CN102587138B - Temperature-sensitive antibacterial finishing agent as well as preparation method and use method thereof - Google Patents
Temperature-sensitive antibacterial finishing agent as well as preparation method and use method thereof Download PDFInfo
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- CN102587138B CN102587138B CN 201110450277 CN201110450277A CN102587138B CN 102587138 B CN102587138 B CN 102587138B CN 201110450277 CN201110450277 CN 201110450277 CN 201110450277 A CN201110450277 A CN 201110450277A CN 102587138 B CN102587138 B CN 102587138B
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Abstract
The invention relates to a temperature-sensitive antibacterial finishing agent as well as the preparation method and the use method thereof. The temperature-sensitive antibacterial finishing agent is prepared by taking hydroxypropyl cellulose and dimethyl diallyl ammonium chloride as raw materials with a solution polymerization method. The antibacterial finishing agent provided by the invention has the functions of automatic regulation of the air and moisture permeability of base material and targeted rapid release of an antibacterial agent, and is a real intelligent antibacterial finishing agent.
Description
Technical field
The invention belongs to the hygienic function finishing field of textiles, leather, synthetic leather, non-woven fabrics, be specifically related to a kind of Thermo-sensitive antibacterial finishing agent and preparation and application thereof.
Background technology
According to statistics, nineteen ninety-five the whole world because the murderous number of bacterial infection is about 1,700 ten thousand people, account for 1/3 of dead population; 1996, the infection event of pathogenic Escherichia coli " 0-157 " occurred in Japanese nationwide; In October, 2000, Chinese knot pyrenomycetes number of the infected (containing the carrier) has reached 400,000,000 more than; Spring in 2003, SARS virus spreads; On 2004 Chinese international antibiotic and sterilizings, nanometer and ozone Industry Exhibition, antibiotic product innovation has become the new lover of exhibition; Within 2005, Chinese Shanghai is held again the exhibition of international antibiotic and sterilizing technical products, again will how control and to mention schedule with kill bacteria in the world; In January, 2008, International Standards Organization (ISO) formally issues two antibiotic international standards " ISO 22196:2007 surface of plastic products anti-microbial property evaluation method " and " anti-microbial property of ISO 20743:2007 antibacterial finish textiles is measured "; In June, 2011, occurred that the superbacteria of Cray Bai Shi pneumobacillus (Klebsiella Pneumoniae) infects.In collective's inhabitation accumulation area after the disasters such as experience earthquake, infectious cause of disease bacterium occurring mainly contains Acinetobacter bauamnnii, Pseudomonas aeruginosa, streptococcus aureus, intestinal bacteria, thunder Bai Shi pneumobacillus and enterobacter cloacae; and these bacterial classifications can be killed by some antiseptic-germicides, thereby play the effect of protecting human-body safety.
In life, people inevitably can touch the microorganisms such as various bacteriums, fungi, these microorganisms are breeding rapidly under suitable ambient conditions, and spreads disease by modes such as contacts, affects people's healthy and normal work, studying and living.Japan is active at the antibacterial deodourizing area research, technological precedence, and the antimicrobial product of production also has been extended to the fields such as Sportswear, carpet, medical treatment product.The emphasis of its research has avoided from the protection textiles that bacteria attack is transferred to protection of the environment and the user avoids the bacteria attack aspect.Textile fiber belongs to porous material, after weaving, can form lacunose structure again, makes fabric be easier to adsorb some mushroom microorganisms.Antibacterial finish is exactly to make fabric have the function that suppresses microorganism growth, guarantees the health of human body.The part antibacterial finishing agent is carcinogenic owing to existing, teratogenecity is disabled, these antiseptic-germicides have 2,4,4 '-tri-chloro-2 '-dihydroxy diphenyl ether (THDE), alpha-bromo-cinnamaldehyde (BCA), 2-(4-thiazolyl) benzoglyoxaline (TBI), 2-(3,5-dimethyl pyrazole base)-4-hydroxyl-6-phenyl pyrimidine, 2,2 '-dihydroxyl-5,5 '-dichloro diphenyl methane and 2,2 '-dihydroxyl-5,5 '-bis-chloro diphenyl sulfides.Therefore the security of antibacterial finishing agent and running product thereof is of crucial importance, must meet the ecological, environmental protective requirement.
Summary of the invention
The object of the present invention is to provide a kind of Thermo-sensitive antibacterial finishing agent and preparation and application thereof.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of Thermo-sensitive antibacterial finishing agent, hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, this finishing composition is the compound had suc as formula 1 structure, molecular weight M
w=60000～80000, the solubleness in water is good, after dissolving, is clear solution,
A kind of method for preparing above-mentioned Thermo-sensitive antibacterial finishing agent comprises the following steps:
(1) preparation of hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product
Hydroxypropylcellulose (HPC) is dissolved in deionized water and obtains hydroxypropyl cellulose solution, by dimethyl diallyl ammonium chloride (DMDAAC) at logical nitrogen, under stirring action, join in hydroxypropyl cellulose solution, stir 20～30min and obtain monomer solution, hydroxypropylcellulose in monomer solution: the amount of substance of dimethyl diallyl ammonium chloride is than being (1: 2)～(5: 4), monomer total amount: deionized water=1～2: 100g/ml, at logical nitrogen, add initiator under stirring action in monomer solution, then heating in water bath to 40～90 ℃, reaction 4～8h, be cooled to 13～17 ℃ after reaction, perhaps do not add initiator, adopt source of radiation at room temperature radiation 4～8h monomer solution, then shift out source of radiation and finish reaction,
(2) purifying of hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product
By hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, be heated to be more than or equal to 50 ℃ but filtered after being no more than 70 ℃, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 8-12 hour to remove unreacted hydroxypropylcellulose and homopolymer thereof, will obtain Thermo-sensitive antibacterial finishing agent powder through filter cake lyophilize or the spraying drying of Soxhlet extraction.
Described initiator is the oxidation-reduction initiator that ceric ammonium nitrate, Potassium Persulphate, ammonium persulphate or Potassium Persulphate, ammonium persulphate form with sodium bisulfite respectively, and Potassium Persulphate or ammonium persulphate in oxidation-reduction initiator: the amount of substance ratio of sodium bisulfite is 1～2: 1.
Described initiator: the mass ratio of monomer total amount is 0.03～0.06: 1.
Described source of radiation is
60the gamma-radiation of Co or UV-light.
Described ultraviolet light wavelength is 250-340nm.
Described cryodesiccated processing parameter is: material thickness 5-8mm, kiln vacuum tightness 15-25pa, 1-1.5 ℃/min of pre-freeze speed, pre-freeze temperature-40--50 ℃, the vacuum tightness 30-40pa of cryodesiccation chamber, sublimation temperature 70-80 ℃; Described spray-dired processing parameter is: the mass ratio of inlet temperature 100-130 ℃, air outlet temperature 70-85 ℃, centrifuge speed 10000-14500r/min, input speed 50-63.4ml/min, hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride and solvent dehydrated alcohol is 1: 2-4.
A kind of using method of above-mentioned Thermo-sensitive antibacterial finishing agent, comprise the following steps: 1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent, addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 25-30 ℃, make the Thermo-sensitive antibacterial finishing agent of preparation can in the aqueous solution, present good extended configuration, with dressing liquid, fabric is arranged, the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 10-25 ℃, the Thermo-sensitive antibacterial finishing agent that makes to arrange on fabric can again change extended configuration into from crimped configuration in ventilative process of cooling, and forms and be uniformly distributed on fabric.
Described silicone based linking agent is methyl silicate, tetraethyl silicate or butyl silicate.
Thermo-sensitive antibacterial finishing agent of the present invention adopts initiator to cause radical polymerization or adopts radiation to cause two kinds of modes of radical polymerization and is prepared from, the activity hydroxy free radical that the chemical site that chemical reaction occurs is the hydroxypropylcellulose that generates under initiator or radiation initiation and the allyl radical of dimethyl diallyl ammonium chloride.Utilization of the present invention has the hydroxypropylcellulose of biocompatibility and good ecological, environmental protective requirement and the intelligent antiseptic-germicide that dimethyl diallyl ammonium chloride has temperature sensitivity for the raw material preparation, this antiseptic-germicide is a kind of superior to the aldehyde antiseptic-germicide, good permeability, but film forming on the base materials such as fabric, leather, synthetic leather, also can improve the dyefastness of coloured base material in antibiotic, all be easy to use before dyeing or after dyeing.
The hydroxypropylcellulose prepared in the present invention-g-dimethyl diallyl ammonium chloride Thermo-sensitive antibacterial finishing agent can be in 30-42 ℃ of realization " intelligent switch " function, utilize it can play on the one hand by the temperature height and automatically regulate the thin film void size, realize that base material takes the automatic adjusting breathable moisture permeability in process in dress, and improve its sanitation performance; To belong to target antibiotic for this antiseptic-germicide on the other hand, can improve antimicrobial efficiency in utmost point killing microorganisms fast in the short period of time, have advantages of simple to operate, suitability is wide, antimicrobial efficiency is high, teratogenesis, not carcinogenic not.
The accompanying drawing explanation
Fig. 1 is the infrared spectrogram that embodiment 1 prepares product (initiator initiation);
Fig. 2 is that embodiment 6 prepares product (UV-light causes γ=340nm) infrared spectrogram;
The transition temperature schematic diagram that Fig. 3 is product.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but embodiments of the present invention are not limited to this.
Hydroxypropylcellulose 6000 (HPC): dimethyl diallyl ammonium chloride (DMDAAC)=1: 2 (mol: mol), deionized water is solvent, monomer total amount: solvent=1.5: 100g/ml, be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 1.5g, initiator is ceric ammonium nitrate, initiator: the mass ratio of monomer total amount is 0.05: 1, the add-on that is initiator be in monomer solution hydroxypropylcellulose and dimethyl diallyl ammonium chloride total mass 5%, concrete steps are:
(1) hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in the deionized water in reactor; (2) in will slowly joining hydroxypropyl cellulose solution than the dimethyl diallyl ammonium chloride accurately measured under logical nitrogen, stirring action by metering, stir 30min; (3) pass into nitrogen and discharge the oxygen in reactor, and slowly add in stirring action downhill reaction device by metering than the initiator ceric ammonium nitrate calculated; (4) add initiator after heating in water bath to 50 ℃ of temperature of reaction, the reaction times is 6h; (5) be cooled to rapidly 15 ℃ after the reaction, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product; (6) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 70 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 8 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, will obtain Thermo-sensitive antibacterial finishing agent powder through the filter cake lyophilize of Soxhlet extraction.
Described cryodesiccated processing parameter is: 80 ℃ of material thickness 5mm, kiln vacuum tightness 25pa, 1 ℃/min of pre-freeze speed, pre-freeze temperature-40 ℃, the vacuum tightness 30pa of cryodesiccation chamber, sublimation temperatures.
The infrared spectra of purifying after product as shown in Figure 1.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate), addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 30 ℃, with dressing liquid to fabric by soaking-roll-baking-roasting technique arranged, the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 10 ℃.
Hydroxypropylcellulose 6000: dimethyl diallyl ammonium chloride=2: 3 (mol: mol), deionized water is solvent, monomer total amount: solvent=1: 100 (g/ml), be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 1g, initiator is Potassium Persulphate, initiator: the mass ratio of monomer total amount is 0.04: 1, the add-on that is initiator be in monomer solution hydroxypropylcellulose and dimethyl diallyl ammonium chloride total mass 4%, concrete steps are:
(1) hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in the deionized water in reactor; (2) in will slowly joining hydroxypropyl cellulose solution than the dimethyl diallyl ammonium chloride accurately measured under logical nitrogen, stirring action by metering, stir 25min; (3) pass into nitrogen and discharge the oxygen in reactor, and slowly add in stirring action downhill reaction device by metering than the initiator potassium persulfate of calculating; (4) add initiator after heating in water bath to 70 ℃ of temperature of reaction, the reaction times is 5h; (5) be cooled to rapidly 16 ℃ after the reaction, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product; (6) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 60 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 8 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, will obtain Thermo-sensitive antibacterial finishing agent powder through the filter cake spraying drying of Soxhlet extraction.
Described spray-dired processing parameter is: the mass ratio of 100 ℃ of inlet temperature, 85 ℃ of air outlet temperatures, centrifuge speed 14000r/min, input speed 50ml/min, hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride and solvent dehydrated alcohol is 1: 2.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate, addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 28 ℃, with dressing liquid to fabric by soaking-roll-baking-roasting technique arranged, the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 25 ℃.
Hydroxypropylcellulose 6000: dimethyl diallyl ammonium chloride=5: 4 (mol: mol), deionized water is solvent, monomer total amount: solvent=2: 100 (g/ml), be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 2g, initiator is the oxidation-reduction initiator that Potassium Persulphate and sodium bisulfite form, Potassium Persulphate in oxidation-reduction initiator: the amount of substance ratio of sodium bisulfite is 1: 1, initiator: the mass ratio of monomer total amount is 0.03: 1, the add-on that is initiator be in monomer solution hydroxypropylcellulose and dimethyl diallyl ammonium chloride total mass 3%, concrete steps are:
(1) hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in the deionized water in reactor; (2) in will slowly joining hydroxypropyl cellulose solution than the dimethyl diallyl ammonium chloride accurately measured under logical nitrogen, stirring action by metering, stir 20min; (3) pass into nitrogen and discharge the oxygen in reactor, and slowly add in stirring action downhill reaction device by metering than the initiator calculated; (4) add initiator after heating in water bath to 90 ℃ of temperature of reaction, the reaction times is 4h; (5) be cooled to rapidly 13 ℃ after the reaction, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product; (6) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 70 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 12 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, will obtain Thermo-sensitive antibacterial finishing agent powder through the filter cake lyophilize of Soxhlet extraction.
Described cryodesiccated processing parameter is: 75 ℃ of material thickness 6mm, kiln vacuum tightness 20pa, 1.5 ℃/min of pre-freeze speed, pre-freeze temperature-50 ℃, the vacuum tightness 35pa of cryodesiccation chamber, sublimation temperatures.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate), addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 25 ℃, with dressing liquid to fabric by soaking-roll-dry (hot-air seasoning: 80-100 ℃, 2-3min, or infrared preliminary drying: 90 ℃, 3min)-roasting (150-160 ℃, 2-3min) technique is arranged, and the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 20 ℃.
Hydroxypropylcellulose 6000: dimethyl diallyl ammonium chloride=3: 4 (mol: mol), deionized water is solvent, monomer total amount: solvent=1: 100 (g/ml), be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 1g, initiator is the oxidation-reduction initiator that ammonium persulphate and sodium bisulfite form, ammonium persulphate in oxidation-reduction initiator: the amount of substance ratio of sodium bisulfite is 2: 1, initiator: the mass ratio of monomer total amount is 0.06: 1, the add-on that is initiator be in monomer solution hydroxypropylcellulose and dimethyl diallyl ammonium chloride total mass 6%, concrete steps are:
(1) hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in the deionized water in reactor; (2) in will slowly joining hydroxypropyl cellulose solution than the dimethyl diallyl ammonium chloride accurately measured under logical nitrogen, stirring action by metering, stir 30min; (3) pass into nitrogen and discharge the oxygen in reactor, and slowly add in stirring action downhill reaction device by metering than the initiator calculated; (4) add initiator after heating in water bath to 40 ℃ of temperature of reaction, the reaction times is 8h; (5) be cooled to rapidly 17 ℃ after the reaction, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product; (6) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 50 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 10 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, will obtain Thermo-sensitive antibacterial finishing agent powder through the filter cake spraying drying of Soxhlet extraction.
Described spray-dired processing parameter is: the mass ratio of 110 ℃ of inlet temperature, 70 ℃ of air outlet temperatures, centrifuge speed 10000r/min, input speed 63.4ml/min, hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride and solvent dehydrated alcohol is 1: 4.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate), addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 26 ℃, with dressing liquid to fabric by soaking-roll-dry (hot-air seasoning: 80-100 ℃, 2-3min, or infrared preliminary drying: 90 ℃, 3min)-roasting (150-160 ℃, 2-3min) technique is arranged, and the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 15 ℃.
Hydroxypropylcellulose 6000: dimethyl diallyl ammonium chloride=1: 2 (mol: mol), deionized water is solvent, monomer total amount: solvent=1.5: 100 (g/ml), be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 1.5g, concrete steps are:
(1) hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in deionized water, (2) measure dimethyl diallyl ammonium chloride by metering than accurately, pass into nitrogen and discharge the air in reactor, and, under stirring action, dimethyl diallyl ammonium chloride slowly being joined to hydroxypropyl cellulose solution, stir 30min, the sealing tube sealing, (3) reactor is placed in
60in the gamma-radiation source of radiation of Co, in room temperature (25 ± 2 ℃) radiation 4h, (4) rapidly reactor is shifted out
60the gamma-radiation source of radiation of Co, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product, (5) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 70 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 9 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, the filter cake lyophilize that will extract through Soxhlet obtains Thermo-sensitive antibacterial finishing agent powder.
Described cryodesiccated processing parameter is: 80 ℃ of material thickness 8mm, kiln vacuum tightness 15pa, 1 ℃/min of pre-freeze speed, pre-freeze temperature-45 ℃, the vacuum tightness 40pa of cryodesiccation chamber, sublimation temperatures.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate), addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 25 ℃, with dressing liquid to fabric by soaking-roll-dry (hot-air seasoning: 80-100 ℃, 2-3min, or infrared preliminary drying: 90 ℃, 3min)-roasting (150-160 ℃, 2-3min) technique is arranged, and the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 20 ℃.
Embodiment 6
Hydroxypropylcellulose 6000: dimethyl diallyl ammonium chloride=2: 3 (mol: mol), deionized water is solvent, monomer total amount: solvent=2: 100 (g/ml), be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 2g, concrete steps are:
(1) hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in deionized water, (2) measure dimethyl diallyl ammonium chloride by metering than accurately, pass into nitrogen and discharge the air in reactor, and, under stirring action, dimethyl diallyl ammonium chloride slowly being joined to hydroxypropyl cellulose solution, stir 20min, the sealing tube sealing, (3) reactor is placed in to UV radiation source, in room temperature (25 ± 2 ℃) radiation 6h, described ultraviolet light wavelength is 340nm, (4) rapidly reactor is shifted out to UV radiation source, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product, (5) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 50 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 12 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, the filter cake spraying drying that will extract through Soxhlet obtains Thermo-sensitive antibacterial finishing agent powder.
Described spray-dired processing parameter is: the mass ratio of 120 ℃ of inlet temperature, 80 ℃ of air outlet temperatures, centrifuge speed 14500r/min, input speed 60ml/min, hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride and solvent dehydrated alcohol is 1: 2.
The infrared spectra of purifying after product as shown in Figure 2.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate), addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 30 ℃, with dressing liquid to fabric by soaking-roll-baking-roasting technique arranged, the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 25 ℃.
Embodiment 7
Hydroxypropylcellulose 6000: dimethyl diallyl ammonium chloride=1: 1 (mol: mol), deionized water is solvent, monomer total amount: solvent=1: 100 (g/ml), be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 1g, concrete steps are:
The hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in deionized water, (2) measure dimethyl diallyl ammonium chloride by metering than accurately, pass into nitrogen and discharge the air in reactor, and, under stirring action, dimethyl diallyl ammonium chloride slowly being joined to hydroxypropyl cellulose solution, stir 25min, the sealing tube sealing, (3) reactor is placed in to UV radiation source, in room temperature (25 ± 2 ℃) radiation 8h, described ultraviolet light wavelength is 250nm, (4) rapidly reactor is shifted out to UV radiation source, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product, (5) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 60 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 10 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, the filter cake lyophilize that will extract through Soxhlet obtains Thermo-sensitive antibacterial finishing agent powder.
Described cryodesiccated processing parameter is: 70 ℃ of material thickness 7mm, kiln vacuum tightness 25pa, 1.5 ℃/min of pre-freeze speed, pre-freeze temperature-40 ℃, the vacuum tightness 35pa of cryodesiccation chamber, sublimation temperatures.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate), addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 27 ℃, with dressing liquid to fabric by soaking-roll-dry (hot-air seasoning: 80-100 ℃, 2-3min, or infrared preliminary drying: 90 ℃, 3min)-roasting (150-160 ℃, 2-3min) technique is arranged, and the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 15 ℃.
Embodiment 8
Hydroxypropylcellulose 6000: dimethyl diallyl ammonium chloride=5: 4 (mol: mol), deionized water is solvent, monomer total amount: solvent=1: 100 (g/ml), be that the hydroxypropylcellulose that adds in every 100mL deionized water and the total amount of dimethyl diallyl ammonium chloride are 1g, concrete steps are:
The hydroxypropylcellulose of accurate weighing is dissolved in to the stable thick hydroxypropyl cellulose solution of formation in deionized water, (2) measure dimethyl diallyl ammonium chloride by metering than accurately, pass into nitrogen and discharge the air in reactor, and, under stirring action, dimethyl diallyl ammonium chloride slowly being joined to hydroxypropyl cellulose solution, stir 25min, the sealing tube sealing, (3) reactor is placed in to UV radiation source, in room temperature (25 ± 2 ℃) radiation 8h, described ultraviolet light wavelength is 300nm, (4) rapidly reactor is shifted out to UV radiation source, finish reaction, obtain hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product, (5) by hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, after being heated to equal 60 ℃, filtered, retain filter cake, filter cake comprises unreacted hydroxypropylcellulose and hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride, filter cake be take to acetone and as solvent carries out Soxhlet, extract 10 hours to remove unreacted hydroxypropylcellulose and homopolymer thereof, the filter cake spraying drying that will extract through Soxhlet obtains Thermo-sensitive antibacterial finishing agent powder.
Described spray-dired processing parameter is: the mass ratio of 130 ℃ of inlet temperature, 75 ℃ of air outlet temperatures, centrifuge speed 12500r/min, input speed 55ml/min, hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride and solvent dehydrated alcohol is 1: 2.
1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent (as tetraethyl silicate), addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 29 ℃, with dressing liquid to fabric by soaking-roll-dry (hot-air seasoning: 80-100 ℃, 2-3min, or infrared preliminary drying: 90 ℃, 3min)-roasting (150-160 ℃, 2-3min) technique is arranged, and the specific embodiment of arrangement is consistent with existing textiles antibacterial finishing technological process and parameter with parameter; 2) through step 1) after, by fabric ventilative cooling cropping under the temperature condition of 10 ℃.
The Thermo-sensitive antibacterial finishing agent prepared according to the described method of above embodiment 1-8, by soaking-roll-dry-roasting technique arrange after the bacteriostasis property of fabric as shown in following table 1, table 2.
The bacteriostasis property of table 1 antibacterial finish fabric (a: pure cotton woven fabric b: pure cotton knitted fabric)
The temperature adjusting performance of table 2 antibacterial finish fabric (a: pure cotton woven fabric b: pure cotton knitted fabric)
The Thermo-sensitive antibacterial finishing agent prepared according to the described method of above embodiment 1-8, test its susceptibility to temperature by the cloud point method, as shown in Figure 3.In Fig. 3, transition temperature refers to corresponding temperature when the hydroxypropylcellulose for preparing in heat-processed-g-dimethyl diallyl ammonium chloride Thermo-sensitive antibacterial finish agent solution becomes muddy state by clear state, by Fig. 3, can show that the transition temperature of this Thermo-sensitive antibacterial finishing agent is at 30-42 ℃.
The Thermo-sensitive antibacterial finishing agent prepared according to the described method of above embodiment 1-8, as shown in table 3 below by the permeability of soaking-rolling-drying-roast the rear fabric of technique arrangement.
The ventilation property of table 3 antibacterial finish fabric
(technique one: HPC: DMDAAC=1: 2, technique two: HPC: DMDAAC=1: 1 technique three: HPC: DMDAAC=2: 3)
(a: probe temperature T=25 ℃, b: probe temperature T=45 ℃)
By table 3, found out, Thermo-sensitive antibacterial finishing agent prepared by the present invention makes ventilation property and the temperature correlation connection of fabric, the ventilation property of fabric when transition temperature is above is greater than the ventilation property of transition temperature when following, and the ventilation property that arranges rear fabric has been played to intelligent regulating effect.
Claims (9)
1. a Thermo-sensitive antibacterial finishing agent, it is characterized in that: this finishing composition is the compound had suc as formula 1 structure, molecular weight Mw=60000～80000:
2. one kind prepares the method for Thermo-sensitive antibacterial finishing agent as claimed in claim 1, it is characterized in that: comprise the following steps:
(1) preparation of hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product
Hydroxypropylcellulose is dissolved in deionized water and obtains hydroxypropyl cellulose solution, during dimethyl diallyl ammonium chloride is joined to hydroxypropyl cellulose solution under logical nitrogen, stirring action, stir 20～30min and obtain monomer solution, hydroxypropylcellulose in monomer solution: the amount of substance of dimethyl diallyl ammonium chloride is than being (1:2)～(5:4), monomer total amount: deionized water=1～2:100g/ml;
Add initiator under logical nitrogen, stirring action in monomer solution, then heating in water bath to 40～90 ℃, react 4～8h, is cooled to 13～17 ℃ after reaction, or adopt source of radiation at room temperature radiation 4～8h monomer solution, then shifts out source of radiation and finish reaction;
(2) purifying of hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product
By hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride raw product heating, be heated to be more than or equal to 50 ℃ but filtered after being no more than 70 ℃, retain filter cake, filter cake be take to acetone as solvent carries out Soxhlet extraction 8-12 hour, will obtain Thermo-sensitive antibacterial finishing agent powder through filter cake lyophilize or the spraying drying of Soxhlet extraction.
3. a kind of method for preparing the Thermo-sensitive antibacterial finishing agent according to claim 2, it is characterized in that: oxidation-reduction initiator, ceric ammonium nitrate or Potassium Persulphate that oxidation-reduction initiator, ammonium persulphate and the sodium bisulfite that described initiator is Potassium Persulphate and sodium bisulfite composition forms, Potassium Persulphate or ammonium persulphate in oxidation-reduction initiator: the amount of substance ratio of sodium bisulfite is 1～2:1.
4. according to a kind of described method for preparing the Thermo-sensitive antibacterial finishing agent of claim 2 or 3, it is characterized in that: described initiator: the mass ratio of monomer total amount is 0.03～0.06:1.
5. a kind of method for preparing the Thermo-sensitive antibacterial finishing agent according to claim 2, it is characterized in that: described source of radiation is
60the gamma-radiation of Co or UV-light.
6. a kind of method for preparing the Thermo-sensitive antibacterial finishing agent according to claim 5, it is characterized in that: described ultraviolet light wavelength is 250-340nm.
7. a kind of method for preparing the Thermo-sensitive antibacterial finishing agent according to claim 2, it is characterized in that: described cryodesiccated processing parameter is: material thickness 5-8mm, kiln vacuum tightness 15-25Pa, 1-1.5 ℃/min of pre-freeze speed, pre-freeze temperature-40--50 ℃, the vacuum tightness 30-40Pa of cryodesiccation chamber, sublimation temperature 70-80 ℃; Described spray-dired processing parameter is: the mass ratio of inlet temperature 100-130 ℃, air outlet temperature 70-85 ℃, centrifuge speed 10000-14500r/min, input speed 50-63.4mL/min, hydroxypropylcellulose-g-dimethyl diallyl ammonium chloride and solvent dehydrated alcohol is 1:2-4.
8. the using method of Thermo-sensitive antibacterial finishing agent as claimed in claim 1, it is characterized in that: comprise the following steps: 1) above-mentioned Thermo-sensitive antibacterial finishing agent is dissolved in the water, then add silicone based linking agent, addition is 2g/L, then heating for dissolving is made the dressing liquid that temperature is 25-30 ℃, with dressing liquid, fabric is arranged; 2) after step 1), by fabric ventilative cooling cropping under the temperature condition of 10-25 ℃.
9. a kind of using method of Thermo-sensitive antibacterial finishing agent according to claim 8, it is characterized in that: described silicone based linking agent is methyl silicate, tetraethyl silicate or butyl silicate.
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| CN105755831A (en) * | 2016-02-29 | 2016-07-13 | 苏州纺友新材料有限公司 | Antibacterial deodorization type finishing agent and preparation method thereof |
| CN107724083A (en) * | 2017-10-09 | 2018-02-23 | 马多浩 | A kind of fire-retardant anti-ultraviolet finishing agent of polyester cotton |
| CN110117343A (en) * | 2019-05-10 | 2019-08-13 | 上海纳旭实业有限公司 | Preparation method of nano-cellulose with anti-microbial property and products thereof and application |
| CN112062904B (en) * | 2020-08-28 | 2022-03-29 | 华南理工大学 | Genipin cross-linked antibacterial peptide/quaternized cellulose composite hydrogel bacteriostatic agent and preparation method and application thereof |
| CN115323764B (en) * | 2022-09-14 | 2023-06-27 | 浙江加佳领带服装有限公司 | Antibacterial finishing process for clothes |
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