CN103182271B - A kind of organic silicon surfactant and its preparation method and application - Google Patents
A kind of organic silicon surfactant and its preparation method and application Download PDFInfo
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- CN103182271B CN103182271B CN201110446125.3A CN201110446125A CN103182271B CN 103182271 B CN103182271 B CN 103182271B CN 201110446125 A CN201110446125 A CN 201110446125A CN 103182271 B CN103182271 B CN 103182271B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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Abstract
The invention discloses a kind of organic silicon surfactant and its preparation method and application, described organic silicon surfactant has structure shown in formula (I), and wherein, c is not 0; A, b, c are integer and 10 < a+b+c < 200; M=0 ~ 40; N=0 ~ 30; X=3 ~ 30; X, m, n are integer, and are 0 when m, n are different; R is C
6 ~ 20straight chain or isomery chain alkyl, or be alkyl phenyl; R ' is H, CH
3, C
2h
5, C
3h
7, C
4h
9.Described organic silicon surfactant has novel structure, has excellent emulsifying capacity; Described organic silicon surfactant is to the dimethyl silicone polymer of very large range of viscosities and various modified dimethyl polysiloxane, all there is excellent emulsifying capacity, single use can reach good emulsifying effectiveness, without the need to composite with other emulsifying agents, and emulsifying process is simple, without the need to crossing homogenizer or other special emulsifying process, stable O/W type silicone oil emulsion just can be obtained, easy to use.
Description
Technical field
The present invention relates to organic silicon surfactant chemical field, be specifically related to a kind of organic silicon surfactant and its preparation method and application.
Background technology
Organic silicon surfactant is a kind of novel surfactant along with organosilicon new material grows up, and it has won wide survival and development space with the performance of uniqueness, has now become more and more important a kind of surfactant.
Organic silicon surfactant mainly refers to dimethyl silicone polymer to be hydrophobic main chain, introduces one or more polar organic group wherein and the class surfactant formed.Except the general character with conventional surfactants, also there is surface-active more better than conventional surfactants, be the efficient surfactant of a class, there is emulsibility, dispersed, easy spread, wetability, antistatic behaviour, the performances such as froth breaking, steady bubble, foaming.These characteristics are because of dimethyl silicone polymer low surface tension and weak intermolecular force.
Emulsifying agent is the important component part of emulsion, and it is the bridge connecting oil phase and aqueous phase.Meet to make system in useful life, keep stable, be developed miscellaneous emulsifying agent, or be one-component or be Compositional type, or be universal or be tailored version.
Along with the development of organosilicon material, the kind of silicone based emulsifying agent is on the increase, and performance also improves constantly, but single use is applied to the rarely seen report of O/W organosilyl surfactant in silicone oil emulsion formulations.Obtain stable Si/W type emulsion if want, existing method is, by being undertaken composite by the emulsifying agent of different HLB value, makes the HLB value of the HLB value of emulsifier system and emulsified silicone oil suitable, or by special emulsifying process such as mechanical homogenizers.But the silicone oil of different viscosities, not quite the same to the requirement of emulsifier hlb value, different modified silicon oils, its HLB generally also has certain difference.This just requires that formula engineer is to different silicone oil emulsion systems, composite go out different emulsifier system.
Summary of the invention
The object of the present invention is to provide a kind of organic silicon surfactant.The architectural feature of this organic silicon surfactant is, polysiloxane side chain is through hydrosilylation, grafting is with the polyethers of chain alkyl or alkyl phenyl end-blocking, it is to the dimethyl silicone polymer of very large range of viscosities and various modified dimethyl polysiloxane, all there is excellent emulsifying capacity, single use can reach good emulsifying effectiveness, without the need to composite with other emulsifying agents, and emulsifying process is simple, without the need to crossing homogenizer or other special emulsifying process, just stable silicone oil emulsion can be obtained, easy to use.
The present invention also aims to provide the application of described organic silicon surfactant in O/W type silicone oil emulsion formula.
Above-mentioned purpose of the present invention is achieved by following proposal:
A kind of organic silicon surfactant, has structure shown in formula (I):
Wherein, c is non-vanishing; A, b, c are integer and 10 < a+b+c < 200; M=0 ~ 40; N=0 ~ 30; X=3 ~ 30; X, m, n are integer, and are 0 when m, n are different; R is C
6 ~ 20straight chain or isomery chain alkyl, or be alkyl phenyl; R ' is H, CH
3, C
2h
5, C
3h
7, C
4h
9.
As a kind of preferred version, the structure of described organic silicon surfactant is preferably a=0 ~ 150; B=0 ~ 60; C=1 ~ 60.
As a kind of preferred version, the structure of described organic silicon surfactant is preferably a=1 ~ 60; B=1 ~ 20; C=1 ~ 20; A, b, c are integer and 20 < a+b+c < 100;
M=5 ~ 15; N=6 ~ 20; X=6 ~ 12; X, m, n are integer;
R is C
8 ~ 16straight chain or isomery chain alkyl.
The preparation method of described organic silicon surfactant is as follows:
Comprise the steps: to add in reactor by having formula (III) structure or formula (II), the allyl polyether of formula (III) structure and containing hydrogen silicone oil; under the protection of nitrogen atmosphere; stir; be heated to 80 ~ 100 DEG C; add chloroplatinic acid-Isopropanol catalysis agent; continue to be heated to 110 ~ 180 DEG C of reactions, until system becomes transparent, obtain described organic silicon surfactant.
Described organic silicon surfactant is colourless to light yellow liquid or paste.
The application of described organic silicon surfactant in emulsifying agent.
Described organic silicon surfactant has excellent emulsifiability, as the emulsifying agent of O/W type silicone oil emulsion formula, can be used alone.
Described organic silicon surfactant fill a prescription as O/W type silicone oil emulsion emulsifying agent time, its consumption is organic silicon surfactant in mass ratio: silicone oil=1: 2 ~ 6.
Described organic silicon surfactant as cream frost formula emulsifying agent time, its consumption is this organic silicon surfactant in mass ratio: system=1 to be emulsified: 5 ~ 9.
Organic silicon surfactant of the present invention, to the dimethyl silicone polymer of very large range of viscosities (such as about 2cSt ~ 12500cSt) and various modified dimethyl polysiloxane, all has excellent emulsifying capacity.
Compared with prior art, tool of the present invention has the following advantages:
Novel organosilicon surfactant of the present invention, the alkane two kinds of hydrophobic segments containing polysiloxane in structure and be directly connected with polyethers chain link, there is the polyethers hydrophilic radical of multiple polarity centre, thus has excellent emulsifying capacity; Described novel organosilicon surfactant is to the dimethyl silicone polymer of very large range of viscosities and various modified dimethyl polysiloxane, all there is excellent emulsifying capacity, single use can reach good emulsifying effectiveness, without the need to composite with other emulsifying agents, and emulsifying process is simple, without the need to crossing homogenizer or other special emulsifying process, stable O/W type silicone oil emulsion just can be obtained, easy to use.
Detailed description of the invention
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
In embodiment, used catalyst is chloroplatinic acid-Isopropanol catalysis agent that this area is commonly used.
Embodiment 1
With agitating device, drum N
2in the three-neck flask of device and thermometer, add 0.3mol allyl polyether formula (II) (m=10, n=6, R ' be C
3h
7), (x=9, R are C to 0.3mol allyl polyether formula (III)
12h
25); 0.5mol is about containing hydrogen silicone oil (the a+b+c ≈ 80 of 0.3% (mass percent) containing hydrogen number; b+c ≈ 18 as can be seen here; a: b: c ≈ 62: 9: 9), under the protection of nitrogen atmosphere, when heating to 80 DEG C; add 0.03g catalyst; continue to be heated to 120 DEG C ~ 130 DEG C reactions, until system bleach, namely obtain the organic silicon surfactant of light yellow clear.
Embodiment 2
With agitating device, drum N
2in the three-neck flask of device and thermometer, add 0.2mol allyl polyether (II) (m=38, n=0, R ' be H), (x=3, R are C to 0.3mol allyl polyether (III)
16h
33); 0.4mol is about containing hydrogen silicone oil (the a+b+c ≈ 130 of 0.2% (mass percent) containing hydrogen number; b+c ≈ 20 as can be seen here; a: b: c ≈ 110: 8: 12), under the protection of nitrogen atmosphere, when heating to 100 DEG C; add 0.03g catalyst; continue to be heated to 150 DEG C ~ 160 DEG C reactions, until system bleach, namely obtain the organic silicon surfactant of light yellow clear.
Embodiment 3
With agitating device, drum N
2in the three-neck flask of device and thermometer, add 0.18mol allyl polyether (II) (m=2, n=30, R ' be H), (x=28, R are C to 0.2mol allyl polyether (III)
18h
37); 0.32mol is about containing hydrogen silicone oil (the a+b+c ≈ 30 of 0.35% (mass percent) containing hydrogen number; b+c ≈ 20 as can be seen here; a: b: c ≈ 22: 5: 3), under the protection of nitrogen atmosphere, when heating to 90 DEG C; add 0.03g catalyst; continue to be heated to 130 DEG C ~ 140 DEG C reactions, until system bleach, namely obtain the organic silicon surfactant of light yellow clear.
Embodiment 4
With agitating device, drum N
2in the three-neck flask of device and thermometer, add 0.25mol allyl polyether (II) (m=16, n=10, R ' be CH
3), (x=7, R are C to 0.22mol allyl polyether (III)
6h
13); 0.4mol is about (mass percent) containing hydrogen silicone oil (a+b+c ≈ 140 of 0.17% containing hydrogen number; b+c ≈ 20 as can be seen here; a: b: c ≈ 120: 11: 9), under the protection of nitrogen atmosphere, when heating to 94 DEG C; add 0.03g catalyst; continue to be heated to 160 DEG C ~ 170 DEG C reactions, until system bleach, namely obtain the organic silicon surfactant of light yellow clear.
Embodiment 5
With agitating device, drum N
2in the three-neck flask of device and thermometer, (x=25, R are C to add 0.33mol allyl polyether (III)
20h
41); 0.3mol is about (mass percent) containing hydrogen silicone oil (a+c ≈ 95 of 0.28% containing hydrogen number; b=0, c ≈ 20, a: c ≈ 75: 20 as can be seen here); under the protection of nitrogen atmosphere; when heat temperature raising is heated to 90 DEG C, add 0.03g catalyst, continue to be heated to 160 DEG C ~ 170 DEG C reactions; until system bleach, namely obtain the organic silicon surfactant of light yellow clear.
Embodiment 6
20 parts of dimethyl siloxanes (different viscosities) are added in emulsifying kettle, and the organic silicon surfactant of 6 parts of embodiment 1 gained, after stirring, disposablely add about 6 parts of distilled water (or purified water), continue fully to be uniformly mixed, the now transparent paste of system.Subsequently under agitation, slowly add remaining 68 parts of water, the milky white liquid of blueing can be obtained.2500r/min × 15min is centrifugal, not stratified.Specifically in table 1.
The dimethicone of table 1 emulsification different viscosities
Embodiment 7
In emulsifying kettle, add 20 parts of modified silicon oils, and the organic silicon surfactant of 6 parts of embodiment 1 gained, after stirring, disposablely add about 6 parts of distilled water (or purified water), continue fully to be uniformly mixed, the now transparent paste of system.Subsequently under agitation, slowly add remaining 68 parts of water, the milky white liquid of blueing can be obtained.2500r/min × 15min is centrifugal, not stratified.Specifically in table 2.
The modified silicon oil that table 2 emulsification is different
Embodiment 8
In emulsifying kettle, add 20 parts of silicone oil, and the organic silicon surfactant of 7 parts of embodiment 4 gained, after stirring, disposablely add about 5 parts of distilled water (or purified water), continue fully to be uniformly mixed, the now transparent paste of system.Subsequently under agitation, slowly add remaining 68 parts of water, the milky white liquid of blueing can be obtained.2500r/min × 15min is centrifugal, not stratified.Specifically in table 3.
The silicone oil that table 3 emulsification is different
Claims (7)
1. an organic silicon surfactant, is characterized in that, has such as formula structure (I) Suo Shi:
（Ⅰ）
Wherein, c is non-vanishing; A, b, c are integer and 10 < a+b+c < 200; M=0 ~ 40; N=0 ~ 30; X=3 ~ 30; X, m, n are integer, and are 0 when m, n are different; R is C
6 ~ 20straight chain or isomery chain alkyl; R ' is H, CH
3, C
2h
5, C
3h
7, C
4h
9;
Described a=0 ~ 150; B=0 ~ 60; C=1 ~ 60.
2. organic silicon surfactant as claimed in claim 1, is characterized in that, described a=1 ~ 60; B=1 ~ 20; C=1 ~ 20; A, b, c are integer and 20 < a+b+c < 100; M=5 ~ 15; N=6 ~ 20; X=6 ~ 12; X, m, n are integer; R is C
8 ~ 16straight chain or isomery chain alkyl.
3. the preparation method of organic silicon surfactant described in claim 1, it is characterized in that, comprise the steps: to add in reactor by having formula (III) structure or formula (II), the allyl polyether of formula (III) structure and containing hydrogen silicone oil, under the protection of nitrogen atmosphere, stirring is warming up to 80 ~ 100 DEG C, adds chloroplatinic acid-Isopropanol catalysis agent, continues to be heated to 110 ~ 180 DEG C of reactions, until system becomes transparent, obtain described organic silicon surfactant;
（Ⅱ）；
（Ⅲ）。
4. the application of organic silicon surfactant described in claim 1 or 2 in emulsifying agent.
5. apply as claimed in claim 4, it is characterized in that, described organic silicon surfactant is separately as the emulsifying agent of O/W type silicone oil emulsion formula.
6. apply as claimed in claim 4, it is characterized in that, described organic silicon surfactant fill a prescription as O/W type silicone oil emulsion emulsifying agent time, its consumption is organic silicon surfactant in mass ratio: silicone oil=1:2 ~ 6.
7. apply as claimed in claim 4, it is characterized in that, described organic silicon surfactant as cream frost formula emulsifying agent time, its consumption is organic silicon surfactant in mass ratio: system=1:5 ~ 9 to be emulsified.
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|---|---|---|---|
| CN201110446125.3A CN103182271B (en) | 2011-12-27 | 2011-12-27 | A kind of organic silicon surfactant and its preparation method and application |
| PCT/CN2011/084992 WO2013097167A1 (en) | 2011-12-27 | 2011-12-30 | Silicone surfactant, and preparation method and use thereof |
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| CN201110446125.3A CN103182271B (en) | 2011-12-27 | 2011-12-27 | A kind of organic silicon surfactant and its preparation method and application |
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| CN103182271B true CN103182271B (en) | 2015-10-28 |
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| CN103342818B (en) * | 2013-07-16 | 2015-08-12 | 扬州晨化新材料股份有限公司 | A kind of preparation method of Siloxane-Oxyalkylene Copolymers foam stabilizer |
| EP3172262B1 (en) | 2014-07-23 | 2023-07-05 | Dow Silicones Corporation | Silicone emulsions |
| CN105199111A (en) * | 2015-10-22 | 2015-12-30 | 烟台德邦先进硅材料有限公司 | Preparation method of organosilicone surfactant for polyurethane flexible foams |
| CN108623810B (en) * | 2018-05-11 | 2021-05-11 | 广东工业大学 | Organic silicon crosslinked polymer and preparation method and application thereof |
| CN111040188B (en) * | 2019-11-29 | 2022-09-02 | 湖北新四海化工股份有限公司 | Organic silicon emulsifier and preparation method thereof |
| CN113577837B (en) * | 2020-04-30 | 2023-05-12 | 南京智茂新材料科技有限公司 | Organic silicon composition |
| CN112574423A (en) * | 2020-11-30 | 2021-03-30 | 山东大易新产业技术研究院有限公司 | Low-molecular organosilicon surfactant for contact killing of phytophagous thrips |
| CN112574424B (en) * | 2020-11-30 | 2023-01-06 | 山东大易新产业技术研究院有限公司 | Organic silicon surfactant for contact killing of tetranychus urticae and preparation method thereof |
| CN112574422B (en) * | 2020-11-30 | 2023-01-06 | 山东大易新产业技术研究院有限公司 | Organosilicon surfactant for contact killing of spider mite eggs and preparation method thereof |
| CN112616863A (en) * | 2020-12-19 | 2021-04-09 | 李慧 | Disinfectant preparation process |
| CN113461970B (en) * | 2021-07-26 | 2022-07-12 | 浙江新安化工集团股份有限公司 | Organic silicon wax emulsion and preparation method thereof |
| CN114196023B (en) * | 2021-12-30 | 2022-12-20 | 中材高新江苏硅材料有限公司 | Surface modifier and application thereof in preparation of silicon-based composite functional coating material |
| CN114672029B (en) * | 2022-04-27 | 2023-03-31 | 四川大学 | Preparation method of nonionic organic silicon surfactant |
| CN115044044B (en) * | 2022-07-13 | 2023-04-14 | 枣阳市华威硅氟材料有限公司 | Sulfonic group modified silicone oil and preparation method and application thereof |
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| 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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| DE102006040010A1 (en) * | 2006-08-25 | 2008-02-28 | Evonik Goldschmidt Gmbh | Use of polyether-modified siloxane block copolymers as hydrophilic silicone-containing plasticizers for fabrics, non-wovens and / or fibers of natural and / or synthetic raw materials |
| CN101690878A (en) * | 2009-10-13 | 2010-04-07 | 广州天赐有机硅科技有限公司 | Method for manufacturing organosilicon surfactant with T-shaped structure for pesticide |
| CN101914367B (en) * | 2010-08-31 | 2013-05-22 | 广东标美硅氟新材料有限公司 | Compound-type oil outflow round-up agent as well as preparation method and application thereof |
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| 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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| Title |
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| 聚醚改性聚硅氧烷非离子型乳化剂;周宇鹏等;《有机硅材料》;20040727;第18卷(第4期);第18-21页 * |
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| WO2013097167A1 (en) | 2013-07-04 |
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