CN101130634B - High solid content amido silicone oil microemulsion and method of producing the same - Google Patents
High solid content amido silicone oil microemulsion and method of producing the same Download PDFInfo
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- CN101130634B CN101130634B CN2007100704989A CN200710070498A CN101130634B CN 101130634 B CN101130634 B CN 101130634B CN 2007100704989 A CN2007100704989 A CN 2007100704989A CN 200710070498 A CN200710070498 A CN 200710070498A CN 101130634 B CN101130634 B CN 101130634B
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Abstract
The invention discloses a high solid content amido silicon oil microemulsion, which is characterized by the following: allocating with mass percent as 1%-60% amido silicon oil, 5%-19% emulsifying agent, 2. 5%-10% coemulsifier, 0. 01%-0. 1% ionogen and 15%-90% water; adopting antiphase (anti-phase) emulsifying method; mixing the emulsifier and the silicon oil; adding into coemulsifier, water and ionogen; producing bi-continuous phase structural emulsion between O/W and W/O; diluting; changing to amido silicon oil microemulsion of the O/W. This amido silicon oil microemulsion is bi-continuous type structure, which possesses simple course and easy control.
Description
Technical field
The present invention relates to textiles auxiliary agent field, relate in particular to a kind of high solid content amido silicone oil microemulsion and preparation method.
Background technology
Amido silicon oil has excellent adsorption, becomes the characteristics of mould and favorable orientation, can give fabric sofetening mild feel, improves the flexibility and the smooth property of fabric greatly, is the most popular soft finishing agent in textile auxiliary agent field in recent years.Amido silicon oil and methyl-silicone oil backbone structure are similar, molecular backbone chain is very submissive, it is a kind of bent volution linear chain structure of easily disturbing, alternately form by Siliciumatom and Sauerstoffatom, methyl is almost nil around the free energy of Si-O key rotation, very free, can 360 ° of rotations, this characteristic makes silicone oil become the best fabric softener, and amino can with the hydroxyl of fiber surface, interactions such as Suo Ji, be orientated very securely and be adsorbed on the fiber, form very firm film at fiber surface, the static friction coefficient of fiber is descended, just can make with very little power to begin between the fiber to slide, make fabric produce good soft and smooth property, so amido silicon oil have better effect than the silicone oil of other kind.Chinese market year needs about 400,000 tons of textiles soft finishing agent at present, and wherein the consumption of amido silicon oil soft finishing agent has surpassed 20,000 tons.
Amido silicon oil is many to be used with emulsion state, the high viscosity of amido silicon oil and low surface tension have determined its more difficult emulsification, particle size of emulsion and distribution thereof have bigger influence to the result of use of amino silicon oil emulsion, when amido silicon oil uses with the microemulsion state, the moulding property of fiber, the film density, performances such as pliability all are greatly improved, therefore microemulsion can effectively improve the use properties of amido silicon oil, and the many solid contents of amido silicone oil microemulsion that oneself prepare on the Chinese market are lower, bring a lot of inconvenience for storage and transportation, higher solids content and stable amido silicone oil microemulsion have abroad been arranged, but the amido silicone oil microemulsion of import often mixes emulsifying agent and other additives, makes that cost is higher and it is inconvenient to use.
Summary of the invention
The invention provides a kind of simple to operate, lower-cost high solid content amido silicone oil microemulsion and preparation method.
A kind of high solid content amido silicone oil microemulsion, weight percent consists of:
Amido silicon oil 1%～60%
Emulsifying agent 5%～19%
Assistant for emulsifying agent 2.5%～10%
Ionogen 0.01%～0.1%
Water 15%～90%
Described amido silicon oil viscosity is 50mPas～5000mPas, and the ammonia value is 0.1～1.5.
Described amino silicon monomer is N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane or γ-divinyl triammonium propyl group methyl dimethoxysilane.
Described emulsifying agent is that nonionic emulsifier is composite, is nonyl phenol oxyethylene ether and Fatty Alcohol(C12-C14 and C12-C18) oxyethylene ether, and the hydrophile-lipophile balance value (HLB) of the emulsifying agent after composite is 12.0～13.8.
Described assistant for emulsifying agent is a carbonatoms less than 6 low mass molecule alcohol and/or carbonatoms less than 6 low molecular acid.When low mass molecule alcohol and low molecular acid mixing use can be arbitrary proportion.
Described low mass molecule alcohol can be at least a in ethanol, propyl alcohol, propyl carbinol, Pentyl alcohol or the polyoxyethylene glycol, and described low molecular acid can be at least a in acetate or the oxalic acid.
Described ionogen is an an alkali metal salt, as: Repone K, sodium-chlor, Sodium Nitrite, potassium nitrite, saltpetre, sodium sulfate etc.
The preparation method of described high solid content amido silicone oil microemulsion may further comprise the steps:
Add amido silicon oil and emulsifying agent in the reactor, stir 40～60min, add assistant for emulsifying agent (alcohol, organic acid) and water then, continue to stir 40～60min, add ionogen and water, stir 40～60min and obtain high solid content amido silicone oil microemulsion.
The strong stirring rake of shearing of the employing of described stirring, mixing speed is 50r/min～2000r/min.
The temperature that described preparation method suits is 5 ℃～80 ℃, when winter temperature is low, needs suitably heating.
Described preparation method is anti-phase (anti-phase) emulsion process, at first mix by emulsifying agent and silicone oil, then by add assistant for emulsifying agent, power and water is separated the emulsion that matter is prepared the co-continuous phase structure between O/W and W/O, becomes the amido silicone oil microemulsion of O/W during use by dilution.
The high viscosity of amido silicon oil and low surface tension have determined its more difficult emulsification, the many solid contents of amino silicon oil emulsion on the domestic market are not high now, be below 40%, what adopt is that the emulsion polymerization solid content is high or adopt the positive emulsion process to cause particle diameter bigger more, and particle size of emulsion and distribution thereof have bigger influence to the result of use of amino silicon oil emulsion, particle diameter is more little, and performances such as the moulding property of fiber, film density, pliability can be greatly improved.The present invention adopts the anti-phase emulsion process to prepare the high solids content microemulsion of (surpassing 70%), and particle diameter greatly reduces the transportation and the storage cost of amino silicon oil emulsion below 100nm, and smaller particle size has improved its use properties.
The amido silicone oil microemulsion of the inventive method preparation is a doubly-linked ideotype structure, has after the dilution that particle diameter is little, narrowly distributing, solid content can reach higherly, are 20%～80% (w/w).And preparation process is simple, process is easy to control.
Embodiment
Embodiment 1
Adding 140g viscosity in the beaker of 250ml is 850mPas, the ammonia value is 0.38 amido silicon oil, add the composite emulsifying agent of secondary octyl phenol polyethenoxy ether (TX-7 and TX-10), HLB value after emulsifying agent is composite is 13.0, the emulsifying agent consumption is 29% of an amido silicon oil quality, stirs 40min down with the strong stirring rake 400r/min that shears, and adds assistant for emulsifying agent, assistant for emulsifying agent comprises 10% propyl carbinol, 1.15% acetate, water 15g continues to stir 40min, the KCl (being dissolved in advance in the 8g water) of adding 0.1%, add the about 10g of water, continue to stir 40min, can contain the viscous emulsion of more white bubble, bubble collapse after placement for some time is transparence.It is amido silicone oil microemulsion of the present invention.
Weighting method claims to such an extent that solid content is about 78%, when being diluted with water to solid content 10%, obtains the blue light transparent micro emulsion, and it is 5.7 that acidometer is measured its pH value, and recording particle size of emulsion with laser particle analyzer is 23.2nm less than the equal particle diameter of body, and number average bead diameter is 13.6nm.
Annotate: the propyl carbinol of 10% described in the embodiment, 1.15% acetate, 0.1% KCl are benchmark with the quality of amido silicon oil all.
Embodiment 2
According to the operation of embodiment 1, amido silicon oil is used instead and is that viscosity 1000mPas, composite emulsifier use instead and is HLB value 12.8, and other conditions are constant, the preparation amido silicone oil microemulsion.Solid content is 72 ± 2%, and the particle diameter that laser particle analyzer records microemulsion is 64.6nm.
Embodiment 3
According to the operation of embodiment 1, amido silicon oil is used instead and is that viscosity 500mPas, composite emulsifier use instead and is HLB value 13.1, and other conditions are constant, the preparation amido silicone oil microemulsion.Solid content is that the particle diameter that 76 ± 2% laser particle analyzers record microemulsion is 24.6nm
Embodiment 4
According to the operation of embodiment 1, the composite type of emulsifying agent is used instead and is TX-7 and fatty alcohol-polyoxyethylene ether (AEO-9), and other conditions are constant, the preparation amido silicone oil microemulsion.Solid content is about 75%, and the particle diameter that laser particle analyzer records microemulsion is 83.2nm.
Embodiment 5
According to the operation of embodiment 1, propyl carbinol is used instead and is n-propyl alcohol and Pentyl alcohol mixture in the assistant for emulsifying agent, and n-propyl alcohol and Pentyl alcohol part by weight are 2.5: 1, and other conditions are constant, the preparation amido silicone oil microemulsion.Solid content is 73 ± 2%, and the particle diameter that laser particle analyzer records microemulsion is 60.3nm.
Embodiment 6
According to the operation of embodiment 1, amido silicon oil is used instead to the ammonia value is 0.26, acetate consumption 1% in the assistant for emulsifying agent, and other conditions are constant, the preparation amido silicone oil microemulsion.Solid content is about 75%, and the particle diameter that laser particle analyzer records microemulsion is 56.2nm.
Embodiment 7
According to the operation of embodiment 1, ionogen is used instead and is sodium-chlor, and other conditions are constant, the preparation amido silicone oil microemulsion.Solid content is about 77%, and the particle diameter that laser particle analyzer records microemulsion is 63.2nm.
Claims (7)
1. the preparation method of an amido silicone oil microemulsion is characterized in that:
Adding 140g viscosity in the beaker of 250ml is that 850mPas, ammonia value are 0.38 amido silicon oil, add emulsifying agent 40.6g again, with the stirring rake of strong shearing after stirring 40min under the 400r/min condition, add assistant for emulsifying agent and 15g water again, continue to stir 40min, add KCl 0.14g again, this KCl is dissolved in the 8g water in advance, add water 10g, continue to stir 40min, obtain amido silicone oil microemulsion after leaving standstill froth breaking;
Described emulsifying agent is by secondary octyl phenol polyethenoxy ether type emulsifying agent TX-7 and TX-10 is composite forms, and the hydrophile-lipophile balance value of the emulsifying agent after composite is 13.0;
Described assistant for emulsifying agent is propyl carbinol 14g and acetate 1.61g.
2. the preparation method of an amido silicone oil microemulsion is characterized in that:
In the beaker of 250ml, add 140g viscosity and be 1000mPas, ammonia value and be in 0.38 the amido silicon oil, add emulsifying agent 40.6g again, with the stirring rake of strong shearing after stirring 40min under the 400r/min condition, add assistant for emulsifying agent and 15g water again, continue to stir 40min, add KCl 0.14g again, this KCl is dissolved in the 8g water in advance, add water 10g, continue to stir 40min, obtain amido silicone oil microemulsion after leaving standstill froth breaking;
Described emulsifying agent is by secondary octyl phenol polyethenoxy ether type emulsifying agent TX-7 and TX-10 is composite forms, and the hydrophile-lipophile balance value of the emulsifying agent after composite is 12.8;
Described assistant for emulsifying agent is propyl carbinol 14g and acetate 1.61g.
3. the preparation method of an amido silicone oil microemulsion is characterized in that:
Adding 140g viscosity in the beaker of 250ml is that 500mPas, ammonia value are 0.38 amido silicon oil, add emulsifying agent 40.6g again, with the stirring rake of strong shearing after stirring 40min under the 400r/min condition, add assistant for emulsifying agent and 15g water again, continue to stir 40min, add KCl 0.14g again, this KCl is dissolved in the 8g water in advance, add water 10g, continue to stir 40min, obtain amido silicone oil microemulsion after leaving standstill froth breaking;
Described emulsifying agent is by secondary octyl phenol polyethenoxy ether type emulsifying agent TX-7 and TX-10 is composite forms, and the hydrophile-lipophile balance value of the emulsifying agent after composite is 13.1;
Described assistant for emulsifying agent is propyl carbinol 14g and acetate 1.61g.
4. the preparation method of an amido silicone oil microemulsion is characterized in that:
Adding 140g viscosity in the beaker of 250ml is that 850mPas, ammonia value are 0.38 amido silicon oil, add emulsifying agent 40.6g again, with the stirring rake of strong shearing after stirring 40min under the 400r/min condition, add assistant for emulsifying agent and 15g water again, continue to stir 40min, add KCl 0.14g again, this KCl is dissolved in the 8g water in advance, add water 10g, continue to stir 40min, obtain amido silicone oil microemulsion after leaving standstill froth breaking;
Described emulsifying agent is by secondary octyl phenol polyethenoxy ether type emulsifying agent TX-7 and fatty alcohol-polyoxyethylene ether AEO-9 is composite forms, and the hydrophile-lipophile balance value of the emulsifying agent after composite is 13.0;
Described assistant for emulsifying agent is propyl carbinol 14g and acetate 1.61g.
5. the preparation method of an amido silicone oil microemulsion is characterized in that:
Adding 140g viscosity in the beaker of 250ml is that 850mPas, ammonia value are 0.38 amido silicon oil, add emulsifying agent 40.6g again, with the stirring rake of strong shearing after stirring 40min under the 400r/min condition, add assistant for emulsifying agent and 15g water again, continue to stir 40min, add KCl 0.14g again, this KCl is dissolved in the 8g water in advance, add water 10g, continue to stir 40min, obtain amido silicone oil microemulsion after leaving standstill froth breaking;
Described emulsifying agent is by secondary octyl phenol polyethenoxy ether type emulsifying agent TX-7 and TX-10 is composite forms, and the hydrophile-lipophile balance value of the emulsifying agent after composite is 13.0;
Described assistant for emulsifying agent is n-propyl alcohol 10g, Pentyl alcohol 4g and acetate 1.61g.
6. the preparation method of an amido silicone oil microemulsion is characterized in that:
In the beaker of 250ml, add 140g viscosity and be 850mPas, ammonia value and be in 0.26 the amido silicon oil, add emulsifying agent 40.6g again, with the stirring rake of strong shearing after stirring 40min under the 400r/min condition, add assistant for emulsifying agent and 15g water again, continue to stir 40min, add KCl 0.14g again, this KCl is dissolved in the 8g water in advance, add water 10g, continue to stir 40min, obtain amido silicone oil microemulsion after leaving standstill froth breaking;
Described emulsifying agent is by secondary octyl phenol polyethenoxy ether type emulsifying agent TX-7 and TX-10 is composite forms, and the hydrophile-lipophile balance value of the emulsifying agent after composite is 13.0;
Described assistant for emulsifying agent is propyl carbinol 14g and acetate 1.4g.
7. the preparation method of an amido silicone oil microemulsion is characterized in that:
Adding 140g viscosity in the beaker of 250ml is that 850mPas, ammonia value are 0.38 amido silicon oil, add emulsifying agent 40.6g again, with the stirring rake of strong shearing after stirring 40min under the 400r/min condition, add assistant for emulsifying agent and 15g water again, continue to stir 40min, add NaCl 0.14g again, this NaCl is dissolved in the 8g water in advance, add water 10g, continue to stir 40min, obtain amido silicone oil microemulsion after leaving standstill froth breaking;
Described emulsifying agent is by secondary octyl phenol polyethenoxy ether type emulsifying agent TX-7 and TX-10 is composite forms, and the hydrophile-lipophile balance value of the emulsifying agent after composite is 13.0;
Described assistant for emulsifying agent is propyl carbinol 14g and acetate 1.61g.
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| CN101497744B (en) * | 2008-07-29 | 2011-01-12 | 浙江传化股份有限公司 | Amino silicon oil emulsion and preparation thereof |
| CN102995443A (en) * | 2012-11-29 | 2013-03-27 | 常熟市三利经纬编织造有限公司 | Manufacture method of waterproof polyester fabric |
| CN103059829B (en) * | 2013-01-25 | 2014-08-20 | 中国石油大学(华东) | Nanometer emulsion type water control fracturing fluid for tight gas reservation well and preparation method thereof |
| CN106700095B (en) * | 2016-12-30 | 2019-04-26 | 江西蓝星星火有机硅有限公司 | A kind of super large partial size height glues the preparation method of methyl-silicone oil emulsion |
| CN106633103B (en) * | 2016-12-30 | 2019-06-04 | 江西蓝星星火有机硅有限公司 | A kind of preparation method of the polysiloxane emulsion of high internal phase viscosities |
| CN109280171B (en) * | 2018-08-28 | 2021-08-06 | 上海树脂厂有限公司 | Small-particle-size amino silicone oil microemulsion and preparation method and application thereof |
| CN112646487A (en) * | 2020-12-24 | 2021-04-13 | 南京曦瑞生物科技有限公司 | Water-based silicone oil and preparation method thereof |
| CN113185710B (en) * | 2021-04-26 | 2021-11-23 | 广东赛安特新材料有限公司 | Amino silicone oil emulsion and preparation method thereof |
| CN113717707A (en) * | 2021-05-25 | 2021-11-30 | 西安石油大学 | Environment-friendly deep nano-drainage agent for compact gas well and preparation method thereof |
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Assignee: Zhejiang in Yiwu Province Li industry and Trade Co., Ltd. Assignor: Zhejiang University Contract record no.: 2011330000316 Denomination of invention: High solid content amido silicone oil microemulsion and method of producing the same Granted publication date: 20110112 License type: Exclusive License Open date: 20080227 Record date: 20110420 |
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