CN111155313B - Modified spandex fiber material and preparation method thereof - Google Patents
Modified spandex fiber material and preparation method thereof Download PDFInfo
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- CN111155313B CN111155313B CN202010047902.6A CN202010047902A CN111155313B CN 111155313 B CN111155313 B CN 111155313B CN 202010047902 A CN202010047902 A CN 202010047902A CN 111155313 B CN111155313 B CN 111155313B
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- D06M11/53—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 sulfur, selenium, tellurium, polonium or compounds thereof with hydrogen sulfide or its salts; with polysulfides
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- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- 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
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- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
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- 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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- D06M2200/10—Repellency against liquids
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- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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Abstract
The invention provides a modified spandex fiber material and a preparation method thereof, wherein the method comprises the following steps: mixing a polyamino compound and pretreated spandex fibers for grafting reaction, adsorbing metal ions on the surfaces of the spandex fibers, adding sulfur ions for reaction, and finally performing grafting reaction with a fluorine-silicon reagent to obtain the modified spandex fiber material. The invention carries out functional modification on the surface of the spandex fiber in a multi-layer fixing mode, so that the spandex fiber has excellent performance and additional ultraviolet resistance, water repellency and oil repellency, enhances the durability and cleanness of the spandex in the practical application process, and has the advantages of simple operation, wide source of required raw materials, high feasibility and good application prospect.
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 the higher strength, the spandex fiber has other physical and mechanical properties which are very similar to those of natural latex yarn, but the strength of the spandex fiber is 2-3 times higher than that of the natural latex yarn, the linear density of the spandex fiber is thinner, and the spandex fiber 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 properties, how to expand the application field of the polyurethane fiber and realize the maximization of the value of the polyurethane fiber 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) Mixing polyamino compound and pretreated spandex fiber for grafting reaction;
(2) Adsorbing metal ions on the surface of the spandex fiber obtained in the step (1), and then adding sulfur ions for reaction;
(3) And (3) carrying out grafting reaction on the product obtained in the step (2) and a fluorine-silicon reagent, and obtaining the modified spandex fiber material after the reaction is finished.
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 amino groups and metal ions are utilized for chelation, so that a large number of metal ions are adsorbed on the surfaces of the spandex fibers, and then sulfur ions and the metal ions are added for reaction, so that the spandex fibers obtain excellent ultraviolet resistance; furthermore, a fluorine-containing silicon reagent is added for chemical grafting, so that the excellent water and oil repellent capacity is obtained. Through the treatment of the method, the obtained modified spandex fiber material has the properties of spandex fibers, and also has excellent water and oil repellency and ultraviolet resistance, so that the application field of the spandex fibers is expanded.
For the invention, abundant amino groups on the surface of the spandex fiber are needed to chelate a large amount of metal ions and graft a fluorine-silicon reagent, so that 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 to achieve a better modification effect on the spandex fiber, so that 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.
In the step (1), the polyamino compound and the spandex fiber are connected in a chemical bonding mode by using a coupling agent. For the invention, the polyamino compound and the spandex fiber are difficult to be directly connected, and the polyamino compound can be well connected only after the surface treatment is carried out on the spandex fiber by the coupling agent, so the pretreatment is one of the keys for realizing the invention.
Specifically, the coupling agent adopted by the invention is diisocyanate monomer, but the invention is not limited to this, and other coupling agents capable of realizing grafting with polyamino compound after the surface of spandex fiber is pretreated are also suitable for the invention.
Specifically, the pretreatment in the step (1) comprises the following steps: dissolving the coupling agent in a solvent, and then putting spandex fibers into the solvent for reaction.
Specifically, the concentration of the coupling agent in the solvent in the pretreatment in step (1) is 10 to 90wt%, and may be, for example, 10wt%, 30wt%, 50wt%, 70wt%, or 90 wt%. 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 in the pretreatment in the step (1) is (5-20): 1, and for example, the mass ratio can be 5:1, 8:1, 10, 1, 13.
Specifically, the temperature of the reaction in the pretreatment in step (1) is 30 to 80 ℃, and may be, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃.
Specifically, the reaction time in the pretreatment in step (1) is 4-20h, and may be 4h, 8h, 10h, 13h, 15h, 18h or 20h, for example.
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 temperature of the grafting reaction in the step (1) is 30 to 80 ℃, and may be, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃.
Specifically, the time of the grafting reaction in the step (1) is 4-20h, for example, 4h, 8h, 10h, 13h, 15h, 18h or 20h, etc.
Specifically, the mass ratio of the polyamino compound to the spandex fiber in the step (1) is (2-10): 1, and for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10 can be.
For the present invention, the more the polyamino compound is added, the more amino groups it provides to the spandex fiber, and the more metal ions can be adsorbed. 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) comprises the following steps: and (2) soaking the spandex fiber obtained in the step (1) into a solution containing metal ions for adsorption, and soaking the product obtained after adsorption into a solution containing sulfur ions for reaction.
According to the invention, metal ions such as copper ions, cobalt ions, iron ions and/or molybdenum ions can be selected, and the metal ions and sulfur ions can be combined to generate excellent ultraviolet resistance.
Specifically, the concentration of the metal ion in the metal ion-containing solution is 0.01 to 0.2mol/L, and may be, for example, 0.01mol/L, 0.03mol/L, 0.05mol/L, 0.08mol/L, 0.1mol/L, 0.13mol/L, 0.15mol/L, 0.18mol/L, or 0.2 mol/L.
The bath ratio referred to herein refers to the mass ratio of liquid to fiber solids in the mixture.
Specifically, the bath ratio of the adsorption process in the step (2) is (10-50): 1, and for example, the bath ratio can be 10.
Specifically, the adsorption time in step (2) is 2-24h, and may be, for example, 2h, 6h, 10h, 14h, 18h, 20h, or 24 h.
For the present invention, the solution containing sulfur ions in step (2) is only required to contain sulfur ions, and the specific type thereof is not particularly limited in the present application, and the solution containing sulfur ions may be a sodium sulfide solution, but is not limited thereto.
Specifically, the bath ratio in the step (2) and the sulfur ion reaction process is (5-25): 1, and can be, for example, 5:1, 10.
Specifically, the time for the reaction with the sulfide ions in the step (2) is 2-24h, and may be, for example, 2h, 6h, 10h, 14h, 18h, 20h or 24 h.
Specifically, the step (3) of the invention comprises: and (3) immersing the product obtained in the step (2) into a solution of a fluorine-silicon reagent for grafting reaction, and obtaining the modified spandex fiber material after the reaction is finished.
For the invention, the fluorine-silicon reagent is selected from the fluorine-silicon reagents commonly used in the field, as long as the fluorine-silicon reagent can perform good grafting reaction with the product obtained in the step (2) to ensure that the product has water and oil repellent performance. Illustratively, the fluorosilicate reagent comprises a fluorine-containing reagent or a silicon-containing reagent, or a fluorosilicate mix.
Specifically, the fluorosilicone reagent is a reagent commonly used in the art, and can be specifically selected according to needs, for example, chromium perfluorocarboxylate complexes, silicones and the like, and the invention is not exhaustive for reasons of space and simplicity.
Specifically, the concentration of the fluorosilicone reagent in the solution is 5 to 20wt%, and may be, for example, 5wt%, 10wt%, 15wt%, 20wt%, or the like.
Specifically, the temperature of the grafting reaction in the step (3) is 30 to 80 ℃, and may be, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃.
Specifically, the time of the grafting reaction in the step (3) is 4-24h, and may be, for example, 4h, 8h, 10h, 13h, 15h, 18h, 20h or 24 h.
Specifically, the bath ratio of the grafting reaction in the step (3) is (5-30): 1, and for example, 5:1, 10, 1, 15.
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) Immersing the product obtained after the grafting reaction in the step (b) into a solution containing metal ions for adsorption, and immersing the product obtained after adsorption into a solution containing sulfide ions for reaction;
(d) And (c) immersing the product obtained in the step (c) into a solution of a fluorine-silicon reagent for grafting reaction, and obtaining the modified spandex fiber material after the reaction is finished.
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:
the invention firstly utilizes the coupling agent to pretreat the surface of the spandex fiber and then chemically graft the spandex fiber with the polyamino compound, then utilizes abundant amino groups of the spandex fiber to chelate with metal ions and then react with sulfur ions, so that the spandex fiber has good ultraviolet resistance, and finally chemically grafts with the fluorine-containing silicon reagent, so that the spandex fiber has good water and oil repellency. The invention carries out functional modification on the surface of the spandex fiber in a multi-layer fixing mode, so that the spandex fiber has excellent performance and additional ultraviolet resistance, water repellency and oil repellency, enhances the durability and cleanness of the spandex in the practical application process, and has the advantages of simple operation, wide source of required raw materials, high feasibility and good application prospect.
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.
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 55wt%, the mass ratio of the diisocyanate to the spandex is 15, the reaction temperature is 50 ℃, and the reaction time is 8h;
(2) And (3) grafting reaction: adding an end 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 reaction temperature is 65 ℃, and the reaction time is 10 hours;
(3) And (3) adsorption reaction: soaking the spandex fiber obtained after the reaction in the step (2) in a solution containing cobalt ions for adsorption, wherein the concentration of the cobalt ions is 0.15mol/L, the adsorption time is 12h, and the bath ratio is 25;
(4) Reaction with sulfide ion: soaking the spandex fiber which is adsorbed by the cobalt ions in the step (3) in a sodium sulfide solution for reaction, wherein the concentration of sodium sulfide is 3wt%, the bath ratio is 15;
(5) Grafting reaction: and (4) soaking the product obtained after the reaction in the step (3) in a solution containing a fluorine reagent for chemical grafting, wherein the concentration of the fluorine reagent is 10wt%, the reaction temperature is 50 ℃, the reaction time is 10h, the bath ratio is 20.
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 80wt%, the mass ratio of the diisocyanate to the spandex is 8:1, the reaction temperature is 45 ℃, and the reaction time is 20 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 6:1, the reaction temperature is 40 ℃, and the reaction time is 24 hours;
(3) And (3) adsorption reaction: soaking the spandex fiber obtained after the reaction in the step (2) in a solution containing copper and cobalt ions for adsorption, wherein the concentration of metal ions is 0.1mol/L, the adsorption time is 18h, and the bath ratio is 30;
(4) Reaction with sulfide ion: soaking the spandex fiber which is adsorbed by the cobalt ions in the step (3) in a sodium sulfide solution for reaction, wherein the concentration of sodium sulfide is 3.5wt%, the bath ratio is 20;
(5) And (3) grafting reaction: and (3) soaking the product obtained after the reaction in the step (3) in a solution containing a silicon reagent for chemical grafting, wherein the concentration of the silicon reagent is 15wt%, the reaction temperature is 70 ℃, the reaction time is 6h, the bath ratio is 25.
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 70wt%, the mass ratio of the diisocyanate to the spandex is 5:1, the reaction temperature is 80 ℃, and the reaction time is 4 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 10, the reaction temperature is 60 ℃, and the reaction time is 24 hours;
(3) And (3) adsorption reaction: soaking the spandex fiber obtained after the reaction in the step (2) in a solution containing iron and molybdenum ions for adsorption, wherein the concentration of metal ions is 0.2mol/L, the adsorption time is 10h, and the bath ratio is 50;
(4) Reaction with sulfide ion: soaking the spandex fiber which is adsorbed with the cobalt ions in the step (3) in a sodium sulfide solution for reaction, wherein the concentration of sodium sulfide is 1wt%, the bath ratio is 25;
(5) Grafting reaction: and (3) soaking the product obtained after the reaction in the step (3) in a solution containing a fluorine-containing silicon reagent for chemical grafting, wherein the concentration of the fluorine-containing silicon reagent is 20wt%, the reaction temperature is 55 ℃, the reaction time is 16h, the bath ratio is 10.
And (3) performance detection:
and (3) detecting the ultraviolet resistance: the modified spandex materials obtained in the examples were placed under ultraviolet light for 24 hours, and the strength change of the modified spandex before and after irradiation was compared, and the results are shown in table 1.
And (3) detecting the water and oil repellency: the contact angle of the modified spandex materials obtained in each example was measured by a fully automatic contact angle measuring instrument, and the contact angle of the liquid between the modified spandex materials was observed and recorded, and the results are shown in table 1.
TABLE 1
As can be seen from the content in Table 1, the method disclosed by the invention is used for functionally modifying the surface of the spandex fiber, so that the spandex fiber has excellent ultraviolet resistance, water and oil repellency and good application prospect.
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 (2)
1. A method for preparing a modified spandex fiber material, characterized in that the method comprises the following steps:
(1) Mixing polyamino compound and pretreated spandex fiber for grafting reaction; the polyamino compound is an amino-terminated hyperbranched polymer; the pretreatment comprises the following steps: dissolving a coupling agent in a solvent, and then putting spandex fibers into the solvent for reaction;
the coupling agent is diisocyanate;
the concentration of the coupling agent in the solvent is 10-90wt%;
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 4-20h;
the solvent does not dissolve spandex fibers;
the temperature of the grafting reaction is 30-80 ℃, and the time of the grafting reaction is 4-20h; the mass ratio of the polyamino compound to the spandex fiber is (2-10) to 1;
(2) Adsorbing metal ions on the surface of the spandex fiber obtained in the step (1), and then adding sulfur ions for reaction; the method specifically comprises the following steps: soaking the obtained spandex fiber into a solution containing metal ions for adsorption, and soaking the product obtained after adsorption into a solution containing sulfur ions for reaction; the metal ions comprise copper ions, cobalt ions, iron ions and/or molybdenum ions; the concentration of the metal ions in the solution containing the metal ions is 0.01-0.2mol/L; the bath ratio in the adsorption process is (10-50) to 1; the adsorption time is 2-24h; the solution containing sulfur ions comprises a sodium sulfide solution; the bath ratio in the process of the reaction with the sulfide ions is (5-25) to 1; the time for the reaction with the sulfur ions is 2-24h;
(3) Carrying out grafting reaction on the product obtained in the step (2) and a fluorine-silicon reagent, and obtaining the modified spandex fiber material after the reaction is finished; the method specifically comprises the following steps: immersing the product obtained in the step (2) into a solution of a fluorine-silicon reagent for grafting reaction, and obtaining the modified spandex fiber material after the reaction is finished;
the fluorine-silicon reagent comprises a fluorine-containing reagent, a silicon-containing reagent and/or a fluorine-silicon mixed reagent;
the concentration of the fluorine-silicon reagent in the solution is 5-20wt%;
the temperature of the grafting reaction is 30-80 ℃, and the reaction time is 4-24 h;
the bath ratio of the grafting reaction is (5-30): 1.
2. A modified spandex fiber material, characterized in that it is prepared by the method of claim 1.
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