CN102488630A - 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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- CN102488630A CN102488630A CN2011104395961A CN201110439596A CN102488630A CN 102488630 A CN102488630 A CN 102488630A CN 2011104395961 A CN2011104395961 A CN 2011104395961A CN 201110439596 A CN201110439596 A CN 201110439596A CN 102488630 A CN102488630 A CN 102488630A
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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 the chemical sunscreen polysiloxane composite particles of a kind of coating, more particularly relate to a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters and preparation method thereof.
Background technology
The chemistry sunscreen mainly is meant the organic compound with the ultraviolet radiation that can be absorbed with injury effect, is commonly referred to chemical ultraviolet absorbent.Different according to the radiating wave band of protection, UV (ultraviolet) absorbent can be divided into UVA (life ultraviolet) and two kinds of absorbent of UVB (outdoor ultraviolet).On chemical constitution, can be divided into para-amino benzoic acid and esters, salicylic acid esters and derivant thereof, o-aminobenzoa class, benzophenone and derivant thereof, p-methoxycinnamic acid class, methane analog derivative and Camphora analog derivative etc.Be applied to the chemical sunscreen in the cosmetics because its photo-labile property and to the zest of skin can produce certain side effect, belong at European Union's part sunscreen and limit the use of raw material, the part sunscreen then belongs to the forbidding raw material.Simultaneously, general sunscreen only has anti-sunlight function in a kind of wavelength band to UVA or UVB wave band.
The p-methoxycinnamic acid esters is the good absorption agent in UVB district, and it is respond well.Very in vogue in Europe, like the product methyl cinnamic acid monooctyl ester (CTFA names the methoxycinnamate into octyl) of American I SP and Dutch DSM N. V., its commodity are called Parsol MCX, molecular formula C
18H
26O
3, being the good UV absorbent in UVB district, λ max is 310nm, is pale yellow lightweight oily liquids, 198～200 ℃ of boiling points, freezing point-25 ℃, maxima solubility is l0% in formic acid.
The organosilicon microsphere is that the organosilan monomer carries out polyreaction under certain conditions and gets.The organosilicon microsphere has characteristics such as hardness height, fusing point are high, wear-resisting, lubricious, nontoxic, tasteless, transparent, gloss, and Stability Analysis of Structures, and therefore environmental friendliness is widely used as the 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.
At present domestic disclosed relevant core-shell type polysiloxane composite particles; But Shang Weijian openly coats the polysiloxanes particle of the formed chemical sunscreen of p-methoxycinnamic acid esters; Difference of the present invention mainly is to form earlier the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters, carries out siloxanes hydrolysis, polycondensation formation coating shell afterwards again; And the distinctive stability of polysiloxanes particle makes the polysiloxane composite particles stable performance of the prepared formed chemical sunscreen of coating p-methoxycinnamic acid esters, in application system, has improved the stability of the formed chemical sunscreen of p-methoxycinnamic acid esters greatly.
Summary of the invention
One of the object of the invention is for a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters is provided.
Two of the object of the invention provides above-mentioned a kind of method for preparing that coats the polysiloxane composite particles of the formed chemical sunscreen of p-methoxycinnamic acid esters.
Technical scheme of the present invention
A kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters prepares through following method:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of p-methoxycinnamic acid esters
The described nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters is calculated by mass percentage, and its raw material composition and content are following:
Sunscreen 0.1～10%
Emulsifying agent 0.1～20%
Oils and fats 0.1～10%
Help Emulsion 0.1～20%
Surplus is a water;
It is following that the above-mentioned nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters prepares process:
At first with p-methoxycinnamic acid esters chemistry formed chemical sunscreen, emulsifying agent, oils and fats with help mixing of Emulsion; Then in homogenizing water; To comprise the formed chemical sunscreen of p-methoxycinnamic acid esters, emulsifying agent, oils and fats and help the mixture that mixes gained of Emulsion to be added to the water; Proceed homogenizing 0.1～30min; Homogenizing speed is 10000～50000r/min, and stirring is cooled to room temperature and promptly gets the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters behind the homogenizing, above-mentioned whipping process control mixing speed 10～1000r/min;
Described sunscreen is the formed chemical sunscreen of p-methoxycinnamic acid esters;
Described p-methoxycinnamic acid esters is one or more the formed mixed ester of ester in p-methoxycinnamic acid ethyl ester, p-methoxycinnamic acid monooctyl ester, the different monooctyl ester of p-methoxycinnamic acid;
Wherein said anion surfactant is an 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, and m is generally 2～20, and M is Na, K or NH
3
Said non-ionic surface active agent is a fatty alcohol-polyoxyethylene ether series; Its structural formula is:
; Wherein aliphatic alcohol carbon number n is between 7～19, and oxygen ethylene is counted m between 3～20 in the polyoxyethylene;
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 a fatty acid ester, like isopropyl myristate, isopropyl palmitate, iso-octyl palmitate, isopropyl stearate or sad capric acid 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 an ethylene glycol, 1,2-propylene glycol, 1, one or more mixed alcohols formed in ammediol, 1,3 butanediol, propylene glycol carbonic ester and the glycerin;
(2), the preparation of organic silicon monomer hydrolysising product solution
Organosilicon is added in the mixture of entry and/or organic solvent, then under acid or alkali effect, control pH be 1～6 or pH be 7.5～11.5 reactions that are hydrolyzed; Hydrolysis time is preferably 2～5h at 0.1～10h, 1～100 ℃ of temperature; Be preferably 20～35 ℃; Mixing speed 10～1000r/min is preferably 50～120r/min, obtains the organic silicon monomer hydrolysising product solution after having reacted;
It is organosilicon that described organosilyl addition is calculated by mass ratio: the mixture of water and/or organic solvent is 1～50:100;
Described organosilicon is an organosiloxane, and its structural formula is R
1NSiX
(4-n)
R wherein
1Representative is selected from substitutedly or unsubstituted has a C atom directly to be connected alkyl or the univalent perssad of alkenyl phenyl on the Si atom; N is 0～3 integer; X is a hydrolysising group, is hydroxyl, hydrogen, alkoxyl, halogen group, carboxyl, amino or siloxy;
When n＞1, each R1 group can be identical or different;
And when (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 the sulfurous acid;
Described alkali is one or more mixed bases in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, DMA, ethamine, diethylamine and the triethylamine;
Said organic solvent is methanol, ethanol, ethylene glycol, propanol, isopropyl alcohol, butanols, isobutanol, propylene glycol carbonic ester, glycerol, Methanamide, N; N-dimethyl acetylamide, N, one or more mixture in dinethylformamide, acetone, oxolane, dimethylsulfone, ethyl acetate, pyridine and the acetonitrile;
(3), contain the preparation of the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters
The organic silicon monomer hydrolysising product solution that step (2) is obtained and the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters of step (1) gained calculate by mass ratio; The nanoemulsions that promptly comprises the formed chemical sunscreen of p-methoxycinnamic acid esters: the organic silicon monomer hydrolysising product solution is that 0.1:99.9～50:50 mixes; Use alkaline matter to regulate pH then and carry out the suspension that polycondensation reaction obtains containing the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters under 7.5～13.5 the condition; The polycondensation process control reaction temperature is 0 ℃～100 ℃; Be preferably 10～25 ℃, rotating speed is 10～1000r/min, is preferably 100～150r/min; Time is 0.1～24h, is preferably 5～20h;
After polycondensation reaction is accomplished with the suspension that contains the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of gained; Water, ethanol cycle washing 3 times; And centrifugal, filter, control centrifugal rotational speed 10000r/min～15000r/min; Filtration time 10min～100min, dry under 100～200 ℃, the solids that finally obtain are the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters;
Wherein said alkaline matter is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, DMA, ethamine, diethylamine or triethylamine.
A kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of the present invention is suitable for being applied in the sunscreen product, like articles for use such as sun care preparations, sun-proof umbrellas.Simultaneously; For fear of the permeability of the formed chemical sunscreen of p-methoxycinnamic acid esters on skin; The particle diameter of lipid particles is difficult for too little; The particle diameter of the polysiloxane composite particles of the formed chemical sunscreen of nano level coating p-methoxycinnamic acid esters through gained of the present invention between 80nm～500nm, preferred 100nm～300nm.
Beneficial effect of the present invention
A kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of the present invention; Owing to form the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters earlier, carry out siloxanes hydrolysis, polycondensation formation coating shell afterwards again in the preparation process; The distinctive stability of polysiloxanes particle makes that the polysiloxane composite particles performance of the prepared formed chemical sunscreen of coating p-methoxycinnamic acid esters is more stable like this, in application system, has improved the stability of the formed chemical sunscreen of p-methoxycinnamic acid esters greatly.
And; Because a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of the present invention; Be that the formed chemical sunscreen of p-methoxycinnamic acid esters is coated in the polysiloxanes particle; Thereby avoided contacting, greatly reduced the zest of the formed chemical sunscreen of p-methoxycinnamic acid esters skin with the direct of skin.Can embody sun-proof result preferably.
In addition; A kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of the present invention; Owing to be as raw material with the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters, organosilicon; Therefore method for preparing is easy, and productive rate is high, has the suitability for industrialized production prospect.
The specific embodiment
Through embodiment the present invention is further set forth below, but do not limit the present invention.
Embodiment 1
A kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester prepares through following method:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester
The described nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester is calculated by mass percentage, and its raw material composition and content are following:
Sunscreen 5%
Emulsifying agent 5%
Oils and fats 5%
Help Emulsion 5%
Surplus is a water;
Described sunscreen is the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester, the product that the chemical company limited of BASF (BASF) is produced;
Described emulsifying agent is fatty alcohol-polyoxyethylene ether (21EO), the emulsifying agent for cosmetics that the chemical company limited of CRODA (standing grain is big) is produced;
Described oils and fats is an isopropyl palmitate, the used for cosmetic oils and fats that the chemical company limited of BASF (BASF) is produced;
Described co-emulsifier is a propylene glycol, the SILVER REAGENT product of traditional Chinese medicines group;
It is following that the above-mentioned nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester prepares process:
At first with the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester, emulsifying agent, oils and fats with help mixing of Emulsion, with the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester, emulsifying agent, oils and fats with help the mixture that mixes gained of Emulsion and water to be heated to 60～80 ℃ respectively; In homogenizing water with the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester, emulsifying agent, oils and fats and help Emulsion mix the back gained mixture be added to the water; Continue homogenizing; Control homogenizing speed is 10000r/min; Homogenizing time 3min, stirring is cooled to room temperature and promptly gets the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester then, and above-mentioned whipping process control rate is 100r/min;
(2), the preparation of organic silicon monomer hydrolysising product solution
8g trimethyl methoxy silane is placed 92g water and alcohol mixeding liquid; Water: ethanol is 1:99; With pH regulator to 3.0～4.0 reaction that is hydrolyzed, hydrolysis time is 3.5h, 20 ℃ of temperature with hydrochloric acid solution; Mixing speed 100r/min obtains the organic silicon monomer hydrolysising product solution after having reacted;
(3), contain the preparation of the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester
The organic silicon monomer hydrolysising product solution 70g that step (2) is obtained mixes with the nanoemulsions 30g that comprises the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester of step (1) gained; Using ammonia to regulate pH then is 7.5～8.5; Mixing speed is 100r/min; Temperature is 15 ℃, obtains containing the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester behind the time 5h;
The suspension that contains the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester with gained; Water, ethanol cycle washing 3 times; And centrifugal, filtration; At 100 ℃ of following dry 10h, promptly get the polysiloxane composite particles of the nano level coating p-methoxycinnamic acid of 11.6g ethyl ester chemistry sunscreen, its particle diameter is 0.8 μ m.
With ultraviolet spectrophotometry the sun-proof performance of the polysiloxane composite particles of the formed chemical sunscreen of nano level coating p-methoxycinnamic acid ethyl ester of above-mentioned gained is measured; This mensuration adopts the evaluation methodology-ultraviolet spectrophotometry of the sun-proof performance of GB QB/T2410-98 to measure, and the used spectrophotometric of the present invention is counted Shanghai exact science instrument company and made 759 ultraviolet spectrophotometers.Determination step is following:
(1), breathable adhesive tape that 3M company is produced is cut into lcm * 4cm size, stick on the quartz colorimetric utensil printing opacity and survey on the surface;
(2), energized, the preheating spectrophotometer, setting UVB district, to detect wavelength be 280nm, 290nm, 300nm, 310nm and 320nm, UVA district detection wavelength is 330nm, 340nm, 350nm, 360nm, 370nm, 380nm, 390nm and 400nm;
The quartz colorimetric utensil that (3), will post adhesive tape places sample light path and reference light paths, the adjustment instrument zero;
(4), get the powder sample of 1g preparation, be scattered in the water, mass concentration is 10% dispersion liquid, accurately take by weighing dispersion liquid 8mg (error 0.2mg), sample is evenly spread upon on the quartz colorimetric utensil 3M adhesive tape, claims five parallel kind;
(5), the sample cuvette for preparing is placed under the room temperature dry 30min;
(6), the testing sample cuvette is placed the sample light path, another quartz cell that posts adhesive tape places reference light paths, measures the ultraviolet absorptivity value that 280nm～400nm district sets wavelength respectively, then measured value is asked arithmetic mean of instantaneous value ā;
Five parallel sample ā of sequentially determining, 1～ā 5 asks arithmetic mean of instantaneous value, is exactly the ultraviolet absorptivity value ā appearance of sample, and the result sees table 1.
Table 1 coats the sun-proof performance measurement data of polysiloxane composite particles of the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester
| 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 has absorbability preferably between wavelength 290nm～330nm, can explain that the polysiloxane composite particles of the formed chemical sunscreen of coating p-methoxycinnamic acid ethyl ester of the present invention has certain anti-sunlight function.
Embodiment 2
A kind of nano polysilicon oxygen alkane compound particle that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester prepares through following method:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester
The described nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester is calculated by mass percentage, and its raw material composition and content are following:
Sunscreen 0.1%
Emulsifying agent 0.1%
Oils and fats 0.1%
Help Emulsion 0.1%
Surplus is a water;
Described sunscreen is for comprising the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester, the product that the chemical company limited of BASF (BASF) is produced;
Described emulsifying agent is fatty alcohol-polyoxyethylene ether (2EO), the emulsifying agent for cosmetics that the chemical company limited of CRODA (standing grain is big) is produced;
Described oils and fats is a macadimia nut oil, the product that lipo (Lai Baokang) daily use chemicals (Shanghai) Co., Ltd. produces;
Described co-emulsifier is a glycerin, the SILVER REAGENT product of traditional Chinese medicines group;
It is following that the above-mentioned nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester prepares process:
At first with the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester, emulsifying agent, oils and fats with help mixing of Emulsion, with the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester, emulsifying agent, oils and fats with help the mixture that mixes gained of Emulsion and water to be heated to 60～80 ℃ respectively; In homogenizing water with the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester, emulsifying agent, oils and fats and help Emulsion mix the back gained mixture be added to the water; Continue homogenizing; Control homogenizing speed is 10000r/min; Homogenizing time 3min, stirring is cooled to room temperature and promptly gets the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester behind the homogenizing, and above-mentioned whipping process control mixing speed is 100r/min;
(2), the preparation of organic silicon monomer hydrolysising product solution
3g trimethyl methoxy silane is placed 97g water and alcohol mixeding liquid, water: ethanol is 25:75, with hydrochloric acid solution with pH regulator to 4.0～5.0 reaction that is hydrolyzed; Hydrolysis time is 5h; 30 ℃ of temperature, mixing speed 50r/min obtains the organic silicon monomer hydrolysising product solution after having reacted
(3), contain the preparation of the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester
The organic silicon monomer hydrolysising product solution 50g that step (2) is obtained mixes with the nanoemulsions 50g that comprises the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester of step (1) gained; Using ammonia to regulate pH then is 8.5～9.5; Mixing speed is 150r/min; Temperature is 10 ℃, obtains containing the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester behind the time 5h;
The suspension that contains the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester with gained; Water, ethanol cycle washing 3 times; And centrifugal, filtration; At 150 ℃ of following dry 8h, promptly get the polysiloxane composite particles of the formed chemical sunscreen of 1.7g nano level coating p-methoxycinnamic acid monooctyl ester, its particle diameter is 0.7 μ m.
Embodiment 3
A kind of polysiloxane composite particles that coats the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid prepares through following method:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid
The described nanoemulsions that comprises the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid is calculated by mass percentage, and its raw material composition and content are following:
Sunscreen 10%
Emulsifying agent 20%
Oils and fats 10%
Help Emulsion 20%
Surplus is a water;
Described sunscreen is the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid, the product that the chemical company limited of BASF (BASF) is produced;
Described emulsifying agent is fatty alcohol-polyoxyethylene ether (25EO), the emulsifying agent for cosmetics that the chemical company limited of BASF (BASF) is produced;
Described oils and fats is an iso-octyl palmitate, the used for cosmetic oils and fats that the chemical company limited of BASF (BASF) is produced;
Described co-emulsifier is an isopropyl alcohol, the SILVER REAGENT product of traditional Chinese medicines group;
It is following that the above-mentioned nanoemulsions that comprises the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid prepares process:
At first with the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid, emulsifying agent, oils and fats with help mixing of Emulsion, with the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid, emulsifying agent, oils and fats with help the mixture that mixes gained of Emulsion and water to be heated to 80～90 ℃ respectively; In homogenizing water with the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid, emulsifying agent, oils and fats and help Emulsion mix or the mixture of gained is added to the water; Continue homogenizing; Control homogenizing speed is 50000r/min; Homogenizing time 2min, stirring is cooled to room temperature and promptly gets the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters then, and above-mentioned whipping process control mixing speed is 150 r/min;
(2), the preparation of organic silicon monomer hydrolyzate product solution
The 15g dimethyldichlorosilane is placed 85g water and alcohol mixeding liquid; Water: ethanol is 50:50; With pH regulator to 3.0～4.0 reaction that is hydrolyzed, hydrolysis time is 3.0h, 25 ℃ of temperature with hydrochloric acid solution; Mixing speed 80r/min obtains the organic silicon monomer hydrolysising product solution after having reacted;
(3), contain the preparation of the suspension of the nano polysilicon oxygen alkane compound particle that coats the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid
The organic silicon monomer hydrolysising product solution 90g that step (2) is obtained mixes with the nanoemulsions 10g that step (1) comprises the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid; Using ammonia to regulate pH then is 7.5～8.5; Mixing speed is 100r/min; Temperature is 20 ℃, obtains containing the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid behind the time 10h;
The suspension that contains the polysiloxane composite particles that coats the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid with gained; Water, ethanol cycle washing 3 times; And centrifugal, filtration; At 200 ℃ of following dry 5h, promptly get the polysiloxane composite particles of the nano level coating p-methoxycinnamic acid of 19.5g esters chemistry sunscreen, its particle diameter is 0.9 μ m.
Embodiment 4
A kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester prepares through following method:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester
With embodiment 1;
(2), the preparation of organic silicon monomer hydrating solution
The 8g trimethyl silanol is placed 92g water and alcohol mixeding liquid, water: ethanol is 1:99, with hydrochloric acid solution with pH regulator to 3.5～4.5 reaction that is hydrolyzed; Hydrolysis time is 4h; 30 ℃ of temperature, mixing speed 120r/min obtains the organic silicon monomer hydrolysising product solution after having reacted;
(3), contain the preparation of the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester
The organic silicon monomer hydrolysising product solution 70g that step (2) is obtained mixes with the nanoemulsions 30g that comprises the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester of step (1) gained; Using ammonia to regulate pH then is 7.5～8.5; Mixing speed is 100 r/min; Temperature is 15 ℃, obtains containing the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester behind the time 9h;
The suspension that contains the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid ethyl ester with gained; Water, ethanol cycle washing 3 times; And centrifugal, filtration; At 100 ℃ of following dry 10h, promptly get the polysiloxane composite particles of the nano level coating p-methoxycinnamic acid of 11.6g ethyl ester chemistry sunscreen, its particle diameter is 0.8 μ m.
Embodiment 5
A kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester prepares through following method:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester
With embodiment 2;
(2), the preparation of organic silicon monomer hydrolysising product solution
3g diphenyl diethoxy silane is placed 97g water and alcohol mixeding liquid; Water: ethanol is 25:75; With pH regulator to 3.0～4.0 reaction that is hydrolyzed, hydrolysis time is 2.0h, 35 ℃ of temperature with hydrochloric acid solution; Mixing speed 40r/min obtains the organic silicon monomer hydrolysising product solution after having reacted;
(3), contain the preparation of the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester
The organic silicon monomer hydrolysising product solution 50g that step (2) is obtained mixes with the nanoemulsions 50g that comprises the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester of step (1) gained; Using ammonia to regulate pH then is 8.5～9.5; Mixing speed is 150r/min; Temperature is 10 ℃, obtains containing the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester behind the time 15h;
The suspension that contains the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid monooctyl ester with gained; Water, ethanol cycle washing 3 times; And centrifugal, filtration; At 150 ℃ of following dry 8h, promptly get the polysiloxane composite particles of the formed chemical sunscreen of 1.7g nano level coating p-methoxycinnamic acid monooctyl ester, its particle diameter is 0.7 μ m.
Embodiment 6
A kind of nano polysilicon oxygen alkane compound particle that coats the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid prepares through following method:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid
With embodiment 3;
(2), the preparation of organic silicon monomer hydrolysising product solution
The 15g VTES is placed 85g water and alcohol mixeding liquid; Water: ethanol is 50:50; With pH regulator to 3.0～4.0 reaction that is hydrolyzed, hydrolysis time is 3.5h, 20 ℃ of temperature with hydrochloric acid solution; Mixing speed 100r/min obtains the organic silicon monomer hydrolysising product solution after having reacted;
(3), coat the preparation of the nano polysilicon oxygen alkane compound particle suspension of the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid
The organic silicon monomer hydrolysising product solution 90g that step (2) is obtained mixes the back, and to use ammonia to regulate pH be 7.5～8.5 with the nanoemulsions 10g that comprises the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid of step (1) gained; The control mixing speed is 100r/min; Temperature is 25 ℃, obtains containing the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid behind the time 20h;
The suspension that contains the polysiloxane composite particles that coats the formed chemical sunscreen of the different monooctyl ester of p-methoxycinnamic acid with gained; Water, ethanol cycle washing 3 times; And centrifugal, filtration,, dry 5h under 200 ℃; Promptly get the polysiloxane composite particles of the different monooctyl ester chemistry of the nano level coating p-methoxycinnamic acid of 19.5g sunscreen, its particle diameter is 0.9 μ m.
Foregoing is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (8)
1. polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters is characterized in that through following method preparation:
(1), comprises the preparation of the nanoemulsions of the formed chemical sunscreen of p-methoxycinnamic acid esters
The described nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters is calculated by mass percentage, and its raw material composition and content are following:
Sunscreen 0.1～10%
Emulsifying agent 0.1～20%
Oils and fats 0.1～10%
Help Emulsion 0.1～20%
Surplus is a water;
Described sunscreen is for comprising the formed chemical sunscreen of p-methoxycinnamic acid esters;
It is following that the above-mentioned nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters prepares process:
At first, with the formed chemical sunscreen of p-methoxycinnamic acid esters, emulsifying agent, oils and fats with help mixing of Emulsion;
Then; In homogenizing water; With the formed chemical sunscreen of above-mentioned p-methoxycinnamic acid esters, emulsifying agent, oils and fats and help Emulsion mix the back gained mixture be added to the water; Control homogenizing speed is that 10000～50000r/min proceeds homogenizing 0.1～30min, controls mixing speed 10～1000r/min again and stirs and be cooled to room temperature and promptly get the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters;
Described emulsifying agent is anion surfactant or non-ionic surface active agent;
Wherein said anion surfactant is an 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, and m is generally 2～20, and M is Na, K or NH
3
Said non-ionic surface active agent is a fatty alcohol-polyoxyethylene ether series; Its structural formula is:
; Wherein aliphatic alcohol carbon number n is between 7～19, and oxygen ethylene is counted m between 3～20 in the polyoxyethylene;
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 isopropyl myristate, isopropyl palmitate, iso-octyl palmitate, isopropyl stearate or sad capric acid 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 an ethylene glycol, 1,2-propylene glycol, 1, one or more mixed alcohols formed in ammediol, 1,3 butanediol, propylene glycol carbonic ester and the glycerin;
(2), the preparation of organic silicon monomer hydrolysising product solution
Organosilicon is added in the mixture of entry and/or organic solvent; Then under acid or alkali effect; Control pH be 1～6 or pH be 7.5～11.5 reactions that are hydrolyzed, hydrolysis time is at 0.1～10h, 1～100 ℃ of temperature; Mixing speed 10～1000r/min obtains the organic silicon monomer hydrolysising product solution after having reacted;
It is organosilicon that described organosilyl addition is calculated by mass ratio: the mixture of water and/or organic solvent is 1～50:100;
Described organosilicon is an organosiloxane, and its structural formula is R
1NSiX
(4-n)
R wherein
1Representative is selected from substitutedly or unsubstituted has a C atom directly to be connected alkyl or the univalent perssad of alkenyl phenyl on the Si atom;
N is 0～3 integer;
X is a hydrolysising group, is hydroxyl, hydrogen, alkoxyl, halogen group, carboxyl, amino or siloxy;
When n＞1, each R1 group can be identical or different;
And when (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 glycol carbonic ester, glycerol, Methanamide, N; N-dimethyl acetylamide, N, the mixture of one or more compositions in dinethylformamide, acetone, oxolane, dimethylsulfone, ethyl acetate, pyridine and the acetonitrile;
(3), contain the preparation of the suspension of the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters
The organic silicon monomer hydrolysising product solution that step (2) is obtained and the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters of step (1) gained calculate by mass ratio; The nanoemulsions that promptly comprises the formed chemical sunscreen of p-methoxycinnamic acid esters: the organic silicon monomer hydrolysising product solution is that 0.1:99.9～50:50 mixes; Use alkaline matter to regulate pH then and carry out the suspension that polycondensation reaction obtains containing the polysiloxane composite particles that coats p-methoxycinnamic acid esters chemistry sunscreen under 7.5～13.5 the condition; The polycondensation process control reaction temperature is 0 ℃～100 ℃; Rotating speed is 10 ~ 1000r/min, and the time is 0.1～24h;
Coated the suspension of the polysiloxane composite particles of p-methoxycinnamic acid esters chemistry sunscreen containing of gained; Water, ethanol cycle washing 3 times; And centrifugal, filtration; The filter cake that obtains is dry under 100～200 ℃, and the solids that finally obtain are the polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters.
2. a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters as claimed in claim 1 is characterized in that p-methoxycinnamic acid esters in the chemical sunscreen that the described p-methoxycinnamic acid esters of step in the preparation process (1) forms is one or more the formed mixed ester of ester in p-methoxycinnamic acid ethyl ester, p-methoxycinnamic acid monooctyl ester and the different monooctyl ester of p-methoxycinnamic acid.
3. a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters as claimed in claim 1 is characterized in that the described organosilan of step in the preparation process (2) is one or more the organosilan mixture formed in trimethyl methoxy silane, 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 dimethoxy silane, methyl trimethoxy base silane, 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, four butoxy silanes and the tetrachloro silicane.
4. a kind of according to claim 1 polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters is characterized in that:
The described acid of step (2) is one or more mixture formed in citric acid, acetic acid, oxalic acid, tartaric acid, hydrochloric acid, phosphoric acid, carbonic acid and the sulfurous acid;
The described alkali of step (2) is the mixture of one or more compositions in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, DMA, ethamine, diethylamine and the triethylamine.
5. a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters as claimed in claim 1, the alkaline matter that it is characterized in that step (3) is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonia, methylamine, DMA, ethamine, diethylamine or triethylamine.
6. like the arbitrary described a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of claim 1 ~ 5, it is characterized in that:
Step (2) the preferred control time of described hydrolysis is 2～5h, and temperature is 20～35 ℃, and mixing speed is 50～120r/min;
It is 10～25 ℃ that the described polycondensation process of step (3) is preferably controlled temperature, and rotating speed is 100～150r/min, and the time is 5～20h.
7. like the arbitrary described a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of claim 1 ~ 5, it is characterized in that the particle diameter of the polysiloxane composite particles of the formed chemical sunscreen of described coating p-methoxycinnamic acid esters is preferably 100nm～300nm.
8. like the described nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters of step (1) in the preparation process of the arbitrary described a kind of polysiloxane composite particles that coats the formed chemical sunscreen of p-methoxycinnamic acid esters of claim 1 ~ 5, it is characterized in that the described nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters counts by weight percentage that its raw material is formed and content is following:
Sunscreen 0.1～10%
Emulsifying agent 0.1～20%
Oils and fats 0.1～10%
Help Emulsion 0.1～20%
Surplus is a water;
P-methoxycinnamic acid esters in the formed chemical sunscreen of wherein said p-methoxycinnamic acid esters is one or more the formed mixed ester of ester in p-methoxycinnamic acid ethyl ester, p-methoxycinnamic acid monooctyl ester and the different monooctyl ester of p-methoxycinnamic acid;
Described emulsifying agent is anion surfactant or non-ionic surface active agent;
Wherein said anion surfactant is an 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, and m is generally 2～20, and M is Na, K or NH
3
Said non-ionic surface active agent is a fatty alcohol-polyoxyethylene ether series; Its structural formula is:
; Wherein aliphatic alcohol carbon number n is between 7～19, and oxygen ethylene is counted m between 3～20 in the polyoxyethylene;
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 that fatty acid ester is isopropyl myristate, isopropyl palmitate, iso-octyl palmitate, isopropyl stearate or sad capric acid 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 an ethylene glycol, 1,2-propylene glycol, 1, one or more mixed alcohols formed in ammediol, 1,3 butanediol, propylene glycol carbonic ester and the glycerin;
The system of the above-mentioned nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters
Preparation Method is following:
At first, will comprise the formed chemical sunscreen of p-methoxycinnamic acid esters, emulsifying agent, oils and fats and help mixing of Emulsion;
Then; In homogenizing water; With above-mentioned comprising the formed chemical sunscreen of p-methoxycinnamic acid esters, emulsifying agent, oils and fats and help the mixture that mixes the back gained of Emulsion to be added to the water; Control homogenizing speed is that 10000～50000r/min proceeds homogenizing 0.1～30min, controls mixing speed 10～1000r/min again and stirs and be cooled to room temperature and promptly get the nanoemulsions that comprises the formed chemical sunscreen of p-methoxycinnamic acid esters.
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| CN108042382A (en) * | 2018-01-02 | 2018-05-18 | 上海应用技术大学 | The sunscreen composition and its application of a kind of particle containing octyl methoxycinnamate and Avobenzone |
| CN109718122A (en) * | 2019-03-15 | 2019-05-07 | 派能生物科技（深圳）有限公司 | A kind of anti-oxidant lightening compositions of skin 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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