CN104479139B - Modified polysiloxane copolymer, preparation method thereof and application thereof in cosmetics - Google Patents
Modified polysiloxane copolymer, preparation method thereof and application thereof in cosmetics Download PDFInfo
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Abstract
The invention discloses a modified polysiloxane copolymer, a preparation method thereof and application thereof in the cosmetics, and belongs to the technical field of chemical industry. The structural formula of the modified polysiloxane copolymer is as shown in a formula I, wherein x is 25-100, z is 0-25, the sum of y, z and r is not less than 5 and not larger than 40, and the sum of y and r is not less than 0 and not greater than 25; G=-(CH2)3-O-(C2H4O)a-(C3H6O)b-OH, G1=-(CH2)3-O-(C2H4O)a-(C3H6O)b-OY, wherein a is 1-100, and b is 0-60; R=-CH2-(CH2)p-CH3, wherein p is 0-38; Y=H2PO3-; G0=G, G1 or R. Application of the modified polysiloxane copolymer in the formulas of cosmetics, such as creams, ointments and emulsions, has excellent effects.
Description
Technical field
The invention belongs to chemical technology field, particularly to a kind of modified polyorganosiloxane copolymer and preparation method thereof and
Application in cosmetics.
Background technology
Polydimethylsiloxane has many properties such as hydrophobicity, interfacial activity, heat stability, and widely should
For commercial production, polyurethane foam stabilizer, emulsifying agent, defoamer, releasing agent etc..However, polydimethylsiloxane indissoluble
In organic solvent and water, therefore limit the application of polydimethylsiloxane.By organically-modified polydimethylsiloxane,
In the polysiloxanes end of the chain or/and two ends or/and side introduce oil-soluble/or and water miscible organic group, then can effectively solve
This problem of determining is so that the purposes of polydimethylsiloxane is more extensive.
Organo-functional group is connected on polydimethylsiloxane strand, generally has two kinds of chemical bond connected modes：Si-C
Key and Si-O-C key.The former is that containing hydrogen silicone oil is passed through under platinum (Pt) catalyst action with the olefin(e) compound containing carbon-carbon double bond
Hydrosilylation is realized, and the synthetic method of Si-O-C key is the poly dimethyl silicon containing Si-X (X is Cl, the halogen atom such as Br) key
Oxygen alkane is synthesized with the compound containing hydroxyl (- OH).It is then logical that this patent is wanted disclosed modified polyorganosiloxane copolymer
Cross the first connected mode：Si-C key.
Alkyl, polyether comodified polysiloxane has the characteristic of oleophylic, hydrophilic and close silicone oil simultaneously, by adjusting alkyl
With the ratio of the ratio, polysiloxane-grafted alkyl and polyethers of polyethers and the size of polysiloxane molecule amount, difference can be obtained
Performance and there is specific use, have with mineral grease, vegetable oil, sunscreen and active component particularly in cosmetic formulations
The compatibility well.The cosmetics cream of alkyl, polyether co-modified organosilicon emulsifying agent preparation, emulsion, soft frost etc. have height
Emulsion stability, splendid heat-resisting and cold-resistant stability.The synthetic technology patent of the common modified siloxane of alkyl, polyether is open to drape over one's shoulders
Dew, German Gauss Mitt USA Corporation it was recently reported that a kind of high activity hydrosilylation catalyst, and is implementing in patent US 7157541
In example 5, disclose α-hexadecylene hydrocarbon, allyl polyether and silicone oil synthesis technique, this technique relies primarily on US 7157541 patent
Disclosed high activated catalyst, is not suitable for typical catalyst.Japan Patent JP 5-105614, JP 5-178733, JP 7-
268105 report a kind of synthetic method of silicone oil emulsification agent, employ active solvent, and the reaction of this active solvent cannot after terminating
Remove.U.S. General Electric Company discloses the conjunction of alkyl, polyether co-modified silicone oil in US 5401870
Become, this technique adopts Deca toluene and allyl polyether mixture, the disposable method adding of catalyst, will to catalyst activity
Ask high, reaction conversion ratio is not high.South China Science ＆ Engineering University Yang Hui reports a kind of solventless method synthesis of alkyl in its Master's thesis
Polyethers co-modified silicone oil, employs alpha-olefin and allyl polyether mixing Deca technique, allyl polyether and α-alkene in this technique
Hydrocarbon poor compatibility, is unfavorable for that reaction is carried out.
Content of the invention
For overcoming the shortcoming and defect of above-mentioned prior art, the primary and foremost purpose of the present invention is to provide a kind of modified poly- silica
Alkyl copolymer.Contain chain alkyl, two kinds of polysiloxanes hydrophobic in described modified polyorganosiloxane copolymer molecule structure simultaneously
Property segment and hydrophilic polyethers and phosphate ion segment.
Another object of the present invention is to providing the preparation method of above-mentioned modified polyorganosiloxane copolymer.Described preparation
The synthesis technique of method is simple, easily-controlled operation, using the polymerization technique of progressively addition, under innoxious solvent promotes, using city
Common pt catalyst on face, you can reach very high conversion ratio, product appearance is colourless or light yellow clear, no solvent residue.
The yet another object of the present invention there are provided application in cosmetics for the above-mentioned modified polyorganosiloxane copolymer.Institute
The modified polyorganosiloxane polymer stated can be used as the primary emulsion of the products such as cosmetics cream, emulsion or co-emulsifier.
The purpose of the present invention is realized by following technical schemes：A kind of modified polyorganosiloxane copolymer, its structural formula is such as
Shown in formula I：
Wherein：X=25～100, z=0～25,5≤y+z+r≤40,0≤y+r≤25；
G=- (CH2)3-O-(C2H4O)a-(C3H6O)b- OH, wherein a=1～100, b=0～60；
G1=-(CH2)3-O-(C2H4O)a-(C3H6O)b- OY, wherein a=1～100, b=0～60；
R=-CH2-(CH2)p-CH3, wherein p=0～38；
Y=H2PO3-；
G0=G, G1Or R；
The preparation method of above-mentioned modified polyorganosiloxane copolymer, including following elementary reaction：
Elementary reaction one (olefine reaction stage), N2Under atmosphere, in the four-hole boiling flask with backflow and agitating device, plus
Enter silicon oil of low hydrogen content, be warming up to reaction temperature T1, add catalyst, Deca alkene, temperature can substantially rise, after temperature stabilization,
Control to reaction temperature T2, insulation reaction；
Elementary reaction two (the allyl polyether stage of reaction), adds allyl polyether and solvent mixture, is warming up to reaction
Temperature T3, add catalyst, insulation reaction, until system is transparent；
Elementary reaction three (Si-H addition reaction completes the stage), the remaining alkene of Deca, add catalyst, in T4At a temperature of be incubated
Reaction, vacuum deviates from solvent；
Elementary reaction four (phosphating reaction), on the basis of in the stage three, reaction completes, by temperature control in T5, add bonderite
Insulation reaction, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance after having reacted,
Obtain colourless or light yellow clear modified polyorganosiloxane copolymer.
Synthesize this catalyst used by modified polyorganosiloxane copolymer be commercially available Ka Shi platinum catalyst, consumption be 15～
60ppm.
Reaction temperature T described in elementary reaction one1For 30～80 DEG C.
Catalyst loading described in elementary reaction one is the 30～50% of reaction total catalyst consumption.
Silicon oil of low hydrogen content described in elementary reaction one has structure as shown in formula II：
Wherein：O=25～100, m=5～40；
R0=Me or H.
Alkene described in elementary reaction one has having structure：
CH2=CH- (CH2)p-CH3；
Wherein：P=0～37.
Alkene time for adding described in elementary reaction one is 15～60min.
Reaction temperature T described in elementary reaction one2For 100～120 DEG C, the insulation reaction time is 30～90min.
The consumption of alkene described in elementary reaction one is the 20～60% of Si -- H bond content molar percentage.
Described Si -- H bond is the Si -- H bond in silicon oil of low hydrogen content.
Reaction temperature T described in elementary reaction two3For the reflux temperature of reaction system, insulation reaction 30～120min.
Solvent described in elementary reaction two is toluene or isopropanol.
Catalyst loading described in elementary reaction two is the 20～40% of reaction total catalyst consumption.
Allyl polyether described in elementary reaction two has following chemical constitution：
CH2=CH-CH2-O-(C2H4O)a-(C3H6O)b-OH；
Wherein：A=1～30, b=0～30.
The consumption of allyl polyether described in elementary reaction two is the 20～60% of Si -- H bond content molar percentage.
Alkene described in elementary reaction three has having structure：
CH2=CH- (CH2)p-CH3；
Wherein：P=0～37；
Alkene consumption described in elementary reaction three is the 20～40% of Si -- H bond content molar percentage.
Catalyst loading described in elementary reaction three is the 20～40% of reaction total catalyst consumption；
Reaction temperature T described in elementary reaction three4For 90～110 DEG C, the insulation reaction time is 120～360min.
Bonderite described in elementary reaction four is P2O5, consumption is the 5～80% of polyethers (mole amount of substance)；
Reaction temperature T described in elementary reaction four5For 40～100 DEG C；The insulation reaction time is 30～150min；
Alkali liquor described in elementary reaction four is 40% potassium hydroxide solution.
Application in cosmetics cream, soft frost, emulsion formulations for the above-mentioned modified polyorganosiloxane copolymer.
Specific technical scheme is as follows：
Application in cosmetic composition for the modified polyorganosiloxane copolymer of said structure, can not only be used for primary emulsion,
But also as emulsion adjuvant, its consumption is 0.05～5%.
As cosmetic emulsifier it is necessary to each component has certain compatibility with cosmetics, cosmetic formulations technique is easy
Operation, cosmetics prepared therefrom have good stability at low temperatures and high temperatures.By structural design optimization and substantial amounts of
Formula application experiment, has found out molecular structure and the preparation that the present invention is used as cosmetic emulsifier modified polyorganosiloxane copolymer
Technique has following optimization feature.
After optimization, modified polyorganosiloxane copolymer molecule of the present invention has as structure shown in formula I：
Wherein:X=30～90, z=1～20,8≤y+z+r≤35,1≤y+r≤20；
G=- (CH2)3-O-(C2H4O)a-(C3H6O)b- OH, wherein a=1～20, b=0～10；
G1=-(CH2)3-O-(C2H4O)a-(C3H6O)b- OY, wherein a=1～20, b=0～10；
R=-CH2-(CH2)p-CH3, wherein p=6～16；
Y=H2PO3-；
G0=G, G1Or R；
After optimization, synthesizing this catalyst used by modified polyorganosiloxane copolymer is commercially available Ka Shi platinum catalyst, consumption
For 20～40ppm.
After optimization, reaction temperature T described in elementary reaction one1For 35～70 DEG C；
After optimization, catalyst described in elementary reaction one is the Ka Shi platinum catalyst sold on the market, and addition is reaction
The 35～40% of total catalyst consumption.
After optimization, alkene time for adding described in elementary reaction one is 20～40min.
Reaction temperature T after optimization, described in elementary reaction one2For 105～115 DEG C, the insulation reaction time be 40～
60min.
After optimization, the silicon oil of low hydrogen content described in elementary reaction one has following formula II and optimizes structure：
Wherein：O=30～90, m=8～35；
R0=Me or H；
After optimization, alkene described in elementary reaction one has following optimization structure：
CH2=CH- (CH2)p-CH3；
Wherein：P=5～15；
The consumption of alkene is 25～40% (molar percentages).
Reaction temperature T after optimization, described in elementary reaction two3For the reflux temperature of reaction system, react 30～60min.
After optimization, solvent described in elementary reaction two is isopropanol.
After optimization, catalyst described in elementary reaction two is the Ka Shi platinum catalyst sold on the market, and addition is reaction
The 25～35% of total catalyst consumption；
After optimization, the allyl polyether described in elementary reaction two has following optimization structure：
CH2=CH-CH2-O-(C2H4O)a-(C3H6O)b-OH；
Wherein：A=1～20, b=0～10.
The consumption of allyl polyether is 25～50% (molar percentages).
After optimization, alkene described in elementary reaction three has following optimization structure
CH2=CH- (CH2)p-CH3
Wherein：P=5～15, addition is 25～35% (molar percentages).
After optimization, catalyst described in elementary reaction three is the Ka Shi platinum catalyst sold on the market, and addition is reaction
The 25～35% of total catalyst consumption；
Reaction temperature T after optimization, described in elementary reaction three4For 95～105 DEG C, the insulation reaction time be 180～
300min.
After optimization, the polyethers consumption described in elementary reaction four is the 20～40% of (mole amount of substance)；
Reaction temperature T after optimization, described in elementary reaction four5For 60～80 DEG C；The insulation reaction time is 60～120min；
The modified polyorganosiloxane copolymer that the present invention provides, the ratio of C=C double bond and the amount of the material of Si -- H bond is 1.1～
1.25.
The preparation of the modified polyorganosiloxane copolymer that the present invention provides, in order to prevent unsaturated reactant from autohemagglutination, oxygen occurring
The side reactions such as change, isomery occur, it is necessary in noble gases such as N in addition polymerization process2Deng protection under carry out.Adopt simultaneously
Deca contains the mode of the organic group reactant of reaction double bond, is that thiazolinyl is stable, suppression isomerization occurs.
The modified polyorganosiloxane copolymer of the present invention, is to be used for cosmetics with the relatively small amount of 0.05～5.0% weight
In formula, preferably 0.05～2.0%, most preferably 0.1～1.0% weight.
The modified polyorganosiloxane copolymer of the present invention, can be used for preparing multiple microemulsion, with all of cosmetics oils and fatss and
Active additive is compatible, cold join, heat is joined and all may be used.
A kind of Water-In-Oil water outlet cream, including following components：
The present invention compared with prior art has the advantages that have as follows and effect：
1. the modified polyorganosiloxane copolymer process is simple of present invention synthesis, easy to operate.
2. the modified polyorganosiloxane copolymer of present invention synthesis is to catalyst strong adaptability, common commercial catalyst.
3. the modified polyorganosiloxane copolymer of present invention synthesis no toxic solvent residual.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
The raw material (hydrogen containing siloxane and alkenes compounds) that the embodiment of the present invention is used all can be from commercially available product
In buy.
Below by way of specific embodiment, the present invention is further elaborated.
In embodiment, raw material used has following structure：
The structure of silicon oil of low hydrogen content such as formula II is：
The structure of alkene is：
CH2=CH- (CH2)p-CH3；
The structure of allyl polyether is：
CH2=CH-CH2-O-(C2H4O)a-(C3H6O)b-OH；
Embodiment 1
Elementary reaction one, adds 0.01mol silicon oil of low hydrogen content 1 (R in the four-hole boiling flask with backflow and agitating device0
=Me, o=50, m=25), it is warming up to 50 DEG C of reaction temperature, add the catalyst of 4.2ppm, Deca 0.058mol in 20min
Alkene 1 (p=5), temperature can be obvious, after dripping off, 110 DEG C of insulation reaction 45min.
Elementary reaction two, adds the mixture of 0.145mol allyl polyether 1 (a=15, b=3) and isopropanol, rises to back
After stream temperature, add the catalyst of 4.2ppm, after system bleach, continue reaction 40min.
Elementary reaction three, Deca 0.087mol alkene 2 (p=9) in 20min, it is subsequently adding the catalyst of 3.6ppm, 100
DEG C insulation reaction 240min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 70 DEG C, adds 0.044molP2O5Protect
Warm 80min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance after having reacted,
Obtain colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 2
Elementary reaction one, adds 0.02mol silicon oil of low hydrogen content 2 (R in the four-hole boiling flask with backflow and agitating device0
=Me, o=45, m=10), it is warming up to 35 DEG C of reaction temperature, add the catalyst of 6.0ppm, Deca 0.096mol in 30min
Alkene 3 (p=13), temperature can substantially rise, after dripping off, 105 DEG C of insulation reaction 45min.
Elementary reaction two, adds the mixture of 0.06mol allyl polyether 2 (a=20, b=5) and isopropanol, rises to back
After stream temperature, add the catalyst of 5.25ppm, after system bleach, continue reaction 40min.
Elementary reaction three, Deca 0.084mol alkene 3 (p=13) in 20min, the catalyst then plus as 3.75ppm,
100 DEG C of insulation reaction 240min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 65 DEG C, adds 0.024molP2O5Protect
Warm 120min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance after having reacted,
Obtain colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 3
Elementary reaction one, adds 0.02mol silicon oil of low hydrogen content 3 (R in the four-hole boiling flask with backflow and agitating device0
=Me, o=80, m=10), it is warming up to 70 DEG C of reaction temperature, add the catalyst of 5.32ppm, Deca 0.084mol in 35min
Alkene 2 (p=9), temperature can substantially rise, after dripping off, 110 DEG C of insulation reaction 45min.
Elementary reaction two, adds the mixture of 0.084mol allyl polyether 3 (a=10, b=1) and isopropanol, rises to back
After stream temperature, add the catalyst of 4.48ppm, after system bleach, continue reaction 60min.
Elementary reaction three, Deca 0.072mol alkene 4 (p=15) in 20min, the catalyst then plus as 4.2ppm, 95
DEG C insulation reaction 300min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 60 DEG C, adds 0.017molP2O5Protect
Warm 90min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance after having reacted,
Obtain colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 4
Elementary reaction one, adds 0.01mol silicon oil of low hydrogen content 4 (R in the four-hole boiling flask with backflow and agitating device0
=H, o=75, m=25), it is warming up to 40 DEG C of reaction temperature, add the catalyst of 4.5ppm, the alkene of Deca 0.09mol in 40min
Hydrocarbon 4 (p=15), temperature can substantially rise, after dripping off, 105 DEG C of insulation reaction 50min.
Elementary reaction two, adds the mixture of 0.105mol allyl polyether 4 (a=1, b=10) and isopropanol, rises to back
After stream temperature, add the catalyst of 6.0ppm, after system bleach, continue reaction 30min.
Elementary reaction three, Deca 0.105mol alkene 4 (p=15) in 20min, the catalyst then plus as 4.5ppm, 105
DEG C insulation reaction 180min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 60 DEG C, adds 0.026molP2O5Protect
Warm 100min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance after having reacted,
Obtain colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 5
Elementary reaction one, adds 0.012mol silicon oil of low hydrogen content 5 (R in the four-hole boiling flask with backflow and agitating device0
=Me, o=65, m=20), it is warming up to 60 DEG C of reaction temperature, add the catalyst of 4.0ppm, Deca 0.072mol alkene in 25min
Hydrocarbon 5 (p=7), temperature can substantially rise, after dripping off, 110 DEG C of insulation reaction 40min.
Elementary reaction two, adds the mixture of 0.115mol allyl polyether 2 (a=20, b=5) and isopropanol, rises to back
After stream temperature, add the catalyst of 3.0ppm, after system bleach, continue reaction 30min.
Elementary reaction three, Deca 0.101mol alkene 5 (p=7) in 20min, the catalyst then plus as 3.0ppm, 95 DEG C
Insulation reaction 300min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 60 DEG C, adds 0.04molP2O5Insulation
120min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance, obtains after having reacted
Colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 6
Elementary reaction one, adds 0.02mol silicon oil of low hydrogen content 6 (R in the four-hole boiling flask with backflow and agitating device0
=H, o=75, m=18), it is warming up to 50 DEG C of reaction temperature, add the catalyst of 3.6ppm, Deca 0.192mol alkene in 30min
Hydrocarbon 4 (p=15), temperature can substantially rise, after dripping off, 105 DEG C of insulation reaction 55min.
Elementary reaction two, adds the mixture of 0.168mol allyl polyether 6 (a=12, b=0) and isopropanol, rises to back
After stream temperature, add the catalyst of 4.2ppm, after system bleach, continue reaction 50min.
Elementary reaction three, Deca 0.12mol alkene 4 (p=15) in 20min, the catalyst then plus as 4.2ppm, 105
DEG C insulation reaction 210min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 75 DEG C, adds 0.07molP2O5Insulation
60min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance, obtains after having reacted
Colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 7
Elementary reaction one, adds 0.02mol silicon oil of low hydrogen content 7 (R in the four-hole boiling flask with backflow and agitating device0
=H, o=30, m=8), it is warming up to 55 DEG C of reaction temperature, add the catalyst of 4.5ppm, Deca 0.05mol alkene 2 in 35min
(p=9) and 0.034mol alkene 3 (p=13) mixture, temperature can substantially rise, after dripping off, 110 DEG C of insulation reaction 60min.
Elementary reaction two, adds the mixture of 0.084mol allyl polyether 3 (a=10, b=1) and isopropanol, rises to back
After stream temperature, add the catalyst of 6.0ppm, after system bleach, continue reaction 50min.
Elementary reaction three, Deca 0.03mol alkene 2 (p=9) and 0.042mol alkene 3 (p=13) mixture in 20min,
It is subsequently adding the catalyst of 4.5ppm, 100 DEG C of insulation reaction 270min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 80 DEG C, adds 0.017molP2O5Protect
Warm 110min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance after having reacted,
Obtain colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 8
Elementary reaction one, adds 0.01mol silicon oil of low hydrogen content 8 (R in the four-hole boiling flask with backflow and agitating device0
=Me, o=90, m=30), it is warming up to 45 DEG C of reaction temperature, add the catalyst of 5.32ppm, Deca 0.09mol alkene in 25min
Hydrocarbon 2 (p=9), temperature can substantially rise, after dripping off, 105 DEG C of insulation reaction 60min.
Elementary reaction two, adds the mixture of 0.18mol allyl polyether 7 (a=10, b=10) and isopropanol, rises to back
After stream temperature, add the catalyst of 4.48ppm, after system bleach, continue reaction 60min.
Elementary reaction three, Deca 0.09mol alkene 2 (p=9) in 20min, the catalyst then plus as 0.072mol, 95
DEG C insulation reaction 300min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 60 DEG C, adds 0.04molP2O5Insulation
120min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance, obtains after having reacted
Colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 9
Elementary reaction one, adds 0.01mol silicon oil of low hydrogen content 9 (R in the four-hole boiling flask with backflow and agitating device0
=Me, o=85, m=35), it is warming up to 65 DEG C of reaction temperature, add the catalyst of 4.2ppm, Deca 0.16mol alkene in 35min
Hydrocarbon 5 (p=7), temperature can substantially rise, after dripping off, 105 DEG C of insulation reaction 50min.
Elementary reaction two, adds the mixture of 0.14mol allyl polyether 8 (a=15, b=15) and isopropanol, rises to back
After stream temperature, add the catalyst of 4.2ppm, after system bleach, continue reaction 30min.
Elementary reaction three, Deca 0.1mol alkene 5 (p=7) in 20min, it is subsequently adding the catalyst of 3.6ppm, 105 DEG C
Insulation reaction 270min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 65 DEG C, adds 0.05molP2O5Insulation
100min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance, obtains after having reacted
Colourless or light yellow clear modified polyorganosiloxane copolymer.
Embodiment 10
Elementary reaction one, adds 0.015mol silicon oil of low hydrogen content 10 in the four-hole boiling flask with backflow and agitating device
(R0=H, o=60, m=20), it is warming up to 60 DEG C of reaction temperature, add the catalyst of 4.0ppm, Deca 0.126mol in 20min
Alkene 2 (p=9), temperature can substantially rise, after dripping off, 110 DEG C of insulation reaction 60min.
Elementary reaction two, adds the mixture of 0.126mol allyl polyether 9 (a=12, b=3) and isopropanol, rises to back
After stream temperature, add the catalyst of 3.0ppm, after system bleach, continue reaction 30min.
Elementary reaction three, Deca 0.108mol alkene 2 (p=9) in 20min, it is subsequently adding the catalyst of 3.0ppm, 95 DEG C
Insulation reaction 300min, reaction terminates rear solvent removed by vacuum.
Elementary reaction four, on the basis of reaction completes in the stage three, by temperature control at 60 DEG C, adds 0.025molP2O5Protect
Warm 120min, adds appropriate water, insulation a period of time, is then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance after having reacted,
Obtain colourless or light yellow clear modified polyorganosiloxane copolymer.
Application Example
Modified polyorganosiloxane copolymer prepared by embodiment 10 and win wound Degussa trade name ABIL EM 90 breast
Application in Water-In-Oil water outlet cream formula for the agent, prepares formula as shown in table 1：
Table 1 Water-In-Oil water outlet cream formula
| Formula A | Formula B | |
| Oil phase | ||
| Embodiment 10 sample | 1.0 | 0 |
| ABIL EM 90 | 0 | 1.0 |
| Silicone oil (DC 200) | 1.2 | 1.2 |
| Cyclic silicone oils (DC 345) | 4.5 | 4.5 |
| Isononyl isononanoate (INO) | 2.5 | 2.5 |
| Three caprylic/capric glyceride (GTCC) | 1.3 | 1.3 |
| Aqueous phase | ||
| Propylene glycol | 5.0 | 5.0 |
| Glycerol | 10.0 | 10.0 |
| NaCl | 2.0 | 2.0 |
| Deionized water | to 100.0 | to 100.0 |
As primary emulsion, in water outlet cream, application effect is relatively shown in Table 2：
Table 2 water outlet cream application effect compares
| Sample number into spectrum | Apparent condition | Go out water speed | Spreadability | Water yield |
| Formula A sample | Mastic, gloss light | Comparatively fast | Good | Many, and the globule is thin |
| Formula B sample | Mastic, gloss is dim mute | Comparatively fast | Good | More, and the globule is big |
Water outlet cream stability is relatively shown in Table 3：
Table 3 water outlet cream stability compares
| Sample | Cold cycling is tested | Centrifugal test |
| Heat stability | Low temperature resistant stability | ||
| Formula A sample | Stablize not stratified | Stable, not water outlet | Not stratified |
| Formula B sample | Stablize not stratified | Bottom water outlet | Not stratified |
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (9)
1. a kind of modified polyorganosiloxane copolymer is it is characterised in that structural formula is as shown in formula I：
Wherein：X=25～100, z=0～25,5≤y+z+r≤40,0≤y+r≤25；
G=- (CH2)3-O-(C2H4O)a-(C3H6O)b- OH, wherein a=1～100, b=0～60；
G1=-(CH2)3-O-(C2H4O)a-(C3H6O)b- OY, wherein a=1～100, b=0～60；
R=-CH2-(CH2)p-CH3, wherein p=0～38；
Y=H2PO3-；
G0=G, G1Or R；
The preparation method of described modified polyorganosiloxane copolymer, including following elementary reaction：
Elementary reaction one, N2Under atmosphere, in the four-hole boiling flask with backflow and agitating device, add silicon oil of low hydrogen content, be warming up to
Reaction temperature T1, add catalyst, Deca alkene, temperature can substantially rise, and after temperature stabilization, controls to reaction temperature T2, insulation
Reaction；
Elementary reaction two, adds allyl polyether and solvent mixture, is warming up to reaction temperature T3, add catalyst, insulation is anti-
Should, until system is transparent；
Elementary reaction three, the remaining alkene of Deca, add catalyst, in T4At a temperature of insulation reaction, vacuum deviate from solvent；
Elementary reaction four, on the basis of in the stage three, reaction completes, by temperature control in T5, add bonderite insulation reaction, reacted
Add appropriate water, insulation a period of time afterwards, be then adjusted to neutrality with alkali liquor, vacuum deviates from low-boiling-point substance, obtains colourless or light yellow
Transparent modified polysiloxane copolymer.
2. modified polyorganosiloxane copolymer according to claim 1 it is characterised in that：
Synthesizing this catalyst used by modified polyorganosiloxane copolymer is commercially available Ka Shi platinum catalyst, and consumption is 15～40ppm；
Reaction temperature T described in elementary reaction one1For 30～80 DEG C；
Catalyst loading described in elementary reaction one is the 30～50% of reaction total catalyst consumption；
Silicon oil of low hydrogen content described in elementary reaction one has structure as shown in formula II：
Wherein：O=25～100, m=5～40；
R0=Me or H；
Alkene described in elementary reaction one has having structure：
CH2=CH- (CH2)p-CH3；
Wherein：P=0～37；
Alkene time for adding described in elementary reaction one is 15～60min；
Reaction temperature T described in elementary reaction one2For 100～120 DEG C, the insulation reaction time is 30～90min；
The consumption of alkene described in elementary reaction one is the 20～60% of Si -- H bond content molar percentage.
3. modified polyorganosiloxane copolymer according to claim 1 it is characterised in that：Reaction temperature described in elementary reaction two
Degree T3For the reflux temperature of reaction system, insulation reaction 30～120min；
Solvent described in elementary reaction two is toluene or isopropanol；
Catalyst loading described in elementary reaction two is the 20～40% of reaction total catalyst consumption；
Allyl polyether described in elementary reaction two has following chemical constitution：
CH2=CH-CH2-O-(C2H4O)a-(C3H6O)b-OH；
Wherein：A=1～30, b=0～30；
The consumption of allyl polyether described in elementary reaction two is the 20～60% of Si -- H bond content molar percentage.
4. modified polyorganosiloxane copolymer according to claim 1 it is characterised in that：Alkene described in elementary reaction three has
Having structure：
CH2=CH- (CH2)p-CH3；
Wherein：P=0～37；
The consumption of alkene described in elementary reaction three is the 20～40% of Si -- H bond content molar percentage；
Catalyst loading described in elementary reaction three is the 20～40% of reaction total catalyst consumption；
Reaction temperature T described in elementary reaction three4For 90～110 DEG C, the insulation reaction time is 120～360min.
5. modified polyorganosiloxane copolymer according to claim 1 it is characterised in that：Bonderite described in elementary reaction four
For P2O5, consumption is the 5～80% of polyethers mole amount of substance；
Reaction temperature T described in elementary reaction four5For 40～100 DEG C；The insulation reaction time is 30～150min；
Alkali liquor described in elementary reaction four is 40% potassium hydroxide solution.
6. modified polyorganosiloxane copolymer according to claim 3 it is characterised in that：Described modified polyorganosiloxane copolymerization
In thing, the amount sum of allyl polyether and olefinic material and the ratio of the amount of the material of Si -- H bond are 1.1～1.25.
7. application in cosmetics cream, soft frost, emulsion formulations for the modified polyorganosiloxane copolymer described in claim 1.
8. application in cosmetic composition for the modified polyorganosiloxane copolymer described in claim 1 it is characterised in that：As
Primary emulsion or emulsion adjuvant, its consumption is 0.05～5%.
9. a kind of Water-In-Oil water outlet cream it is characterised in that：Including following components：
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| CN105832574B (en) * | 2016-06-07 | 2019-08-16 | 广州立白企业集团有限公司 | A kind of sun-proof skin care day cream and preparation method thereof with water outlet cream feature |
| EP3713538A4 (en) * | 2017-11-20 | 2021-07-07 | Evonik Operations GmbH | Water in oil emulsifier composition and the use thereof |
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| CN101087827A (en) * | 2004-12-23 | 2007-12-12 | 巴斯福股份公司 | Urethane compound comprising an incorporated polyether group-containing silicone derivative and a nitrogen heterocycle |
| CN101208069A (en) * | 2005-06-22 | 2008-06-25 | 3M创新有限公司 | Hydrophilized curable silicone impression materials with improved storage behavior |
| CN101081899A (en) * | 2006-05-29 | 2007-12-05 | 深圳市海川实业股份有限公司 | Preparation method of polyoxyalkylenes ether grafted polysiloxane |
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Application publication date: 20150401 Assignee: Guangzhou Jincheng biological science and Technology Co Ltd Assignor: Guangzhou Startec Science and Technology Co., Ltd. Contract record no.: 2018440000149 Denomination of invention: Modified polysiloxane copolymer, preparation method thereof and application thereof in cosmetics Granted publication date: 20170222 License type: Common License Record date: 20181126 |