CN101225601B - Multifunctional reactive cotton ultraviolet absorbent, synthetic method and use thereof - Google Patents
Multifunctional reactive cotton ultraviolet absorbent, synthetic method and use thereof Download PDFInfo
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- CN101225601B CN101225601B CN2007101722382A CN200710172238A CN101225601B CN 101225601 B CN101225601 B CN 101225601B CN 2007101722382 A CN2007101722382 A CN 2007101722382A CN 200710172238 A CN200710172238 A CN 200710172238A CN 101225601 B CN101225601 B CN 101225601B
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Abstract
The invention relates to a multifunctional reactive ultraviolet absorbent which is used for cotton fiber, a synthetic method and application, the general formula I of the absorbent is as the right formula, the synthetic method comprises that: triclosan antibacterial compounds, hindered amine light stabilizing compounds or amino silicone oil softening finishing compounds and other functional finishing agents are added into cyanuric chloride, the solvent is water, the reaction time is 1-2h, at 0-5 DEG C, the groups of functional finishing agents are introduced; (2) the materials connecting the groups are added, the solvent is water, the reaction time is 3-4h, at 40-50 DEG C, the two triazine rings are connected; (3) or with other reacting active material, water as the solvent, reacting 3-4h,at 80-90 DEG C, other active groups are introduced on the triazine rings. The multifunctional reactive ultraviolet absorbent has the advantages of good reactivity, water soluble, ultraviolet absorbing capacity and other finishing functions as antibacterial property, light stability on cotton fabric.
Description
Technical field
The invention belongs to the ultra-violet absorber field, particularly relate to multifunctional reactive cotton ultraviolet absorbent, its synthetic method and application.
Background technology
Ultraviolet ray is the electromagnetic wave of wavelength at 180～400nm.An amount of ultra-violet radiation has bactericidal action, and can promote the synthetic of vitamin D, help health, but excessive ultraviolet ray is extremely harmful to human body.Modern scientific research shows, ultraviolet ray will be much larger than its advantageous effect to the adverse effect of human body, and excessive ultraviolet radiation can be brought out skin disease, even cutaneum carcinoma, also can cause cataract and reduce the immunologic function of human body.Therefore, Ultraviolet rays protection is more and more paid close attention to by people.
Ultra-violet absorber be a class consumingly selectivity absorb the high-energy ultraviolet light and carry out power conversion, with the material that energy discharges or consumes, be widely used in macromolecular material, textiles processing and other fields with heat energy or harmless low forms of radiation.Common ultra-violet absorber mainly comprises salicylate class, benzophenone, benzotriazole, hindered amines, group-substituted acrylonitrile, triazines or the like, and wherein benzophenone and benzotriazole ultra-violet absorber are used comparatively extensive.
Traditional ultra-violet absorber is fixed in the textile fabric by physical absorption, bonding, means such as crosslinking agent is crosslinked, doping mostly, in use there is following shortcoming in product: it is poor that (1) ultra-violet absorber agent and textile fabric combine fastness, easily run off, along with the prolongation of service time or increasing of washing times, anti-ultraviolet function reduces gradually and finally disappears; (2) adopt crosslinked or bonding method, not only can the performance of textiles be exerted an influence, and also can reduce anti-ultraviolet property sometimes; (3) method of Can Zaing mainly is applicable to the arrangement of synthetic fiber, needs to carry out before spinning owing to mix, and therefore, the compatibility between ultra-violet absorber and the textile fabric is most important.For addressing the above problem, in recent years, cotton ultraviolet absorbent just develops towards directions such as reactivity, durability and multifunctionalities.
At present, cotton ultraviolet reactive, durability has a large amount of research both at home and abroad.Synthesized a series of novel 1 such as Clariant company, 3,5-s-triazine compound, find that this compounds can and make fiber obtain lasting antiultraviolet and antifouling property with hydroxyl on the fiber or amino reaction, and the method for dying fiber on the method for handling fiber and the REACTIVE DYES is similar, can carry out simultaneously with reactive dyeing; The plateau of Donghua University is that raw material has synthesized a kind of cotton ultraviolet absorbent that self has reaction active groups with aminobenzenesulfonic acid, Cyanuric Chloride and 2,4 dihydroxyl benzophenone; The Wang Fang of Shenyang Institute of Chemical Technology with absorbability by force, the benzotriazole ultra-violet absorber is a parent safely and effectively, in molecule, introduce the Cyanuric Chloride or the vinyl sulfone(Remzaol isoreactivity group that can react with cotton fiber, synthesized a kind of cotton and used reactive ultra-violet absorber; People such as Jin Fang have synthesized a kind of ultra-violet absorber with halogenated heterocyclic active group, and its water soluble group is a sulfonic group, and linking group is-NH-that the ultraviolet radiation absorption base is the structure of fragrant lopps; People such as Cui Guoshi are raw material with cinnamic acid derivative and γ-r-chloropropyl trimethoxyl silane, have synthesized γ-to a series of silicon alkoxyl cinnamate compounds such as methoxyl group cinnamoyloxy group propyl trimethoxy silicane or the like by esterification.Though domesticly obtaining certain progress aspect the research of reactive ultra-violet absorber, developed and a series ofly not only had and the ability of cotton fiber reaction but also compound with certain ultraviolet radiation absorption effect, but the compound of being reported does not possess other arrangement functions, does not satisfy the growing multifunction demand of people.
In sum, research and development had both had good reaction activity, water-soluble and ultraviolet radiation absorption effect, and the reactive cotton ultraviolet absorbent that possesses other arrangement functions simultaneously becomes a crucial problem.
Summary of the invention
The purpose of this invention is to provide a kind of multifunctional reactive cotton ultraviolet absorbent, its synthetic method and application, has the group of finishing functions effect by in the molecule of triazines ultra-violet absorber, introducing other, make this compound not only have good reaction activity and good ultraviolet radiation absorption effect, also possessed other arrangement functions.
Multifunctional reactive cotton ultraviolet absorbent of the present invention, I is as follows for its general structure:
Wherein, X represents reaction active groups in the general formula I: halogen groups such as F-, Cl-,
R is-NHCH in the general formula I
2CH
2NH-,-NHCH
2CH
2CH
2NH-,-NHCH
2CH
2CH
2CH
2NH-,-NHCH
2CH
2CH
2CH
2CH
2Aliphatic diamine compound groups such as NH-or
Deng the aromatic diamine compound group.
R ' represents other finishing functions groups in the general formula I:
Stablize group Deng the hindered amines light that contains amino or hydroxyl,
Deng the antibiotic group of triclosan class,
Deng amido silicon oil class soft finish group.
The synthetic method of multifunctional reactive cotton ultraviolet absorbent of the present invention is to be raw material with functional finishing agent, Cyanuric Chloride and linking group material etc., and it is synthetic that substitution reaction takes place, and its concrete synthesis step is as follows:
(1) adding functional finishing agent in the Cyanuric Chloride, is solvent with water, and 0～5 ℃ of reaction 1～2h introduces the functional finishing agent group;
(2) adding the linking group material, is solvent with water, and 40～50 ℃ of reaction 3～4h connect two triazine rings;
(3) or again with other reactivity material, be solvent with water, 80～90 ℃ of reaction 3～4h introduce other active group on triazine ring.
Mole dosage ratio between reactant Cyanuric Chloride, functional finishing agent, linking group material, other reactivity material is 1: 1: 0.5: 1.
Described functional finishing agent is
Deng triclosan class antimicrobial compound or
The hindered amine light stabilizer that contains amino or hydroxyl;
Deng the amido silicon oil compounds.
Described linking group material is H
2NCH
2CH
2NH
2, H
2NCH
2CH
2CH
2NH
2, H
2NCH
2CH
2CH
2CH
2NH
2, H
2NCH
2CH
2CH
2CH
2CH
2NH
2Deng the aliphatic diamine compound group or
Deng the aromatic diamine compound group;
Described other reactivity materials are
Deng the aliphatic or the aromatic series ethyl sulfone compound group that contain amino.
The application of multifunctional reactive cotton ultraviolet absorbent of the present invention, its step:
(1) adopt orthogonal experiment to draw the optimization finishing technique;
(2) on the basis of optimizing finishing technique, test uvioresistant performance and washing fastness;
(3) on the basis of optimizing finishing technique, test other arrangement functions (as antibacterial effect, light fastness etc.).
Beneficial effect of the present invention:
The ultraviolet absorber that the present invention synthesizes has good reaction activity, water-soluble, ultraviolet absorption ability and other arrangement functions (as antibiotic property, photostability etc.) on COTTON FABRIC.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The water that uses in following examples is running water, and chemicals is chemical pure, and the specification of textile poplin cloth is yarn count JC40 * 40, through close 100 * filling density 90, fabric width 67 ".
Embodiment 1
Take by weighing 2 of 30.6g23.5%, 4-two chloro-5-(2, the 4-dichloro-benzenes) the oxygen base benzene sulfonic acid aqueous solution also adds in the four-hole boiling flask, and the NaOH aqueous solution with 30% is regulated pH value to 6～8, adds 47g water then in solution.Ice bath is cooled to 0～5 ℃.Slowly add the 5g Cyanuric Chloride, and at 0～5 ℃ of following insulation reaction 90min.Regulate pH value to 6.0～6.2 with the 30%NaOH aqueous solution more subsequently, be warming up to 50 ℃, add 2.2g2 again, the 4-diamino benzene sulfonic acid, insulation reaction 3h uses 10%Na every half an hour between this stage of reaction
2CO
3Solution is regulated the pH value, and it is remained in 5～6 the scope.Obtain the yellowish-brown clear solution at last, separation obtains compound a after purifying, and compound a is that the cotton that has uvioresistant performance and anti-microbial property is simultaneously used multifunction finishing agent.Gained solution can be directly used in the COTTON FABRIC arrangement without arrangement.
Embodiment 2
Present embodiment is the research to the uvioresistant of compound a and antibacterial applications performance, comprises determining to optimize finishing technique, uvioresistant performance test result and anti-microbial property test result.
To the optimization finishing technique of compound a on textile poplin cloth, adopted five factors, six horizontal quadratures experiments to draw at last to optimize finishing technique to be: bath raio 1: 15, room temperature are put into finishing agent and cotton, the finishing agent consumption be fabric heavy 1～10%, be warming up to 65 ℃, add glauber salt 40g/L, insulation 40min, add soda ash 30g/L then, be warming up to 90 ℃, insulation 25min, hot water wash is once, cold water is cleaned, oven dry.
Optimizing under the finishing technique condition, adopt the light brown thick liquid of gained among the embodiment 1 directly textile poplin cloth to be carried out anti UV finishing, and textile poplin cloth after putting in order is carried out 50 times soap, respectively to before the textile finishing, arrangement back and the UPF value of soaping after 50 times test, test result sees Table 1.The UPF value of the textile poplin cloth in arrangement back significantly increases along with the increase of ultra-violet absorber consumption, and when the finishing agent consumption reached fabric weight 3%, fabric UPF can reach more than 50.The retention rate of the textile Dense Poplin in arrangement back UPF value after 50 washings is still more than 90%.
Table 1 uvioresistant performance and washing fastness test result
Optimizing under the finishing technique condition, resulting yellowish-brown transparency liquid directly carries out antibiotic finish to textile poplin cloth among the employing embodiment 1, be that test organisms carries out antibacterial test with Escherichia coli and staphylococcus aureus respectively, investigate the anti-microbial property of different strain, the results are shown in Table 2.Along with the increase of finishing agent consumption, fabric all constantly increases the antibiotic rate of Escherichia coli and staphylococcus aureus, and its reason is the increase along with consumption, and finishing agent and fibroplastic covalent bond increase, and the antibiotic effective ingredient of fiber surface increases.In a word, this finishing agent all has good antibacterial effect to Escherichia coli and staphylococcus aureus.
Table 2 anti-microbial property test result
Embodiment 3
The 4.3g sodium bicarbonate is joined in the 80g frozen water, complete molten after, slowly add 7.8g2,2,6, the 6-tetramethylpiperidinol is stirred to the solution clarification.Small lot repeatedly adds the 9.2g Cyanuric Chloride then, 0～5 ℃ of insulation reaction 90min.Reaction finishes the back with certain density sodium hydroxide solution adjusting pH to 6～6.2, is warming up to 40 ℃ then, inwardly drips 4.7g 2,4-diamino benzene sulfonic acid, insulation reaction 3h.Regulate pH to 5～6 every half an hour with certain density sodium hydroxide solution in the course of reaction.The last 16g that slowly adds is to (beta-sulfuric ester ethyl sulfonyl) aniline, and 85～90 ℃ were stirred 3 hours.Obtain the solution of light brown after reaction finishes, isolated by filtration obtains compound b after the oven dry, and compound b is the multifunction finishing agent that has uvioresistant performance and light stability simultaneously.Gained solution can be directly used in the COTTON FABRIC arrangement without arrangement.
Embodiment 4
Present embodiment is the research to compound b uvioresistant and light stability, comprises determining to optimize finishing technique, uvioresistant performance test and light fastness test.
To the optimization finishing technique of compound b on textile poplin cloth, adopted five factors, six horizontal quadratures experiments to draw at last to optimize finishing technique to be: bath raio 1: 15, room temperature are put into ultra-violet absorber and cotton, the finishing agent consumption be fabric heavy 1～10%, be warming up to 50 ℃, add glauber salt 20g/L, insulation 35min, add soda ash 30g/L then, be warming up to 80 ℃, insulation 25min, hot water wash is once, cold water is cleaned, oven dry.
Optimizing under the finishing technique condition, resulting white emulsion liquid directly carries out anti UV finishing to textile poplin cloth among the employing embodiment 3, and textile poplin cloth after putting in order is carried out 50 times soap, respectively to before the textile finishing, arrangement back and the UPF value of soaping after 50 times test, test result sees Table 3.The UPF value of the textile poplin cloth in arrangement back significantly increases along with the increase of ultra-violet absorber consumption, and when the finishing agent consumption reached fabric weight 1%, fabric UPF can reach more than 50, and when consumption reached 9%, fabric UPF had reached more than 80.As seen, the textile poplin cloth of arrangement has splendid ultraviolet protection performance.The retention rate of the textile Dense Poplin in arrangement back UPF value after 50 washings shows thus that still more than 90% the ultra-violet absorber of preparation has good washing durability.
Table 3 uvioresistant performance and washing fastness test result
Optimizing under the finishing technique condition, adopt fabric to weigh 5%, 10%, 15% and 20% finishing agent respectively textile poplin cloth is carried out anti UV finishing, and dye to putting back cloth specimen and former cloth in order, the light fastness of test cloth specimen, with the use of the investigating ultra-violet absorber influence to the fabric light fastness, test result sees Table 4.As can be seen from Table 4, the light fastness of former cloth is lower, and this is because in the Exposure to Sunlight process, illumination has produced influence to dyestuff.Stablize group and weakened the influence of ultraviolet ray owing to be reacted to hindered amine light on the fabric dyestuff, thus arrangement afterwards the light fastness of cloth specimen improve.Along with the increase of finishing agent consumption, light fastness promotes effect to be increased obviously; And when the finishing agent consumption reach fabric weight 10% the time, its light fastness can promote about 1 grade.
Table 4 light fastness test result
Claims (2)
1. a multifunctional reactive cotton ultraviolet absorbent is characterized in that, the structural formula of this absorbent is
2. the synthetic method of multifunctional reactive cotton ultraviolet absorbent as claimed in claim 1, its concrete synthesis step is as follows:
(1) adds functional finishing agent in the Cyanuric Chloride
With water is solvent, and 0～5 ℃ of reaction 1～2h introduces the finishing functions group;
(2) add the linking group material
With water is solvent, and 40～50 ℃ of reaction 3～4h connect two triazine rings;
(3) or again with other reactivity material
With water is solvent, and 80～90 ℃ of reaction 3～4h introduce other active group on triazine ring.
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Cited By (1)
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| KR20150120725A (en) * | 2014-04-18 | 2015-10-28 | 주식회사 알파켐 | Dye-hybridized pigment derivatives, pigment dispersion composition, photo-sensitive color composition, and color filte |
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| CN102304227B (en) * | 2011-07-13 | 2012-11-14 | 大连理工大学 | Water-soluble poly-s-triazine high polymer material |
| CN102584727B (en) * | 2011-11-28 | 2015-04-29 | 江南大学 | Method for synthesizing novel reactive ultraviolet absorbent and application thereof |
| CN103031712A (en) * | 2012-12-21 | 2013-04-10 | 江南大学 | Method for improving color fastness to light of fabric dyed by active dye |
| CN104003952B (en) * | 2013-12-13 | 2016-09-28 | 保定市乐凯化学有限公司 | The preparation method of 4-[(4,6-bis-pungent sulfenyl-1,3,5-triazine-2-base) amino]-2,6 di t butyl phenol |
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| CN111205510A (en) * | 2020-02-13 | 2020-05-29 | 西安工业大学 | Dual-functional ultraviolet absorbent and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5760227A (en) * | 1994-03-24 | 1998-06-02 | Clariant Finance (Bvi) Limited | Compounds of the s-triazine series |
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2007
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5760227A (en) * | 1994-03-24 | 1998-06-02 | Clariant Finance (Bvi) Limited | Compounds of the s-triazine series |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150120725A (en) * | 2014-04-18 | 2015-10-28 | 주식회사 알파켐 | Dye-hybridized pigment derivatives, pigment dispersion composition, photo-sensitive color composition, and color filte |
| KR101597603B1 (en) * | 2014-04-18 | 2016-02-25 | 주식회사 알파켐 | Dye-hybridized pigment derivatives, pigment dispersion composition, photo-sensitive color composition, and color filte |
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Assignee: Guangdong Demei Fine Chemical Co., Ltd. Assignor: Donghua University Contract record no.: 2012440000153 Denomination of invention: Multifunctional reactive cotton ultraviolet absorbent, synthetic method and use thereof Granted publication date: 20100602 License type: Exclusive License Open date: 20080723 Record date: 20120329 |
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