CN101435160B - Organosilicon fluorine multifunctional fabric finishing agent and preparing method thereof - Google Patents
Organosilicon fluorine multifunctional fabric finishing agent and preparing method thereof Download PDFInfo
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- CN101435160B CN101435160B CN2008101633631A CN200810163363A CN101435160B CN 101435160 B CN101435160 B CN 101435160B CN 2008101633631 A CN2008101633631 A CN 2008101633631A CN 200810163363 A CN200810163363 A CN 200810163363A CN 101435160 B CN101435160 B CN 101435160B
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- polyoxyethylene ether
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Abstract
The invention discloses an organic fluosilicic multifunctional textile finishing agent. Aiming at the problem existing in the current commercially available organic silicone finishing agent, a small amount of organic fluorin radical is introduced to the organic silicone finishing agent; under the condition of not changing the original effect of the organic silicone finishing agent, the smooth property of the finishing agent is further improved, simultaneously, water-and-oil-repellent effect is increased to a certain extent; the finishing agent is innocuous and pollution-free, and has high cost performance and wide application prospect. The invention also discloses a preparation method of the organic fluosilicic multifunctional textile finishing agent which has simple technological operation, the prepared latex has strong stability and difficult emulsion breaking, delamination does not happen after the latex is placed for a long time, the use is simple, the hand-feeling of the textile is obviously improved and the additional value is increased.
Description
Technical field
The present invention relates to a kind of fabric finishing agent, particularly a kind of organosilicon fluorine multifunctional fabric finishing agent and preparation method thereof.
Background technology
Organic silicon emulsion is a kind of important finishing agent in the fabric last handling process, and it can improve the feel of fabric significantly, makes it have feels such as smooth, soft, plentiful.Early stage fabric of organosilicon finishing agent mainly is the mechanical impurity of dimethicone and containing hydrogen silicone oil, and this organosilicon is owing to lack active group, and to combine fastness poor with fabric, be easy to come off, and the fabric feeling after handling is also poor.Having occurred the high viscosity hydroxy silicon oil subsequently is the flexible smooth finishing agent of main component, but this type of finishing agent effect is general, and exists stability of emulsion poor, easily layering, shortcomings such as easy breakdown of emulsion require high to environment for use, easy floating oil can damage textiles in the use.Selling more in recent years on the market is fabric sofetening smoothing processing agent based on amido silicon oil, though reached soft effect preferably, smooth property is not enough.Simultaneously several organic silicon emulsions are carried out compositely, the multifunctional assistant of making has been obtained effect preferably
Summary of the invention
The deficiency that the present invention is directed to existing organosilicon textile finishing technology provides a kind of organosilicon fluorine multifunctional finishing agent and preparation technology thereof, in organic silicone finishing agent, introduce a spot of Organic fluoride group, do not changing under the former situation about producing effect of organic silicone finishing agent, further improve the smooth property of finishing agent, also increased the effect of water and oil repellant simultaneously to a certain extent.
For achieving the above object, the present invention takes following technical scheme:
A kind of organosilicon fluorine multifunctional fabric finishing agent by weight percentage, is grouped into by following one-tenth:
Amido silicon oil: 5～20%
Long carbochain modified amino silicon oil: 5～20%
Fluorine-containing modified silicon oil: 5～20%
Emulsifying agent: 3～10%
Assistant for emulsifying agent: 1～10%
Glacial acetic acid: 0.5～1%
Surplus is a deionized water;
Described amido silicon oil is:
R is CH
2CH
2CH
2NHCH
2CH
2NH
2M1=10～2000, n1=1～200;
Described long carbochain modified amino silicon oil is:
R
1Be CH
2(CH
2)
qCH
3
m2＝10～2000，n2＝1～200，p2＝1～200，q＝1～20；
Described fluorine-containing modified silicon oil is:
R
2Be CH
2CH
2CH
2NHCH
2CH
2NHCF
2CF (CF
3) O-[CF
2CF (CF
3) O]
n-H;
m3＝10～2000，n3＝1～200，p3＝1～200，n＝0～9。
Three kinds of compositions all can be provided for oneself, and the preparation method is as follows:
The preparation of amido silicon oil: with D
4(octamethylcy-clotetrasiloxane) or DMC are (with D
4Mixture for main body), amino silicane coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, H
2O, catalyst KOH and promoter dimethyl sulfoxide (DMSO) reacted 1～15 hour under 80～150 ℃ of temperature, and inorganic acid or the organic acid with equimolar amounts neutralizes then, obtains amido silicon oil.It feeds intake, and mole is comparable to be: D
4Or DMC: amino silicane coupling agent: H
2O: catalyst KOH: promoter=1: (0.05～0.45): (0.02～0.35): (0.001～0.008): (0.0009～0.008), the used inorganic acid that neutralizes is watery hydrochloric acid or dilute sulfuric acid, organic acid is formic acid, acetate, propionic acid, butyric acid or valeric acid, the ammonia value scope of gained amido silicon oil is: 0.1～0.9, and viscosity 2000～200000mP.S.
The preparation of long carbochain modified amino silicon oil: with D
4Or DMC, amino silicane coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, long carbochain silane coupler dodecyl methyl dimethoxy silane, H
2O, catalyst KOH and promoter dimethyl sulfoxide (DMSO) reacted 1～15 hour under 80～150 ℃ of temperature, and inorganic acid or the organic acid with equimolar amounts neutralizes then, obtained long carbochain modified amino silicon oil.Its molar ratio can be: DMC: amino silicane coupling agent: long carbochain silane coupler: H
2O: catalyst: promoter=1: (0.05～0.45): (0.05～0.45): (0.02～0.35): (0.001～0.008): (0.0009～0.008), the used inorganic acid that neutralizes is watery hydrochloric acid or dilute sulfuric acid, organic acid is formic acid, acetate, propionic acid, butyric acid or valeric acid, the ammonia value scope of the long carbochain modified amino silicon oil of gained is: 0.2～0.8, and viscosity 5000～100000mP.S.
The preparation of fluorine-containing modified silicon oil: at first, prepare amido silicon oil according to the method described above, then amido silicon oil, perfluoro propene oxid, isopropyl alcohol and catalyst KOH are added in the reaction bulb, compressive reaction 3～12h, use the glacial acetic acid catalyst neutralisation, rotary evaporation removes and desolvates, and obtains fluorine-containing modified silicon oil.
Described emulsifying agent is a compound emulsifying agent, be any two kinds mixture in fatty alcohol-polyoxyethylene ether-3 (AEO-3), fatty alcohol-polyoxyethylene ether-9 (AEO-9), the isomery alcohol polyoxyethylene ether, as long as the HLB value of the HLB value of compound emulsifying agent and emulsified system is approaching; Mentioned emulsifier all can adopt the commercially available prod, as the XP series of isomery alcohol polyoxyethylene ether, XL series etc.Be preferably the mixture of fatty alcohol-polyoxyethylene ether-3 and fatty alcohol-polyoxyethylene ether-9, perhaps the mixture of fatty alcohol-polyoxyethylene ether-3 and isomery alcohol polyoxyethylene ether XL50.
Described assistant for emulsifying agent mainly is C
2～C
8Alcohol, as propylene glycol, n-amyl alcohol, n-hexyl alcohol etc., consumption is 1～10% of a finishing agent gross weight, preferred 2～5%.
The preparation technology of above-mentioned organosilicon fluorine multifunctional fabric finishing agent, comprise: at first, adding amido silicon oil, long carbochain modified amino silicon oil, fluorine-containing modified silicon oil, emulsifying agent and assistant for emulsifying agent in reactor mixes, stir 10min, add the part deionized water then earlier, stir 20min, add glacial acetic acid and regulate pH value to 6～7, add remaining deionized water again, stir 1～2h and can obtain microemulsion.
Compare of the present invention having the following advantages with existing organic silicone finishing agent:
(1) adds long carbochain modified amino silicon oil in this fabric finishing agent, when guaranteeing soft effect, also further strengthened smooth effect.
(2) introduced the Organic fluoride group in this fabric finishing agent, it has good water and oil repellant effect, though price is higher, in the present invention, application quantity is less, and only uses on a small quantity, and effect can be improved significantly.
(3) this preparation technology is simple to operate, and stability of emulsion is strong, is difficult for breakdown of emulsion, and long-term storage is not stratified, uses simply, has significantly improved the feel of textiles, and has improved added value.
The specific embodiment
Embodiment 1
In weight portion, 20 parts of amido silicon oils, 5 parts of long carbochain modified amino silicon oils, 5 parts of fluorine-containing modified silicon oils, 10 parts of emulsifying agents (mass ratio of AEO-3 and AEO-9 is 1: 1), 3 parts of n-butanols stir 10min, add 30 parts of deionized waters then, stir 20min, add glacial acetic acid and regulate pH value to 6～7 for 0.5 part, add deionized water to 100 part, stir 1～2h, emulsification obtains transparency emulsion.
Embodiment 2
In weight portion, 15 parts of amido silicon oils, 10 parts of long carbochain modified amino silicon oils, 5 parts of fluorine-containing modified silicon oils, 10 parts of emulsifying agents (mass ratio of AEO-9 and XP50 is 2: 1), 3 parts of n-hexyl alcohols stir 10min, add 30 parts of deionized waters then, stir 20min, add glacial acetic acid and regulate pH value to 6～7 for 0.5 part, add deionized water to 100 part, stir 1～2h, emulsification obtains transparency emulsion.
Embodiment 3
In weight portion, 10 parts of amido silicon oils, 15 parts of long carbochain modified amino silicon oils, 5 parts of fluorine-containing modified silicon oils, 10 parts of emulsifying agents (mass ratio of AEO-3 and AEO-9 is 2: 3), 3 parts of n-butanols stir 10min, add 30 parts of deionized waters then, stir 20min, add glacial acetic acid and regulate pH value to 6～7 for 0.7 part, add deionized water to 100 part, stir 1～2h, emulsification obtains transparency emulsion.
Embodiment 4
In weight portion, 5 parts of amido silicon oils, 20 parts of long carbochain modified amino silicon oils, 5 parts of fluorine-containing modified silicon oils, 10 parts of emulsifying agents (mass ratio of AEO-3 and AEO-9 is 1: 2), 3 parts of n-amyl alcohols stir 10min, add 30 parts of deionized waters then, stir 20min, add glacial acetic acid and regulate pH value to 6～7 for 0.6 part, add deionized water to 100 part, stir 1～2h, emulsification obtains transparency emulsion.
Embodiment 5
In weight portion, 5 parts of amido silicon oils, 15 parts of long carbochain modified amino silicon oils, 10 parts of fluorine-containing modified silicon oils, 10 parts of emulsifying agents (mass ratio of AEO-3 and XL50 is 3: 5), 3 parts of n-butanols stir 10min, add 30 parts of deionized waters then, stir 20min, add glacial acetic acid and regulate pH value to 6～7 for 1 part, add deionized water to 100 part, stir 1～2h, emulsification obtains transparency emulsion.
Embodiment 6
In weight portion, 5 parts of amido silicon oils, 10 parts of long carbochain modified amino silicon oils, 15 parts of fluorine-containing modified silicon oils, 10 parts of emulsifying agents (mass ratio of AEO-3 and XL50 is 1: 1), 3 parts of propylene glycol stir 10min, add 30 parts of deionized waters then, stir 20min, add glacial acetic acid and regulate pH value to 6～7 for 0.5 part, add ionized water to 100 part, stir 1～2h, emulsification obtains transparency emulsion.
Embodiment 7
In weight portion, 5 parts of amido silicon oils, 5 parts of long carbochain modified amino silicon oils, 20 parts of fluorine-containing modified silicon oils, 10 parts of emulsifying agents (mass ratio of AEO-3 and XL50 is 2: 1), 3 parts of n-butanols stir 10min, add 30 parts of deionized waters then, stir 20min, add glacial acetic acid and regulate pH value to 6～7 for 1 part, add ionized water to 100 part, stir 1～2h, emulsification obtains transparency emulsion.
Performance test:
The emulsion that makes in the various embodiments described above is made into the solution of 40g/L respectively, and bath raio 1: 20 is soaked two roll process by two cotton fabric is carried out measure of merit, after 3min is cured in 100 ℃ of oven dry, 160 ℃, measures the whiteness of fabric with the WSB-2 leucometer; Feel please the expert is blind be touched, evaluation rank (wherein 6 grades best, 1 grade the poorest).
Result such as following table:
Table 1 organosilicon fluorine multifunctional finishing agent serviceability
Claims (4)
1. organosilicon fluorine multifunctional fabric finishing agent by weight percentage, is grouped into by following one-tenth:
Amido silicon oil: 5～20%
Long carbochain modified amino silicon oil: 5～20%
Fluorine-containing modified silicon oil: 5～20%
Emulsifying agent: 3～10%
Assistant for emulsifying agent: 1～10%
Glacial acetic acid: 0.5～1%
Surplus is a deionized water;
Described amido silicon oil is:
R is CH
2CH
2CH
2NHCH
2CH
2NH
2M1=10～2000, n1=1～200;
Described long carbochain modified amino silicon oil is:
R
1Be CH
2(CH
2)
qCH
3
m2＝10～2000，n2＝1～200，p2＝1～200，q＝1～20；
Described fluorine-containing modified silicon oil is:
R
2Be CH
2CH
2CH
2NHCH
2CH
2NHCF
2CF (CF
3) O-[CF
2CF (CF
3) O]
n-H;
m3＝10～2000，n3＝1～200，p3＝1～200，n＝0～9；
Described emulsifying agent is any two kinds mixture in fatty alcohol-polyoxyethylene ether-3, fatty alcohol-polyoxyethylene ether-9, the isomery alcohol polyoxyethylene ether;
Described assistant for emulsifying agent is C
2～C
8Alcohol.
2. organosilicon fluorine multifunctional fabric finishing agent as claimed in claim 1, it is characterized in that: described emulsifying agent is the mixture of fatty alcohol-polyoxyethylene ether-3 and fatty alcohol-polyoxyethylene ether-9, perhaps the mixture of fatty alcohol-polyoxyethylene ether-3 and isomery alcohol polyoxyethylene ether XL50.
3. organosilicon fluorine multifunctional fabric finishing agent as claimed in claim 1 is characterized in that: described assistant for emulsifying agent consumption occupies 2～5% of machine fluosilicic multifunction finishing agent gross weight.
4. the preparation method of organosilicon fluorine multifunctional fabric finishing agent as claimed in claim 1, comprise, amido silicon oil, long carbochain modified amino silicon oil, fluorine-containing modified silicon oil, emulsifying agent and assistant for emulsifying agent are mixed, stir 10min, add the part deionized water then, stir 20min, add glacial acetic acid and regulate pH value to 6～7, add remaining deionized water again, stir 1～2h.
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747511B (en) * | 2010-01-20 | 2011-08-03 | 华东理工大学 | Polysiloxane containing fluorine and application thereof |
| CN102031692B (en) * | 2010-11-16 | 2012-09-26 | 南通大学 | Multifunctional organic silicon finishing agent and preparation method thereof |
| CN103437190B (en) * | 2013-08-29 | 2015-07-01 | 华南理工大学 | Amino-silicone oil softener containing fluorine group and quaternary ammonium salt group as well as preparation method and application thereof |
| CN103668948A (en) * | 2013-11-28 | 2014-03-26 | 南通市通州区大达麻纺织有限公司 | Three-proofing finishing agent for fabric |
| CN103757890B (en) * | 2013-12-31 | 2015-12-09 | 湖南东方时装有限公司 | A kind of western-style clothes finishing agent and preparation method thereof |
| CN105155280B (en) * | 2015-10-10 | 2016-05-04 | 珠海华大浩宏化工有限公司 | A kind of ice sense finishing agent and preparation method thereof |
| CN105421068A (en) * | 2015-12-31 | 2016-03-23 | 温天平 | Environmental protection waterproof cloth material and preparation method therefor |
| CN105821672A (en) * | 2016-06-03 | 2016-08-03 | 上海洋帆实业有限公司 | Nano hybridized SiO2 water-proofing agent and preparation method thereof |
| CN108484933B (en) * | 2018-05-10 | 2020-11-27 | 浙江科峰新材料有限公司 | Organic silicon emulsion and production process thereof |
| CN108677541A (en) * | 2018-05-31 | 2018-10-19 | 江苏尼美达科技有限公司 | The agent of wool fabric soft and bright and preparation method |
| CN112746365A (en) * | 2020-12-25 | 2021-05-04 | 江苏锐晟纺织科技有限公司 | Production process of high-hydrophobicity pure cotton super-soft waffle fabric and waffle fabric |
| CN112962159A (en) * | 2021-03-01 | 2021-06-15 | 太仓逸枫化纤有限公司 | High-strength polyester filament yarn, preparation method and preparation device |
| CN115161993A (en) * | 2022-05-25 | 2022-10-11 | 浙江理工大学 | Organic/inorganic bonding type composite antibacterial agent, preparation method and application thereof |
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| CN101003946A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳高分子材料有限公司 | Waterproof, grease proof treating compound of fluorine silicon modified polyurethane, and preparation method |
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Patent Citations (3)
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| EP1217119B1 (en) * | 2000-12-22 | 2004-04-21 | Shin-Etsu Chemical Co., Ltd. | Water-soluble, water/oil repellent treating composition and method of making |
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