CN105131177A - Environment-friendly type perfluoro fabric finishing agent and preparation method thereof - Google Patents
Environment-friendly type perfluoro fabric finishing agent and preparation method thereof Download PDFInfo
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- CN105131177A CN105131177A CN201510510343.7A CN201510510343A CN105131177A CN 105131177 A CN105131177 A CN 105131177A CN 201510510343 A CN201510510343 A CN 201510510343A CN 105131177 A CN105131177 A CN 105131177A
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Abstract
The invention discloses an environment-friendly type perfluoro fabric finishing agent and a preparation method thereof. An allyl perfluoroalkenoxybenzonate monomer and other acrylic monomers are subjected to copolymerization for obtaining an emulsion with stable properties, and the emulsion is applied to fabric finishing and performance detection, and is good in water and oil repellent performances. The disclosed fluorine-containing fabric finishing agent is capable of replacing C8 type fabric finishing agent, gives play to environment protection effect on the basis of endowing fabric with good water and oil repellent performances.
Description
Technical field
The present invention relates to textile finishing auxiliary agent field, particularly relate to a kind of environment-friendly type perfluor fabric finishing agent preparation method.
Background technology
As everyone knows, fluorine atom electronegativity is large, radius is little, large with carbon Cheng Jianhou bond energy, this makes fluorochemical surfactant have the characteristic of " three is high ", " two hate ", i.e. high surface, high heat-resistant stability, high chemical stability and hydrophobic and lyophobic property, therefore fluorochemical surfactant is widely used, and becomes the excellent finishing composition of the wide variety of substrates such as current fabric, leather, paper.
Fluorine-containing textile finishing agent can give fabric excellent refuse water and oil repellent energy, be that other fabric finishing agents are irreplaceable.Aggretion type fluorine-containing textile finishing agent carries out emulsion copolymerization by fluorine-containing Acrylic Acid Monomer and multiple hydrocarbon class Acrylic Acid Monomer according to certain ratio to obtain, the film-forming properties that the adding of hydrocarbon class Acrylic Acid Monomer can improve polymkeric substance, to reduce costs, and other functions of polymkeric substance can be increased, as fiber tack, rub resistance, washing fastness etc.
Generally use the fluorine-containing textile finishing agent of C8 type in the market, this type of finishing composition has very excellent low surface energy and water and oil repellant effect, but owing to there is refractory organics, transport property and cumulative toxicity, the whole world has prohibitted the use perfluorinated octyl sulfuryl amine derivative (PFOS) and Perfluorocaprylic Acid (PFOA), therefore finds the study hotspot that alternative environment-friendlytype type fabric finishing composition becomes current textile auxiliaries field.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly type perfluor fabric finishing agent and preparation method thereof, it can substitute C8 type fabric finishing agent, plays environmental-protection function, and gives fabric excellent water and oil repellant performance.
To achieve the above object of the invention, the technical solution adopted in the present invention is to provide a kind of environment-friendly type perfluor fabric finishing agent, it is prepared component and comprises perfluoro alkene oxygen yl benzoic acid propylene esters monomer, stearyl acrylate esters of gallic acid monomer, N hydroxymethyl acrylamide, compound emulsifying agent, chain-transfer agent, initiator and water, and the weight percent content of each component is:
Perfluoro alkene oxygen yl benzoic acid propylene: 10 ~ 20 parts;
Stearyl acrylate acid esters: 10 ~ 15 parts;
N hydroxymethyl acrylamide: 1 ~ 5 part;
Compound emulsifying agent: cationic emulsifier 1 ~ 2 part, nonionic emulsifying agent 1 ~ 2 part;
Chain-transfer agent: 0.01 ~ 0.05 part;
Initiator: 0.2 ~ 1 part;
Water: 60 ~ 80 parts;
The preparation method of environment-friendly type perfluor fabric finishing agent provided by the invention, comprises the steps:
1), pre-emulsification
By weight, take perfluoro alkene oxygen yl benzoic acid propylene 10 ~ 20 parts, stearyl acrylate acid esters 10 ~ 15 parts, N hydroxymethyl acrylamide 1 ~ 5 part, compound emulsifying agent totally 3 parts, chain-transfer agent 0.01 ~ 0.05 part, add the there-necked flask of 1000 milliliters, 800 ~ 1300rpm high-speed stirring carries out pre-emulsification in 10 ~ 20 minutes, then adds deionized water 60 ~ 80 parts, pre-emulsification 20 ~ 30 minutes, obtains milky pre-emulsion.
2), be polymerized
Pour above-mentioned pre-emulsion 1/3rd into 1000 milliliters of there-necked flasks, stir and lead to nitrogen, be warming up to 50 ~ 60 DEG C and add 0.2 ~ 1 part of initiator and be then warming up to 60 ~ 70 DEG C, after reacting half an hour, adopt semi-continuous feed way, start the pre-emulsion dripping another 2/3rds, temperature remains on 60 ~ 70 DEG C, drip in 2 ~ 4 hours, then insulation reaction 1 ~ 2 hour, then raised temperature 2 ~ 5 DEG C reaction 1 ~ 2 hour, cooling discharge, filter, obtain finishing composition emulsion.
The monomer that in the present invention, fluorine-containing textile finishing agent adopts is perfluorinated nonene aminobenzoic acid propylene or perfluor hexene aminobenzoic acid propylene, on the basis of shortcoming effectively overcoming short carbon chain water and oil repellant difference, successfully instead of C8 type fluorine-contained finishing agent.
The present invention has the following advantages compared with traditional technology:
1. positively charged ion and nonionic composite emulsifying system.Select the emulsifying agent of positively charged ion and nonionic compound system can improve emulsifying effectiveness on the one hand and increase emulsion intercalation method, on the other hand because fabric fibre is generally in electronegativity, cationic emulsion particle easily evenly adheres to securely at fiber surface.
2. have employed the feed way of semi continuous in polymerization process, the smaller emulsion of particle diameter can be obtained like this, advantageously in the package stability of emulsion.
Embodiment
Below by embodiment, the present invention is specifically described
Embodiment 1:
Take perfluor rare aminobenzoic acid propylene in ninth of the ten Heavenly Stems 100g, stearyl acrylate acid esters 75g, N hydroxymethyl acrylamide 25g, compound emulsifying agent 15g, chain-transfer agent lauryl mercaptan 0.25g, adds the there-necked flask of 1000 milliliters, 1300rpm high-speed stirring carries out pre-emulsification in 20 minutes, then add deionized water 400g, pre-emulsification 30 minutes, obtains milky pre-emulsion.
Above-mentioned pre-emulsion 1/3rd is poured into the there-necked flask of 1000 milliliters, stir and lead to nitrogen, add 5g initiator azo diisobutyl amidine hydrochloride when being warming up to 60 DEG C and be then warming up to 70 DEG C, after reacting half an hour, adopt semicontinuous feed way, start the pre-emulsion dripping another 2/3rds, temperature remains on 70 DEG C, drip in 4 hours, then insulation reaction 2 hours, then raised temperature 5 DEG C reaction 2 hours, cooling discharge, filter, obtain finishing composition emulsion.
Embodiment 2:
Take perfluor rare aminobenzoic acid propylene in ninth of the ten Heavenly Stems 50g, stearyl acrylate acid esters 50g, N hydroxymethyl acrylamide 5g, compound emulsifying agent 15g, chain-transfer agent lauryl mercaptan 0.05g, adds the there-necked flask of 1000 milliliters, 800rpm high-speed stirring carries out pre-emulsification in 10 minutes, then add deionized water 300g, pre-emulsification 20 minutes, obtains milky pre-emulsion.
Above-mentioned pre-emulsion 1/3rd is poured into the there-necked flask of 1000 milliliters, stir and lead to nitrogen, add 1g initiator azo dicyano valeric acid when being warming up to 50 DEG C and be then warming up to 60 DEG C, after reacting half an hour, adopt semicontinuous feed way, start the pre-emulsion dripping another 2/3rds, temperature remains on 60 DEG C, drip in 2 hours, then insulation reaction 1 hour, then raised temperature 2 DEG C reaction 1 hour, cooling discharge, filter, obtain finishing composition emulsion.
Textile finishing is applied
Get emulsion 250 ~ 300g, with 5 liters of tap water dilutions, adopt leaching one roll process to be processed by fabric sample, the baking oven then test cloth specimen being placed in 120 DEG C dries 2min, then 2min is dried in training at 160 DEG C, and cooling, carries out water repellency detection after moisture regain.
Performance test
The detection of water repellency is carried out by AATCC-22 method (spraying process), after Y (B) 813 type fabric degree of getting wet tester Water spray, observe fabric face adhesional wetting degree, 0 point, 50 points, 60 points, 70 points, 80 points, 90 points, 100 points are divided into according to wetted areas, wherein 0 point represents that water permeation crosses fabric, without water repellency, 100 points of expressions are dripped by the without water stained on its surface drenched, and water repellency is best.
Spring Asia is spun, cream-coloured cotton poplin cloth carries out water repellency detected result and sees the following form to adopt the fluorine-containing fabric water repellent finishing agent FC-510 for preparing of hexafluoropropene oligomers entirely to wash at grey nylon Ta Silong, black.
Claims (7)
1. an environment-friendly type perfluor fabric finishing agent, it is prepared component and comprises perfluoro alkene oxygen yl benzoic acid propylene esters monomer, stearyl acrylate esters of gallic acid monomer, N hydroxymethyl acrylamide, compound emulsifying agent, chain-transfer agent, initiator and water, it is characterized in that: the weight percent content of each component is:
Perfluoro alkene oxygen yl benzoic acid propylene: 10 ~ 20 parts;
Stearyl acrylate acid esters: 10 ~ 15 parts;
N hydroxymethyl acrylamide: 1 ~ 5 part;
Compound emulsifying agent: cationic emulsifier 1 ~ 2 part, nonionic emulsifying agent 1 ~ 2 part;
Chain-transfer agent: 0.01 ~ 0.05 part;
Initiator: 0.2 ~ 1 part;
Water: 60 ~ 80 parts.
2. the preparation method of environment-friendly type perfluor fabric finishing agent according to claim 1, is characterized in that: comprise the steps:
1), pre-emulsification
By weight, take perfluoro alkene oxygen yl benzoic acid propylene 10 ~ 20 parts, stearyl acrylate acid esters 10 ~ 15 parts, N hydroxymethyl acrylamide 1 ~ 5 part, compound emulsifying agent totally 3 parts, chain-transfer agent 0.01 ~ 0.05 part, add the there-necked flask of 1000 milliliters, 800 ~ 1300rpm high-speed stirring carries out pre-emulsification in 10 ~ 20 minutes, then adds deionized water 60 ~ 80 parts, pre-emulsification 20 ~ 30 minutes, obtains milky pre-emulsion;
2), be polymerized
Pour above-mentioned pre-emulsion 1/3rd into 1000 milliliters of there-necked flasks, stir and lead to nitrogen, be warming up to 50 ~ 60 DEG C and add 0.2 ~ 1 part of initiator and be then warming up to 60 ~ 70 DEG C, after reacting half an hour, adopt semi-continuous feed way, start the pre-emulsion dripping another 2/3rds, temperature remains on 60 ~ 70 DEG C, drip in 2 ~ 4 hours, then insulation reaction 1 ~ 2 hour, then raised temperature 2 ~ 5 DEG C reaction 1 ~ 2 hour, cooling discharge, filter, obtain finishing composition emulsion.
3. the preparation method of environment-friendly type perfluor fabric finishing agent according to claim 2, it is characterized in that, perfluoro alkene oxygen yl benzoic acid acrylic ester monomer has two classes, is perfluorinated nonene aminobenzoic acid acrylic ester monomer or perfluor hexene aminobenzoic acid acrylic ester monomer respectively.
4. the preparation method of environment-friendly type perfluor fabric finishing agent according to claim 2, is characterized in that, described step 1) in adopt chain-transfer agent be lauryl mercaptan or aliphatics mercaptan.
5. the preparation method of environment-friendly type perfluor fabric finishing agent according to claim 2, is characterized in that, described step 1) in have employed positively charged ion and nonionic compound emulsifier.
6. the preparation method of environment-friendly type perfluor fabric finishing agent according to claim 2, is characterized in that, described step 2) in initiator used be the hydrochloride of water miscible azo.
7. the preparation method of environment-friendly type perfluor fabric finishing agent according to claim 2, is characterized in that, described step 2) in pre-emulsion add rear temperature of reaction and remain 65 ~ 70 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510510343.7A CN105131177A (en) | 2015-08-19 | 2015-08-19 | Environment-friendly type perfluoro fabric finishing agent and preparation method thereof |
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| CN201510510343.7A CN105131177A (en) | 2015-08-19 | 2015-08-19 | Environment-friendly type perfluoro fabric finishing agent and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105908510A (en) * | 2016-06-23 | 2016-08-31 | 无锡市金五星针纺有限公司 | Fluorine-containing fabric finishing agent and preparation method thereof |
| CN105924573A (en) * | 2016-06-13 | 2016-09-07 | 苏州大学 | Perfluoroalkyl polyene ester waterproof agent, preparation method and application |
| CN108018718A (en) * | 2016-11-04 | 2018-05-11 | 中昊晨光化工研究院有限公司 | A kind of cation fluoride fabric finishing agent and preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105924573A (en) * | 2016-06-13 | 2016-09-07 | 苏州大学 | Perfluoroalkyl polyene ester waterproof agent, preparation method and application |
| CN105924573B (en) * | 2016-06-13 | 2017-11-03 | 苏州大学 | A kind of perfluoroalkyl polyolefin acid ester waterproofing agent, preparation method and application |
| CN105908510A (en) * | 2016-06-23 | 2016-08-31 | 无锡市金五星针纺有限公司 | Fluorine-containing fabric finishing agent and preparation method thereof |
| CN108018718A (en) * | 2016-11-04 | 2018-05-11 | 中昊晨光化工研究院有限公司 | A kind of cation fluoride fabric finishing agent and preparation method |
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Application publication date: 20151209 |