CN113666886A - Antibacterial spandex fiber for diaper and preparation method thereof - Google Patents
Antibacterial spandex fiber for diaper and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
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Abstract
The invention discloses an antibacterial spandex fiber for a diaper and a preparation method thereof, and relates to the technical field of chemical fiber materials. The preparation method of the antibacterial spandex fiber comprises the following steps: carrying out prepolymerization reaction on PTG and MDI to synthesize an isocyanate-terminated prepolymer by adopting a continuous polymerization production process; adding a chain extender into the prepolymer for chain extension to obtain a polyurethane stock solution; and (3) mixing the polyurethane stock solution with an antibacterial agent and a functional assistant, curing to obtain a spinning solution, and carrying out dry spinning, false twisting, oiling and winding to obtain the antibacterial spandex fiber. The spandex fiber prepared by the invention has better mechanical property and elastic recovery property, excellent antibacterial effect and good deodorization effect; meanwhile, the creep resistance of the polyurethane adhesive is stronger, and the bonding firmness of spandex passing through glue and non-woven fabric is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of chemical fiber materials, and particularly relates to an antibacterial spandex fiber for a diaper and a preparation method thereof.
Background
Spandex has the characteristics of high breaking strength, high elongation at break and high resilience, is widely used in the fields of underwear, sportswear, silk stockings, woven belts, paper diapers, medical and sanitary articles and the like, and has more and more attention to antibacterial property and deodorization performance because the products are in direct contact with human skin. Researches show that polyurethane macromolecular chains in spandex have no antibacterial property and deodorization property, and under a proper environmental condition, some bacteria harmful to human bodies can be propagated and metabolized on common spandex fibers, so that the micro-ecological dynamic balance of normal skin of the human bodies is destroyed, and the health of the human bodies is damaged. A large part of body odor is from ammonia, acetic acid and isovaleric acid formed by decomposing and metabolizing sweat or lipid secretion substances by odor bacteria such as staphylococcus epidermidis and corynebacteria. The antibacterial treatment of the fiber can effectively prevent body odor caused by bacteria, besides infectious diseases and skin diseases.
Spandex is more and more widely applied in the field of paper diapers, and has higher and higher requirements on antibacterial performance and environmental protection because spandex has certain elasticity due to the fact that spandex is directly contacted with private parts of special groups such as infants, old people and the like, so that the antibacterial performance of spandex is more and more important.
In the case of chemical fibers, imparting antimicrobial properties is accomplished primarily by adding antimicrobial agents to the fibers. The antibacterial agent mainly comprises inorganic antibacterial agent, organic antibacterial agent, and small amount of natural antibacterial agent. Among inorganic antibacterial agents, silver ions are most widely used, but are not easily dispersed and are expensive. Among the organic antibacterial agents, quaternary ammonium salts are widely used, but have the problems of easy loss and poor washing resistance.
Disclosure of Invention
The invention aims to provide an antibacterial spandex fiber for diaper and a preparation method thereof, wherein the spandex fiber has better mechanical property and elastic recovery property, excellent antibacterial effect and good deodorization effect; meanwhile, the creep resistance of the polyurethane adhesive is stronger, and the bonding firmness of spandex passing through glue and non-woven fabric is remarkably improved.
The technical scheme adopted by the invention for realizing the purpose is as follows:
an antibacterial agent comprising a compound of formula I:
A process for preparing a compound of formula I, comprising: modifying hydroxyl in a vanillin structure by using 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide, and preparing the vanillin structure through substitution reaction.
Further, the preparation method of the vanillin derivative shown in the formula I comprises the following steps:
adding vanillin into acetonitrile for dissolving, adding potassium carbonate, and stirring at room temperature for 0.5-1 h; then adding 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide and potassium iodide, heating to reflux, stirring for reaction, monitoring by TLC until the reaction is finished, decompressing and desolventizing, adding ethyl acetate and water for extraction, washing by saturated sodium bicarbonate and saturated sodium chloride in turn, finally drying by anhydrous sodium sulfate, and separating and purifying by silica gel column chromatography to obtain the vanillin derivative.
In some embodiments of the invention, the molar ratio of vanillin to potassium carbonate is 1: 1.9-2.1; the molar ratio of vanillin, 2-chloro-n- [4- (6-methyl-1, 3-benzothiazol-2-yl) phenyl ] acetamide and potassium iodide is 1: 0.9-1.2: 0.18 to 0.24.
The invention also discloses application of the antibacterial agent in preparation of antibacterial spandex fibers or medical antibacterial materials.
A preparation method of antibacterial spandex fiber comprises the following steps:
carrying out prepolymerization reaction on PTG and MDI to synthesize an isocyanate-terminated prepolymer by adopting a continuous polymerization production process;
adding a chain extender into the prepolymer for chain extension to obtain a polyurethane stock solution;
and (3) mixing the polyurethane stock solution with an antibacterial agent and a functional assistant, curing to obtain a spinning solution, and carrying out dry spinning, false twisting, oiling and winding to obtain the antibacterial spandex fiber.
Furthermore, the preparation method of the antibacterial spandex fiber comprises the following specific steps:
mixing PTG and MDI, adding N, N-dimethylacetamide, and reacting at 60-70 ℃ for 1.5-4 h to synthesize an isocyanate-terminated prepolymer;
then adding a chain extender solution under the condition of stirring to carry out chain extension reaction to obtain a polyurethane stock solution;
and finally, adding an antibacterial agent and a functional assistant, blending, uniformly mixing, curing to obtain a spinning solution, spinning by a dry method in a high-temperature channel through a spinneret plate, and then performing false twisting, oiling and winding to obtain the antibacterial spandex fiber.
In some embodiments of the invention, the mass ratio of PTG to MDI is 2.9-5.1: 1.
in some embodiments of the invention, the mass ratio of PTG to N, N-dimethylacetamide is 1: 1.8 to 2.5.
In some embodiments of the invention, the addition amount of the chain extender is 2.1-5.8% of the total mass of the PTG and the MDI; the chain extender is a mixture of ethylenediamine, 1, 5-pentanediamine and ethanolamine, and the molar ratio of the ethylenediamine, the 1, 5-pentanediamine and the ethanolamine is 5.6-8.3: 1.5-2.5: 1.
in some embodiments of the invention, a method of preparing a chain extender solution comprises: dissolving ethylenediamine, 1, 5-pentanediamine and ethanolamine in an N, N-dimethylacetamide solution to obtain a chain extender solution; wherein the mass ratio of the ethylenediamine to the N, N-dimethylacetamide is 1: 12.5 to 18.
In some embodiments of the present invention, the antimicrobial agent comprises, by weight, 4-8 parts of a compound represented by formula I, 0.5-2 parts of sorbitol, 5-10 parts of a cationic surfactant; the addition amount of the antibacterial agent is 3.2-6.4% of the total mass of PTG and MDI. The antibacterial agent and the polyurethane solution provided by the invention are easy to mix uniformly, easy to store, small in addition amount, green, environment-friendly and convenient to operate, and a new idea is provided for preparation of antibacterial spandex fibers in the field of medical materials and textile materials.
In some embodiments of the invention, the addition amount of the functional additive is 1.8-3.4% of the total mass of PTG and MDI; the functional auxiliary agent comprises titanium dioxide, an antioxidant AT245, UV 320, magnesium stearate and a lubricant, and the mass ratio of the titanium dioxide to the antioxidant AT245 to the UV 320 to the magnesium stearate to the lubricant is 1.2-1.6: 1-1.5: 1: 2-4: 1.8 to 3.6.
In some embodiments of the present invention, the lubricant in the functional adjuvant comprises an epoxy polysiloxane or a cyclooctadiene-modified epoxy polysiloxane.
Further, the preparation method of the lubricant specifically comprises the following steps:
dissolving 4-vinylbenzyl glycidyl ether in toluene, adding 0.5% of chloroplatinic acid isopropanol solution, uniformly stirring, heating to 60-65 ℃, and then, adding n (C ═ C): n (Si-H) is 1.05 to 1.25: 1, slowly dripping PMDS-co-PHMS, raising the temperature of a system to 90-95 ℃ after dripping, reacting, sampling at regular time, detecting by infrared until an Si-H bond absorption peak in a spectrum disappears, stopping the reaction, and distilling under reduced pressure (110-120 ℃) to obtain the lubricant.
Or the like, or, alternatively,
adding toluene to dissolve cycloopilalenol and 4-vinylbenzyl glycidyl ether, then adding 0.5% of isopropanol solution of chloroplatinic acid, uniformly stirring, heating to 60-65 ℃, and then, adding n (C ═ C): n (Si-H) is 1.05 to 1.25: 1, slowly dripping PMDS-co-PHMS, raising the temperature of a system to 90-95 ℃ after dripping, reacting, sampling at regular time, detecting by infrared until an Si-H bond absorption peak in a spectrum disappears, stopping the reaction, and distilling under reduced pressure (110-120 ℃) to obtain the lubricant. According to the invention, the epiopiate sterkenol modified epoxy polysiloxane is used as a special lubricant and added into the polyurethane stock solution, the chemical structure of the epiopiate sterenol modified epoxy polysiloxane is similar to that of polyurethane macromolecule which is a main component of spandex, and the epiopiate sterenol modified epoxy polysiloxane is further added into the spandex stock solution to have good stable dispersibility, so that the breaking strength of spandex fibers can be effectively enhanced, and the mechanical property of the spandex fibers can be improved; and the creep resistance of spandex fibers can be obviously enhanced, and the bonding firmness of spandex fibers with non-woven fabrics through glue is improved. In addition, due to the presence of the cycloopimatter sterol modified epoxy polysiloxane in the spandex fiber, the deodorization performance of the spandex fiber can be enhanced. Meanwhile, under the condition of existence of the vanillin derivatives, the vanillin derivatives and the spandex derivatives are compounded for use, so that the effect of enhancing the creep resistance and the deodorization performance of the spandex fibers is better.
In some embodiments of the present invention, the amount of the isopropanol solution of chloroplatinic acid (calculated by the mass of Pt simple substance) is 14-16 ppm of the total mass of the reactants.
The antibacterial spandex fiber prepared by the preparation method has the bacteriostasis rate of more than 90 percent.
In some embodiments of the invention, the spandex fiber has a retraction rate of < 3.5%; the elastic recovery rate is more than 98 percent; the breaking strength is more than 1.1N.
The invention also discloses application of the antibacterial spandex fiber in preparing products such as diapers, paper diapers, wet tissues and protection pads.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide to put hydroxyl into a vanillin structure for chemical modification to prepare a derivative thereof, and the derivative is used as an antibacterial agent and added into a preparation process of spandex, so that the prepared spandex fiber has excellent antibacterial effect, wherein the antibacterial rate to escherichia coli is more than 95 percent, the antibacterial rate to staphylococcus aureus is more than 90 percent, and the antibacterial rate to candida albicans is more than 99 percent; the polyurethane fiber can be used in combination with other components, so that the breaking strength of the polyurethane fiber can be enhanced, and the mechanical property of the polyurethane fiber can be improved; and the elastic recovery performance of the spandex fiber is obviously improved. In addition, the epiopiate sterkenol modified epoxy polysiloxane is used as a special lubricant and added into the polyurethane stock solution, so that the breaking strength of the spandex fiber can be effectively enhanced, the creep resistance of the spandex fiber is improved, and the bonding firmness of the spandex and the non-woven fabric through glue is improved; and also can enhance the deodorizing performance of spandex fibers. Meanwhile, under the condition of existence of vanillin derivatives, the modified epoxy polysiloxane is compounded with the cycloopiantel for use, so that the creep resistance and the deodorization performance of the spandex fiber are enhanced better.
Therefore, the invention provides the antibacterial spandex fiber for the diaper and the preparation method thereof, the spandex fiber has better mechanical property and elastic recovery property, and the antibacterial effect is excellent, so that the spandex fiber has a good deodorization effect; meanwhile, the creep resistance of the polyurethane adhesive is stronger, and the bonding firmness of spandex passing through glue and non-woven fabric is remarkably improved.
Drawings
FIG. 1 shows the results of mid-IR spectroscopy in test example 1 of the present invention;
FIG. 2 shows SEM test results in test example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the cationic surfactant used in the embodiment of the invention is octadecyl trimethyl ammonium chloride, which is purchased from new materials GmbH of Kwangtung Weiwei industry of Jinan.
The PMDS-co-PHMS is prepared by the prior art and a reference document [ Wangxinghui, the synthesis of long-chain alkyl epoxy polysiloxane and the application of lubricating and scratch-resistant functions [ D ]. university of south China ].
Example 1:
preparation of vanillin derivatives of formula I:
dissolving vanillin in acetonitrile, adding potassium carbonate (the molar ratio of vanillin to potassium carbonate is 1: 2.05), and stirring at room temperature for 1 h; adding 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide and potassium iodide, heating to reflux, stirring for reaction, monitoring by adopting TLC (thin layer chromatography) until the reaction is finished, performing desolventizing under reduced pressure, adding ethyl acetate and water for extraction, sequentially washing by using saturated sodium bicarbonate and saturated sodium chloride, finally drying by using anhydrous sodium sulfate, and performing silica gel column chromatography separation and purification to obtain a vanillin derivative; in the reaction process, the molar ratio of vanillin, 2-chloro-n- [4- (6-methyl-1, 3-benzothiazol-2-yl) phenyl ] acetamide and potassium iodide is 1: 1.1: 0.21. the chemical structure of the product is shown below:
1H NMR(400MHz,DMSO-d6)δppm：9.87(s,1H,O＝C-H),8.1～7.8、7.55～7.25(10H,Ph-H),7.36(s,1H,N-H),4.81(s,2H,O-CH2),4.45(s,3H,Ph-CH3),3.92(s,3H,O-CH3)。HRMS(ESI)：Calcd for C24H20N2SO4，m/z[M+H]+，432.09。
13C NMR(150MHz,DMSO-d6)δ：195.4、177.2、173.1、159.0、156.4、152.7、140.1、137.6、134.9、131.7、129.8、125.4、124.7、122.8、121.5、120.9、113.3、111.8、70.0、59.4、25.5。
preparation of an antibacterial spandex fiber:
according to the mass ratio of 3.9: 1, mixing PTG and MDI, adding N, N-dimethylacetamide (the mass ratio of PTG to N, N-dimethylacetamide is 1: 2.2), and reacting for 3 hours at 68 ℃ to synthesize an isocyanate-terminated prepolymer;
adding N, N-dimethylacetamide solution containing a chain extender under the condition of stirring to perform chain extension reaction to obtain polyurethane stock solution; wherein the addition amount of the chain extender is 4.3 percent of the total mass of PTG and MDI; the chain extender is a mixture of ethylenediamine, 1, 5-pentanediamine and ethanolamine, and the molar ratio of the ethylenediamine, the 1, 5-pentanediamine and the ethanolamine is 6.8: 1.9: 1; and the mass ratio of the ethylenediamine to the N, N-dimethylacetamide is 1: 16;
and finally, adding an antibacterial agent (the addition amount is 5.2 percent of the total mass of the PTG and the MDI) and a functional additive for blending (the addition amount is 2.7 percent of the total mass of the PTG and the MDI), uniformly mixing, curing to obtain spinning solution, spinning in a high-temperature channel by a spinneret plate in a dry method, and then performing false twisting, oiling and winding to obtain the antibacterial spandex fiber.
The antibacterial agent used in the preparation process comprises 6 parts of vanillin derivatives, 1.2 parts of sorbitol and 7 parts of cationic surfactant in parts by weight.
The functional auxiliary agents used in the preparation process comprise titanium dioxide, antioxidants AT245, UV 320, magnesium stearate and lubricating agents, and the mass ratio of the titanium dioxide to the antioxidants AT245 to the UV 320 to the magnesium stearate to the lubricating agents is 1.4: 1.3: 1: 2.8: 2.7.
preparation of the lubricant:
dissolving 4-vinylbenzyl glycidyl ether in toluene, adding 0.5% of chloroplatinic acid isopropanol (the dosage is 14.8ppm of the total mass of reactants), uniformly stirring, heating to 64 ℃, and adding n (C ═ C): n (Si-H) ═ 1.18: 1, slowly dripping PMDS-co-PHMS, raising the temperature of the system to 92 ℃ after dripping is finished, carrying out reaction, sampling at regular time, carrying out infrared detection until an Si-H bond absorption peak in a spectrum disappears, stopping the reaction, and carrying out reduced pressure distillation (115 ℃) to obtain the lubricant.
Example 2:
the vanillin derivatives of formula I were prepared as in example 1.
An antibacterial spandex fiber was prepared differently from example 1 in that:
the mass ratio of PTG to MDI was 3.1: 1; the addition of the chain extender is 5.4 percent of the total mass of PTG and MDI; the chain extender is a mixture of ethylenediamine, 1, 5-pentanediamine and ethanolamine, and the molar ratio of the ethylenediamine, the 1, 5-pentanediamine and the ethanolamine is 5.7: 1.9: 1;
the antibacterial agent comprises, by weight, 5 parts of vanillin derivatives, 0.9 part of sorbitol and 6 parts of cationic surfactant;
the functional auxiliary agents comprise titanium dioxide, antioxidants AT245, UV 320, magnesium stearate and a lubricant, wherein the mass ratio of the titanium dioxide to the antioxidants AT245 to the UV 320 to the magnesium stearate to the lubricant is 1.3: 1.5: 1: 4: 3.4.
the lubricant was prepared as in example 1.
Example 3:
the vanillin derivatives of formula I were prepared as in example 1.
An antibacterial spandex fiber was prepared differently from example 1 in that:
the mass ratio of PTG to MDI was 5: 1; the addition of the chain extender is 3.1 percent of the total mass of PTG and MDI; the chain extender is a mixture of ethylenediamine, 1, 5-pentanediamine and ethanolamine, and the molar ratio of the ethylenediamine, the 1, 5-pentanediamine and the ethanolamine is 8.2: 1.8: 1;
the antibacterial agent comprises 8 parts of vanillin derivatives, 1.5 parts of sorbitol and 7 parts of cationic surfactant in parts by weight;
the functional auxiliary agents comprise titanium dioxide, antioxidants AT245, UV 320, magnesium stearate and a lubricant, wherein the mass ratio of the titanium dioxide to the antioxidants AT245 to the UV 320 to the magnesium stearate to the lubricant is 1.5: 1.1: 1: 2: 1.8.
the lubricant was prepared as in example 1.
Example 4:
the vanillin derivatives of formula I were prepared as in example 1.
An antibacterial spandex fiber was prepared differently from example 1 in that:
the mass ratio of PTG to MDI was 4.7: 1; the addition of the chain extender is 2.8 percent of the total mass of PTG and MDI; the chain extender is a mixture of ethylenediamine, 1, 5-pentanediamine and ethanolamine, and the molar ratio of the ethylenediamine, the 1, 5-pentanediamine and the ethanolamine is 7.7: 2.3: 1;
the antibacterial agent comprises 7 parts of vanillin derivatives, 2 parts of sorbitol and 8.5 parts of cationic surfactant in parts by weight;
the functional auxiliary agents comprise titanium dioxide, antioxidants AT245, UV 320, magnesium stearate and a lubricant, wherein the mass ratio of the titanium dioxide to the antioxidants AT245 to the UV 320 to the magnesium stearate to the lubricant is 1.35: 1.25: 1: 3.6: 3.1.
the lubricant was prepared as in example 1.
Example 5:
the vanillin derivatives of formula I were prepared as in example 1.
An antibacterial spandex fiber was prepared differently from example 1 in that: the lubricant was prepared in this example.
Preparation of the lubricant:
adding toluene to dissolve cycloopilalenol and 4-vinylbenzyl glycidyl ether (the mass ratio of the cycloopilalenol to the 4-vinylbenzyl glycidyl ether is 1: 1.45), then adding 0.5% of chloroplatinic acid isopropanol solution (the dosage is 14.8ppm of the total mass of reactants), stirring uniformly, heating to 64 ℃, and then adding n (C ═ C): n (Si-H) ═ 1.18: 1, slowly dripping PMDS-co-PHMS, raising the temperature of the system to 92 ℃ after dripping is finished, carrying out reaction, sampling at regular time, carrying out infrared detection until an Si-H bond absorption peak in a spectrum disappears, stopping the reaction, and carrying out reduced pressure distillation (115 ℃) to obtain the lubricant.
Example 6:
an antibacterial spandex fiber was prepared differently from example 5 in that: vanillin is used to replace vanillin derivatives.
Comparative example 1:
an antibacterial spandex fiber was prepared differently from example 1 in that: vanillin is used to replace vanillin derivatives.
Test example 1:
1. characterization of the Infrared Spectrum
The Fourier transform infrared spectrum analyzer manufactured by Bruker company of Germany is used at 4000-500 cm-1And (3) carrying out structural characterization on the sample in the wave number range, standing and humidifying the spandex sample for 4 hours according to the national standard requirements, and then testing by using a transmission method. Wherein the test wave number range is 4000-500 cm-1Scanning frequency 32, resolution 8cm-1。
The above tests were carried out on PMDS-co-PHMS and the lubricant prepared in example 5, the results of which are shown in FIG. 1. From the analysis of the figure, the IR spectrum of the lubricant obtained in example 5 was 3490cm, compared with that of PMDS-co-PHMS-1A characteristic absorption peak of-OH appears nearby, and is 3000-2800 cm-1The characteristic absorption peak of methyl and methylene appears in the range of 2206cm-1And 927cm-1The expansion and contraction and bending vibration peaks of Si-H do not exist nearby, which indicates that the silicon-hydrogen bond on the hydrogen-containing silicone oil has completely reacted; at 1274cm-1And 829cm-1The vicinity is a characteristic absorption peak of Si-C bond; the above results indicate that the lubricant of example 5 was successfully prepared.
2. SEM test
10 antibacterial spandex fiber samples with the length of about 8cm are randomly sheared from the roll, cleaned and dried, then placed on an observation copper table, placed on a vacuum coating table for spraying gold, and observed and photographed by a scanning electron microscope.
The above test was performed on the sample prepared in example 1, and the results are shown in fig. 2. As can be seen from the analysis in the figure, the surface of the spandex fiber prepared in the example 1 of the invention presents granular protrusions and has a plurality of fine particles.
3. Breaking Strength and elongation at Break test
The breaking strength and breaking elongation of spandex are tested according to the requirements of national standard FZ/T50006-2013 stretch performance test method of spandex filament, 10 parallel tests are carried out on each group of samples, and the average value of the results is taken.
4. Elastic recovery test
According to the requirements of national standard FZ/T5007-2012 'elasticity experiment method for spandex filaments', the 300% recovery rate of 24h of spandex samples is tested, and the average value is taken after each group of samples are tested for 10 times.
The results of the above two tests on spandex prepared in comparative example 1 and examples 1 to 6 are shown in table 1:
TABLE 1 mechanical Properties and Return Rate test results
| Sample (I) | Fineness/dtex | Breaking strength/N | Elongation at break/% | 300% recovery/%) |
| Comparative example 1 | 44 | 0.81 | 599.4 | 96.67 |
| Example 1 | 44 | 1.15 | 611.5 | 98.73 |
| Example 2 | 44 | 1.13 | 608.4 | 99.11 |
| Example 3 | 44 | 1.18 | 612.7 | 99.03 |
| Example 4 | 44 | 1.14 | 607.2 | 98.69 |
| Example 5 | 44 | 1.43 | 612.1 | 99.15 |
| Example 6 | 44 | 1.06 | 601.8 | 96.97 |
As can be seen from the analysis in Table 1, the breaking strength of the spandex fiber prepared in example 1 is obviously higher than that of comparative example 1, and the breaking elongation is equivalent to that of comparative example 1, which shows that the mechanical properties of the spandex fiber can be improved to a certain extent by adding 2-chloro-n- [4- (6-methyl-1, 3-benzothiazol-2-yl) phenyl ] acetamide modified vanillin in the antibacterial agent for preparing the spandex fiber. The breaking strength enhancing effect of example 5 is better than that of example 1, and the effect of example 6 is better than that of comparative example 1, which shows that the presence of the cycloartane enol modified epoxy polysiloxane in the functional additive for preparing the spandex fiber can also enhance the mechanical properties of the spandex fiber.
Meanwhile, the recovery rate of the spandex fiber prepared in the example 1 is obviously higher than that of the comparative example 1, which shows that the elastic recovery performance of the spandex fiber can be improved by adding the 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide modified vanillin in the antibacterial agent for preparing the spandex fiber. The effect of example 5 is equivalent to that of example 1, and the effect of example 6 is equivalent to that of comparative example 1, which shows that the presence of the cyclic opioid enol-modified epoxy polysiloxane in the functional additive for preparing the spandex fiber does not negatively affect the elastic recovery performance of the spandex fiber.
Test example 2:
1. test of antibacterial Property
The test method comprises the following steps: reference is made to the standard GB/T20944.3-2008 "evaluation of antibacterial properties of textiles section 3: the oscillation method tests the bacteriostatic performance of spandex.
The results of the above tests on the spandex fibers prepared in comparative example 1 and examples 1 to 6 are shown in table 2:
TABLE 2 antibacterial Property test results
| Sample (I) | Inhibition of E.coli/%) | Inhibition of Staphylococcus aureus/%) | Candida albicans inhibition rate/%) |
| Comparative example 1 | 78.4 | 72.1 | 68.4 |
| Example 1 | 96.8 | 92.5 | 99.5 |
| Example 2 | 95.9 | 91.6 | 99.6 |
| Example 3 | 96.1 | 92.8 | 99.1 |
| Example 4 | 97.1 | 93.3 | 99.8 |
| Example 5 | 97.0 | 92.9 | 99.9 |
| Example 6 | 77.2 | 73.6 | 70.2 |
As can be seen from the analysis in Table 2, the inhibition rate of the spandex fiber prepared in example 1 on Escherichia coli, Staphylococcus aureus and Candida albicans is obviously higher than that of comparative example 1, which shows that the antibacterial effect of the spandex fiber can be remarkably enhanced by adding 2-chloro-n- [4- (6-methyl-1, 3-benzothiazol-2-yl) phenyl ] acetamide modified vanillin in the antibacterial agent for preparing the spandex fiber. The effect of example 5 is equivalent to that of example 1, and the effect of example 6 is equivalent to that of comparative example 1, which shows that the presence of the cyclic opioid enol-modified epoxy polysiloxane in the functional additive for preparing the spandex fiber does not negatively affect the antibacterial performance of the spandex fiber.
2. Creep resistance test
The creep resistance is the bonding firmness of spandex and non-woven fabric through glue, and the test method specifically comprises the following steps: straightening the non-woven fabric adhered with the spandex, fixing the non-woven fabric on a flat plate, measuring the length as L1, cutting off two ends of the spandex inside, marking two ends of the spandex and the corresponding flat plate, placing the non-woven fabric in an oven at 40 ℃ for 5 hours, and measuring the length of the spandex at the marked position after retraction as L2. The creep resistance of spandex is represented by the retraction ratio S of spandex, and is calculated according to the following formula:
the retraction rate S ═ L1-L2)/L1X 100%
The results of the above tests on the spandex fibers prepared in comparative example 1 and examples 1 to 6 are shown in table 3:
TABLE 3 creep resistance test results
From the analysis in table 3, it can be seen that the retraction rate of the spandex fiber prepared in example 1 is not significantly different from that of comparative example 1, the retraction rate of the spandex fiber prepared in example 5 is significantly lower than that of example 1 and lower than that of example 6, and the effect of example 6 is significantly better than that of comparative example 1, which indicates that the presence of the cycloartame alcohol modified epoxy polysiloxane in the functional additive for preparing the spandex fiber can effectively enhance the creep resistance of the spandex fiber and improve the bonding firmness of the spandex and the non-woven fabric through glue; and under the condition that the derivative of the 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide modified vanillin exists, the two are compounded for use, so that the effect of enhancing the creep resistance of spandex fibers is better.
3. Deodorization Performance test
The deodorizing performance was measured by the inspection tube method in section 2 of "measurement of deodorizing performance of textile".
The results of the above tests on the spandex fibers prepared in comparative example 1 and examples 1 to 6 are shown in table 4:
TABLE 4 deodorant Performance test results
From the analysis in table 4, it can be seen that the concentration reduction rate of the spandex fiber prepared in example 1 for three odor components is not significantly different from that of comparative example 1, the concentration reduction rate of the spandex fiber prepared in example 5 for three odor components is significantly higher than that of examples 1 and 6, and the effect of example 6 is significantly better than that of comparative example 1, which indicates that the presence of the cycloartanol-modified epoxy polysiloxane in the functional additive for preparing the spandex fiber can effectively enhance the deodorization performance of the spandex fiber; and under the condition that the derivative of the 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide modified vanillin exists, the two are compounded for use, so that the effect of improving the deodorization performance of spandex fibers is better.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. An antibacterial agent comprising a compound of formula I:
2. a process for preparing a compound of formula I, comprising: modifying hydroxyl in a vanillin structure by using 2-chloro-n- [4- (6-methyl-1, 3-benzothiazole-2-yl) phenyl ] acetamide, and preparing the vanillin structure through substitution reaction.
3. A preparation method of antibacterial spandex fiber comprises the following steps:
carrying out prepolymerization reaction on PTG and MDI to synthesize an isocyanate-terminated prepolymer by adopting a continuous polymerization production process;
adding a chain extender into the prepolymer for chain extension to obtain a polyurethane stock solution;
and (3) blending the polyurethane stock solution with an antibacterial agent and a functional assistant, curing to obtain a spinning solution, and carrying out dry spinning, false twisting, oiling and winding to obtain the antibacterial spandex fiber.
4. The method for preparing the antibacterial spandex fiber according to claim 3, characterized in that: the mass ratio of PTG to MDI is 2.9-5.1: 1.
5. the method for preparing the antibacterial spandex fiber according to claim 3, characterized in that: the chain extender is a mixture of ethylenediamine, 1, 5-pentanediamine and ethanolamine, and the molar ratio of the ethylenediamine, the 1, 5-pentanediamine and the ethanolamine is 5.6-8.3: 1.5-2.5: 1.
6. the method for preparing the antibacterial spandex fiber according to claim 3, characterized in that: the antibacterial agent comprises, by weight, 4-8 parts of a compound shown in formula I, 0.5-2 parts of sorbitol and 5-10 parts of a cationic surfactant; the addition amount of the antibacterial agent is 3.2-6.4% of the total mass of PTG and MDI.
7. The method for preparing the antibacterial spandex fiber according to claim 3, characterized in that: the functional auxiliary agents comprise titanium dioxide, antioxidants AT245, UV 320, magnesium stearate and lubricating agents.
8. The method for preparing the antibacterial spandex fiber according to claim 7, characterized in that: the lubricant in the functional auxiliary agent comprises epoxy polysiloxane or cyclopia steroid enol modified epoxy polysiloxane.
9. Use of the antibacterial spandex fiber prepared by the preparation method of any one of claims 3 to 7 in preparation of products such as diapers, paper diapers, wet tissues and protection pads.
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