CN111155299A - Modified spandex fiber material and preparation method thereof - Google Patents
Modified spandex fiber material and preparation method thereof Download PDFInfo
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- CN111155299A CN111155299A CN202010047127.4A CN202010047127A CN111155299A CN 111155299 A CN111155299 A CN 111155299A CN 202010047127 A CN202010047127 A CN 202010047127A CN 111155299 A CN111155299 A CN 111155299A
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- 229920002334 Spandex Polymers 0.000 title claims abstract description 121
- 239000004759 spandex Substances 0.000 title claims abstract description 121
- 239000002657 fibrous material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000835 fiber Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000002791 soaking Methods 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006143 cell culture medium Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Life Sciences & Earth Sciences (AREA)
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- Artificial Filaments (AREA)
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Abstract
The invention relates to a modified spandex fiber material and a preparation method thereof, wherein the method comprises the following steps: connecting the polyamino compound with spandex fibers; and then fixing the nano particles on the surface of the obtained spandex fiber to obtain the modified spandex fiber material. According to the invention, the surface of the spandex fiber is modified by the simple and easy method, the excellent performances of other nanoparticles can be added on the spandex fiber, and the obtained modified spandex fiber material has the excellent performances and additional performances, so that the application field of the spandex is expanded, the functions of the spandex are enriched, the process is mature, the operation is simple, the raw material source of the product is wide, and the application prospect is good.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a spandex fiber material, and especially relates to a modified spandex fiber material and a preparation method thereof.
Background
Spandex fibers have high elongation at break (above 400%), low modulus, and high elastic recovery, and are widely used. Besides higher strength, other physical and mechanical properties of the spandex fiber are very similar to those of natural latex yarn. But the strength of the composite material is 2-3 times higher than that of the latex yarn, the linear density is thinner, and the composite material is more resistant to chemical degradation. The spandex has better acid and alkali resistance, sweat resistance, seawater resistance, dry cleaning resistance and wear resistance, and can resist various dry cleaning agents and most of sun protection oil.
Currently, spandex fibers are generally used for most dyes and finishing agents of synthetic fibers and natural fibers, and are also suitable for dyeing and finishing spandex, but the application range of the spandex fibers has larger limitation. Based on the excellent performance, how to expand the application field and realize the maximization of the spandex fiber value becomes a problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a modified spandex fiber material and also provides the modified spandex fiber material.
In a first aspect, the present invention provides a process for preparing a modified spandex fiber material, the process comprising the steps of:
(1) connecting the polyamino compound with spandex fibers;
(2) and (2) fixing nano particles on the surface of the spandex fiber obtained in the step (1) to obtain the modified spandex fiber material.
According to the invention, firstly, a polyamino compound is connected with spandex fibers in a chemical bonding mode, so that the surfaces of the spandex fibers are provided with a plurality of amino groups, then, the alkaline obtained after hydrolysis of the amino groups is used for precipitating and adsorbing a nanoparticle precursor, so that nanoparticles are fixed on the surfaces of the fibers, and further, the spandex fiber material with the nanoparticles loaded on the surfaces is obtained. The obtained modified spandex fiber material has the properties of the spandex fiber, and also has the properties of nanoparticles, so that the application field of the spandex fiber is expanded.
For the invention, a plurality of nano-particles are required to be fixed on the surface of the spandex fiber through amino groups, so that the obtained modified spandex material can obtain the properties of the nano-particles, and therefore, a polyamino compound is selected to be connected with the spandex fiber.
In particular, compounds having multiple amino groups and capable of bonding to spandex fibers are suitable for use in the present invention. A large number of experiments prove that the amino-terminated hyperbranched polymer and the spandex fiber are connected, so that the spandex fiber is better modified, and therefore the polyamino compound is preferably the amino-terminated hyperbranched polymer.
The amino-terminated hyperbranched polymer can be prepared by a method commonly used in the art, for example, the amino-terminated hyperbranched polymer can be synthesized by diethylenetriamine and N, N methylene bisacrylamide, and can also be synthesized by triethylene tetramine, tetraethylene pentamine and other monomers, and the invention is not particularly limited in this regard.
Specifically, before the step (1), the method pretreats the spandex fiber, wherein the pretreatment is to adopt a coupling agent to carry out surface treatment on the spandex fiber. The modified spandex is characterized in that a polyamino compound is connected with spandex fibers in a chemical bonding mode by using a coupling agent, the polyamino compound is difficult to be directly connected with the spandex fibers, and the spandex fibers can be well connected with the polyamino compound only after being subjected to surface treatment by using the coupling agent, so that the pretreatment is one of the keys for realizing the invention.
Specifically, the pretreatment comprises the following steps: dissolving the coupling agent in a solvent, and then putting spandex fibers into the solvent for reaction.
For the present invention, any coupling agent is suitable which can make the spandex fiber well connected with the polyamino compound after surface treatment. Experiments prove that after the surface treatment is carried out on the spandex fiber by adopting the diisocyanate as the coupling agent, the connection effect of the spandex fiber and the polyamino compound is better, so that the coupling agent is preferably the diisocyanate.
Specifically, the concentration of the coupling agent in the solvent is 10 to 90% by weight, and may be, for example, 10%, 30%, 50%, 70%, or 90% by weight, or the like. Further, the effect is best when the concentration of the coupling agent in the solvent is 50 to 70 wt%.
Specifically, the mass ratio of the coupling agent to the spandex fiber is (5-20):1, and may be, for example, 5:1, 8:1, 10:1, 13:1, 15:1, 18:1, or 20: 1.
Specifically, the reaction temperature is 30-80 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃.
Specifically, the reaction time is 4 to 20 hours, and for example, the reaction time may be 4 hours, 8 hours, 10 hours, 13 hours, 15 hours, 18 hours, 20 hours, or the like.
For the present invention, the solvent employed must be effective in dissolving the coupling agent, but not the spandex fiber. For example, ethanol, methanol, acetone, etc., but not limited thereto, and other solvents satisfying the above requirements are also suitable for the present invention.
Specifically, the step (1) of the invention comprises the following steps: mixing polyamino compound and pretreated spandex fiber for grafting reaction. For example, the polyamino compound may be directly added to the mixture obtained after the pretreatment to perform the grafting reaction, or the mixture obtained after the pretreatment may be treated to obtain spandex fibers, and then the spandex fibers and the polyamino compound may be mixed in a solvent to perform the grafting reaction, and the former is generally selected from the viewpoint of simplifying the process and reducing the cost.
Specifically, the temperature of the grafting reaction is 30 to 80 ℃, and may be, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃.
Specifically, the time of the grafting reaction is 4 to 20 hours, and for example, the time can be 4 hours, 8 hours, 10 hours, 13 hours, 15 hours, 18 hours or 20 hours.
Specifically, the mass ratio of the polyamino compound to the spandex fiber is (2-10: 1), and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10: 1.
For the present invention, the more the polyamino compound is added, the more amino groups it provides to the spandex fiber, and more nanoparticles can be fixed. Therefore, the amount of the polyamino compound to be added may be specifically selected according to actual needs, and the present invention is not particularly limited thereto.
Specifically, the step (2) of the invention comprises the following steps: and immersing a product obtained after the grafting reaction is finished into a nanoparticle precursor solution for fixation to obtain the modified spandex fiber material.
The invention can select specific nano particles according to the property of the spandex fiber needing to be increased, for example, when the spandex fiber needs to be added with antibacterial performance, zinc oxide nano particles and/or titanium dioxide nano particles can be selected. After the nano-particles are fixed on the spandex fiber by the method, the modified spandex fiber obtains good antibacterial performance of the nano-particles such as zinc oxide and titanium dioxide, and the modified spandex fiber material with good hydrophilicity and antibacterial performance is obtained by combining the excellent performance of the spandex fiber.
In particular, the present invention can specifically select the nanoparticles to be fixed according to actual requirements. For example, when the spandex fiber needs to be added with antioxidant capacity, nanoparticles with antioxidant capacity can be selected for fixation, and when a catalytic function is needed, nanoparticles with catalytic capacity can be selected for fixation as well, so that the method is not limited to the antibacterial performance.
For the purposes of the present invention, the process of preparing nanoparticles into a sol is a well-known technique in the art, and is not described in detail for reasons of space and brevity.
Specifically, the fixing process time is 3-24h, and may be, for example, 3h, 6h, 9h, 12h, 15h, 18h, 21h or 24 h. The actual fixation time can be specifically adjusted as desired, but is not limited thereto.
Specifically, the bath ratio in the fixing step is (10-100):1, and may be, for example, 10:1, 30:1, 50:1, 80:1 or 100:1, and the fixing amount may be adjusted as necessary, but is not limited thereto.
For the purposes of the present invention, the above-mentioned bath ratio refers to the mass ratio of liquid to fiber solids in the mixture.
Specifically, the concentration of the nanoparticle precursor solution is 2 to 8 wt%, and may be, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, or 8 wt%.
Specifically, after the fixation is finished, the obtained product is generally selected to be dried, and the solvent is removed, so that the modified spandex fiber material is obtained. The drying method can be specifically selected according to actual conditions, such as freeze drying, evaporation drying and the like, and the invention is not particularly limited.
As a preferred technical scheme, the method for preparing the modified spandex fiber material comprises the following steps:
(a) dissolving diisocyanate in a solvent, and then putting spandex fibers into the solvent for reaction;
(b) adding an amino-terminated hyperbranched polymer into the mixture obtained after the reaction in the step (a) is completed for grafting reaction, so that the amino-terminated hyperbranched polymer and spandex fibers are connected in a chemical bonding manner;
(c) and (c) immersing the product obtained after the grafting reaction in the step (b) into a nanoparticle precursor solution for fixation, fixing the nanoparticles on the surface of spandex fibers by using amino, and drying to obtain the modified spandex fiber material.
In a second aspect, the invention provides a modified spandex fiber material prepared by the method of the first aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the invention, the surface of the spandex fiber is modified by the simple and easy method, the excellent performances of other nanoparticles can be added on the spandex fiber, and the obtained modified spandex fiber material has the excellent performances and additional performances, so that the application field of the spandex is expanded, the functions of the spandex are enriched, the process is mature, the operation is simple, the raw material source of the product is wide, and the application prospect is good.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The preparation method of the nanoparticle sol in each embodiment of the invention comprises the following steps: quantitative zinc acetate or tetrabutyl titanate is stirred and dissolved in ethanol, and then diethanolamine is slowly dripped until the solution is clarified to obtain a stable sol system.
Example 1
The embodiment provides a preparation method of a modified spandex fiber material, which comprises the following steps:
(1) surface pretreatment: dissolving diisocyanate reagents in ethanol, and adding spandex fibers for reaction; wherein the concentration of the diisocyanate is 50 wt%, the mass ratio of the diisocyanate to the spandex is 10:1, the reaction temperature is 50 ℃, and the reaction time is 15 hours;
(2) grafting reaction: adding an amino hyperbranched polymer into the mixture subjected to surface pretreatment in the step (1) to perform grafting reaction; wherein the mass ratio of the hyperbranched polymer to the spandex is 3:1, the concentration of the amino-terminated hyperbranched polymer is 6 wt%, the reaction temperature is 60 ℃, and the reaction time is 20 hours;
(3) fixation of nanoparticles: and (2) soaking the product obtained after the grafting modification reaction in the step (1) in a precursor sol of zinc oxide nano particles for fixation, wherein the soaking bath ratio is 30:1, the soaking time is 18h, the concentration of the precursor sol is 6 wt%, and freeze drying is carried out after the fixation is finished, so as to obtain the modified spandex fiber material.
Example 2
The embodiment provides a preparation method of a modified spandex fiber material, which comprises the following steps:
(1) surface pretreatment: dissolving diisocyanate reagents in ethanol, and adding spandex fibers for reaction; wherein the concentration of the diisocyanate is 70 wt%, the mass ratio of the diisocyanate to the spandex is 15:1, the reaction temperature is 60 ℃, and the reaction time is 12 hours;
(2) grafting reaction: adding an amino hyperbranched polymer into the mixture subjected to surface pretreatment in the step (1) to perform grafting reaction; wherein the mass ratio of the hyperbranched polymer to the spandex is 5:1, the concentration of the amino-terminated hyperbranched polymer is 8 wt%, the reaction temperature is 80 ℃, and the reaction time is 6 hours;
(3) fixation of nanoparticles: and (2) soaking the product obtained after the grafting modification reaction in the step (1) in a precursor sol of titanium dioxide nanoparticles for fixation, wherein the soaking bath ratio is 50:1, the soaking time is 18h, the concentration of the precursor sol is 8 wt%, and freeze drying is carried out after the fixation is finished, so as to obtain the modified spandex fiber material.
Example 3
The embodiment provides a preparation method of a modified spandex fiber material, which comprises the following steps:
(1) surface pretreatment: dissolving diisocyanate reagents in ethanol, and adding spandex fibers for reaction; wherein the concentration of the diisocyanate is 40 wt%, the mass ratio of the diisocyanate to the spandex is 8:1, the reaction temperature is 40 ℃, and the reaction time is 24 hours;
(2) grafting reaction: adding an amino hyperbranched polymer into the mixture subjected to surface pretreatment in the step (1) to perform grafting reaction; wherein the mass ratio of the hyperbranched polymer to the spandex is 3:1, the concentration of the amino-terminated hyperbranched polymer is 10 wt%, the reaction temperature is 30 ℃, and the reaction time is 24 hours;
(3) fixation of nanoparticles: and (2) soaking the product obtained after the grafting modification reaction in the step (1) in a precursor sol of titanium dioxide nanoparticles for fixing, wherein the soaking bath ratio is 100:1, the soaking time is 5 hours, the concentration of the precursor sol is 4 wt%, and freeze drying is carried out after the fixing is finished, so as to obtain the modified spandex fiber material.
And (3) performance detection:
the antibacterial ability of the modified spandex material obtained in each example is detected by a turbidity method, and the method specifically comprises the following steps: the modified spandex fiber is soaked in a cell culture medium, is placed in a shaking table at 37 ℃ for culture after being inoculated with bacteria, is taken out after 24 hours, is subjected to turbidity detection by an ultraviolet-visible spectrophotometer, and is compared with a control group, so that the obtained result is shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| 24h bacteriostasis rate | 87.4％ | 89.2％ | 84.1％ |
As can be seen from the data in Table 1, after the surface of the spandex fiber is modified by adopting the method, the modified spandex fiber material has additional antibacterial property, the application field of spandex is expanded, the functions of spandex are enriched, and the application prospect is good.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing a modified spandex fiber material, characterized in that the method comprises the following steps:
(1) connecting the polyamino compound with spandex fibers;
(2) and (2) fixing nano particles on the surface of the spandex fiber obtained in the step (1) to obtain the modified spandex fiber material.
2. The method of preparing a modified spandex fiber material of claim 1, wherein the polyamino compound is an amino-terminated hyperbranched polymer.
3. The method for preparing a modified spandex fiber material of claim 1, wherein the spandex fiber is pretreated before step (1), and the pretreatment comprises: dissolving the coupling agent in a solvent, and then putting spandex fibers into the solvent for reaction.
4. The method for preparing a modified spandex fiber material of claim 3, wherein the coupling agent is a diisocyanate;
the concentration of the coupling agent in the solvent is 10-90 wt%;
the mass ratio of the coupling agent to the spandex fiber is (5-20) to 1;
the reaction temperature is 30-80 ℃, and the reaction time is 4-20 h;
the solvent does not dissolve the spandex fiber.
5. The method for preparing a modified spandex fiber material as claimed in claim 3, wherein the step (1) comprises: mixing polyamino compound and pretreated spandex fiber for grafting reaction.
6. The method for preparing a modified spandex fiber material of claim 5, wherein the temperature of the grafting reaction is 30-80 ℃ and the time of the grafting reaction is 4-20 hours;
the mass ratio of the polyamino compound to the spandex fiber is (2-10) to 1.
7. The method for preparing a modified spandex fiber material of claim 5, wherein step (2) includes: and immersing a product obtained after the grafting reaction is finished into a nanoparticle precursor solution for fixation to obtain the modified spandex fiber material.
8. The method of preparing a modified spandex fiber material of claim 7, wherein the nanoparticles comprise zinc oxide nanoparticles and/or titanium dioxide nanoparticles;
the time of the fixation process is 3-24 h;
the bath ratio in the fixing process is (10-100) to 1;
the concentration of the nanoparticle precursor solution is 2-8 wt%;
and drying after the fixation is finished to obtain the modified spandex fiber material.
9. The method of preparing a modified spandex fiber material of claim 1, wherein the method comprises the steps of:
(a) dissolving diisocyanate in a solvent, and then putting spandex fibers into the solvent for reaction;
(b) adding an amino-terminated hyperbranched polymer into the mixture obtained after the reaction in the step (a) is completed for grafting reaction, so that the amino-terminated hyperbranched polymer and spandex fibers are connected in a chemical bonding manner;
(c) and (c) immersing the product obtained after the grafting reaction in the step (b) into a nanoparticle precursor solution for fixation, fixing the nanoparticles on the surface of spandex fibers by using amino, and drying to obtain the modified spandex fiber material.
10. A modified spandex fiber material prepared by the method of any one of claims 1 to 9.
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| JP2000192329A (en) * | 1998-12-22 | 2000-07-11 | Taiho Ind Co Ltd | Yarn composed of functional grafted polyurethane and its production |
| CN105019085A (en) * | 2015-06-16 | 2015-11-04 | 长兴虹波纺织有限公司 | Spandex composite fibers and preparation method thereof |
| CN105714551A (en) * | 2016-04-07 | 2016-06-29 | 中原工学院 | Preparation method of cuprous sulfide/spandex composite conductive fiber |
| CN105803789A (en) * | 2016-03-29 | 2016-07-27 | 深圳市新纶科技股份有限公司 | Surface modification aramid fiber and preparation method thereof |
| CN106367947A (en) * | 2016-10-12 | 2017-02-01 | 武汉纺织大学 | Method for improving tensile mechanical property of fibers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000192329A (en) * | 1998-12-22 | 2000-07-11 | Taiho Ind Co Ltd | Yarn composed of functional grafted polyurethane and its production |
| CN105019085A (en) * | 2015-06-16 | 2015-11-04 | 长兴虹波纺织有限公司 | Spandex composite fibers and preparation method thereof |
| CN105803789A (en) * | 2016-03-29 | 2016-07-27 | 深圳市新纶科技股份有限公司 | Surface modification aramid fiber and preparation method thereof |
| CN105714551A (en) * | 2016-04-07 | 2016-06-29 | 中原工学院 | Preparation method of cuprous sulfide/spandex composite conductive fiber |
| CN106367947A (en) * | 2016-10-12 | 2017-02-01 | 武汉纺织大学 | Method for improving tensile mechanical property of fibers |
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