CN104086578A - Trisiloxane containing glucosamide group and preparation method of trisiloxane - Google Patents
Trisiloxane containing glucosamide group and preparation method of trisiloxane Download PDFInfo
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- CN104086578A CN104086578A CN201410336032.9A CN201410336032A CN104086578A CN 104086578 A CN104086578 A CN 104086578A CN 201410336032 A CN201410336032 A CN 201410336032A CN 104086578 A CN104086578 A CN 104086578A
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Abstract
The invention provides trisiloxane containing a glucosamide group and a preparation method of the trisiloxane, belonging to the technical field of organic compound synthesis. The trisiloxane is a compound which is obtained through bonding reaction between silicon and nitrogen, oxygen or carbon in molecules. The preparation method comprises the following steps: preparing chloropropyl trisiloxane from hexamethyldisiloxane and chloropropyl silane in the presence of an acid catalyst, preparing N-beta-aminoalkyl-gamma-aminopropyl trisiloxane through reaction between chloropropyl trisiloxane and alkyl diamine and then preparing trisiloxane containing the glucosamide group from N-beta-aminoalkyl-gamma-aminopropyl trisiloxane and saccharic acid or gluconolactone in a low-carbon-alcohol solvent. The interfacial tension of an aqueous solution of trisiloxane containing glucosamide group and n-decane is 5mN/m. The trisiloxane containing the glucosamide group is widely applied in the fields of cosmetics and the like.
Description
Technical field
The present invention relates to silicoorganic compound preparation method field, especially relate to trisiloxanes of a kind of sugary amide group and preparation method thereof.
Background technology
Trisiloxane surfactant is except having the character of conventional surfactants, also have than the more superiority of conventional surfactants, can be applied to non-aqueous system, there is lower surface tension, extremely low physiology toxicity, especially there is good wetting and spreadability etc.
Han Fu (Chinese patent 200410092453.8) has reported a kind of method of preparing glucosyacylamino modification trisiloxane surfactant, by aminosilane, react with hexamethyldisiloxane and generate amino trisiloxanes, react with Gluconolactone again, generate glucosyacylamino trisiloxane surfactant.
In the trisiloxane surfactant of this sugary amide group, carbon chain linker group between trisiloxanes and glucose amide is very short, in the emulsion system of the Application Areass such as makeup, need the carbochain of growing, increase its oil soluble, change the absorption property on oil/water interface.
Summary of the invention
The object of the invention is the high biological degradability of the low surface tension of trisiloxane surfactant and sugar surfactants to combine, and between trisiloxanes and sugared acid amides, introduce longer carbochain, the preparation method of the trisiloxane surfactant of the sugary amide group that a kind of surface tension is low, biological degradability good, oil soluble is stronger is provided.
The molecular structural formula of the trisiloxane surfactant of sugary amide group of the present invention is as follows:
Wherein, R
1for
R
2for
-(CH
2)
3-NH-(CH
2)
x-
R
3for
-H or
X is 3～6 integer.
The preparation method of the trisiloxanes of sugary amide group of the present invention comprises the following steps:
1. by hexamethyldisiloxane, chloropropyl silane and an acidic catalyst, in temperature of reaction, be 40～100 ℃, preferably in the situation of 50～80 ℃, react; Wherein mole proportioning of hexamethyldisiloxane and chloropropyl silane is (1～20): 1, preferably (2～10): 1, the mole dosage of an acidic catalyst is 0.3%～25% of hexamethyldisiloxane and chloropropyl silane mole sum; After having reacted, make an acidic catalyst inactivation, elimination solid, underpressure distillation, obtains chloropropyl trisiloxanes;
2. alkyl diamine and chloropropyl trisiloxanes, be 60～150 ℃ in temperature of reaction, preferably in the situation of 80～120 ℃, reacts; Wherein mole proportioning of alkyl diamine and chloropropyl trisiloxanes is (1～20): 1, preferably (6～15): 1; After having reacted, mixture stratification, upper strata underpressure distillation, obtains N-β-aminoalkyl-γ-aminopropyl trisiloxane;
3.N-β-aminoalkyl-γ-aminopropyl trisiloxane and saccharic acid or saccharic acid lactone, make solvent in low-carbon alcohol, and temperature of reaction is 60～150 ℃, preferably 60～100 ℃ of reactions; Wherein mole proportioning of alkyl diamine and saccharic acid or saccharic acid lactone is 1～2: 1, preferably 1: 1; After having reacted, steaming desolventizes, and obtains the trisiloxanes of sugary amide group.
Chloropropyl silane as above can comprise: chloropropyl dimethoxy-methyl silane, chloropropyl diethoxymethyl silane etc.
An acidic catalyst as above can comprise: the vitriol oil, acidic white earth etc.
An acidic catalyst inactivation that makes as above is when an acidic catalyst is the vitriol oil, adds alkali catalyst neutralisation, makes it inactivation; When an acidic catalyst is acidic white earth, filter, make it to remove.
Alkyl diamine as above can comprise: 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine etc.
Saccharic acid as above or saccharic acid lactone can comprise: gluconic acid or Gluconolactone, lactobionic acid or lactobionic acid lactone, mannonic acid or mannonic acid lactone etc.
Low-carbon alcohol as above can comprise: methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.
The trisiloxane surfactant of the sugary amide group that the present invention is prepared, its advantage is that the high biological degradability of the low surface tension of organic silicon surfactant and sugar surfactants is combined, and between trisiloxanes and sugared acid amides, introduce longer carbochain, the absorption property on oil/water interface is better.Can be used as cosmetic composition for cosmetic formulations.Its using method and other cosmetic material are similar.
Embodiment
Below in conjunction with embodiment, the present invention is made an explanation.
Embodiment 1
In reactor 1, add hexamethyldisiloxane 1.62kg, chloropropyl dimethoxy-methyl silane 1.83kg, vitriol oil 0.006kg, at 40 ℃ of temperature, react 4 hours, hydro-oxidation sodium makes catalyst deactivation, solids removed by filtration, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, 1,3-propylene diamine 0.74kg, is heated to 60 ℃, react 4 hours, and mixture stratification, upper strata underpressure distillation, obtains N-β-aminopropyl-γ-aminopropyl trisiloxane.In reactor 3, add N-β-aminopropyl-γ-aminopropyl trisiloxane 3.36kg, Gluconolactone 1.78kg, makes solvent with methyl alcohol, is heated to 60 ℃, reacts 8 hours, steams and desolventizes methyl alcohol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 4.6mN/m.
Embodiment 2
In reactor 1, add hexamethyldisiloxane 8.12kg, chloropropyl dimethoxy-methyl silane 1.83kg, acidic white earth 0.10kg reacts 4 hours under temperature 50 C, removes by filter catalyzer, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, Putriscine 2.64kg, is heated to 80 ℃, react 3 hours, and mixture stratification, upper strata underpressure distillation, obtains N-β-ammonia butyl-γ-aminopropyl trisiloxane.In reactor 3, add N-β-ammonia butyl-γ-aminopropyl trisiloxane 3.50kg, gluconic acid 1.96kg, makes solvent with ethanol, is heated to 70 ℃, reacts 8 hours, steams and desolventizes ethanol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 4.5mN/m.
Embodiment 3
In reactor 1, add hexamethyldisiloxane 16.24kg, chloropropyl dimethoxy-methyl silane 1.83kg, vitriol oil 0.54kg, under temperature 60 C, react 4 hours, hydro-oxidation sodium makes catalyst deactivation, solids removed by filtration, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, 1,5-pentamethylene diamine 6.12kg, is heated to 90 ℃, react 2 hours, and mixture stratification, upper strata underpressure distillation, obtains N-β-ammonia amyl group-γ-aminopropyl trisiloxane.In reactor 3, add N-β-ammonia amyl group-γ-aminopropyl trisiloxane 3.64kg, mannonic acid lactone 1.78kg, makes solvent with methyl alcohol, is heated to 80 ℃, reacts 10 hours, steams and desolventizes methyl alcohol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 4.4mN/m.
Embodiment 4
In reactor 1, add hexamethyldisiloxane 32.48kg, chloropropyl dimethoxy-methyl silane 1.83kg, acidic white earth 5.59kg reacts 4 hours under temperature 70 C, removes by filter catalyzer, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, 1,6-hexanediamine 11.6kg, is heated to 100 ℃, react 1 hour, and mixture stratification, upper strata underpressure distillation, obtains N-β-ammonia hexyl-γ-aminopropyl trisiloxane.In reactor 3, add N-β-ammonia hexyl-γ-aminopropyl trisiloxane 3.78kg, mannonic acid 1.96kg, makes solvent with ethanol, is heated to 90 ℃, reacts 10 hours, steams and desolventizes ethanol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 4.7mN/m.
Embodiment 5
In reactor 1, add hexamethyldisiloxane 1.62kg, chloropropyl diethoxymethyl silane 2.11kg, vitriol oil 0.20kg, at 80 ℃ of temperature, react 3 hours, hydro-oxidation sodium makes catalyst deactivation, solids removed by filtration, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, 1,3-propylene diamine 8.88kg, is heated to 110 ℃, react 4 hours, and mixture stratification, upper strata underpressure distillation, obtains N-β-aminopropyl-γ-aminopropyl trisiloxane.In reactor 3, add N-β-aminopropyl-γ-aminopropyl trisiloxane 3.36kg, lactobionic acid lactone 3.40kg, makes solvent with methyl alcohol, is heated to 100 ℃, reacts 8 hours, steams and desolventizes methyl alcohol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 5.6mN/m.
Embodiment 6
In reactor 1, add hexamethyldisiloxane 8.12kg, chloropropyl diethoxymethyl silane 2.11kg, acidic white earth 3.19kg reacts 3 hours at 80 ℃ of temperature, removes by filter catalyzer, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, Putriscine 13.2kg, is heated to 120 ℃, react 3 hours, and mixture stratification, upper strata underpressure distillation, obtains N-β-ammonia butyl-γ-aminopropyl trisiloxane.In reactor 3, add N-β-ammonia butyl-γ-aminopropyl trisiloxane 3.50kg, lactobionic acid 3.58kg, makes solvent with ethanol, is heated to 120 ℃, reacts 8 hours, steams and desolventizes ethanol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 5.5mN/m.
Embodiment 7
In reactor 1, add hexamethyldisiloxane 16.24kg, chloropropyl diethoxymethyl silane 2.11kg, vitriol oil 2.70kg, at 90 ℃ of temperature, react 3 hours, hydro-oxidation sodium makes catalyst deactivation, solids removed by filtration, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, 1,5-pentamethylene diamine 18.36kg, is heated to 130 ℃, react 2 hours, and mixture stratification, upper strata underpressure distillation, obtains N-β-ammonia amyl group-γ-aminopropyl trisiloxane.In reactor 3, add N-β-ammonia amyl group-γ-aminopropyl trisiloxane 3.64kg, lactobionic acid lactone 3.40kg, makes solvent with methyl alcohol, is heated to 140 ℃, reacts 9 hours, steams and desolventizes methyl alcohol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 5.4mN/m.
Embodiment 8
In reactor 1, add hexamethyldisiloxane 32.48kg, chloropropyl diethoxymethyl silane 2.11kg, acidic white earth 27.93kg reacts 2 hours at 100 ℃ of temperature, removes by filter catalyzer, and underpressure distillation obtains chloropropyl trisiloxanes.In reactor 2, add chloropropyl trisiloxanes 2.99kg, 1,6-hexanediamine 23.2kg, is heated to 150 ℃, react 1 hour, and mixture stratification, upper strata underpressure distillation, obtains N-β-ammonia hexyl-γ-aminopropyl trisiloxane.In reactor 3, add N-β-ammonia hexyl-γ-aminopropyl trisiloxane 3.78kg, lactobionic acid 3.58kg, makes solvent with ethanol, is heated to 150 ℃, reacts 9 hours, steams and desolventizes ethanol, obtains the trisiloxanes of sugary amide group.The interfacial tension that records its aqueous solution and n-decane is 5.3mN/m.
Claims (8)
1. a trisiloxanes for sugary amide group, is characterized in that the molecular structural formula of trisiloxanes of sugary amide group is as follows:
Wherein, R
1for
R
2for
-(CH
2)
3-NH-(CH
2)
x-
R
3for
-H or
X is 3～6 integer.
2. a preparation method for the trisiloxanes of sugary amide group, is characterized in that comprising the steps:
(1), by hexamethyldisiloxane, chloropropyl silane and an acidic catalyst, in the situation that being 40～100 ℃, temperature of reaction reacts; Wherein mole proportioning of hexamethyldisiloxane and chloropropyl silane is (1～20): 1, and the mole dosage of an acidic catalyst is 0.3%～25% of hexamethyldisiloxane and chloropropyl silane mole sum; After having reacted, make an acidic catalyst inactivation, elimination solid, underpressure distillation, obtains chloropropyl trisiloxanes;
(2) alkyl diamine and chloropropyl trisiloxanes react in the situation that temperature of reaction is 60～150 ℃; Wherein mole proportioning of alkyl diamine and chloropropyl trisiloxanes is (1～20): 1; After having reacted, mixture stratification, upper strata underpressure distillation, obtains N-β-aminoalkyl-γ-aminopropyl trisiloxane;
(3) N-β-aminoalkyl-γ-aminopropyl trisiloxane and saccharic acid or saccharic acid lactone, make solvent in low-carbon alcohol, and temperature of reaction is 60～150 ℃ of reactions; Wherein mole proportioning of alkyl diamine and saccharic acid or saccharic acid lactone is 1～2: 1; After having reacted, steaming desolventizes, and obtains the trisiloxanes of sugary amide group.
3. the preparation method of the trisiloxanes of a kind of sugary amide group as claimed in claim 2, is characterized in that described chloropropyl silane is chloropropyl dimethoxy-methyl silane, chloropropyl diethoxymethyl silane.
4. the preparation method of the trisiloxanes of a kind of sugary amide group as claimed in claim 2, is characterized in that described an acidic catalyst is the vitriol oil, acidic white earth.
5. the preparation method of the trisiloxanes of a kind of sugary amide group as claimed in claim 2, is characterized in that the described an acidic catalyst inactivation that makes is when an acidic catalyst is the vitriol oil, adds alkali catalyst neutralisation, makes it inactivation; When an acidic catalyst is acidic white earth, filter, make it to remove.
6. the preparation method of the trisiloxanes of a kind of sugary amide group as claimed in claim 2, is characterized in that described alkyl diamine is 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine.
7. the preparation method of the trisiloxanes of a kind of sugary amide group as claimed in claim 2, is characterized in that described saccharic acid or saccharic acid lactone are gluconic acid or Gluconolactone, lactobionic acid or lactobionic acid lactone, mannonic acid or mannonic acid lactone.
8. the preparation method of the trisiloxanes of a kind of sugary amide group as claimed in claim 2, is characterized in that described low-carbon alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660882A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Method for preparing oxane trisilicate of containing glucosyacylamino |
| CN101653709A (en) * | 2009-09-22 | 2010-02-24 | 北京工商大学 | Preparation method of trisiloxane surfactant containing amino groups and oxyethyl groups |
| CN102492146A (en) * | 2011-12-07 | 2012-06-13 | 北京工商大学 | Method for preparing polysiloxane containing alkyl and glucosamide |
| CN103752211A (en) * | 2014-02-14 | 2014-04-30 | 北京工商大学 | Trisiloxane quaternary ammonium salt containing glucosamine groups and preparation method |
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2014
- 2014-07-15 CN CN201410336032.9A patent/CN104086578A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660882A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Method for preparing oxane trisilicate of containing glucosyacylamino |
| CN101653709A (en) * | 2009-09-22 | 2010-02-24 | 北京工商大学 | Preparation method of trisiloxane surfactant containing amino groups and oxyethyl groups |
| CN102492146A (en) * | 2011-12-07 | 2012-06-13 | 北京工商大学 | Method for preparing polysiloxane containing alkyl and glucosamide |
| CN103752211A (en) * | 2014-02-14 | 2014-04-30 | 北京工商大学 | Trisiloxane quaternary ammonium salt containing glucosamine groups and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| FU HAN ET AL.: "Synthesis and Characterization of a Quaternized Glucosamide-Based Trisiloxane Surfactant", 《J SURFACT DETERG》 * |
| 韩富等: "糖酰胺改性有机硅表面活性剂的研究进展", 《化工新型材料》 * |
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