CN109851794A - A kind of organosilicon multiple copolymer and preparation method thereof that glycosyl is modified - Google Patents
A kind of organosilicon multiple copolymer and preparation method thereof that glycosyl is modified Download PDFInfo
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- CN109851794A CN109851794A CN201811581108.9A CN201811581108A CN109851794A CN 109851794 A CN109851794 A CN 109851794A CN 201811581108 A CN201811581108 A CN 201811581108A CN 109851794 A CN109851794 A CN 109851794A
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Abstract
The invention discloses a kind of modified organosilicon multiple copolymers and preparation method thereof of glycosyl, belong to multiple copolymer technical field, present invention glycosyl and polyether segment pass through hydrosilylation synthesis modification silicone oil, can it is significantly more efficient control copolymer hydrophilic and oleophilic performance, it solves the problems, such as that copolymer easily greasy and moisture feeling is insufficient, has broad application prospects in related fieldss such as cosmetics, detergent, foam stabilizer, levelling agents.The present invention solves the problems, such as that modified polyorganosiloxane copolymer hydrophilic and hydrophobic is uneven, easily greasy and moisture feeling is insufficient in the prior art.
Description
Technical field
The present invention relates to a kind of organosilicon multiple copolymers and preparation method thereof, have more particularly to a kind of glycosyl is modified
Machine silicon multiple copolymer and preparation method thereof, belongs to multiple copolymer technical field.
Background technique
Glycosyl surfactant active causes the great interest of people in recent decades, is not only because hydrophilic group carbohydrate and is
Renewable resource, it is more related with its unique performance, such as there is splendid biodegradability and biocompatibility, nontoxic secondary work
With etc..So that they in detergent, detergent and cosmetic industry using increasingly extensive.In addition sugar is known in iuntercellular
Not and the characteristic that can generate in terms of biological function has this kind of surfactant in pharmacy, biochemistry and biomedical aspect
Potential application prospect.
Although there is more hydroxyl on sugar unit, in aqueous solution, stronger hydrogen bond action is anti-between hydroxyl
And the water-soluble of simple glycosyl modified polyorganosiloxane is made to be deteriorated, in order to increase the solubility in water, the introducing of polyether group is then
It can more effective solution this problem.United States Patent (USP) US5891977 reports a kind of glycosyl, polyethers comodified polysiloxane
And preparation method thereof, which first carries out silicon hydrogenation with hydrogen-containing siloxane and allyl polyether, then anti-with methylglucosamine
It should be made, the polymer is good to heat, hydrolytic stability, can be used as aggretion type O/W emulsifier;Chinese patent CN104479139A report
A kind of modified polyorganosiloxane copolymer in road and preparation method thereof, in that patent, inventor select allyl polyether and alkene,
Silicon oil of low hydrogen content is modified altogether, for having good application effect in cosmetics cream, soft frost, emulsion formulations.
Alkyl, polyether comodified polysiloxane has oleophylic, hydrophilic and close silicone oil characteristic simultaneously, by adjusting alkyl
With the size of the ratio of polyethers, the ratio of polysiloxane-grafted alkyl and polyethers and polysiloxane molecule amount, difference can get
Performance and purposes, polyether modified silicon oil can improve the water solubility of material, physiological inertia etc., and alkyl modified silicon oil can assign copolymer
Good lubricity and hydrophobicity, but when the two is single modified, be easy to cause that hydrophilic and hydrophobic is uneven, easily greasy and moisture feeling is not
The disadvantages of sufficient.
Summary of the invention
The main object of the present invention is to overcome in the prior art that modified polyorganosiloxane copolymer hydrophilic and hydrophobic is uneven, easy oil
Greasy and insufficient moisture feeling disadvantage, and a kind of organosilicon multiple copolymer and preparation method thereof that glycosyl is modified is provided.
The purpose of the present invention can reach by using following technical solution:
A kind of organosilicon multiple copolymer that glycosyl is modified, which is characterized in that the structural formula of the organosilicon multiple copolymer
It is as follows:
In structural formula: the value that the value that the value that the value of m is 10~80, n is 1~20, p is 1~10, q is 1~10, and n+p+q
Value be 3~40;
R1Structure are as follows:-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR4, wherein the value of a is the value of 4~30, b
Value for 0~10, a+b is 4~40, R4For the alkyl or hydrogen of 1~4 carbon atom number;
R2Structure are as follows: Z- (S1)c, a R is at least contained in each organosilicon multiple copolymer molecule2, wherein S1It is to contain
There is the saccharic composition of 5-12 carbon;
Z is linker, one such selected from amide, carbamate, urea, ester, ether :-R5-NHC(O)-、-R5-NHC
(O)O-、-R5-NHC(O)-NH-、-R5-C(O)-O-、-R5-O-;
R5It is (R for the alkylidene or molecular formula of 1-10 C atom6O)vGroup, wherein the value of v be 1-10, R6It is 1
The bivalent organic group of~10 C atoms;
R3For-CH2-(CH2)w-CH3, wherein the value of w is 8~16.
The organosilicon multiple copolymer be by hydrosilylation in polysiloxane backbone simultaneously graft polyether segment,
The copolymer of glycosyl and alkyl group synthesis.
A kind of preparation method for the organosilicon multiple copolymer that glycosyl is modified, includes the following steps:
Step 1: the synthesis of glycosyl unsaturated monomer
Allyl amine is mixed under solvent condition with saccharic acid or saccharic acid lactone, within the scope of 60~100 DEG C of reaction temperature,
Two kinds of 1~2:1 of reactant molar ratio steam solvent after the reaction was completed, obtain amidated glycosyl unsaturated monomer;
Step 2: the synthesis of glycosyl modified organic silicon multiple copolymer
It is more that the modified organosilicon of glycosyl is made by polyethers, the glycosyl modified polyorganosiloxane stage of reaction and olefine reaction stage
Membered copolymer.
In step 2, the synthesis of glycosyl modified organic silicon multiple copolymer includes the following steps:
Step 201: polyethers, the glycosyl modified polyorganosiloxane stage of reaction
Allyl polyether, glycosyl unsaturated monomer and solvent mixture is added, catalyst is added, in reaction temperature T1Condition
Under, heat preservation, until system is transparent;
Step 202: the olefine reaction stage
Alkene is slowly added dropwise into transparent system, in T2At a temperature of insulation reaction, after reaction, vacuum desolvation agent obtains
The organosilicon multiple copolymer modified to glycosyl.
Or in step 2, the synthesis of glycosyl modified organic silicon multiple copolymer includes the following steps:
Step 211: polyethers, the glycosyl modified polyorganosiloxane stage of reaction
Part allyl polyether, glycosyl unsaturated monomer and solvent mixture is added, catalyst is added, in reaction temperature T1
Under the conditions of, heat preservation, until system is transparent;
Step 212: alkene, polyether reactant stage
Remaining polyethers is added into transparent system, while alkene is slowly added dropwise, in T3At a temperature of insulation reaction, reaction knot
Shu Hou, vacuum desolvation agent obtain the modified organosilicon multiple copolymer of glycosyl.
In step 1, saccharic acid or saccharic acid lactone include gluconolactone, gala sugar lactone, sweet dew sugar lactone and xylose lactone.
In step 2, reaction temperature T1It is 80~100 DEG C, temperature T2It is 100~120 DEG C, temperature T1Under the conditions of soaking time
For 1~3h, temperature T2Under the conditions of soaking time be 2~5h.
In step 2, solvent is toluene or isopropanol.
In step 2, catalyst is platinum catalyst.
Platinum dosage is 3~20ppm of material total amount in platinum catalyst.
Advantageous effects of the invention:
The present invention provides a kind of modified organosilicon multiple copolymer and preparation method thereof of glycosyl, by with glycosyl and poly-
Ether segment synthesizes co-modified silicone oil by hydrosilylation, can be with the amphipathic property of wider regulation and control copolymer
Can, it solves the problems, such as that copolymer easily greasy and moisture feeling is insufficient, makes it in phases such as personal-care supplies, foam stabilizer, levelling agents
Pass field is more widely applied.
Specific embodiment
To make the more clear and clear technical solution of the present invention of those skilled in the art, the present invention is made below further
Detailed description, embodiments of the present invention are not limited thereto.
Embodiment 1:
1, the synthesis of glucose amide unsaturated monomer
8.57g allyl amine and 50mLDMF are uniformly mixed, 17.81g gluconic acid delta-lactone is added, is reacted at 60 DEG C
2h, vacuum desolvation agent, is then washed with hexamethylene, then filtering recrystallizes twice in isopropanol, and vacuum drying obtains Portugal
Grape sugar amide unsaturated monomer.
2, the synthesis of glycosyl modified organic silicon multiple copolymer
By 60g containing hydrogen silicone oil, 41.31g allyl polyether, 5.88g glucose amide unsaturated monomer and 36.53g solvent
Reactor is added in isopropanol, keeps the temperature 1.5h under the conditions of 8ppm platinum catalyst, 100 DEG C, and 14.58g hexadecylene is added into system,
110 DEG C are warming up to, 3h is kept the temperature, subtracts and solvent is evaporated off, obtains the modified organosilicon multiple copolymer of glycosyl, molecular formula are as follows:
Si(CH3)3-O-[Si(CH3)2-O]40-[Si(CH3)R1-O]5-[Si(CH3)R2-O]1.5-[Si(CH3)R3-O]1.5-Si
(CH3)3
Wherein, R1=-CH2CH2CH2O(CH2CH2O)7(CH2CH(CH3)O)2H
R2=-CH2CH2CH2NHC(O)(CHOH)4CH2OH,R3=-(CH2)15CH3。
Embodiment 2:
1, the synthesis of glucose amide unsaturated monomer
8.57g allyl amine and 50mLDMF are uniformly mixed, 17.81g gluconic acid delta-lactone is added, is reacted at 60 DEG C
2h, vacuum desolvation agent, is then washed with hexamethylene, then filtering recrystallizes twice in isopropanol, and vacuum drying obtains Portugal
Grape sugar amide unsaturated monomer.
2, the synthesis of glycosyl modified organic silicon multiple copolymer
By 60g containing hydrogen silicone oil, 39.66g allyl polyether, 3.92g glucose amide unsaturated monomer and 37.86g solvent
Reactor is added in isopropanol, keeps the temperature 1.5h under the conditions of 8ppm platinum catalyst, 100 DEG C, and it is poly- that 9.91g allyl is added into system
Ether and 12.71g hexadecylene are warming up to 110 DEG C, keep the temperature 3h, subtract and solvent is evaporated off, and obtain the modified organosilicon multi-component copolymer of glycosyl
Object, molecular formula are as follows:
Si(CH3)3-O-[Si(CH3)2-O]40-[Si(CH3)R1-O]6-[Si(CH3)R2-O]1-[Si(CH3)R3-O]1-Si
(CH3)3
Wherein, R1=-CH2CH2CH2O(CH2CH2O)7(CH2CH(CH3)O)2H
R2=-CH2CH2CH2NHC(O)(CHOH)4CH2OH
R3=-(CH2)15CH3。
Embodiment 3:
1, the synthesis of galactolipin amide unsaturated monomer
8.57g allyl amine and 50mLDMF are uniformly mixed, addition 17.81gD- galactolipin-Isosorbide-5-Nitrae-lactone, it is anti-at 60 DEG C
2h is answered, then vacuum desolvation agent is washed with hexamethylene, then filtering recrystallizes twice in isopropanol, and vacuum drying obtains
Galactolipin amide unsaturated monomer.
2, the synthesis of glycosyl modified organic silicon multiple copolymer
By 60g containing hydrogen silicone oil, 52.96g allyl polyether, 2.71g galactolipin amide unsaturated monomer and 37.62g solvent
Reactor is added in isopropanol, keeps the temperature 1.5h under the conditions of 8ppm platinum catalyst, 100 DEG C, and 9.71g laurylene is added into system,
110 DEG C are warming up to, 3h is kept the temperature, subtracts and solvent is evaporated off, obtains the modified organosilicon multiple copolymer of glycosyl, molecular formula are as follows:
Si(CH3)3-O-[Si(CH3)2-O]60-[Si(CH3)R1-O]7-[Si(CH3)R2-O]1-[Si(CH3)R3-O]2-Si
(CH3)3
Wherein, R1=-CH2CH2CH2O(CH2CH2O)8(CH2CH(CH3)O)4H
R2=-CH2CH2CH2NHC(O)(CHOH)4CH2OH
R3=-(CH2)11CH3。
Embodiment 4:
1, the synthesis of galactolipin amide unsaturated monomer
8.57g allyl amine and 50mLDMF are uniformly mixed, addition 17.81gD- galactolipin-Isosorbide-5-Nitrae-lactone, it is anti-at 60 DEG C
2h is answered, then vacuum desolvation agent is washed with hexamethylene, then filtering recrystallizes twice in isopropanol, and vacuum drying obtains
Galactolipin amide unsaturated monomer.
2, the synthesis of glycosyl modified organic silicon multiple copolymer
60g containing hydrogen silicone oil, 45.4g allyl polyether, 2.71g galactolipin amide unsaturated monomer and 35.93g solvent is different
Reactor is added in propyl alcohol, keeps the temperature 1.5h under the conditions of 8ppm platinum catalyst, 100 DEG C, and 11.65g laurylene is added into system, rises
Temperature keeps the temperature 3h, subtracts and solvent is evaporated off, obtain glycosyl modified organic silicon multiple copolymer, molecular formula to 110 DEG C are as follows:
Si(CH3)3-O-[Si(CH3)2-O]60-[Si(CH3)R1-O]6-[Si(CH3)R2-O]1-[Si(CH3)R3-O]3-Si
(CH3)3
Wherein, R1=-CH2CH2CH2O(CH2CH2O)8(CH2CH(CH3)O)4H
R2=-CH2CH2CH2NHC(O)(CHOH)4CH2OH
R3=-(CH2)11CH3。
In the present embodiment, a kind of modified organosilicon multiple copolymer of the glycosyl obtained, passes through at least one glycosyl side
It hangs in polysiloxane backbone, by being covalently bonded on polysiloxane, synthesized glycosyl modified organic silicon surface is living
Property agent there is super flexibility, hair conditioning and antistatic property, it is non-stimulated to eyes, skin, and it had not only been dissolved in water, but also be dissolved in and having
Solvent has broad application prospects in related fieldss such as cosmetics, detergent, foam stabilizer, levelling agents.
The above, further embodiment only of the present invention, but scope of protection of the present invention is not limited thereto, and it is any
Within the scope of the present disclosure, according to the technique and scheme of the present invention and its design adds those familiar with the art
With equivalent substitution or change, protection scope of the present invention is belonged to.
Claims (10)
1. a kind of modified organosilicon multiple copolymer of glycosyl, which is characterized in that the structural formula of the organosilicon multiple copolymer is such as
Under:
In structural formula: the value that the value that the value that the value of m is 10~80, n is 1~20, p is 1~10, q is 1~10, and the value of n+p+q
It is 3~40;
R1Structure are as follows:-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR4, wherein the value that the value of a is 4~30, b is 0~
10, a+b value is 4~40, R4For the alkyl or hydrogen of 1~4 carbon atom number;
R2Structure are as follows: Z- (S1)c, a R is at least contained in each organosilicon multiple copolymer molecule2, wherein S1It is containing 5-
The saccharic composition of 12 carbon;
Z is linker, one such selected from amide, carbamate, urea, ester, ether :-R5-NHC(O)-、-R5-NHC(O)
O-、-R5-NHC(O)-NH-、-R5-C(O)-O-、-R5-O-;
R5It is (R for the alkylidene or molecular formula of 1-10 C atom6O)vGroup, wherein the value of v be 1-10, R6It is 1~10
The bivalent organic group of C atom;
R3For-CH2-(CH2)w-CH3, wherein the value of w is 8~16.
2. a kind of modified organosilicon multiple copolymer of glycosyl according to claim 2, which is characterized in that the organosilicon is more
Membered copolymer is graft polyether segment, glycosyl and the alkyl group synthesis simultaneously in polysiloxane backbone by hydrosilylation
Copolymer.
3. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl as described in claim 1-2 any one,
It is characterized in that, includes the following steps:
Step 1: the synthesis of glycosyl unsaturated monomer
Allyl amine is mixed under solvent condition with saccharic acid or saccharic acid lactone, within the scope of 60~100 DEG C of reaction temperature, two kinds
1~2:1 of reactant molar ratio steams solvent after the reaction was completed, obtains amidated glycosyl unsaturated monomer;
Step 2: the synthesis of glycosyl modified organic silicon multiple copolymer
It is polynary total that the modified organosilicon of glycosyl is made by polyethers, the glycosyl modified polyorganosiloxane stage of reaction and olefine reaction stage
Polymers.
4. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl according to claim 3, which is characterized in that
In step 2, the synthesis of glycosyl modified organic silicon multiple copolymer includes the following steps:
Step 201: polyethers, the glycosyl modified polyorganosiloxane stage of reaction
Allyl polyether, glycosyl unsaturated monomer and solvent mixture is added, catalyst is added, in reaction temperature T1Under the conditions of, it protects
Temperature, until system is transparent;
Step 202: the olefine reaction stage
Alkene is slowly added dropwise into transparent system, in T2At a temperature of insulation reaction, after reaction, vacuum desolvation agent obtains glycosyl
Modified organosilicon multiple copolymer.
5. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl according to claim 3, which is characterized in that
In step 2, the synthesis of glycosyl modified organic silicon multiple copolymer includes the following steps:
Step 211: polyethers, the glycosyl modified polyorganosiloxane stage of reaction
Part allyl polyether, glycosyl unsaturated monomer and solvent mixture is added, catalyst is added, in reaction temperature T1Condition
Under, heat preservation, until system is transparent;
Step 212: alkene, polyether reactant stage
Remaining polyethers is added into transparent system, while alkene is slowly added dropwise, in T3At a temperature of insulation reaction, after reaction,
Vacuum desolvation agent obtains the modified organosilicon multiple copolymer of glycosyl.
6. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl according to claim 3, which is characterized in that
In step 1, saccharic acid or saccharic acid lactone include gluconolactone, gala sugar lactone, sweet dew sugar lactone and xylose lactone.
7. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl according to claim 4 or 5, feature exist
In, in step 2, reaction temperature T1It is 80~100 DEG C, temperature T2It is 100~120 DEG C, temperature T1Under the conditions of soaking time be 1~
3h, temperature T2Under the conditions of soaking time be 2~5h.
8. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl according to claim 4 or 5, feature exist
In in step 2, solvent is toluene or isopropanol.
9. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl according to claim 4 or 5, feature exist
In in step 2, catalyst is platinum catalyst.
10. a kind of preparation method of the modified organosilicon multiple copolymer of glycosyl according to claim 9, feature exist
In platinum dosage is 3~20ppm of material total amount in platinum catalyst.
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Application publication date: 20190607 |