CN102936838B - Method for preparing fabric with deodorizing function - Google Patents

Method for preparing fabric with deodorizing function Download PDF

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CN102936838B
CN102936838B CN201210439327.XA CN201210439327A CN102936838B CN 102936838 B CN102936838 B CN 102936838B CN 201210439327 A CN201210439327 A CN 201210439327A CN 102936838 B CN102936838 B CN 102936838B
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beta
fabric
cyclodextrin
schardinger dextrin
catechin
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CN102936838A (en
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尉霞
付春林
孔令豪
王�忠
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Hosa Industrial Fujian Co ltd
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HOSA INDUSTRIAL (FUJIAN) Co Ltd
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Abstract

The invention discloses a method for preparing fabric with a deodorizing function. The method comprises steps of modifying beta-cyclodextrin or preparing sulfonic group-beta-cyclodextrin; preparing a finishing liquor by using the prepared sulfonic group-beta-cyclodextrin, and conducting the grafting for the fabric by using the finishing liquor; and conducting the catechins inclusion for the grafted sulfonic group-beta-cyclodextrin fabric. The method is environment-friendly. The beta-cyclodextrin and the derivate of the beta-cyclodextrin are novel environment-friendly non-toxic finishing agents, the catechins is a natural deodorizer, the beta-cyclodextrin and the derivate of the beta-cyclodextrin are used for finishing the fabric through the catechins inclusion, the fabric has good deodorant, health and environment-friendly functions and is good in washable performance, the added value of textile products is improved, and the application prospects are wide. The fabric after being finished can remove odor molecules at the fetor environment, the fabric is fresh and comfortable and a user feels good.

Description

There is the preparation method of deodorization functions fabric
Technical field
The invention belongs to functional fabric processing technique field, be specifically related to a kind of preparation method with deodorization functions fabric.
Background technology
Textiles is in the process used, and especially clothes can produce stink in wearing process, and this is because textiles is a kind of porous material, easily adsorbs the various impurity of gas phase, liquid phase and solid phase, becomes the breeding carrier of miscellaneous bacteria, thus produces stink.Stink mainly contains two sources: the stink namely fabric generated and the stink absorbed from environment.With regard to the environment that we live at ordinary times, the stink that clothes adsorbs mainly contains the stink of smoke from cigarette and oil smoke.
The high functionality finishing technique that deodorizing has developed rapidly since arranging and being the nineties in 20th century, textiles has good health and health care after deodorizing arranges.Desirable deodorizing finishing effect be have efficient removal effect to various foul smell taste, water-fastness, effect is lasting, security is good, on human body and environment without eco-toxicity and on the original wearability of textiles, color and luster and other arrange without impact.
Current deodorizing running product mainly divides three major types: the first kind removes the stink in daily life; Equations of The Second Kind is the stink (mainly nicotine and acetaldehyde) removing the generation of cigarette smog; 3rd class is the removing residue formaldehyde smell after removing house decoration.It is with deodorant process fiber or fabric that deodorizing arranges, and utilizes physics, chemistry, biological agent absorption also decompose odor material, the imperceptible stink of people is existed.Common are: sensation deodorization process, chemical deodorizing method, physical deodorization method, living things catalysis deodorization process, photocatalysis deodorization process 5 kinds of deodorizing methods.
Beta-schardinger dextrin-, as the nontoxic finishing auxiliaries of a kind of novel environment friendly, because it has molecular structure hydrophobic in the outer hydrophilic loop of unique ring, can form inclusion compound by the many guest molecules of inclusion.The finishing auxiliarieses such as this characteristic inclusion essence, antiseptic, anti ultraviolet agent of beta-schardinger dextrin-are utilized to play the effects such as shielding substrate, Co ntrolled release, prolection; delay the action time of auxiliary agent, be therefore widely used in the every field such as food, cosmetics, medical treatment, dyeing and finishing.
The hydrophobic cavity of beta-schardinger dextrin-uniqueness, makes it be grafted on textiles, and it is multi-functional to give textiles fragrance, deodorizing, health care etc.The deodorizing of beta-schardinger dextrin-arranges textiles, even if in the environment being full of foul smell molecule, can not adsorb foul smell molecule or by foul smell molecular breakdown, make the existence of the imperceptible stink of people, builds comfortable, a healthy living environment.
In beta-schardinger dextrin-deodorizing arranges, studying more is fragrance deodorizing method, namely utilizes the hydrophobic cavity inclusion essence of beta-schardinger dextrin-, essence slow releasing mask malodors during use; After essence releases, again can apply essence, flexible and convenient operation.The method for sorting be affixed to by beta-schardinger dextrin-on fabric is different, deodorizing effect and fabric property change also different, the method used mainly contains: (1) microcapsule method, aromatic substance (referring generally to essence) is utilized to carry out encapsulation method deodorizing, beta-schardinger dextrin-, as the carrier of essence, plays and slowly releases fragrant effect; (2) grafting copolymerization process, reacts beta-schardinger dextrin-, crosslinking agent and fiber, makes it be linked on fiber with bath; (3) modification grafted by beta cyclodextrin method, carries out modification to beta-schardinger dextrin-, makes the beta-cyclodextrin derivative of band active group, carries out cross-linking reaction under suitable condition with fiber; (4) sol-gel process, with inorganic or organic compound (as methyl silicate and ethyl orthosilicate etc.) for raw material, through hydrolysis, polycondensation reaction, solidified gradually by collosol state, form the oxide gel with tridimensional network, make on inclusion compound set and fabric.
Due to the architectural characteristic of wool fibre, beta-schardinger dextrin-is made to have certain restriction on wool fabric deodorizing arranges.In this respect, Japanese researchers develops some deodorant, the amphoteric surfactant Ribflesh W spun comprising clock and the deodorizing wool (using beta-cyclodextrin inclusion compound natural deodorant, by top finish on wool fabric) of she rattan dyer.Concrete grammar is: first carry out pre-treatment with chlorine etc. to wool fibre, makes fiber surface upgrading, electronegative; Then use with positive daiamid epoxy propane resin, the cyclodextrin of natural for inclusion deodorizing plant extracts is fixed on fiber surface, the resin molding that the wool fibre 0.1um of such process is thick covers, cyclodextrin is included in resin molding, and the beta-schardinger dextrin-of inclusion deodorant also can give full play to deodorization in resin molding.The method can affect wearability and the feel of fabric, and is unfavorable for a large amount of production.The BTCA (BTCA) such as Yang Yufang makees crosslinking agent, under inferior sodium phosphate catalysis and high temperature baking conditions, is anchored on fabric by beta-schardinger dextrin-.There is good suction ammonia ability, water-fastness and lasting deodorizing effect after tested, and do not affect wearability and feel.
The effect of mainly ionic bond on wool fibre is anchored at according to beta-schardinger dextrin-, therefore its beta-schardinger dextrin-is modified as sulfonic group-beta-cyclodextrin derivative, in acid condition, be similar to the process of dyeing wool in ACID DYES, be combined with ionic bond with positively charged wool.Wang Chunmeis etc. adopt Direct Sulfonation method that beta-schardinger dextrin-is modified as sulfonic group-beta-cyclodextrin derivative, develop the wool fabric with rose fragrance.After arranging after tested, after fabric 10 washings, essence loss reaches 70%, and washing fastness needs to improve further.Wang Junhuas etc. have studied sulfonated β-cyclodextrin and arrange the storage of wool fabric perfume and increase dark arrangement, all can reach good effect, and little on the rub resistance of fabric, washing fastness impact.As mentioned above, be affixed to by beta-schardinger dextrin-on wool fabric, applying more is chemical crosslink technique, and this have impact on feel and the wearability of fabric to a certain extent, and washing fastness is undesirable.Therefore, the study on the modification of beta-schardinger dextrin-is very important, is also conducive to improving its using value.
Tealeaves has anticancer, anti-ageing, a series of pharmacological function such as elimination human free radical, reducing blood lipid etc. efficiently, progressively causes the concern of people.The complex chemical composition of tealeaves, has kind more than 300, and as polyphenol, flavonols, caffeine, aromatic oil, mineral matter, protein, amino acid, lipoid, vitamin etc., wherein main component is Tea Polyphenols.The content of Tea Polyphenols in tealeaves is maximum, account for fresh cured leaf heavy 30%, being one of Main Ingredients and Appearance forming Tea color fragrance, is also one of Main Ingredients and Appearance having health care in tealeaves.Tea Polyphenols is the general name of Polyphenols of Tea, comprises flavanol compound, anthocyanin class, flavonoids, flavonols and phenolic acid class etc.Wherein important with flavanol compound (catechin), account for 60% ~ 80% of Tea Polyphenols total amount.Catechin (C 15h 14o 6), colourless crystallization shape solid, can be water-soluble, and its aqueous solution is heated or in the presence of a mineral acid, easily aggregates into amorphous tannin.
The scientific research of nearly 20 years both at home and abroad shows, catechin has " three anti-(anticancer, anti-ageing, anti-oxidant) ", " three falling (hypoglycemic, reducing blood lipid, hypotensive) ", " three disappear (sterilization, anti-inflammatory, smelly eliminating) " and prevent and treat the medicinal health care function such as nerve injury disease.The deodorization of catechin is in particular in except foul smell such as ammonia (lavatory is smelly), trimethylamine (fish is smelt as of rotten fish), methyl mercaptan (halitosis), hydrogen sulfide (corrupt smelly), and concentration is higher, and deodorizing effect is better.Have and think, the deodorizing mechanism of catechin is: the reactions such as the hydroxyl that in catechin, activity is stronger, carbonyl can neutralize with foul smell molecule, condensation.
Flavonoids series compound method, comprises flavonols and flavanols, in textiles deodorizing, had relevant investigation and application.Processing method as Japan is padded together with flavonoids with BTCA, anhydrous sodium phosphate with mercerized cotton, then dry, then cure 2min at 160 DEG C, and flavonoids is anchored on fiber.Chen Yanmei etc. have studied the antibacterial effect of Tea Polyphenols finishing of cotton textiles.Experiment finds, COTTON FABRIC is after the pre-complexing of alum, and Tea Polyphenols concentration is 6g/L, and when dressing liquid pH is 6.88, after 50 DEG C of arrangement 60min, fungistatic effect is best.After 20 washings, still can reach more than 70% to the bacteriostasis rate of Escherichia coli, staphylococcus aureus, washability is better.
One chloro-s-triazine such as Yuan Ailin-grafted by beta cyclodextrin COTTON FABRIC, then arrange with Tea Polyphenols, give the anti-microbial property that fabric is good.Experiment finds that finish fabric still can reach more than 80% to bacillus subtilis, colibacillary bacteriostasis rate, and antibacterial persistence is better after 20 washings.
In conjunction with above scientific research and theoretical foundation, the present invention adopts beta-schardinger dextrin-and derivative inclusion catechin thereof to arrange weaving face fabric, and its deodorizing effect is embodied in two aspects: one is the ability that beta-schardinger dextrin-and derivative itself thereof have absorption foul smell molecule; Two is catechin in use slow releasing, reacts with foul smell molecule, thus reaches dual lasting deodorizing effect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with deodorization functions fabric, beta-schardinger dextrin-and derivative inclusion catechin thereof is adopted to arrange fabric, good deodorizing effect can not only be reached, and water-wash resistance is good, to human body and ecological environment without destroying and there is health care.
The technical solution adopted in the present invention is, has the preparation method of deodorization functions fabric, and concrete grammar is according to step enforcement below:
The modification of step 1, beta-schardinger dextrin-or the preparation of sulfonic acid group-beta-cyclodextrin;
The sulfonic acid group-beta-cyclodextrin configuration dressing liquid that step 2, employing are prepared, and utilize dressing liquid to carry out grafting process to fabric;
Step 3, the process of inclusion catechin is carried out to the fabric of grafting sulfonic groups-beta-schardinger dextrin-.
Feature of the present invention is also,
Step 1 is specifically implemented according to following steps:
1) concentrated sulfuric acid and beta-schardinger dextrin-that mass fraction is 70% ~ 90% is measured respectively, mass ratio between the concentrated sulfuric acid and beta-schardinger dextrin-is 5 ~ 6:1, the concentrated sulfuric acid measured is poured in beaker, again the beaker that the concentrated sulfuric acid is housed is put into ice bath, under 0 DEG C ~ 5 DEG C conditions, in the beaker that the concentrated sulfuric acid is housed, add the beta-schardinger dextrin-taken and stir 1h ~ 2h, forming reactions liquid, in reactant liquor, add distilled water, volume ratio 1:15 ~ 25 of reactant liquor and distilled water, be configured to reactant liquor A;
2) get calcium carbonate and pour 1 into) in configuration reactant liquor A in, simultaneously pH value to the pH value of reactant liquor A of test reaction liquid A is 6.5 ~ 7.0, stops adding calcium carbonate, obtains the reactant liquor B containing calcium sulfate precipitation;
3) filter 2) in obtain reactant liquor B, obtain calcium sulfate precipitation and filtrate, calcium sulfate precipitation washed, then by washing after calcium sulfate precipitation and filtrate merge, obtain mixed liquor;
4) by 3) in the filtrate that obtains measure absolute ethyl alcohol, the volume ratio of filtrate and absolute ethyl alcohol is 1:0.5 ~ 1.5, again by 3) in the mixed liquor that obtains add in the absolute ethyl alcohol measured, obtain mixed liquor A, at 0 DEG C ~ 10 DEG C, leave standstill mixed liquor A 12h ~ 24h, the solubility of beta-schardinger dextrin-is low, can separate out as unreacted beta-schardinger dextrin-after low temperature is static, through the unreacted beta-schardinger dextrin-of elimination, namely obtain filtrate A;
5) by 4) in the filtrate A sodium carbonate that obtains regulate, add sodium carbonate while the pH value of filtrates tested A, pH value to filtrate A is 9.0 ~ 11.0, again filtrate A is filtered, because sodium carbonate is lower than the solubility in water at ethanol, again filtrate A being carried out filtering mainly in order to filter out the sodium carbonate of precipitation, obtaining liquor B, then liquor B acetic acid to be adjusted to pH value be 6.0 ~ 7.0;
6) by 5) in the liquor B that obtains adopt evaporating and concentrating process to process, obtain the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, in the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, add absolute ethyl alcohol produce white or pale yellow precipitate, the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin and the volume ratio of absolute ethyl alcohol are 1:20 ~ 30, again the acetic acid concentrate of the sulfonic acid group-beta-cyclodextrin adding absolute ethyl alcohol is carried out suction filtration, be precipitated thing, by sediment ethanol, acetone washing, adopt vacuumize again, namely obtain sulfonic acid group-beta-cyclodextrin.
Step 2 is specifically implemented according to following steps:
1) the sulfonic acid group-beta-cyclodextrin of preparation in step 1 is taken, sodium sulphate is taken by the quality of sulfonic acid group-beta-cyclodextrin, the mass ratio of sulfonic acid group-beta-cyclodextrin and sodium sulphate is 8 ~ 12:1, under 40 DEG C ~ 60 DEG C conditions, the sulfonic acid group-beta-cyclodextrin taken and sodium sulphate are dissolved in deionized water, form mixed solution, add in mixed solution again mass percent be 30% ~ 40% acetic acid regulate the pH of mixed solution to be 3.0 ~ 4.0, mixed solution is incubated 10min ~ 20min under 40 DEG C ~ 60 DEG C conditions, namely obtains dressing liquid;
2) by 1) in the dressing liquid that obtains take and wait to arrange fabric, first wait that arranging fabric deionized water soaks by what take, again wetting is waited that arranging fabric puts into dressing liquid, wait that the bath raio arranging fabric and dressing liquid is 1:15 ~ 30, under 90 DEG C ~ 100 DEG C conditions, heat-insulation soaking 30min ~ 75min, takes out fabric, by fabric through washing post-drying, namely obtain the fabric of grafting sulfonic groups-beta-schardinger dextrin-.
Specifically implementing according to following steps of step 3:
1) take catechin, the mass ratio of the fabric of grafting sulfonic groups-beta-schardinger dextrin-that catechin and step 2 obtain is 1:3.0 ~ 5.5, and catechin being dissolved in distilled water and being configured to mass percent concentration is 4g/L ~ 6g/L catechin solution;
2) fabric of grafting sulfonic groups-beta-schardinger dextrin-step 2 obtained is immersed in 1) in configuration catechin solution in, the fabric of grafting sulfonic groups-beta-schardinger dextrin-and bath raio 1:45 ~ 55 of catechin solution, under 50 DEG C ~ 60 DEG C conditions, adopt ultrasonic oscillation process 70min ~ 90min, make catechin inclusion on the fabric of grafting sulfonic groups-beta-schardinger dextrin-, grafting sulfonic groups-beta-schardinger dextrin-the fabric of the inclusion catechin obtained, finally the grafting sulfonic groups of inclusion catechin-beta-schardinger dextrin-fabric is washed, dry, namely the fabric with deodorization functions of the present invention is obtained.
The invention has the beneficial effects as follows,
Beta-schardinger dextrin-and derivative thereof are the nontoxic finishing agents of a kind of novel environment friendly, and catechin is natural deodorant, the present invention adopts beta-schardinger dextrin-and derivative inclusion catechin thereof to arrange fabric, make the fabric after arrangement have good deodorization health function, ecological, environmental protective performance, improve the added value of textile product simultaneously.Solve the weak effect of existing deodorizing arrangement existence, act on lastingly, affect the problems such as textiles wearability.Even if the fabric after arranging, in the environment being full of stench, can remove foul smell molecule, keep the fresh and comfortable of fabric, wearer is in a cheerful frame of mind.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
The preparation method with deodorization functions fabric of the present invention, specifically implements according to following steps:
The modification of step 1, beta-schardinger dextrin-or the preparation of sulfonic acid group-beta-cyclodextrin:
1) concentrated sulfuric acid and beta-schardinger dextrin-that mass fraction is 70% ~ 90% is measured respectively, mass ratio between the concentrated sulfuric acid and beta-schardinger dextrin-is 5 ~ 6:1, the concentrated sulfuric acid measured is poured in beaker, again the beaker that the concentrated sulfuric acid is housed is put into ice bath, under 0 DEG C ~ 5 DEG C conditions, in the beaker that the concentrated sulfuric acid is housed, add the beta-schardinger dextrin-taken and stir 1h ~ 2h, forming reactions liquid, in reactant liquor, add distilled water, volume ratio 1:15 ~ 25 of reactant liquor and distilled water, be configured to reactant liquor A;
2) get calcium carbonate and pour 1 into) in configuration reactant liquor A in, simultaneously pH value to the pH value of reactant liquor A of test reaction liquid A is 6.5 ~ 7.0, stop adding calcium carbonate, namely use unreacted sulfuric acid in calcium carbonate neutralization reaction liquid B, obtain the reactant liquor B containing calcium sulfate precipitation;
3) filter 2) in obtain reactant liquor B, obtain calcium sulfate precipitation and filtrate, calcium sulfate precipitation washed, then by washing after calcium sulfate precipitation and filtrate merge, obtain mixed liquor;
4) by 3) in the filtrate that obtains measure absolute ethyl alcohol, the volume ratio of filtrate and absolute ethyl alcohol is 1:0.5 ~ 1.5, again by 3) in the mixed liquor that obtains add in the absolute ethyl alcohol measured, obtain mixed liquor A, at 0 DEG C ~ 10 DEG C, leave standstill mixed liquor A 12h ~ 24h, again by leave standstill after mixed liquor A filter, because the solubility of beta-schardinger dextrin-is low, can separate out as unreacted beta-schardinger dextrin-after low temperature is static, through the unreacted beta-schardinger dextrin-of elimination, namely obtain filtrate A;
5) by 4) in the filtrate A sodium carbonate that obtains regulate, add sodium carbonate while the pH value of filtrates tested A, pH value to filtrate A is 9.0 ~ 11.0, again filtrate A is filtered, because sodium carbonate is lower than the solubility in water at ethanol, again filtrate A being carried out filtering mainly in order to filter out the sodium carbonate of precipitation, obtaining liquor B, then liquor B acetic acid to be adjusted to pH value be 6.0 ~ 7.0;
6) by 5) in the liquor B that obtains adopt evaporating and concentrating process to process, obtain the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, in the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, add absolute ethyl alcohol produce white or pale yellow precipitate, the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin and the volume ratio of absolute ethyl alcohol are 1:20 ~ 30, again the acetic acid concentrate of the sulfonic acid group-beta-cyclodextrin adding absolute ethyl alcohol is carried out suction filtration, be precipitated thing, by sediment ethanol, acetone washing, adopt vacuumize again, namely obtain sulfonic acid group-beta-cyclodextrin.
The sulfonic acid group-beta-cyclodextrin configuration dressing liquid that step 2, employing are prepared, and utilize dressing liquid to carry out grafting process to fabric:
1) the sulfonic acid group-beta-cyclodextrin of preparation in step 1 is taken, sodium sulphate is taken by the quality of sulfonic acid group-beta-cyclodextrin, the mass ratio of sulfonic acid group-beta-cyclodextrin and sodium sulphate is 8 ~ 12:1, under 40 DEG C ~ 60 DEG C conditions, the sulfonic acid group-beta-cyclodextrin taken and sodium sulphate are dissolved in deionized water, form mixed solution, add in mixed solution again mass percent be 30% ~ 40% acetic acid regulate the pH of mixed solution to be 3.0 ~ 4.0, mixed solution is incubated 10min ~ 20min under 40 DEG C ~ 60 DEG C conditions, namely obtains dressing liquid;
2) by 1) in the dressing liquid that obtains take and wait to arrange fabric, first wait that arranging fabric deionized water soaks by what take, again wetting is waited that arranging fabric puts into dressing liquid, wait that the bath raio arranging fabric and dressing liquid is 1:15 ~ 30, under 90 DEG C ~ 100 DEG C conditions, heat-insulation soaking 30min ~ 75min, takes out fabric, by fabric through washing post-drying, namely obtain the fabric of grafting sulfonic groups-beta-schardinger dextrin-.
Step 3, the process of inclusion catechin is carried out to the fabric of grafting sulfonic groups-beta-schardinger dextrin-:
1) take catechin, the mass ratio of the fabric of grafting sulfonic groups-beta-schardinger dextrin-that catechin and step 2 obtain is 1:3.0 ~ 5.5, and catechin being dissolved in distilled water and being configured to mass percent concentration is 4g/L ~ 6g/L catechin solution;
2) fabric of grafting sulfonic groups-beta-schardinger dextrin-step 2 obtained is immersed in 1) in configuration catechin solution in, the fabric of grafting sulfonic groups-beta-schardinger dextrin-and bath raio 1:45 ~ 55 of catechin solution, under 50 DEG C ~ 60 DEG C conditions, adopt ultrasonic oscillation process 70min ~ 90min, make catechin inclusion on the fabric of grafting sulfonic groups-beta-schardinger dextrin-, grafting sulfonic groups-beta-schardinger dextrin-the fabric of the inclusion catechin obtained, finally the grafting sulfonic groups of inclusion catechin-beta-schardinger dextrin-fabric is washed, dry, namely the fabric with deodorization functions of the present invention is obtained.
Detect the deodorization functions of the grafting sulfonic groups-beta-schardinger dextrin-fabric of inclusion catechin:
In an airtight container, collect the flue gas of burning 2min ~ 4min containing nicotine, according to absorption-desorption-equilibrium principle, test adopt the fabric with deodorization functions prepared of the inventive method with without arranges fabric adsorb the flue gas containing nicotine after flue gas remain content and after reaching balance from the flue gas content of desorb fabric.The removing taste effect arranging forward and backward fabric is compared by the total ion current abundance of chromatogram and peak area size.Table 1 arranges forward and backward fabric to the chromatogram data of flue gas removal effect for gas chromatograph-mass spectrometer records, specifically as shown in table 1.
Before and after table 1 arranges, fabric is to the chromatogram data of flue gas removal effect
Data in comparative analysis table 1 find, place the total ion current abundance with flue gas in the airtight container of the fabric of deodorization functions prepared of the inventive method and peak area little, namely in airtight container, remaining flue gas content is few, and the flue gas that the fabric that deodorizing arranges absorbs is many; After desorb in airtight container the total ion current abundance of flue gas and area little, namely in airtight container, flue gas content is few, then illustrate that the fabric arranged through deodorizing can adsorb and remove smoke smell.
Along with the extensive investigation and application of nanometer technology, how nanometer technology is applied to textiles deodorizing arrangement and also possesses some special knowledge.Nano aperture molecule, as a branch of nano material, has the advantages such as selective catalysis, the exchange of invertibity Subjective and Objective, molecular recognition, ultra-pure separation, biological conduction, molecular device and chip.Beta-schardinger dextrin-belongs to cyclic oligosaccharide, has the molecular structure of nano-scale, the hydrophobic cavity structure of its uniqueness, can adsorb and discharge a lot of material, also can inclusion deodorant (essence, plant extracts etc.), finishing agent slow releasing during use, thus reach well lasting deodorizing effect.
Due to beta-schardinger dextrin-molecular structure, make its solubility in water low, constrain it to a certain extent and apply widely.For improving the shortcoming of beta-schardinger dextrin-, making beta-cyclodextrin derivative by introducing new substituting group, increasing the quantity of active group, making it that there is excellent performance, and do not affect the Binding ability to guest molecule.Beta-schardinger dextrin-is anchored on different fiber, the method with stock-dye resemble process can be adopted.Therefore, for different fibers, the chemical modification method of employing is different.
Adopt chemical method to anchor on fiber by beta-schardinger dextrin-, persistence is good.Mainly contain following three kinds of methods at present: beta-schardinger dextrin-modification is had the beta-cyclodextrin derivative of active group by (1), under appropriate reaction conditions with fiber generation cross-linking reaction, thus make beta-schardinger dextrin-be affixed on fiber; (2) modification is carried out to fiber, the group that grafting can be reacted with beta-schardinger dextrin-, then react with beta-schardinger dextrin-; (3) beta-schardinger dextrin-, crosslinking agent, fiber carry out, with bathing reaction, beta-schardinger dextrin-being affixed on fiber by crosslinking agent.
The concrete set mode of conventional fiber and beta-schardinger dextrin-is as shown in table 2.
The set mode of table 2 beta-schardinger dextrin-on different fiber
Set mode Cellulose fibre Wool fibre Polyamide fiber Polyester fiber Polypropylene fibre
Crosslinking agent + - - - -
Ionic interaction- + -
Covalent bonds + - -
Van der Waals force--
Note :+indicate effect ,-indicate without effect.
Grafted by beta cyclodextrin is a lot of to the research on cellulose fibre, and the general beta-cyclodextrin derivative used containing active group, as one chlorotriazine-beta-schardinger dextrin-, n-methylolacrylamide-beta-schardinger dextrin-etc.Also epoxy available chloropropane method, polycarboxylic acid crosslinked dose of method etc., wherein use Crosslink bond type finishing of cotton textiles, can improve its wrinkle resistance.For cellulose derivative series fiber, as shitosan, mainly to carry out cross-linked graft with epoxychloropropane.
For polyester fiber, polybasic carboxylic acid and beta-schardinger dextrin-can be formed polymer, make it be wrapped on fiber.Also can use supercritical carbon dioxide solvent method or plasma method, be anchored on polyester fiber.
For wool or polyamide fiber, often adopt sulfonic group-beta-cyclodextrin derivative.Electronegative sulfonic acid group-beta-cyclodextrin is combined with ionic bond form with the amino fibre of positively charged, is similar to dyeing wool fiber in ACID DYES.For silk fiber, by synthesis beta-schardinger dextrin-list aldehyde, it is made to be grafted on silk fiber in suitable conditioned response.
Embodiment 1
Measure the concentrated sulfuric acid and beta-schardinger dextrin-that mass fraction is 90% respectively, mass ratio between the concentrated sulfuric acid and beta-schardinger dextrin-is 5.5:1, the concentrated sulfuric acid measured is poured in beaker, again the beaker that the concentrated sulfuric acid is housed is put into ice bath, under 0 DEG C of condition, in the beaker that the concentrated sulfuric acid is housed, add the beta-schardinger dextrin-taken and stir 1h, forming reactions liquid, reactant liquor is poured in distilled water, the volume ratio of reactant liquor and distilled water is 1:25, be configured to reactant liquor A, getting calcium carbonate pours in reactant liquor A, simultaneously the pH value of test reaction liquid A is 7.0 to the pH of reactant liquor A, stop adding calcium carbonate, reactant liquor B is filtered, filter the calcium sulfate precipitation generated, calcium sulfate precipitation is washed, again the calcium sulfate precipitation after washing and filtrate are merged, obtain mixed liquor, measure absolute ethyl alcohol, the volume ratio of filtrate and absolute ethyl alcohol is 1:1.5, is added by mixed liquor in the absolute ethyl alcohol measured, obtain mixed liquor A, at 0 DEG C, leave standstill mixed liquor A 12h, again by leave standstill after mixed liquor A filter, filter out unreacted beta-schardinger dextrin-, obtain filtrate A, filtrate A sodium carbonate is regulated, add sodium carbonate while the pH value of filtrates tested A, pH value to filtrate A is 9.0, again filtrate A is filtered, because sodium carbonate is lower than the solubility in water at ethanol, again filtrate A being carried out filtering mainly in order to filter out the sodium carbonate of precipitation, obtaining liquor B, then liquor B acetic acid to be adjusted to pH value be 6.0, evaporating and concentrating process is adopted to process liquor B, obtain the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, in the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, add absolute ethyl alcohol produce white or pale yellow precipitate, the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin and the volume ratio of absolute ethyl alcohol are 1:20, again the acetic acid concentrate of the sulfonic acid group-beta-cyclodextrin adding absolute ethyl alcohol is carried out suction filtration, be precipitated thing, by sediment ethanol, acetone washing, adopt vacuumize again, namely obtain sulfonic acid group-beta-cyclodextrin,
Take the sulfonic acid group-beta-cyclodextrin of preparation, sodium sulphate is taken by the quality of sulfonic acid group-beta-cyclodextrin, the mass ratio of sulfonic acid group-beta-cyclodextrin and sodium sulphate is 8:1, under 40 DEG C of conditions, the sulfonic acid group-beta-cyclodextrin taken and sodium sulphate are dissolved in deionized water, form mixed solution, in mixed solution, add mass percent be again the pH of the acetic acid regulator solution of 40% is 3.0, mixed solution is incubated 10min under 40 DEG C of conditions, namely dressing liquid is obtained, take by dressing liquid and wait to arrange fabric, first wait that arranging fabric deionized water soaks by what take, again wetting is waited that arranging fabric puts into the dressing liquid configured, wait that the bath raio arranging fabric and dressing liquid is 1:15, under 90 DEG C of conditions, heat-insulation soaking 30min, take out fabric, by fabric through washing post-drying, obtain the fabric of grafting sulfonic groups-beta-schardinger dextrin-,
Take catechin, the mass ratio of the fabric of catechin and grafting sulfonic groups-beta-schardinger dextrin-is 1:5.5, and catechin being dissolved in distilled water and being configured to mass percent concentration is 4g/L catechin solution; The fabric of grafting sulfonic groups-beta-schardinger dextrin-is immersed in the catechin solution of configuration, the fabric of grafting sulfonic groups-beta-schardinger dextrin-and the bath raio 1:45 of catechin solution, under 50 DEG C of conditions, adopt ultrasonic oscillation process 90min, catechin inclusion is on the fabric of grafting sulfonic groups-beta-schardinger dextrin-, grafting sulfonic groups-beta-schardinger dextrin-the fabric of the inclusion catechin obtained, finally the grafting sulfonic groups of inclusion catechin-beta-schardinger dextrin-fabric is carried out washing, drying, namely obtain the fabric with deodorization functions of the present invention, test result is in table 3.
Table 3 embodiment 1 test result
Grafting weight gaining rate (%) Catechin exhaustion rate (%) Catechin content (mg/g) on fabric Deodorizing effect
3.86 31.78 62.6 Better
Embodiment 2
Measure the concentrated sulfuric acid and beta-schardinger dextrin-that mass fraction is 80% respectively, mass ratio between the concentrated sulfuric acid and beta-schardinger dextrin-is 5:1, the concentrated sulfuric acid measured is poured in beaker, again the beaker that the concentrated sulfuric acid is housed is put into ice bath, under 3 DEG C of conditions, in the beaker that the concentrated sulfuric acid is housed, add the beta-schardinger dextrin-taken and stir 2h, forming reactions liquid, reactant liquor is poured in distilled water, the volume ratio of reactant liquor and distilled water is 1:20, be configured to reactant liquor A, getting calcium carbonate pours in reactant liquor A, simultaneously the pH value of test reaction liquid A is 6.5 to the pH of reactant liquor A, stop adding calcium carbonate, reactant liquor B is filtered, filter the calcium sulfate precipitation generated, calcium sulfate precipitation is washed, again the calcium sulfate precipitation after washing and filtrate are merged, obtain mixed liquor, measure absolute ethyl alcohol, the volume ratio of filtrate and absolute ethyl alcohol is 1:1, is added by mixed liquor in the absolute ethyl alcohol measured, obtain mixed liquor A, at 5 DEG C, leave standstill mixed liquor A 15h, again by leave standstill after mixed liquor A filter, filter out unreacted beta-schardinger dextrin-, obtain filtrate A, filtrate A sodium carbonate is regulated, add sodium carbonate while the pH value of filtrates tested A, pH value to filtrate A is 10.5, again filtrate A is filtered, because sodium carbonate is lower than the solubility in water at ethanol, again filtrate A being carried out filtering mainly in order to filter out the sodium carbonate of precipitation, obtaining liquor B, then liquor B acetic acid to be adjusted to pH value be 6.0, evaporating and concentrating process is adopted to process liquor B, obtain the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, in the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, add absolute ethyl alcohol produce white or pale yellow precipitate, the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin and the volume ratio of absolute ethyl alcohol are 1:25, again the acetic acid concentrate of the sulfonic acid group-beta-cyclodextrin adding absolute ethyl alcohol is carried out suction filtration, be precipitated thing, by sediment ethanol, acetone washing, adopt vacuumize again, namely obtain sulfonic acid group-beta-cyclodextrin,
Take the sulfonic acid group-beta-cyclodextrin of preparation, sodium sulphate is taken by the quality of sulfonic acid group-beta-cyclodextrin, the mass ratio of sulfonic acid group-beta-cyclodextrin and sodium sulphate is 10:1, under 40 DEG C of conditions, the sulfonic acid group-beta-cyclodextrin taken and sodium sulphate are dissolved in deionized water, form mixed solution, in mixed solution, add mass percent be again the pH of the acetic acid regulator solution of 36% is 3.5, mixed solution is incubated 15min under 50 DEG C of conditions, namely dressing liquid is obtained, take by dressing liquid and wait to arrange fabric, first wait that arranging fabric deionized water soaks by what take, again wetting is waited that arranging fabric puts into the dressing liquid configured, wait that the bath raio arranging fabric and dressing liquid is 1:20, under 100 DEG C of conditions, heat-insulation soaking 75min, take out fabric, by fabric through washing post-drying, obtain the fabric of grafting sulfonic groups-beta-schardinger dextrin-,
Take the sulfonic acid group-beta-cyclodextrin of preparation, sodium sulphate is taken by the quality of sulfonic acid group-beta-cyclodextrin, the mass ratio of sulfonic acid group-beta-cyclodextrin and sodium sulphate is 10:1, under 50 DEG C of conditions, the sulfonic acid group-beta-cyclodextrin taken and sodium sulphate are dissolved in deionized water, form mixed solution, in mixed solution, add mass percent be again the pH of the acetic acid regulator solution of 36% is 3.5, mixed solution is incubated 15min under 50 DEG C of conditions, namely dressing liquid is obtained, fabric to be arranged is taken by dressing liquid, first the fabric deionized water to be arranged taken is soaked, again wetting is treated that finish fabric puts into the dressing liquid configured, wait that the bath raio arranging fabric and dressing liquid is 1:20, under 100 DEG C of conditions, heat-insulation soaking 75min, take out fabric, by fabric through washing post-drying, obtain the fabric of grafting sulfonic groups-beta-schardinger dextrin-,
Take catechin, the mass ratio of the fabric of catechin and grafting sulfonic groups-beta-schardinger dextrin-is 1:4, and catechin being dissolved in distilled water and being configured to mass percent concentration is 5g/L catechin solution; The fabric of grafting sulfonic groups-beta-schardinger dextrin-is immersed in the catechin solution of configuration, the fabric of grafting sulfonic groups-beta-schardinger dextrin-and the bath raio 1:50 of catechin solution, under 60 DEG C of conditions, adopt ultrasonic oscillation process 80min, catechin inclusion is on the fabric of grafting sulfonic groups-beta-schardinger dextrin-, grafting sulfonic groups-beta-schardinger dextrin-the fabric of the inclusion catechin obtained, finally the grafting sulfonic groups of inclusion catechin-beta-schardinger dextrin-fabric is carried out washing, drying, namely obtain the fabric with deodorization functions of the present invention, test result is in table 4.
Table 4 embodiment 2 test result
Grafting weight gaining rate (%) Catechin exhaustion rate (%) Catechin content (mg/g) on fabric Deodorizing effect
4.20 35.91 89.7 Very well
Embodiment 3
Measure the concentrated sulfuric acid and beta-schardinger dextrin-that mass fraction is 70% respectively, mass ratio between the concentrated sulfuric acid and beta-schardinger dextrin-is 6:1, the concentrated sulfuric acid measured is poured in beaker, again the beaker that the concentrated sulfuric acid is housed is put into ice bath, under 5 DEG C of conditions, in the beaker that the concentrated sulfuric acid is housed, add the beta-schardinger dextrin-taken and stir 1.5h, forming reactions liquid, reactant liquor is poured in distilled water, the volume ratio of reactant liquor and distilled water is 1:15, be configured to reactant liquor A, getting calcium carbonate pours in reactant liquor A, simultaneously the pH value of test reaction liquid A is 6.8 to the pH of reactant liquor A, stop adding calcium carbonate, reactant liquor B is filtered, filter the calcium sulfate precipitation generated, calcium sulfate precipitation is washed, again the calcium sulfate precipitation after washing and filtrate are merged, obtain mixed liquor, measure absolute ethyl alcohol, the volume ratio of filtrate and absolute ethyl alcohol is 1:0.5, is added by mixed liquor in the absolute ethyl alcohol measured, obtain mixed liquor A, at 10 DEG C, leave standstill mixed liquor A 24h, again by leave standstill after mixed liquor A filter, filter out unreacted beta-schardinger dextrin-, obtain filtrate A, filtrate A sodium carbonate is regulated, add sodium carbonate while the pH value of filtrates tested A, pH value to filtrate A is 11, again filtrate A is filtered, because sodium carbonate is lower than the solubility in water at ethanol, again filtrate A being carried out filtering mainly in order to filter out the sodium carbonate of precipitation, obtaining liquor B, then liquor B acetic acid to be adjusted to pH value be 7.0, evaporating and concentrating process is adopted to process liquor B, obtain the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, in the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, add absolute ethyl alcohol produce white or pale yellow precipitate, the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin and the volume ratio of absolute ethyl alcohol are 1:30, again the acetic acid concentrate of the sulfonic acid group-beta-cyclodextrin adding absolute ethyl alcohol is carried out suction filtration, be precipitated thing, by sediment ethanol, acetone washing, adopt vacuumize again, namely obtain sulfonic acid group-beta-cyclodextrin,
Take the sulfonic acid group-beta-cyclodextrin of preparation, sodium sulphate is taken by the quality of sulfonic acid group-beta-cyclodextrin, the mass ratio of sulfonic acid group-beta-cyclodextrin and sodium sulphate is 12:1, under 40 DEG C of conditions, the sulfonic acid group-beta-cyclodextrin taken and sodium sulphate are dissolved in deionized water, form mixed solution, in mixed solution, add mass percent be again the pH of the acetic acid regulator solution of 40% is 4.0, mixed solution is incubated 20min under 50 DEG C of conditions, namely dressing liquid is obtained, take by dressing liquid and wait to arrange fabric, first wait that arranging fabric deionized water soaks by what take, again wetting is waited that arranging fabric puts into the dressing liquid configured, wait that the bath raio arranging fabric and dressing liquid is 1:30, under 95 DEG C of conditions, heat-insulation soaking 55min, take out fabric, by fabric through washing post-drying, obtain the fabric of grafting sulfonic groups-beta-schardinger dextrin-,
Take catechin, the mass ratio of the fabric of catechin and grafting sulfonic groups-beta-schardinger dextrin-is 1:5.5, and catechin being dissolved in distilled water and being configured to mass percent concentration is 6g/L catechin solution; The fabric of grafting sulfonic groups-beta-schardinger dextrin-is immersed in the catechin solution of configuration, the fabric of grafting sulfonic groups-beta-schardinger dextrin-and the bath raio 1:55 of catechin solution, under 55 DEG C of conditions, adopt ultrasonic oscillation process 70min, catechin inclusion is on the fabric of grafting sulfonic groups-beta-schardinger dextrin-, grafting sulfonic groups-beta-schardinger dextrin-the fabric of the inclusion catechin obtained, finally the grafting sulfonic groups of inclusion catechin-beta-schardinger dextrin-fabric is carried out washing, drying, namely obtain the fabric with deodorization functions of the present invention, test result is in table 5.
Table 5 embodiment 3 test result
Grafting weight gaining rate (%) Catechin exhaustion rate (%) Catechin content (mg/g) on fabric Deodorizing effect
4.35 25.45 75.5 Good

Claims (1)

1. have the preparation method of deodorization functions fabric, it is characterized in that, concrete grammar is according to step enforcement below:
The preparation of step 1, sulfonic acid group-beta-cyclodextrin, specifically implement according to following steps:
Step 1.1, measure the concentrated sulfuric acid and the beta-schardinger dextrin-that mass fraction is 70% respectively, mass ratio between the concentrated sulfuric acid and beta-schardinger dextrin-is 5 ~ 6:1, the concentrated sulfuric acid measured is poured in beaker, again the beaker that the concentrated sulfuric acid is housed is put into ice bath, under 0 DEG C ~ 5 DEG C conditions, in the beaker that the concentrated sulfuric acid is housed, add the beta-schardinger dextrin-taken and stir 1h, forming reactions liquid, in reactant liquor, add distilled water, volume ratio 1:15 ~ 25 of reactant liquor and distilled water, be configured to reactant liquor A;
Step 1.2, get calcium carbonate and to pour in step 1.1 in the reactant liquor A of preparation, pH value to the pH value of reactant liquor A of test reaction liquid A is 6.5 simultaneously, stops adding calcium carbonate, obtains the reactant liquor B containing calcium sulfate precipitation;
Step 1.3, the reactant liquor B obtained through step 1.2 to be filtered, obtain calcium sulfate precipitation and filtrate respectively, the calcium sulfate precipitation obtained is washed, then the water lotion obtained by washing calcium sulfate precipitation and filtrate merge, and obtain mixed liquor;
Step 1.4, measure absolute ethyl alcohol by the filtrate obtained in step 1.3, the volume ratio of filtrate and absolute ethyl alcohol is 1:0.5 ~ 1.5, again the mixed liquor obtained in step 1.3 is added in the absolute ethyl alcohol measured, obtain mixed liquor A, at 0 DEG C ~ 10 DEG C, leave standstill mixed liquor A 12h ~ 24h, solubility based on beta-schardinger dextrin-is low, unreacted beta-schardinger dextrin-can be separated out after stand at low temperature, remove unreacted beta-schardinger dextrin-after filtration, namely obtain filtrate A;
Step 1.5, the filtrate A sodium carbonate obtained in step 1.4 to be regulated, add sodium carbonate while the pH value of filtrates tested A, pH value to filtrate A is 9.0 or 11.0, again filtrate A is filtered, because sodium carbonate is lower than the solubility in water at ethanol, then filtrate A is filtered, filter out the sodium carbonate of precipitation, obtain liquor B, then liquor B acetic acid to be adjusted to pH value be 6.0;
Step 1.6, evaporating and concentrating process is adopted to process the liquor B obtained in step 1.5, obtain the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, in the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin, add absolute ethyl alcohol produce white or pale yellow precipitate, the acetic acid concentrate of sulfonic acid group-beta-cyclodextrin and the volume ratio of absolute ethyl alcohol are 1:20 ~ 30, again the acetic acid concentrate of the sulfonic acid group-beta-cyclodextrin adding absolute ethyl alcohol is carried out suction filtration, be precipitated thing, by sediment ethanol, acetone washs, adopt vacuumize again, namely sulfonic acid group-beta-cyclodextrin is obtained,
The sulfonic acid group-beta-cyclodextrin preparation dressing liquid that step 2, employing are prepared, and utilize dressing liquid to carry out grafting process to fabric, concrete steps are as follows:
Step 2.1, to take in step 1 the sulfonic acid group-beta-cyclodextrin of preparation, sodium sulphate is taken by the quality of sulfonic acid group-beta-cyclodextrin, the mass ratio of sulfonic acid group-beta-cyclodextrin and sodium sulphate is 8 ~ 12:1, under 40 DEG C ~ 60 DEG C conditions, the sulfonic acid group-beta-cyclodextrin taken and sodium sulphate are dissolved in deionized water, form mixed solution, add in mixed solution again mass percent be 30% ~ 40% acetic acid regulate the pH of mixed solution to be 4.0, mixed solution is incubated 10min ~ 20min under 40 DEG C ~ 60 DEG C conditions, namely obtains dressing liquid;
Step 2.2, by step 2.1, in the dressing liquid that obtains take and wait to arrange fabric, first wait that arranging fabric deionized water soaks by what take, again wetting is waited that arranging fabric puts into dressing liquid, wait that the bath raio arranging fabric and dressing liquid is 1:15 ~ 30, under 90 DEG C ~ 100 DEG C conditions, heat-insulation soaking 75min, takes out fabric, by fabric through washing post-drying, namely obtain the fabric of grafting sulfonic groups-beta-schardinger dextrin-;
Step 3, the process of inclusion catechin is carried out to the fabric of grafting sulfonic groups-beta-schardinger dextrin-:
Step 3.1, take catechin, the mass ratio of the fabric of grafting sulfonic groups-beta-schardinger dextrin-that catechin and step 2 obtain is 1:3.0 ~ 5.5, and catechin being dissolved in distilled water and being configured to mass percent concentration is 4g/L ~ 6g/L catechin solution;
Step 3.2, the fabric of grafting sulfonic groups-beta-schardinger dextrin-step 2 obtained is immersed in the catechin solution of configuration in step 3.1, the fabric of grafting sulfonic groups-beta-schardinger dextrin-and bath raio 1:45 ~ 55 of catechin solution, under 50 DEG C ~ 60 DEG C conditions, adopt ultrasonic oscillation process 70min ~ 90min, make catechin inclusion on the fabric of grafting sulfonic groups-beta-schardinger dextrin-, grafting sulfonic groups-beta-schardinger dextrin-the fabric of the inclusion catechin obtained, finally the grafting sulfonic groups of inclusion catechin-beta-schardinger dextrin-fabric is washed, dry, namely the fabric with deodorization functions is obtained.
CN201210439327.XA 2012-11-07 2012-11-07 Method for preparing fabric with deodorizing function Expired - Fee Related CN102936838B (en)

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