CN103306139A - Environment-friendly fluorinated polysiloxane waterproof agent - Google Patents
Environment-friendly fluorinated polysiloxane waterproof agent Download PDFInfo
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- CN103306139A CN103306139A CN2013102876985A CN201310287698A CN103306139A CN 103306139 A CN103306139 A CN 103306139A CN 2013102876985 A CN2013102876985 A CN 2013102876985A CN 201310287698 A CN201310287698 A CN 201310287698A CN 103306139 A CN103306139 A CN 103306139A
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Abstract
The invention discloses an environment-friendly fluorinated polysiloxane waterproof agent. In order to avoid the fact that a textile fabric waterproof agent contains PFOA and PFOS, a fluorosilicone emulsion without perfluorooctanoic acid (PFOA) and perfluorooctane sulfonates (PFOS) is prepared to replace an acrylic resin emulsion which is widely used at present so as to prevent the problem that PFOA and PFOS residues are contained in textile fabric after waterproof treatment. The waterproof agent comprises the following components in percentage by weight: 60%-80% of polysiloxane with fluoro-substitution methyl hydrogenous side chain containing polyoxy alkyl ether, 10%-15% of a solvent and 10%-20% of water. The solvent is one of isopropyl alcohol, butoxyethanol and diethyleneglycolmonobutylether.
Description
Technical field
The present invention relates to the textile water proof field, specifically is a kind of environment-friendly type fluorine silicon waterproofing agent.
Background technology
Human relation with chemical industry is very close, in the modern life, almost all be unable to do without chemical products whenever and wherever possible, from clothing, food, live, material life such as capable is to cultural lives such as culture and arts, amusements, all needs chemical products to serve for it.Some chemical products plays epoch-making important function in human development history.Their production and application, even representing certain historical stage of human civilization.
At present, what be used for the textile fabric WATER REPELLENT TREATMENT is the perfluoroalkyl acrylate polymer emulsion, wherein may contain PFOA (perfluorooctanoic acid) or PFOS (perfluoro octane sulfonate).Owing to can in environment or human body, discharge after PFOA decomposes, environment and human body are caused toxic hazard, therefore European Union proposes requirement for restriction to PFOA in Related product, and the material of PFOS for being present in environment lastingly, having biological savings property and the mankind are harmful to, current PFOS in the exported product material by wide limits.PFOA has in the different characteristic of other persistent pollutants with PFOS.The Kow that at first is them can not be determined, and secondly they are to be enriched in the blood, and they are not aromatic compounds in addition, do not have phenyl ring.This class material has the functional group of polarity, can be water-soluble preferably.But they also have the carbochain of a long perfluoroalkyl simultaneously, and the hydrogen atom on the carbochain is all replaced by fluorine atom.Because the electrophilic effect of fluorine atom, the fluorine atom of its carbochain is to be negative electricity (partial charge) to (water) environment.So in water PFOA and PFOS what present is the structure of a big negative electricity, therefore, its influence to environment is very big.
Also there is not a kind of water resistance good at present, little to environmental hazard, and do not contain the environment-friendly type fluorine silicon waterproofing agent of PFOA and PFOS.
Summary of the invention
The present invention provides a kind of water resistance good just at above technical problem, and is little to environmental hazard, and do not contain the environment-friendly type fluorine silicon waterproofing agent of PFOA and PFOS.
The present invention is achieved through the following technical solutions.
A kind of environment-friendly type fluorine silicon waterproofing agent, its constituent is (percentage by weight): the side chain of hydrogen contains the polysiloxanes 60%～80% of polyoxy alkyl ether, solvent 10%～15%, water 10%～20% on the fluorine replacement part methyl.Solvent is isopropyl alcohol, ethylene glycol monobutyl ether, a kind of in the diethylene glycol monobutyl ether.
The present invention also provides a kind of method of environment-friendly type fluorine silicon waterproofing agent, comprises following a few step:
The first step, the preparation fluorine replaces the hydrogeneous polysiloxanes of side chain of hydrogen on the part methyl:
The polysiloxanes that octamethylcy-clotetrasiloxane, side chain is hydrogeneous, fluorine replace under the cyclosiloxane of hydrogen on the part methyl, HMDO is done strong acid catalyst at the concentrated sulfuric acid the condition and react, and the fluorine that can obtain having certain viscosity replaces the hydrogeneous polysiloxanes of side chain of hydrogen on the part methyl;
In second step, the side chain of hydrogen contains the polysiloxanes of polyoxy alkyl ether on the preparation fluorine replacement part methyl:
With the fluorine for preparing in the first step step replace the hydrogeneous polysiloxanes of the side chain of hydrogen on the part methyl and a certain amount of allyl alcohol polyoxy alkyl ether with isopropyl alcohol solution of chloroplatinic acid as catalyst, at a certain temperature, carry out hydrosilylation, the side chain that the fluorine that can obtain having certain viscosity replaces hydrogen on the part methyl contains the polysiloxanes of polyoxy alkyl ether;
The 3rd step, preparation environment-friendly type fluorine silicon waterproofing agent emulsion:
The polysiloxanes that the side chain that the fluorine of preparation replaces hydrogen on the part methyl in rapid step by step with second contains the polyoxy alkyl ether adds certain amount of solvent, adds water and stirs, and can make environment-friendly type fluorine silicon waterproofing agent emulsion.
During use; it is an amount of to get environment-friendly type fluorine silicon waterproofing agent emulsion of the present invention; can carry out WATER REPELLENT TREATMENT to textiles after the dilution; because environment-friendly type fluorine silicon waterproofing agent of the present invention does not contain PFOA and PFOS; thus avoided textile fabric through after the WATER REPELLENT TREATMENT on textiles residual PFOA and PFOS, safe and efficient.
Description of drawings
In the accompanying drawing, Fig. 1 is the cyclosiloxane molecular structural formula that fluorine of the present invention replaces hydrogen on the part methyl, Fig. 2 is the hydrogeneous polysiloxane molecule structural formula of side chain that fluorine of the present invention replaces hydrogen on the part methyl, Fig. 3 is the polysiloxane molecule structural formula that the side chain of hydrogen on the fluorine replacement part methyl of the present invention contains the polyoxy alkyl ether, wherein:
R1, R2, R3, R4, R5 are CF
3Perhaps CH
2CF
3Perhaps CH
2CH
2CF
3, R6 is H, R7 is CH
2-CH-CH
2O-(C
3H
6O)
y-(C
2H
4O)
x-H.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
The first step, the preparation fluorine replaces the hydrogeneous polysiloxanes of side chain of hydrogen on the part methyl:
Cyclosiloxane, 25Kg HMDO that the polysiloxanes that 600Kg octamethylcy-clotetrasiloxane, 100Kg side chain is hydrogeneous, 200Kg fluorine replace hydrogen on the part methyl drop in the still, add the 30Kg concentrated sulfuric acid, stirring at normal temperature 12 hours, add sodium bicarbonate, regulating the pH value is 7, filter, the fluorine that can obtain viscosity and be 200cps replaces the hydrogeneous polysiloxanes of side chain of hydrogen on the part methyl;
In second step, the side chain of hydrogen contains the polysiloxanes of polyoxy alkyl ether on the preparation fluorine replacement part methyl:
Hydrogeneous polysiloxanes and the 200Kg allyl alcohol polyoxy alkyl ether of side chain that the fluorine for preparing in the 100Kg first step step is replaced hydrogen on the part methyl drops in the still, heating, be warmed up to 100 ℃, add the 1.5g isopropyl alcohol solution of chloroplatinic acid as catalyst, carry out hydrosilylation, the side chain of preparing hydrogen on the fluorine replacement part methyl with certain viscosity contains the polysiloxanes of polyoxy alkyl ether;
The 3rd step, preparation environment-friendly type fluorine silicon waterproofing agent emulsion:
The polysiloxanes that the side chain that the fluorine of preparation replaced hydrogen on the part methyl during 100Kg second is rapid step by step contains the polyoxy alkyl ether adds the solvent (solvent be in isopropyl alcohol, ethylene glycol monobutyl ether, the diethylene glycol monobutyl ether a kind of) of 20Kg, add 28Kg water, fully stir, can make solid content and be 30% environment-friendly type fluorine silicon waterproofing agent emulsion.
During use; it is an amount of to get environment-friendly type fluorine silicon waterproofing agent emulsion of the present invention; can carry out WATER REPELLENT TREATMENT to textiles after the dilution; because environment-friendly type fluorine silicon waterproofing agent of the present invention does not contain PFOA and PFOS; thus avoided textile fabric through after the WATER REPELLENT TREATMENT on textiles residual PFOA and PFOS, safe and efficient.
Claims (3)
1. environment-friendly type fluorine silicon waterproofing agent, its constituent is (percentage by weight): the side chain that fluorine replaces hydrogen on the part methyl contains the polysiloxanes 60%～80% of polyoxy alkyl ether, solvent 10%～15%, water 10%～20%.
2. according to the described a kind of environment-friendly type fluorine silicon waterproofing agent of claim 1, it is characterized in that described solvent is isopropyl alcohol, ethylene glycol monobutyl ether, a kind of in the diethylene glycol monobutyl ether.
3. the preparation method of an environment-friendly type fluorine silicon waterproofing agent emulsion comprises following a few step:
The first step, the preparation fluorine replaces the hydrogeneous polysiloxanes of side chain of hydrogen on the part methyl:
The polysiloxanes that octamethylcy-clotetrasiloxane, side chain is hydrogeneous, fluorine replace under the cyclosiloxane of hydrogen on the part methyl, HMDO is done strong acid catalyst at the concentrated sulfuric acid the condition and react, and the fluorine that can obtain having certain viscosity replaces the hydrogeneous polysiloxanes of side chain of hydrogen on the part methyl;
In second step, the side chain of hydrogen contains the polysiloxanes of polyoxy alkyl ether on the preparation fluorine replacement part methyl:
With the fluorine for preparing in the first step step replace the hydrogeneous polysiloxanes of the side chain of hydrogen on the part methyl and a certain amount of allyl alcohol polyoxy alkyl ether with isopropyl alcohol solution of chloroplatinic acid as catalyst, at a certain temperature, carry out hydrosilylation, the side chain that the fluorine that can obtain having certain viscosity replaces hydrogen on the part methyl contains the polysiloxanes of polyoxy alkyl ether;
The 3rd step, preparation environment-friendly type fluorine silicon waterproofing agent emulsion:
The polysiloxanes that the side chain that the fluorine of preparation replaces hydrogen on the part methyl in rapid step by step with second contains the polyoxy alkyl ether adds certain amount of solvent, adds water and stirs, and can make environment-friendly type fluorine silicon waterproofing agent emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2013102876985A CN103306139A (en) | 2013-07-10 | 2013-07-10 | Environment-friendly fluorinated polysiloxane waterproof agent |
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| CN2013102876985A CN103306139A (en) | 2013-07-10 | 2013-07-10 | Environment-friendly fluorinated polysiloxane waterproof agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103669004A (en) * | 2013-11-22 | 2014-03-26 | 南通市通州区川姜镇盛世王朝家用纺织品设计工作室 | Fabric waterproof finishing agent |
| CN107916072A (en) * | 2017-10-31 | 2018-04-17 | 广州广微包装科技有限公司 | A kind of spray-type watery water-proofing agent and preparation method thereof |
| CN110093782A (en) * | 2019-05-29 | 2019-08-06 | 杭州美高华颐化工有限公司 | A kind of preparation method of the low siliceous degreaser of bubble |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845144A (en) * | 2009-12-16 | 2010-09-29 | 上海诺科生物科技有限公司 | Water-based organic silicon-fluorine resin waterproof agent and preparation method thereof |
| CN101868493A (en) * | 2007-11-21 | 2010-10-20 | 荷兰联合利华有限公司 | Novel compounds for fabric treatment |
| CN102164976A (en) * | 2008-09-15 | 2011-08-24 | 大金工业株式会社 | Fluorosilicones and surface treatment agent |
| EP2505602A1 (en) * | 2011-03-29 | 2012-10-03 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane and cosmetic containing it |
-
2013
- 2013-07-10 CN CN2013102876985A patent/CN103306139A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101868493A (en) * | 2007-11-21 | 2010-10-20 | 荷兰联合利华有限公司 | Novel compounds for fabric treatment |
| CN102164976A (en) * | 2008-09-15 | 2011-08-24 | 大金工业株式会社 | Fluorosilicones and surface treatment agent |
| CN101845144A (en) * | 2009-12-16 | 2010-09-29 | 上海诺科生物科技有限公司 | Water-based organic silicon-fluorine resin waterproof agent and preparation method thereof |
| EP2505602A1 (en) * | 2011-03-29 | 2012-10-03 | Shin-Etsu Chemical Co., Ltd. | Organopolysiloxane and cosmetic containing it |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103669004A (en) * | 2013-11-22 | 2014-03-26 | 南通市通州区川姜镇盛世王朝家用纺织品设计工作室 | Fabric waterproof finishing agent |
| CN107916072A (en) * | 2017-10-31 | 2018-04-17 | 广州广微包装科技有限公司 | A kind of spray-type watery water-proofing agent and preparation method thereof |
| CN110093782A (en) * | 2019-05-29 | 2019-08-06 | 杭州美高华颐化工有限公司 | A kind of preparation method of the low siliceous degreaser of bubble |
| CN110093782B (en) * | 2019-05-29 | 2021-05-18 | 杭州美高华颐化工有限公司 | Preparation method of low-foam silicon-containing degreasing agent |
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Application publication date: 20130918 |