CN1468886A - Amino acid modified polysiloxane organism - Google Patents
Amino acid modified polysiloxane organism Download PDFInfo
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- CN1468886A CN1468886A CNA02134373XA CN02134373A CN1468886A CN 1468886 A CN1468886 A CN 1468886A CN A02134373X A CNA02134373X A CN A02134373XA CN 02134373 A CN02134373 A CN 02134373A CN 1468886 A CN1468886 A CN 1468886A
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- amino acid
- modified polysiloxane
- acid modified
- organism
- coupling agent
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Abstract
The present invention relates to one kind of amino acid modified polysiloxane organism. The materials including pre-polysiloxane organism, L-type or D-type amino acid or its salt with end amino radical, and silane crosslinking agent are connected together under the induction of phase transferring catalyst and/or ionic exchange resin to form the amino acid modified polysiloxane organism. The present invention may be applied in skin care, hair care, cosmetics, biological product and other fields.
Description
Technical field:
The present invention relates to a kind of amino acid modified polysiloxane organism.
Technical background:
The like product kind is a lot of at present, and roughly having of having patented is following several:
Chinese patent 98800231.0 JP65310/97 USP6210690 WO98.38970 disclose a kind of emulsifying composition.Polyether modified siloxane is made emulsifying agent, makes components such as amino acid and its salt, water-soluble polymer that good stability and distribution are arranged in system.This invention is mainly used in skin cosmetics.
USP4701269 has related to a kind of with the silicone oil system of N-acylamino acid as emulsifying agent, aspect leather water-proof good result is arranged.
Chinese patent 00118398.2 FR9907631 has reported the used weight reducing face-care compositions of topical application.It comprises with beauty treatment goes up at least a compound of acceptable vehicle bonded: L-arginine, L-arginine analog etc.Connecing the first siloxane groups on their free alpha-amino groups, become the arginic monomethyl silantriol of L-, is the main component of cosmetic compositions.
USP5243028 has reported a kind of novel organosilicon protein polymer: the amino on chloro-ester in the dimethicone copolyol and protein or the amino acid forms the covalency condensation.This cationic polymers that contains ester bond is suitable for the personal care product field.
All there is the shortcoming and defect part at reaction monomers, chemical reaction mechanism, catalyst type and application, polymer type and structural characterization etc. in above existing patent of lifting aspect many.
Given this, the purpose of this invention is to provide a kind of amino acid modified polysiloxane organism, solve the shortcoming and defect part of existing like product.
Summary of the invention: one, the present invention is directed to the problem that similar prior art or product will solve
The present invention compares with above prior art and product, has solved the problem of the following aspects:
1. adopt silane coupling agent to couple together in amino acid and organo-siloxane performed polymer, make amino acid and polysiloxane be bonded into the linear polymeric polymkeric substance.
2. adopt phase transfer catalysis process and/or ion-exchange-resin process, make end group be amino L-type or D-type amino acid and salt thereof easily and the silane coupling agent condensation, further generate amino acid modified polysiloxane organism.
3. introducing organo-siloxane performed polymer and end group is amino L-type or D-type amino acid and salt binding thereof, can keep amino acid whose nutritional activities for a long time.Two, advantage, characteristics of the present invention:
1. the present invention is joined together organo-siloxane performed polymer and end group by silane coupling agent for amino L-type or D-type amino acid and salt thereof;
2. the present invention shields to amino acid and salt thereof, thereby has kept amino acid whose activity owing to introduced organopolysiloxane;
3. amino acid and polysiloxane are coupled together, in application such as makeup prescription, can obtain better and application widely;
4. be with functional group's difference according to the organo-siloxane performed polymer, can give amino acid modified polysiloxane organism difference in functionality characteristic;
5. the present invention can introduce and have hydrophilic polyether modified siloxanes performed polymer, and the system wetting ability is improved, and polymkeric substance can be made into the product of water base or low organic volatile part.Three, the technical issues that need to address of the present invention and technical scheme:
1. the general formula of organo-siloxane performed polymer is:
Wherein: R1=-H ,-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH
2(OH) CHCH
3,-CH
2CH
2CH
2CH
3,-(CH
2)
3NH
2,-(CH
2)
3NH (CH
2)
2NH
2,-(CH
2)
3-O (C
2H
4O)
x(C
3H
6O)
y-R
1Deng;
(x＝1-40，y＝1-40，R
1＝-H，-CH
3，-COCH
3)
R2=-CH
3,-CH
2CH
3,-OCH
3,-OCH
2CH
3Or-OH etc.;
R3=-CH
3,-OCH
3,-OCH
2CH
3Or-OH etc.;
n＝0~500；m＝0~500
2. the general formula of silane coupling agent is:
Wherein: RX=CH
2=CH-, ClCH
2CH
2CH
2-, HSCH
2CH
2CH
2-,
CH
2=(CH
3) COO (CH
2)
3-, H
2NCH
2CH
2NH (CH
2)
3-etc.;
Y＝R’O(R’＝CH
3-，CH
3CH
2-，CH
3OCH
2CH
2-)，Cl-，CH
3COO-
Patent of the present invention preferably adopts:
ClCH
2CH
2CH
2Si(CH
3)(OCH
3)
2
3. end group for amino amino acid whose general formula is:
Or
In the formula: R
4=-C (O) CH
2-,-C (O) CH
2CH
2-,-CH
2CH
2CH
2CH
2-,-CH
2CH
2CH
2-
-C (NH
2) NHCH
2CH
2CH
2-,-C (O) NHCH
2CH
2CH
2-etc.
Selected L-type of the present invention or D-type amino acid monomer (and salt) comprising: l-asparagine, glutamine, Methionin, arginine, ornithine, citrulline and other end group are amino L-or D-type synthesizing amino acid and its esters.
4. polyreaction formula of the present invention is as follows:
In the formula: [I] amino acid silane coupling agent condenses
[II] amino acid modified polysiloxane organism
1. phase-transfer catalysis is or/and ion-exchange-resin process;
2. base catalysis.
R
5Can be following identical group or other organo-siloxane monomer:
1. alkoxyl group is as methoxyl group, oxyethyl group etc.;
2. methyl, ethyl or hydroxyl;
3. the polymerization degree is 1 ~ 500 polysiloxane.
a＝1-300
5. polyreaction of the present invention was divided into for two steps:
The first step: end group is that amino L-type or D-type amino acid and salt thereof and silane coupling agent are anti-
Answer condensation, generate amino acid silane coupling agent condenses.
This patent invention is adopted phase transfer catalysis process or/and ion is handed under alkaline condition
Change the resin method reaction.
Alkaline condition: the alkaline reagents of selecting for use comprises NaOH, KOH, Na
2CO
3, Ca (OH)
2
And other alkaline reagents.
Second step: amino acid silane coupling agent condenses and the polymerization of organo-siloxane performed polymer, give birth to
Become amino acid modified polysiloxane organism.
This patent invention adopts the base catalysis method to carry out polyreaction.
6. the present invention reacts related catalyzer (and exchange resin) and comprising:
(1) phase-transfer catalysis 1. quaternary ammonium salt, quaternary alkylphosphonium salt and season sulfosalt, as chlorination three
(PTC): n-octyl ammonium methyl, chlorination tetra-n-butyl ammonium, bromination
N-hexadecyl three normal-butyl phosphorus etc.; 2. crown ether, as
Hexaoxacyclooctadecane-6-6, hexichol hexaoxacyclooctadecane-6-6, dicyclohexyl
Hexaoxacyclooctadecane-6-6 etc.; 3. anion surfactant,
As Sodium dodecylbenzene sulfonate; 4. phase-transfer catalysis is set
Fat.
(2) amberlite strongly basic anion exchange resin is as phenolic aldehyde system tree
Fat: fat, chloride type resin, quaternary ammonium type resin etc.
(3) base catalysis: sodium hydroxide, potassium hydroxide etc.Four, the beneficial effect that the present invention produced
Amino acid modified polysiloxane organism involved in the present invention has advantages such as permanent maintenance amino acid active, usage period length.Range of application includes but are not limited to: fields such as skin care, hair care, cosmetics and biological products.
Fig. 1 is a principle flow chart of the present invention.
Among the figure:
In the formula: [I] amino acid silane coupling agent condenses
[II] amino acid modified polysiloxane organism
1. phase-transfer catalysis is or/and ion-exchange-resin process
2. base catalysis
The embodiment of the invention is described in detail below with reference to the accompanying drawings in detail: experimental example one:
Get 10-30 gram L lysine HCL and be dissolved in the 20-80 gram water, add the sodium hydroxide solution of 30-50 milliliter 0.5 mol, in 50-90 ℃ and 30-80 minute; Adding 10-35 gram gamma-chloropropylmethyldimethoxysilane, 0.5-2.0 restrain chlorination three n-octyl ammonium methyls, react 0.5-5 hour down at temperature 70-200 ℃, distill, separate, and get white oily condensation product; Get 8-20 gram condensation product, the end capped polydimethylsiloxane of adding 12-24 gram (viscosity is about 5cS) dimethoxy, 0.4-4 milliliter 2 mol hydrochloric acid solns, 2.0-20 restrain distilled water, at 90-180 ℃ of following stirring reaction 1-4 hour, underpressure distillation, remove residual alcohol, water and other lower-molecular substance, obtain the water white transparency product.Thickness not, good fluidity.Experimental example two:
Get 10-30 gram L-arginic acid salt and be dissolved in the 20-50 gram water, add the sodium hydroxide solution of 30-50 milliliter 0.5 mol, in 50-90 ℃ and 30-80 minute; Add 10-40 gram gamma-chloropropylmethyldimethoxysilane, about 30-40 restrains strongly basic anion exchange resin, 70-200 ℃ stirring reaction 1-10 hour, must light yellow oily condensation product; Get 8-20 gram condensation product, add 4-12 gram methoxyl group end capped polyether modified polyorganosiloxane (viscosity is less than 200cS), 0.4-4 milliliter 2 mol hydrochloric acid solns, 2.0-20 restrain distilled water, at 80-180 ℃ of following stirring reaction 1-6 hour, underpressure distillation, remove residual alcohol, water and other lower-molecular substance, obtain little yellow transparent product.Good fluidity, water-soluble, benzene, ethanol equal solvent.
Claims (8)
1. amino acid modified polysiloxane organism, it is characterized in that: employed polymer raw monomer comprises: the organo-siloxane performed polymer; End group is amino L-type or D-type amino acid and salt thereof; Silane coupling agent.
2. a kind of amino acid modified polysiloxane organism according to claim 1, it is characterized in that: starting monomer at phase-transfer catalyst or/and under the ion exchange resin inducing action, is that amino acid or its salt of amino link together with the covalent linkage form with organo-siloxane performed polymer and end group by silane coupling agent, forms a kind of amino acid modified polysiloxane organism.
3. a kind of amino acid modified polysiloxane organism according to claim 1 is characterized in that: structural formula of the present invention is:
4, a kind of amino acid modified polysiloxane organism according to claim 1 is characterized in that: organo-siloxane performed polymer general formula is:
(R1＝-H，-CH
3，-CH
2CH
3，-CH
2CH
2CH
3，-CH
2(OH)CHCH
3，
-CH
2CH
2CH
2CH
3，-(CH
2)
3NH
2，-(CH
2)
3NH(CH
2)
2NH
2，
-(CH
2)
3-O (C
2H
4O)
x(C
3H
6O)
y-R
1Deng;
(x＝1-40，y＝1-40，R
1＝-H，-CH
3，-COCH
3)
R2=-CH
3,-CH
2CH
3,-OCH
3,-OCH
2CH
3Or-OH etc.;
R3=-CH
3,-OCH
3,-OCH
2CH
3Or-OH etc.
n＝0～500；m＝0～500)
5. a kind of amino acid modified polysiloxane organism according to claim 1 is characterized in that: the general formula of silane coupling agent is:
(RX＝CH
2＝CH-，ClCH
2CH
2CH
2-，HSCH
2CH
2CH
2-，
CH
2=(CH
3) COO (CH
2)
3-, H
2NCH
2CH
2NH (CH
2)
3-etc.
Y＝R’O(R’＝CH
3-，CH
3CH
2-，CH
3OCH
2CH
2-)，Cl-，CH
3COO-)
6. a kind of amino acid modified polysiloxane organism according to claim 1 is characterized in that: end group for amino amino acid general formula is:
(R
4＝-C(O)CH
2-，-C(O)CH
2CH
2-，-CH
2CH
2CH
2CH
2-，-CH
2CH
2CH
2-
-C(NH
2)NHCH
2CH
2CH
2-，-C(O)NHCH
2CH
2CH
2-)
7, a kind of amino acid modified polysiloxane organism according to claim 1, it is characterized in that: this patent invention polyreaction was divided into for two steps: the first step: end group is amino L-type or D-type amino acid and salt and silane coupling agent reaction condensation, generate amino acid silane coupling agent condenses, under alkaline condition, adopt phase transfer catalysis process or/and ion-exchange-resin process reacts, alkaline condition: the alkaline reagents of selecting for use comprises NaOH, KOH, Na
2CO
3, Ca (OH)
2And other alkaline reagents; Second step: amino acid silane coupling agent condenses and the polymerization of organo-siloxane performed polymer, generate amino acid modified polysiloxane organism, this patent invention adopts the base catalysis method to carry out polyreaction.
8. a kind of amino acid modified polysiloxane organism according to claim 1 is characterized in that: temperature of reaction is 30-250 ℃, and the reaction times is 0.2-20 hour
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA02134373XA CN1468886A (en) | 2002-07-17 | 2002-07-17 | Amino acid modified polysiloxane organism |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA02134373XA CN1468886A (en) | 2002-07-17 | 2002-07-17 | Amino acid modified polysiloxane organism |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1468886A true CN1468886A (en) | 2004-01-21 |
Family
ID=34145764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA02134373XA Pending CN1468886A (en) | 2002-07-17 | 2002-07-17 | Amino acid modified polysiloxane organism |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531893A (en) * | 2009-04-28 | 2009-09-16 | 叶俊 | Functional resin tectorial membrane proppant and preparation method thereof |
| CN101942083A (en) * | 2010-09-10 | 2011-01-12 | 广东标美硅氟新材料有限公司 | Organic silicon compounds, and preparation method and application thereof |
-
2002
- 2002-07-17 CN CNA02134373XA patent/CN1468886A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531893A (en) * | 2009-04-28 | 2009-09-16 | 叶俊 | Functional resin tectorial membrane proppant and preparation method thereof |
| CN101942083A (en) * | 2010-09-10 | 2011-01-12 | 广东标美硅氟新材料有限公司 | Organic silicon compounds, and preparation method and application thereof |
| CN101942083B (en) * | 2010-09-10 | 2012-08-22 | 广东标美硅氟新材料有限公司 | Organic silicon compounds, and preparation method and application thereof |
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