invention
A polysiloxane composite particles for the chemical sun that coated p-methoxycinnamic acid esters is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that p-methoxycinnamic acid esters is formed, is comprised
The described nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters is formed is as follows:
First by chemical for the p-methoxycinnamic acid esters chemical sun formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, then while homogenizing water, by the chemical sun comprising p-methoxycinnamic acid esters and formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed gained of Emulsion to be added to the water, proceed homogenizing 0.1 ~ 30min, homogenizing speed is 10000 ~ 50000r/min, after homogenizing, stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters is formed, above-mentioned whipping process controls mixing speed 10 ~ 1000r/min,
The chemical sun that described sunscreen is formed for p-methoxycinnamic acid esters;
The mixed ester that described p-methoxycinnamic acid esters is Ethyl p-methoxy-silicate, one or more ester in OctMet, Octyl methoxycinnamate is formed;
Wherein said anion surfactant is aliphatic alcohol polyoxyvinethene phosphate salt, and its molecular formula is C
nh
2n+1(CH
2ch
2o)
mpO
4m, wherein n is generally 11 ~ 17, m to be generally 2 ~ 20, 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 vaseline, microwax or montan wax;
Described natural origin Vegetable oil lipoprotein is macadimia nut oil, candlenut oil, Oleum Hippophae, water Bulbus Allii mustard oil, cameline oil, grape-pip oil, Flos Rosae Multiflorae fruit oil, Flos Inulae oil, mowrah fat, Adeps Bovis seu Bubali resin or aromatic wax;
Described natural origin animal oil is manhaden oil, returned student's oil, exquisite Adeps Cervi or spermaceti;
Described synthetic ester oil is fatty acid ester, as isopropyl myristate, isopropyl palmitate, iso-octyl palmitate, isopropyl stearate or caprylic capric triglyceride;
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 2 ~ 5h, temperature 1 ~ 100 DEG C, be preferably 20 ~ 35 DEG C, mixing speed 10 ~ 1000r/min, is preferably 50 ~ 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 p-methoxycinnamic acid esters
The organic silicon monomer hydrolysising product solution obtain step (2) and the nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters is formed of step (1) gained calculate in mass ratio, namely the nanoemulsions of the chemical sun that p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters 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, rotating speed is 10 ~ 1000r/min, be preferably 100 ~ 150r/min, time is 0.1 ~ 24h, be preferably 5 ~ 20h,
By the suspension containing the polysiloxane composite particles of the chemical sun that coated p-methoxycinnamic acid esters is formed of gained after polycondensation reaction completes, with water, ethanol circulation cleaning 3 times, and centrifugal, filter, control centrifugal rotational speed 10000r/min ~ 15000r/min, filtration time 10min ~ 100min, dry at 100 ~ 200 DEG C, the solids finally obtained are the polysiloxane composite particles of the chemical sun that coated p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters of the present invention is formed, is suitable for being applied in sunscreen product, as the articles for use such as sun care preparations, sun-screening umbrella.Simultaneously, in order to avoid the permeability of chemical sun on skin that p-methoxycinnamic acid esters 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 nano level coated p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters of the present invention is formed, comprise the nanoemulsions of the chemical sun that p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters be formed is more stable, substantially increases the stability of the chemical sun that p-methoxycinnamic acid esters is formed in application system.
And, due to the polysiloxane composite particles of the chemical sun that a kind of coated p-methoxycinnamic acid esters of the present invention is formed, that the chemical sun that p-methoxycinnamic acid esters is formed is coated in Silicone particles, thus avoid and contact with the direct of skin, greatly reduce chemical sun that p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters of the present invention is formed, owing to being comprise the nanoemulsions of the chemical sun that p-methoxycinnamic acid esters 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 polysiloxane composite particles for the chemical sun that coated Ethyl p-methoxy-silicate is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Ethyl p-methoxy-silicate is formed, is comprised
The described nanoemulsions comprising the chemical sun that Ethyl p-methoxy-silicate 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 Ethyl p-methoxy-silicate, BASF(BASF) product produced of Chemical Co., Ltd.;
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 isopropyl palmitate, 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 Ethyl p-methoxy-silicate is formed is as follows:
First chemical sun Ethyl p-methoxy-silicate formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, the chemical sun that Ethyl p-methoxy-silicate 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, Ethyl p-methoxy-silicate formed, emulsifying agent, oils and fats and after helping being uniformly mixed of Emulsion the mixture of gained be added to the water, continue homogenizing, controlling homogenizing speed is 10000r/min, homogenizing time 3min, then stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that Ethyl p-methoxy-silicate is formed, and above-mentioned whipping process control rate is 100r/min;
(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; pH regulator to 3.0 ~ 4.0 to be hydrolyzed reaction with hydrochloric acid solution; hydrolysis time is 3.5h; 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 Ethyl p-methoxy-silicate
Organic silicon monomer hydrolysising product solution 70g step (2) obtained mixes with the nanoemulsions 30g comprising the chemical sun that Ethyl p-methoxy-silicate is formed of step (1) gained, then pH is regulated to be 7.5 ~ 8.5 with ammonia, mixing speed is 100r/min, temperature is 15 DEG C, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated Ethyl p-methoxy-silicate after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated Ethyl p-methoxy-silicate is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 10h at 100 DEG C, obtain the polysiloxane composite particles of the nano level coated Ethyl p-methoxy-silicate chemical sun of 11.6g, its particle diameter is 0.8 μm.
The sun-proof performance of the polysiloxane composite particles of the chemical sun formed with the nano level coated Ethyl p-methoxy-silicate 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 Table 1.
the sun-proof capacity measurement data of polysiloxane composite particles of the chemical sun that the coated Ethyl p-methoxy-silicate of table 1 is formed
| Sequence number | Wavelength | Absorbance (ā) |
| 1 | 280.00nm | 0.885A |
| 2 | 290.00nm | 1.321A |
| 3 | 300.00nm | 1.290A |
| 4 | 310.00nm | 1.300A |
| 5 | 320.00nm | 1.313A |
| 6 | 330.00nm | 1.294A |
| 7 | 340.00nm | 0.883A |
| 8 | 350.00nm | 0.861A |
| 9 | 360.00nm | 0.853A |
| 10 | 370.00nm | 0.867A |
| 11 | 380.00nm | 0.794A |
| 12 | 390.00nm | 0.798A |
| 13 | 400.00nm | 0.786A |
(test condition: slit: 2.00 nm wavelength numbers: 13)
Result from table 1 can find out there is good absorbability between wavelength 290nm ~ 330nm, can illustrate that the polysiloxane composite particles of the chemical sun that coated Ethyl p-methoxy-silicate 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 OctMet is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that OctMet is formed, is comprised
The described nanoemulsions comprising the chemical sun that OctMet 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 comprising OctMet, 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 macadimia nut oil, lipo(Lai Baokang) daily use chemicals (Shanghai) Co., Ltd. produce product;
Described co-emulsifier is the grade product of glycerol, traditional Chinese medicines group;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that OctMet is formed is as follows:
First chemical sun OctMet formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, the chemical sun that OctMet 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, OctMet formed, emulsifying agent, oils and fats and after helping being uniformly mixed of Emulsion the mixture of gained be added to the water, continue homogenizing, controlling homogenizing speed is 10000r/min, homogenizing time 3min, after homogenizing, stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that OctMet is formed, and 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, pH regulator to 4.0 ~ 5.0 is hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 5h, temperature 30 DEG C, mixing speed 50r/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 OctMet
Organic silicon monomer hydrolysising product solution 50g step (2) obtained mixes with the nanoemulsions 50g comprising the chemical sun that OctMet is formed of step (1) gained, then pH is regulated to be 8.5 ~ 9.5 with ammonia, mixing speed is 150r/min, temperature is 10 DEG C, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated OctMet after time 5h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated OctMet is formed of gained, 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 OctMet of 1.7g is formed, its particle diameter is 0.7 μm.
embodiment 3
A polysiloxane composite particles for the chemical sun that coated Octyl methoxycinnamate is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Octyl methoxycinnamate is formed, is comprised
The described nanoemulsions comprising the chemical sun that Octyl methoxycinnamate 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 Octyl methoxycinnamate, BASF(BASF) product produced of Chemical Co., Ltd.;
Described emulsifying agent is fatty alcohol-polyoxyethylene ether (25EO), BASF(BASF) Chemical Co., Ltd. produce emulsifying agent for cosmetics;
Described oils and fats is iso-octyl palmitate, BASF(BASF) Chemical Co., Ltd. produce oils and fats used for cosmetic;
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 Octyl methoxycinnamate is formed is as follows:
First chemical sun Octyl methoxycinnamate formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion, the chemical sun that Octyl methoxycinnamate 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, Octyl methoxycinnamate formed, emulsifying agent, oils and fats and help Emulsion be uniformly mixed or the mixture of gained is added to the water, continue homogenizing, controlling homogenizing speed is 50000r/min, homogenizing time 2min, then stirring is cooled to room temperature and namely obtains the nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters is formed, and it is 150 r/min that above-mentioned whipping process controls mixing speed;
(2), the preparation of organic silicon monomer hydrolyzate reaction mixture
15g dimethyldichlorosilane is placed in 85g water and alcohol mixeding liquid, water: ethanol is 50:50, pH regulator to 3.0 ~ 4.0 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 3.0h, temperature 25 DEG C, mixing speed 80r/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 Octyl methoxycinnamate
The nanoemulsions 10g that organic silicon monomer hydrolysising product solution 90g step (2) obtained and step (1) comprise the chemical sun that Octyl methoxycinnamate is formed mixes, then pH is regulated to be 7.5 ~ 8.5 with ammonia, mixing speed is 100r/min, temperature is 20 DEG C, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated Octyl methoxycinnamate after time 10h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated Octyl methoxycinnamate is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 5h at 200 DEG C, obtain the polysiloxane composite particles of the nano level coated p-methoxycinnamic acid esters chemical sun of 19.5g, its particle diameter is 0.9 μm.
embodiment 4
A polysiloxane composite particles for the chemical sun that coated Ethyl p-methoxy-silicate is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Ethyl p-methoxy-silicate is formed, is comprised
With embodiment 1;
(2), the preparation of organic silicon monomer hydrating solution
8g trimethyl silanol is placed in 92g water and alcohol mixeding liquid, water: ethanol is 1:99, pH regulator to 3.5 ~ 4.5 is hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 4h, temperature 30 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 Ethyl p-methoxy-silicate
Organic silicon monomer hydrolysising product solution 70g step (2) obtained mixes with the nanoemulsions 30g comprising the chemical sun that Ethyl p-methoxy-silicate is formed of step (1) gained, then pH is regulated to be 7.5 ~ 8.5 with ammonia, mixing speed is 100 r/min, temperature is 15 DEG C, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated Ethyl p-methoxy-silicate after time 9h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated Ethyl p-methoxy-silicate is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 10h at 100 DEG C, obtain the polysiloxane composite particles of the nano level coated Ethyl p-methoxy-silicate chemical sun of 11.6g, its particle diameter is 0.8 μm.
embodiment 5
A polysiloxane composite particles for the chemical sun that coated OctMet is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that OctMet is formed, is comprised
With embodiment 2;
(2), the preparation of organic silicon monomer hydrolysising product solution
3g diphenyl diethoxy silane is placed in 97g water and alcohol mixeding liquid, water: ethanol is 25:75, pH regulator to 3.0 ~ 4.0 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 2.0h, temperature 35 DEG C, mixing speed 40r/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 OctMet
Organic silicon monomer hydrolysising product solution 50g step (2) obtained mixes with the nanoemulsions 50g comprising the chemical sun that OctMet is formed of step (1) gained, then pH is regulated to be 8.5 ~ 9.5 with ammonia, mixing speed is 150r/min, temperature is 10 DEG C, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated OctMet after time 15h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated OctMet is formed of gained, 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 OctMet 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 Octyl methoxycinnamate is formed, prepare by the following method:
(1) preparation of the nanoemulsions of the chemical sun that Octyl methoxycinnamate is formed, is comprised
With embodiment 3;
(2), the preparation of organic silicon monomer hydrolysising product solution
15g VTES is placed in 85g water and alcohol mixeding liquid, water: ethanol is 50:50, pH regulator to 3.0 ~ 4.0 to be hydrolyzed reaction with hydrochloric acid solution, hydrolysis time is 3.5h, temperature 20 DEG C, mixing speed 100r/min, obtains organic silicon monomer hydrolysising product solution after having reacted;
(3), the preparation of the nano polysilicon oxygen alkane compound particle suspension of chemical sun that formed of coated Octyl methoxycinnamate
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 Octyl methoxycinnamate is formed of step (1) gained, control mixing speed is 100r/min, temperature is 25 DEG C, obtains the suspension of the polysiloxane composite particles of the chemical sun formed containing coated Octyl methoxycinnamate after time 20h;
By the suspension containing the polysiloxane composite particles of the chemical sun that coated Octyl methoxycinnamate is formed of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, dry 5h at 200 DEG C, obtain the polysiloxane composite particles of the nano level coated Octyl methoxycinnamate chemical sun of 19.5g, 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 p-methoxycinnamic acid esters, is characterized in that preparing by the following method:
(1) preparation of the nanoemulsions of the chemical sun that p-methoxycinnamic acid esters is formed, is comprised
The described nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters 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 comprising p-methoxycinnamic acid esters;
The mixed ester that p-methoxycinnamic acid esters esters in the chemical sun that described p-methoxycinnamic acid esters is formed is Ethyl p-methoxy-silicate, one or more ester in OctMet and Octyl methoxycinnamate is formed;
The above-mentioned nanoemulsions preparation process comprising the chemical sun that p-methoxycinnamic acid esters is formed is as follows:
First, chemical sun p-methoxycinnamic acid esters formed, emulsifying agent, oils and fats and help being uniformly mixed of Emulsion;
Then, while homogenizing water, the chemical sun that above-mentioned p-methoxycinnamic acid esters is formed, emulsifying agent, oils and fats and help the mixture being uniformly mixed rear gained of Emulsion to be added to the water, controlling homogenizing speed is that 10000 ~ 50000r/min proceeds homogenizing 0.1 ~ 30min, then controls mixing speed 10 ~ 1000r/min and stir and be cooled to room temperature and namely obtain the nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters is formed;
Described emulsifying agent is anion surfactant or non-ionic surface active agent;
Wherein said anion surfactant is aliphatic alcohol polyoxyvinethene phosphate salt, and its molecular formula is C
nh
2n+1(CH
2ch
2o)
mpO
4m, wherein n is generally 11 ~ 17, m to be generally 2 ~ 20, 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 vaseline, microwax or montan wax;
Described natural origin Vegetable oil lipoprotein is macadimia nut oil, candlenut oil, Oleum Hippophae, water Bulbus Allii mustard oil, cameline oil, grape-pip oil, Flos Rosae Multiflorae fruit oil, Flos Inulae oil, mowrah fat, Adeps Bovis seu Bubali resin or aromatic wax;
Described natural origin animal oil is manhaden oil or spermaceti;
Described synthetic ester oil is isopropyl myristate, isopropyl palmitate, iso-octyl palmitate, isopropyl stearate or caprylic capric triglyceride;
Described co-emulsifier is monohydric alcohol or polyhydric alcohol;
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 is at 0.1 ~ 10h, 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 p-methoxycinnamic acid esters
The organic silicon monomer hydrolysising product solution obtain step (2) and the nanoemulsions comprising the chemical sun that p-methoxycinnamic acid esters is formed of step (1) gained calculate in mass ratio, namely the nanoemulsions of the chemical sun that p-methoxycinnamic acid esters is formed is comprised: organic silicon monomer hydrolysising product solution is that 0.1:99.9 ~ 50:50 mixes, then pH is regulated to carry out the suspension that polycondensation reaction obtains the polysiloxane composite particles containing coated p-methoxycinnamic acid esters chemical sun under the condition of 7.5 ~ 13.5 with alkaline matter, it is 0 DEG C ~ 100 DEG C that polycondensation process controls reaction temperature, rotating speed is 10 ~ 1000r/min, time is 0.1 ~ 24h,
By the suspension of the polysiloxane composite particles containing coated p-methoxycinnamic acid esters chemical sun of gained, with water, ethanol circulation cleaning 3 times, and centrifugal, filtration, by dry at 100 ~ 200 DEG C for the filter cake obtained, the solids finally obtained are the polysiloxane composite particles of the chemical sun that coated p-methoxycinnamic acid esters is formed.
2. the polysiloxane composite particles of chemical sun that formed of a kind of coated p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters 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 p-methoxycinnamic acid esters 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 2 ~ 5h, and temperature is 20 ~ 35 DEG C, and mixing speed is 50 ~ 120r/min;
The preferred control temperature of polycondensation process described in step (3) is 10 ~ 25 DEG C, and rotating speed is 100 ~ 150r/min, and the time is 5 ~ 20h.
6. a kind of coated p-methoxycinnamic acid esters 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 coated p-methoxycinnamic acid esters is formed is preferably 100nm ~ 300nm.
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| CN103202782B (en) * | 2012-09-29 | 2015-01-14 | 广州环亚化妆品科技有限公司 | Lip balm with sun-screening and anti-free radical effects |
| CN103202783B (en) * | 2012-09-29 | 2014-10-15 | 广州环亚化妆品科技有限公司 | Non-irritant sunscreen cream and preparation method thereof |
| CN108042382B (en) * | 2018-01-02 | 2020-03-20 | 上海应用技术大学 | Sunscreen composition containing octyl methoxycinnamate particles and avobenzone and application thereof |
| CN109718122B (en) * | 2019-03-15 | 2021-10-22 | 派能生物科技（深圳）有限公司 | Skin antioxidant whitening composition and preparation method thereof |
| CN110074993A (en) * | 2019-06-05 | 2019-08-02 | 山东大学 | A method of preparing ultraviolet absorber nano particle |
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| CN1216515A (en) * | 1996-02-21 | 1999-05-12 | 花王株式会社 | Ultraviolet-screening composite particulate and process for the production thereof |
| 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 |
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| 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 |
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|---|---|---|---|---|
| CN1216515A (en) * | 1996-02-21 | 1999-05-12 | 花王株式会社 | Ultraviolet-screening composite particulate and process for the production thereof |
| 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 |
| CN1798538A (en) * | 2003-06-03 | 2006-07-05 | 默克专利股份有限公司 | Photostable organic sunscreen composition |
| CN101849891A (en) * | 2008-12-04 | 2010-10-06 | 国际香料和香精公司 | The microcapsule that contains active component |
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