CN112358554B - Cross-linking agent for water-repellent and oil-repellent finishing, and preparation method and application thereof - Google Patents
Cross-linking agent for water-repellent and oil-repellent finishing, and preparation method and application thereof Download PDFInfo
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- CN112358554B CN112358554B CN202011189526.0A CN202011189526A CN112358554B CN 112358554 B CN112358554 B CN 112358554B CN 202011189526 A CN202011189526 A CN 202011189526A CN 112358554 B CN112358554 B CN 112358554B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention relates to a cross-linking agent, a preparation method and application thereof, wherein the cross-linking agent is prepared by the grafting reaction of chitosan and isopropyl isocyanate under the action of a catalyst. The modified chitosan oligomer has both hydroxymethyl group and epoxy group as cross-linking agent and filming property, and may be used together with fluoric finishing agent to raise the water and oil repellency of fabric.
Description
Technical Field
The invention belongs to the technical field of textile after-finishing, and particularly relates to a cross-linking agent for water-repellent and oil-repellent finishing, and a preparation method and application thereof.
Background
Under the form of epidemic outbreak, the safety protection problem of medical care personnel is particularly remarkable, and the protection personnel can contact body fluid, blood, liquid medicine and the like of a patient at any time in the process of closely contacting the patient, so that the protection clothes have extremely strong anti-permeability performance. In order to improve the permeability resistance of protective clothing, the water-proof, oil-proof, blood-proof and alcohol-proof abilities of the fabric need to be improved at the same time, the fabric needs to be finished by using a fluorine water-repellent and oil-repellent finishing agent, and a higher water-repellent and oil-repellent grade needs to be achieved. However, the technical problems in two aspects exist at present, on one hand, the polypropylene material is the most commonly used non-woven fabric material, the glass transition temperature of the polypropylene material is low, and the water-repellent and oil-repellent finishing agent cannot be efficiently and orderly arranged through high-temperature baking so as to achieve a good water-repellent and oil-repellent effect; on the other hand, C8 series water and oil repellent performance is high in general markets, but C8 waterproof agents contain PFOA and PFOS which are potentially harmful to human bodies, the industrial standards of European and American markets limit, and the textiles with the PFOA and PFOS content exceeding 0.05% are forbidden to be sold, so C6 fluorine-containing finishing agents are mostly adopted to carry out water and oil repellent finishing on the textiles in the markets, but the water and oil repellent function of C6 series finishing is lower than that of C8 series finishing agents, the components of the medical protective fabric are polyethylene, the glass transition temperature of the polyethylene is lower, and the water and oil repellent function cannot be improved by improving the neatness degree of the arrangement of the waterproof agents in a baking temperature mode.
Disclosure of Invention
The invention aims to provide a cross-linking agent, when the cross-linking agent and a fluorine-containing finishing agent are used together, the cross-linking effect and the film forming effect of the cross-linking agent enable the fluorine-containing finishing agent to be firmly combined with a fabric, the water and oil repellency of a non-woven fabric can be greatly improved, the capability of the non-woven fabric for resisting blood and alcohol permeation is enhanced, and a higher safety protection level is achieved.
In order to achieve the purpose, the invention adopts the technical scheme that:
one aspect of the present invention provides a crosslinking agent having the formula:
The second aspect of the invention provides a preparation method of a cross-linking agent, wherein the cross-linking agent is prepared by grafting chitosan and propyl isocyanate under the action of a catalyst.
Preferably, the grafting reaction of the chitosan and the propyl isocyanate under the action of the catalyst has the following equation:
preferably, the feeding molar ratio of the hydroxymethyl group in the chitosan to the isocyanate group in the propyl isocyanate is 1: 0.8-1.2.
Preferably, the feeding mass of the catalyst is 0.06-0.1 time of that of the chitosan, and preferably 0.08-0.1 time of that of the chitosan.
Preferably, the preparation method comprises the following specific steps: adding the chitosan and the catalyst into acetic acid and ethyl acetate to prepare a mixed solution A, adding the propyl isocyanate into the ethyl acetate to prepare a mixed solution B, then dropwise adding the mixed solution B into the mixed solution A, controlling the temperature to be 70-80 ℃ to react after the dropwise adding is finished, and performing post-treatment after the reaction is finished to obtain the cross-linking agent.
Preferably, in the mixed solution a, the mass ratio of the chitosan, the acetic acid and the ethyl acetate is 1: 0.8-1.2: 1.1-1.6, preferably 1: 1-1.2: 1.2 to 1.6.
Preferably, in the mixed solution B, the mass ratio of the propyl isocyanate to the ethyl acetate is 1:2 to 3, and preferably 1:2.5 to 3.
Preferably, the feeding volume ratio of the mixed solution A to the mixed solution B is 1: 0.45-0.55, and preferably 1: 0.5-0.55.
Preferably, the dropping temperature of the mixed solution B is controlled to be 30-40 ℃, the dropping speed is 3-5 mL/min, and preferably 4-5 mL/min.
Further preferably, the reaction time is controlled to be 2-3 h.
Preferably, the post-treatment method comprises the following steps: and (3) cooling the reaction solution to 10-30 ℃, preferably 20-25 ℃, then adjusting the temperature to-10-15 ℃ to precipitate crystals, and then filtering and washing to obtain the cross-linking agent.
Preferably, the washing is three times with ethanol.
Preferably, the chitosan is water-soluble chitosan with deacetylation degree of more than 85% and number average molecular weight of 5000-10000.
Preferably, the catalyst is one or more of dibutyltin diacetate, stannous octoate and dibutyltin didodecyl sulfide.
A third aspect of the invention provides the use of a cross-linking agent as described above in the after-finishing of textiles.
The fourth aspect of the invention provides a textile after-finishing method: and treating the textile by using finishing liquor containing a cross-linking agent and a fluorine-containing finishing agent, wherein the cross-linking agent is the cross-linking agent or the cross-linking agent prepared by the preparation method.
Preferably, the method of finishing the textile comprises: and uniformly mixing the cross-linking agent and the fluorine-containing finishing agent, adding the mixture into a soaking and rolling tank, soaking the textile, rolling the textile by a uniform compression roller until the water content is 30-40%, and drying the textile at 120-130 ℃.
Preferably, the textile is treated in a dip-and-roll manner.
Preferably, the finishing liquid further contains a penetrating agent, and the mass ratio of the cross-linking agent to the fluorine-containing finishing agent to the penetrating agent to the water in the finishing liquid is controlled to be 5-10: 1-2: 0.8-1: 100, and preferably 8-10: 1.5-2: 0.9-1: 100.
Preferably, the textile is a non-woven fabric.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the modified oligochitosan has both hydroxymethyl group and epoxy group, and chitosan has film forming property, after partial hydroxymethyl of the modified oligochitosan participates in the reaction, the rest hydroxymethyl still has the crosslinking effect, the modified oligochitosan is used as a crosslinking agent together with a fluorine-containing finishing agent, and the crosslinking effect and the film forming effect of the crosslinking agent ensure that the finishing agent is firmly combined with the fabric, so that the water and oil repellent performance of the fabric can be greatly improved.
Detailed Description
The present invention will be further described with reference to the following examples.
The following examples and comparative examples refer to the following sources of raw materials:
water-soluble chitosan, Shandong Onkang Biotech Ltd;
propyl isocyanate, chemically pure, Jiangsu Aikang biomedical research & development Co., Ltd;
c6 three-proofing finishing agent, HK GUARD HG-6617, Zhejiang Hui Kai New materials science and technology Co., Ltd;
SMS nonwoven, 50g/m 2 Suzhou Huafutian new materials, Inc.
The water repellency of the products in the following examples and comparative examples was tested according to the national standard GB/T4745-.
Example one
According to the mass ratio of 1:0.06:0.8:1.1, putting chitosan, dibutyltin diacetate, acetic acid and ethyl acetate into a four-neck flask to prepare a mixed solution A, and starting a stirrer to stir. And dissolving propyl isocyanate in ethyl acetate according to the mass ratio of 1:2 to prepare a mixed solution B, uniformly stirring, and then dripping the mixed solution B into the mixed solution A at the speed of 3ml/min, wherein the feeding volume ratio of the mixed solution A to the mixed solution B is 1: 0.45. And in the dropping process, keeping the temperature of 30 ℃ constant, after the dropping is finished, slowly heating the liquid to 70 ℃, continuously stirring for 2 hours, stopping heating, slowly cooling the liquid to 20 ℃, then placing a four-neck flask into a cold bath, adjusting the temperature to-10 ℃, after crystals are separated out, filtering, washing with ethanol for three times, and thus obtaining the modified chitosan crosslinking agent for later use.
Uniformly mixing the three-proofing finishing agent, the cross-linking agent, the Ludou penetrant FN and water according to the mass ratio of 5:1:0.8:100, adding the mixture into a padding tank, impregnating the textile, rolling the textile by a uniform compression roller, finishing to the water content of 30%, drying at 120 ℃ to obtain a sample No. 1, and detecting according to a detection method, wherein the detection result is shown in Table 1.
Example two
Putting chitosan, stannous octoate, acetic acid and ethyl acetate into a four-neck flask A according to the mass ratio of 1:0.08:1.0:1.2 to prepare a mixed solution A, and starting a stirrer to stir. And dissolving the propyl isocyanate in ethyl acetate according to the mass ratio of 1:2.5 to prepare a mixed solution B, uniformly stirring, and then dripping the mixed solution B into the mixed solution A at the speed of 4ml/min, wherein the feeding volume ratio of the mixed solution A to the mixed solution B is 1: 0.5. And in the dropping process, keeping the constant temperature of 35 ℃, after the dropping is finished, slowly heating the liquid to 75 ℃, continuously stirring for 2.5 hours, stopping heating, slowly cooling the liquid to 20 ℃, then placing the four-neck flask into a cold bath, adjusting the temperature to-12 ℃, after crystals are separated out, filtering, washing with ethanol for three times, and obtaining the modified chitosan cross-linking agent for later use.
Uniformly mixing the three-proofing finishing agent, the cross-linking agent, the Ludou penetrant FN and water according to the mass ratio of 8:1.5:0.9:100, adding the mixture into a padding tank, impregnating the textile, rolling the textile by a uniform compression roller until the water content is 35%, drying the textile at 125 ℃ to obtain a sample No. 2, and detecting according to a detection method.
EXAMPLE III
According to the mass ratio of 1:0.1:1.2:1.6, chitosan, dibutyltin bis (dodecyl sulfide), acetic acid and ethyl acetate are put into a four-neck flask to prepare a mixed solution A, and a stirrer is started to stir. And dissolving the propyl isocyanate in ethyl acetate according to the mass ratio of 1:3 to prepare a mixed solution B, uniformly stirring, and dripping the mixed solution B into the mixed solution A at the speed of 5ml/min, wherein the feeding volume ratio of the mixed solution A to the mixed solution B is 1: 0.55. And in the dropping process, keeping the temperature of 40 ℃ constant, after the dropping is finished, slowly heating the liquid to 80 ℃, continuously stirring for 3 hours, stopping heating, slowly cooling the liquid to 20 ℃, then placing the four-neck flask into a cold bath, adjusting the temperature to-15 ℃, after crystals are separated out, filtering, washing with ethanol for three times, and obtaining the modified chitosan cross-linking agent for later use.
Uniformly mixing the three-proofing finishing agent, the cross-linking agent, the Ludou penetrant FN and water according to the mass ratio of 10:2:1:100, adding the mixture into a padding tank, impregnating the textile, rolling the textile by a uniform compression roller until the water content is 40%, drying the textile at 130 ℃ to obtain a sample No. 3, and detecting according to a detection method, wherein the detection result is shown in Table 1.
Comparative example 1
Uniformly mixing the three-proofing finishing agent, the Ludoufu penetrant FN and water according to the mass ratio of 10:1:100, adding the mixture into a soaking and rolling tank, soaking the textile, rolling the textile by a uniform compression roller until the water content is 40%, drying the textile at 130 ℃ to obtain a sample No. 4, and detecting according to a detection method, wherein the detection results are shown in Table 1.
TABLE 1
| 1# | 2# | 3# | 4# | |
| Water repellency (grade) | 4 | 4 | 5 | 3 |
| Oil repellency (grade) | 6 | 5 | 7 | 3 |
| Anti-permeability to blood (grade) | 5 | 6 | 6 | 4 |
When copolymer containing hydroxymethyl or epoxy group is used together with fluorine-containing finishing agent, the crosslinking of finishing agent and fabric can be promoted, the water-repellent and oil-repellent performance of fabric can be improved, and the water-repellent, oil-repellent and blood permeation-resistant properties of fabric can be improved.
The present invention has been described in detail for the purpose of illustration and description, and it will be apparent to those skilled in the art that the invention can be practiced without limitation to such detail, and all changes and modifications that come within the spirit of the invention are desired to be protected.
Claims (7)
1. Use of a crosslinking agent in the post-finishing of textiles, characterized in that: the cross-linking agent and the fluorine-containing finishing agent are used together, chitosan and propyl isocyanate are subjected to grafting reaction under the action of a catalyst to prepare the cross-linking agent, and the textile is polypropylene non-woven fabric.
2. Use of a crosslinking agent according to claim 1 in the post-finishing of textiles, characterized in that: the feeding molar ratio of hydroxymethyl in the chitosan to isocyanate in the propyl isocyanate is 1: 0.8-1.2; the feeding mass of the catalyst is 0.06-0.1 time of that of the chitosan.
3. Use of a crosslinking agent according to claim 1 in the post-finishing of textiles, characterized in that: the specific steps of carrying out the grafting reaction of the chitosan and the propyl isocyanate under the action of the catalyst are as follows: adding the chitosan and the catalyst into acetic acid and ethyl acetate to prepare a mixed solution A, adding the propyl isocyanate into the ethyl acetate to prepare a mixed solution B, then dropwise adding the mixed solution B into the mixed solution A, controlling the temperature to be 70-80 ℃ to react after the dropwise adding is finished, and performing post-treatment after the reaction is finished to obtain the cross-linking agent.
4. Use of a crosslinking agent according to claim 3 in the post-finishing of textiles, characterized in that: in the mixed solution A, the mass ratio of the chitosan to the acetic acid to the ethyl acetate is 1: 0.8-1.2: 1.1-1.6; in the mixed solution B, the mass ratio of the propyl isocyanate to the ethyl acetate is 1: 2-3; the feeding volume ratio of the mixed liquid A to the mixed liquid B is 1: 0.45-0.55.
5. Use of a crosslinking agent according to claim 3 in the post-finishing of textiles, characterized in that: and controlling the dropping temperature of the mixed solution B to be 30-40 ℃, and controlling the dropping speed to be 3-5 mL/min.
6. Use of a crosslinking agent according to claim 3 in the post-finishing of textiles, characterized in that: controlling the reaction time to be 2-3 h; the post-treatment method comprises the following steps: and cooling the reaction liquid to 10-30 ℃, then adjusting the temperature to-10 to-15 ℃ to precipitate crystals, and then filtering and washing to obtain the cross-linking agent.
7. Use of a crosslinking agent according to any one of claims 1 to 6 in the post-finishing of textiles, characterized in that: the chitosan is water-soluble chitosan with deacetylation degree more than 85% and number average molecular weight of 5000-10000; the catalyst is one or more of dibutyltin diacetate, stannous octoate and dibutyltin didodecyl sulfide.
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| CN104471450A (en) * | 2012-07-26 | 2015-03-25 | 大日本印刷株式会社 | Resin composition for reverse wavelength dispersion film, and reverse wavelength dispersion film and reverse wavelength dispersion sheet which comprise same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5070596B2 (en) * | 2005-05-09 | 2012-11-14 | 国立大学法人名古屋大学 | Chitosan derivative and method for producing the same |
| JP2009057530A (en) * | 2007-08-30 | 2009-03-19 | Ft-Net Co Ltd | Fluorine-based surface reforming composition |
| CN106283669A (en) * | 2016-08-31 | 2017-01-04 | 苏州市恒信针织印染有限责任公司 | A kind of crease proofing agent of wash-and-wear of shirt |
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| CN102417575A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of fluorine-containing aqueous polyurethane water-repellent oil-repellent finishing agent |
| CN104471450A (en) * | 2012-07-26 | 2015-03-25 | 大日本印刷株式会社 | Resin composition for reverse wavelength dispersion film, and reverse wavelength dispersion film and reverse wavelength dispersion sheet which comprise same |
| CN105567119A (en) * | 2016-03-03 | 2016-05-11 | 苏州棠华纳米科技有限公司 | Chitosan adhesive and preparation method and application thereof |
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Denomination of invention: A crosslinking agent for water and oil repellent finishing and its preparation method and application Effective date of registration: 20230816 Granted publication date: 20220909 Pledgee: China Construction Bank Corporation Wujiang Shengze sub branch Pledgor: SUZHOU TANGHUA NANO TECHNOLOGY Co.,Ltd. Registration number: Y2023980052408 |
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