阅读说明：本技术 基于石墨烯的持久抗菌复合服装面料 (Graphene-based lasting antibacterial composite garment fabric ) 是由 崔勇 王蓉 于 2020-07-08 设计创作，主要内容包括：本发明提供一种基于石墨烯的持久抗菌复合服装面料的制备方法,通过烯基酰氯单体与氧化石墨烯表面的羟基反应,以三乙胺为缚酸剂,将烯基双键接枝在氧化石墨烯上,再与表面巯基改性的棉纤维进行巯基-烯反应,将石墨烯以共价键接枝在棉纤维上,再将石墨烯抗菌纤维经纺纱、织造制得所述基于石墨烯的持久抗菌复合服装面料,本申请通过纤维表面改性,再以表面改性的纤维纺织成面料,使得所述面料在获得功能改性的同时保留面料良好透气性,提高面料的服用性,通过共价接枝,提高石墨烯在纤维上的附着力,耐洗牢度高。(The invention provides a preparation method of a graphene-based lasting antibacterial composite garment fabric, which comprises the steps of reacting alkenyl acyl chloride monomers with hydroxyl on the surface of graphene oxide, taking triethylamine as an acid-binding agent, grafting alkenyl double bonds on the graphene oxide, carrying out sulfydryl-alkene reaction on cotton fibers with surface sulfydryl modification, grafting graphene on the cotton fibers by covalent bonds, and spinning and weaving the graphene antibacterial fibers to obtain the graphene-based lasting antibacterial composite garment fabric.)

1. A preparation method of a graphene-based lasting antibacterial composite garment fabric is characterized by comprising the following steps:

(1) modification of fibres

Dissolving a mercaptosilane coupling agent in ethyl acetate according to the mass ratio of 5-20:100 to obtain a modified solution, immersing cotton fibers in the modified solution, carrying out closed oscillation for 1-2 hours at normal temperature, squeezing the cotton fibers after the reaction is finished, rinsing the cotton fibers with absolute ethyl alcohol, and evaporating the solvent under reduced pressure to obtain the surface-modified cotton fibers; the mercaptosilane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane or a composition of the 3-mercaptopropyltrimethoxysilane and the 3-mercaptopropyltriethoxysilane;

(2) graphene oxide modification

Mixing trichloromethane, acetone and triethylamine according to a volume ratio of 5: 5: 1, mixing to obtain a reaction solvent, ultrasonically dispersing graphene oxide in the solvent, wherein the dispersion ratio is 0.3-0.4g/L, adding 0.4mol/g of acyl chloride monomer containing at least one carbon-carbon double bond functional group based on the addition amount of the graphene oxide, stirring and reacting at the constant temperature of 35-40 ℃ for 20-24h, adding absolute ethyl alcohol for diluting after the reaction is finished, continuously stirring for 1-2h, filtering out precipitate, washing with the absolute ethyl alcohol, and drying to obtain modified graphene oxide;

(3) preparation of graphene antibacterial fiber

Dissolving a cross-linking agent and a photoinitiator in dichloromethane or acetone or N, N-dimethylformamide to prepare solutions with the concentrations of 0.2-0.4% and 2.0-3.0%, ultrasonically dispersing the modified graphene oxide in the solutions with the dispersion ratio of 0.5-1g/L to prepare a finishing solution, immersing the cotton fiber with surface sulfydryl modified in the finishing solution, taking out the cotton fiber, irradiating the cotton fiber with ultraviolet light, repeatedly immersing the cotton fiber and performing ultraviolet treatment for 1-3 times, rinsing the cotton fiber with absolute ethyl alcohol and deionized water respectively after the treatment is finished, and drying the cotton fiber at the temperature of 60-70 ℃ to obtain the graphene antibacterial fiber;

(4) weaving of antibacterial fabric

And spinning and weaving the graphene antibacterial fiber to obtain the graphene-based lasting antibacterial composite garment fabric.

2. The preparation method of the graphene-based durable antibacterial composite garment fabric according to claim 1, characterized by performing fiber pretreatment before performing fiber modification, specifically: and (3) soaking and cleaning the cotton wool fibers subjected to impurity removal in a hot sodium hydroxide solution, rinsing with clean water after soaking, and drying at 70-90 ℃ to obtain the pretreated cotton fibers.

3. The preparation method of the graphene-based durable antibacterial composite garment fabric according to claim 1, wherein the acyl chloride monomer is acryloyl chloride.

4. The preparation method of the graphene-based durable antibacterial composite garment material according to claim 1, wherein the cross-linking agent is pentaerythritol triacrylate, trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.

5. The method for preparing a graphene-based durable antibacterial composite garment fabric according to claim 1, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone or 2, 2-dimethoxy-2-phenyl acetophenone.

6. The preparation method of the graphene-based durable antibacterial composite garment fabric according to claim 1, wherein 0.08-0.15g/L of quaternized vinyl imidazolium salt is further added to the finishing liquid.

7. The preparation method of the graphene-based durable antibacterial composite garment fabric according to claim 6, wherein the preparation method of the quaternized vinyl imidazolium salt is as follows:

mixing and dissolving vinyl imidazole and bromoalkane or iodoalkane in a molar ratio n in absolute ethyl alcohol with the same volume, performing reflux reaction for 20-24h at 60-70 ℃ under the protection of nitrogen, and evaporating the solvent under reduced pressure after the reaction is finished to obtain the quaternized vinyl imidazole onium salt, wherein the molar ratio n meets 1.9< n < 2.0.

8. The preparation method of the graphene-based durable antibacterial composite garment material according to claim 1, wherein the number of carbons in the brominated alkane or the iodoalkane is 12-18.

9. A graphene-based durable antibacterial composite garment fabric, characterized by being prepared by the preparation method of any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of antibacterial fabrics, and particularly relates to a graphene-based lasting antibacterial composite garment fabric.

Background

The textile fiber fabric with the porous structure is easy to adsorb bacteria in the using process, sweat, fallen skin fat and the like discharged by a human body provide rich nutrition for fungus reproduction, so that bacteria breeding is caused, the breeding of the bacteria is easy to cause cross infection to spread diseases, peculiar smell is generated, and the fibers are easy to damage, so that the development of the textile fabric with the antibacterial function is one of necessary requirements for textile development.

Graphene oxide can destroy cell membranes of bacteria, so that intracellular substances can be leaked out and the bacteria can be killed, a plurality of antibacterial fabrics based on graphene finishing are developed since the antibacterial effect of graphene oxide is found out for the first time in 2010 experimentally, most of the existing graphene antibacterial fabrics are prepared by directly arranging a bonding coating on the fabrics, the air permeability of the fabrics can be greatly reduced by directly arranging a coating on the fabrics, the washing fastness is poor, and the lasting antibacterial effect cannot be exerted.

Disclosure of Invention

Aiming at the problems, the invention provides a graphene-based lasting antibacterial composite garment fabric and a preparation method thereof.

The purpose of the invention is realized by adopting the following technical scheme:

a preparation method of a graphene-based durable antibacterial composite garment fabric comprises the following steps:

(1) modification of fibres

Dissolving a mercaptosilane coupling agent in ethyl acetate according to the mass ratio of 5-20:100 to obtain a modified solution, immersing cotton fibers in the modified solution, carrying out closed oscillation for 1-2 hours at normal temperature, squeezing the cotton fibers after the reaction is finished, rinsing the cotton fibers with absolute ethyl alcohol, and evaporating the solvent under reduced pressure to obtain the surface-modified cotton fibers; the mercaptosilane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane or a composition of the 3-mercaptopropyltrimethoxysilane and the 3-mercaptopropyltriethoxysilane;

(2) graphene oxide modification

Mixing trichloromethane, acetone and triethylamine according to a volume ratio of 5: 5: 1, mixing to obtain a reaction solvent, ultrasonically dispersing graphene oxide in the solvent, wherein the dispersion ratio is 0.3-0.4g/L, adding 0.4mol/g of acyl chloride monomer containing at least one carbon-carbon double bond functional group based on the addition amount of the graphene oxide, stirring and reacting at the constant temperature of 35-40 ℃ for 20-24h, adding absolute ethyl alcohol for diluting after the reaction is finished, continuously stirring for 1-2h, filtering out precipitate, washing with the absolute ethyl alcohol, and drying to obtain modified graphene oxide;

(3) preparation of graphene antibacterial fiber

Dissolving a cross-linking agent and a photoinitiator in dichloromethane or acetone or N, N-dimethylformamide to prepare solutions with the concentrations of 0.2-0.4% and 2.0-3.0%, ultrasonically dispersing the modified graphene oxide in the solutions with the dispersion ratio of 0.5-1g/L to prepare a finishing solution, immersing the cotton fiber with surface sulfydryl modified in the finishing solution, taking out the cotton fiber, irradiating the cotton fiber with ultraviolet light, repeatedly immersing the cotton fiber and performing ultraviolet treatment for 1-3 times, rinsing the cotton fiber with absolute ethyl alcohol and deionized water respectively after the treatment is finished, and drying the cotton fiber at the temperature of 60-70 ℃ to obtain the graphene antibacterial fiber;

(4) weaving of antibacterial fabric

And spinning and weaving the graphene antibacterial fiber to obtain the graphene-based lasting antibacterial composite garment fabric.

Preferably, before the fiber modification, fiber pretreatment is performed, specifically: and (3) soaking and cleaning the cotton wool fibers subjected to impurity removal in a hot sodium hydroxide solution, rinsing with clean water after soaking, and drying at 70-90 ℃ to obtain the pretreated cotton fibers.

Preferably, the acid chloride monomer is acryloyl chloride.

Preferably, the crosslinking agent is pentaerythritol triacrylate, trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.

Preferably, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone or 2, 2-dimethoxy-2-phenylacetophenone.

Preferably, 0.08-0.15g/L of quaternized vinyl imidazolium salt is further added into the finishing liquid.

More preferably, the method for preparing the quaternized vinylimidazolium salt comprises the following steps:

mixing and dissolving vinyl imidazole and bromoalkane or iodoalkane in a molar ratio n in absolute ethyl alcohol with the same volume, performing reflux reaction for 20-24h at 60-70 ℃ under the protection of nitrogen, and evaporating the solvent under reduced pressure after the reaction is finished to obtain the quaternized vinyl imidazole onium salt, wherein the molar ratio n meets 1.9< n < 2.0.

Preferably, the carbon number of the alkyl bromide or alkyl iodide is 12-18.

The invention has the beneficial effects that:

(1) according to the fabric, the surface of the fiber is modified, and the surface modified fiber is woven into the fabric, so that the fabric can obtain functional modification, and simultaneously, the good air permeability of the fabric is kept, and the serviceability of the fabric is improved.

(2) This application is through alkenyl acyl chloride monomer and the hydroxyl reaction on oxidation graphite alkene surface to triethylamine is acid-binding agent, with alkenyl double bond grafting on oxidation graphite alkene, reduces the gathering between oxidation graphite alkene and piles up, improves the dispersibility, and the arrangement effect is even, reduces the arrangement flaw, does benefit to with fibrous complex.

(3) This application carries out surface mercapto modification to cotton fiber, to the alkenyl double bond grafting modification of oxidation graphite alkene, and mercapto-alkene reaction through ultraviolet light initiation is with covalent bond grafting graphite alkene on cotton fiber, improves the adhesive force of graphite alkene on the fibre, and graphite alkene can be fixed on the fibre for a long time, and the fastness to washing is high.

Detailed Description

The invention is further described with reference to the following examples.

The embodiment of the application relates to a preparation method of a graphene-based lasting antibacterial composite garment fabric, which comprises the following steps:

(1) modification of fibres

Dissolving a mercaptosilane coupling agent in ethyl acetate according to the mass ratio of 5-20:100 to obtain a modified solution, immersing cotton fibers in the modified solution, carrying out closed oscillation for 1-2 hours at normal temperature, squeezing the cotton fibers after the reaction is finished, rinsing the cotton fibers with absolute ethyl alcohol, and evaporating the solvent under reduced pressure to obtain the surface-modified cotton fibers; the mercaptosilane coupling agent is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane or a composition of the 3-mercaptopropyltrimethoxysilane and the 3-mercaptopropyltriethoxysilane;

the main component of the cotton fiber is cellulose, the surface of the cotton fiber contains a large amount of hydroxyl, and a sulfydryl coupling agent is covalently grafted on the cotton fiber through a-O-Si-bond by a silane coupling agent, so that the cotton fiber with the surface sulfydryl modified is obtained;

(2) graphene oxide modification

Mixing trichloromethane, acetone and triethylamine according to a volume ratio of 5: 5: 1, mixing to obtain a reaction solvent, ultrasonically dispersing graphene oxide in the solvent, wherein the dispersion ratio is 0.3-0.4g/L, adding 0.4mol/g of acyl chloride monomer containing at least one carbon-carbon double bond functional group based on the addition amount of the graphene oxide, stirring and reacting at the constant temperature of 35-40 ℃ for 20-24h, adding absolute ethyl alcohol for diluting after the reaction is finished, continuously stirring for 1-2h, filtering out precipitate, washing with the absolute ethyl alcohol, and drying to obtain modified graphene oxide;

(3) preparation of graphene antibacterial fiber

Dissolving a cross-linking agent and a photoinitiator in dichloromethane or acetone or N, N-dimethylformamide to prepare solutions with the concentrations of 0.2-0.4% and 2.0-3.0%, ultrasonically dispersing the modified graphene oxide in the solutions with the dispersion ratio of 0.5-1g/L to prepare a finishing solution, immersing the cotton fiber with surface sulfydryl modified in the finishing solution, taking out the cotton fiber, irradiating the cotton fiber with ultraviolet light, repeatedly immersing the cotton fiber and performing ultraviolet treatment for 1-3 times, rinsing the cotton fiber with absolute ethyl alcohol and deionized water respectively after the treatment is finished, and drying the cotton fiber at the temperature of 60-70 ℃ to obtain the graphene antibacterial fiber;

(4) weaving of antibacterial fabric

And spinning and weaving the graphene antibacterial fiber to obtain the graphene-based lasting antibacterial composite garment fabric.

Compared with the method for directly sticking graphene on the surface of the fabric by directly padding the fabric in the prior art, the method has the advantages that the surface of the fabric is modified, and the fabric is woven by the surface-modified fiber, so that the fabric can keep good air permeability of the fabric while the fabric is subjected to functional modification, the serviceability of the fabric is improved, meanwhile, the surface-modified fiber can be mixed with other fabric fibers for weaving, and the application range is greatly widened.

Due to the microstructure of graphene, a strong stacking tendency is generated between graphene sheet layers, so that the graphene is not well dispersed in various solvents, adhesives or polymers and is easy to agglomerate; this application is through alkenyl acyl chloride monomer and the hydroxyl reaction on oxidation graphite alkene surface to triethylamine is acid-binding agent, with alkenyl double bond grafting on oxidation graphite alkene, reduces the gathering between oxidation graphite alkene and piles up, improves the dispersibility, and the arrangement effect is even, reduces the arrangement flaw, does benefit to with fibrous complex.

Most of the existing graphene antibacterial fabrics are prepared by directly arranging a bonding coating on a fabric, the air permeability of the fabric is greatly reduced by directly arranging the coating on the fabric, and the fabric has poor washing fastness, is easy to fall off and cannot exert a lasting antibacterial effect; according to the application, the surface sulfydryl modification is carried out on cotton fibers, the alkenyl double bond of graphene oxide is subjected to graft modification, graphene is grafted on the cotton fibers through covalent bonds through ultraviolet-initiated sulfydryl-alkene reaction, the adhesive force of the graphene on the fibers is improved, the graphene can be fixed on the fibers by a polymer film for a long time, and the fastness to washing is high.

Preferably, before the fiber modification, fiber pretreatment is performed, specifically: and (3) soaking and cleaning the cotton wool fibers subjected to impurity removal in a hot sodium hydroxide solution, rinsing with clean water after soaking, and drying at 70-90 ℃ to obtain the pretreated cotton fibers.

The main component of the cotton fiber is cellulose, the alkali resistance is good, after the treatment of hot alkali solution, the surface pollution of the fiber can be removed, the natural turning and straightening of the fiber can be realized, a certain glossiness is realized, and the mechanical strength of the cotton fiber is improved.

Preferably, the acid chloride monomer is acryloyl chloride.

Preferably, the crosslinking agent is pentaerythritol triacrylate, trimethylolpropane trimethacrylate or trimethylolpropane triacrylate.

Preferably, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone or 2, 2-dimethoxy-2-phenylacetophenone.

Preferably, 0.08-0.15g/L of quaternized vinyl imidazolium salt is further added into the finishing liquid.

The existing research shows that the antibacterial mechanism of graphene is probably that the unique two-dimensional structure of graphene and phospholipid molecules on bacterial cell membranes generate super-strong interaction, so that a large number of phospholipid molecules are separated from the cell membranes and adsorbed to the surfaces of the graphene to damage the cell membranes, and the graphene and the bacteria need to have enough contact area and time, so that the antibacterial rate is different from the theoretical rate; according to the method, quaternized vinyl imidazolium salt is added into finishing liquid, wherein vinyl covalently grafts imidazole ring and graphene on cotton fiber through mercapto-alkene reaction, and the quaternized imidazole ring is positively charged, is easily combined with negatively charged bacterial cell membrane to generate static electricity, and has capturing and fixing effects on attached bacteria, so that the graphene can play an antibacterial role, and the antibacterial effect is further improved by cooperating with the graphene.

More preferably, the method for preparing the quaternized vinylimidazolium salt comprises the following steps:

mixing and dissolving vinyl imidazole and bromoalkane or iodoalkane in a molar ratio n in absolute ethyl alcohol with the same volume, performing reflux reaction for 20-24h at 60-70 ℃ under the protection of nitrogen, and evaporating the solvent under reduced pressure after the reaction is finished to obtain the quaternized vinyl imidazole onium salt, wherein the molar ratio n satisfies 1.9< n <2.0, and the reaction equation is as follows:

preferably, the carbon number of the alkyl bromide or alkyl iodide is 12-18.

The vinyl imidazole is quaternized by the long-carbon-chain alkyl bromide or alkyl iodide, and the long carbon chain is introduced to the surface of the fiber, so that on one hand, the hydrophobicity of the long carbon chain can reduce bacterial adhesion, the antibacterial aging of the fiber is improved, and the fiber has a certain antifouling self-cleaning effect, and on the other hand, the long carbon chain and the quaternized imidazole ring form a hydrophobic end and a hydrophilic end respectively, so that the fiber has a cation-like surfactant structure, the fabric is endowed with good softening performance, and the loss of the modification on the fiber softening performance is filled.

If the carbon number is too small, the hydrophobic effect cannot be embodied, and if the carbon number is too large, interweaving is easy to occur, uniform grafting is not facilitated, and rinsing of the fabric is also not facilitated.