CN109881292B - Polyurethane elastic fiber with excellent antibacterial property and preparation method thereof - Google Patents
Polyurethane elastic fiber with excellent antibacterial property and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyurethane elastic fiber with excellent antibacterial property and a preparation method thereof. The invention has the following beneficial effects: 1. the branched quaternary ammonium salt with a special structure is added into the polyurethane stock solution, so that the problem of poor compatibility of the inorganic antibacterial particles and the stock solution is solved; 2. the excellent antibacterial polyurethane fiber has dual bactericidal effects of contact and slow release; 3. the prepared polyurethane fiber containing the antibacterial particles has lasting antibacterial capacity; 4. the branched quaternary ammonium salt can also embed functional guest molecules such as dye and the like, and the multifunctional property of the polyurethane fiber is improved.
Description
Technical Field
The invention relates to the field of preparation and application of a branched quaternary ammonium salt and an antibacterial composite material thereof, in particular to application of a branched quaternary ammonium salt antibacterial composite material in polyurethane elastic fibers. The polyurethane elastic fiber prepared by the invention has multiple functions of antistatic property, easy dyeing, contact antibacterial property, release antibacterial property and the like.
Background
Spandex is a polyurethane elastic fiber, is one of fibers with the best elasticity in synthetic fibers, and has the characteristics of high elasticity, high elongation, low modulus, high hydrolysis resistance and the like. Spandex has gradually replaced traditional rubber filament products since the 21 st century and is widely applied to the clothing and textile industry. The application fields include high performance structural composites, swimwear, silk stockings, diapers, and the like. However, with the continuous improvement of living standard, people have higher and higher requirements for fabrics, and functional spandex fibers and fabrics thereof with antibacterial and health-care functions gradually become the focus of attention of people.
The preparation method of the antibacterial spandex at present is mainly realized by adding a nano inorganic antibacterial agent, an organic antibacterial agent and a natural antibacterial agent. The nano inorganic antibacterial agent has the advantages of wide use source, safe use and the like, and has become the mainstream of the antibacterial agent, but a pure nano inorganic auxiliary agent is often poor in compatibility with a base material and the antibacterial effect lasts for a long time. For example, common inorganic additives such as nano Ag and nano ZnO are difficult to achieve good dispersion of the antibacterial powder in spandex fibers, and the formed aggregate has certain influence on the spinnability of spandex. US20120115386a1 discloses a method for preparing nanofiber non-woven fabric, the method loads nano silver on ceramic-based metal oxide, the problem of nano silver dispersion and agglomeration cannot be solved, and newly introduced metal oxide zirconium is combined with nano to enlarge the sedimentation process of slurry to a certain extent. The currently widely used organic antibacterial auxiliary agents are mainly quaternary ammonium salt products, and typically materials containing functional groups of quaternary ammonium groups and cationic polymers have an antibacterial effect by destroying the cell structure of bacteria, but have the defect of insensitivity to gram-negative bacteria and specific resistant bacteria. Chinese patent CN103668544B discloses a polyurethane elastic fiber with multi-element functionality and a preparation method thereof, the method prepares synthesized glycyrrhetinic chitosan quaternary ammonium salt into nano particles, solves the problems of dispersibility and compatibility of the quaternary ammonium salt to a certain extent, but cannot completely avoid the problem of partial agglomeration of the nano particle quaternary ammonium salt composite material, and the single use of a quaternary ammonium salt antibacterial agent cannot meet the universality of the current antibacterial product. Therefore, there is a need to develop multifunctional materials combining the advantages of inorganic and organic adjuvants, while trying to overcome the respective disadvantages.
At present, no reports and patents related to functional materials combining the nano inorganic auxiliary agent and the branched quaternary ammonium salt with a special structure proposed by the patent and polyurethane elastic fibers with excellent antibacterial performance obtained by adding the functional materials into polyurethane spinning solution are found.
Disclosure of Invention
The technical problem is as follows: in order to solve the problems of the background art, an object of the present invention is to provide a polyurethane elastic fiber having excellent antibacterial properties and a method for preparing the same. The polyurethane elastic fiber prepared by the process method has excellent antibacterial property, is simple in preparation method and has wide industrial application prospect.
The technical scheme is as follows: the polyurethane elastic fiber with excellent antibacterial performance comprises functional branched quaternary ammonium salt and a polyurethane elastomer, wherein the functional branched quaternary ammonium salt is prepared from branched quaternary ammonium salt and antibacterial particles, and the addition amount of the branched quaternary ammonium salt is 0.1-3 wt% of the solid content of a polyurethane stock solution for preparing the polyurethane elastic fiber with excellent antibacterial performance.
The functional branched quaternary ammonium salt is prepared by reacting branched polyethyleneimine with a halogenated compound, and has the following chemical structural formula:
in the formula I
Having the conventional meaning in the art means that it is not the end point of a segment here, but continues to have repeating units or segments attached.
The above-mentioned
Represented as one or more repetitions of the structure of the following structural units;
wherein each R in formula I is independently selected from:
(3) saturated or unsaturated aliphatic hydrocarbon group containing terminal epoxy group C3-C15;
(4) containing a saturated or unsaturated aromatic hydrocarbon group having C6-C20.
The polyurethane elastomer is any one of polyether polyurethane, polyester polyurethane and polyether-polyester polyurethane.
The preparation method of the polyurethane elastic fiber with excellent antibacterial property comprises the following steps:
1) performing prepolymerization reaction on polytetramethylene ether glycol and 4, 4-diphenylmethane diisocyanate in an N, N-dimethylacetamide solution, and performing chain extension reaction on a mixture of ethylenediamine, 1, 2-propylenediamine and diethylamine to obtain a polyurethane stock solution;
2) synthesizing multifunctional branched quaternary ammonium salt and preparing a branched quaternary ammonium salt composite material containing antibacterial particles;
3) fully mixing a multifunctional branched quaternary ammonium salt composite material, N-dimethylacetamide, an anti-ultraviolet auxiliary agent UV-320, a delustering agent titanium dioxide and a lubricant magnesium stearate with a part of the polyurethane stock solution in a grinding machine to form low-viscosity additive slurry, and adding the low-viscosity additive slurry into the polyurethane stock solution to prepare a spinning stock solution;
4) curing the spinning stock solution, and then carrying out dry spinning to obtain polyurethane elastic fiber;
wherein:
in the step 1), the molar ratio of the polytetramethylene ether glycol to the 4, 4-diphenylmethane diisocyanate is 1: 1.6-1: 2.1, and the molar ratio of the ethylenediamine to the 1, 2-propylenediamine is 10: 1-1: 10;
the method for synthesizing the branched quaternary ammonium salt in the step 2) comprises the following steps:
(1) dissolving branched polyethyleneimine in water, adding a certain amount of formic acid and formaldehyde, and performing aminomethylation reaction for 1-10 days at the temperature of 70-100 ℃ to obtain methylated branched polyethyleneimine;
(2) dissolving the methylated branched polyethyleneimine obtained in the step (1) in a DMAC solution, adding a certain amount of halogenated compound containing epoxy end group or halogenated compound containing aromatic group, and reacting at 50-80 ℃ for 1-10 days to obtain the branched polyquaternary ammonium salt.
In the synthesis of the multifunctional branched quaternary ammonium salt, the molar ratio of the branched polyethyleneimine to the formic acid to the formaldehyde is 1: 20-50: 10-30, and the amount of the halogenated compound containing the epoxy end group or the halogenated compound containing the amine end group is 1.5-3 times of the molar amount of the branched polyethyleneimine.
In the preparation of the multifunctional branched quaternary ammonium salt, the weight ratio of the branched quaternary ammonium salt to the antibacterial particles or the dye is 1: 0.1-1.
Has the advantages that:
1. the branched quaternary ammonium salt with a special structure is added into the polyurethane stock solution, so that the problem of poor compatibility of the inorganic antibacterial particles and the stock solution is solved;
2. the excellent antibacterial polyurethane fiber has dual bactericidal effects of contact and slow release;
3. the prepared polyurethane fiber containing the antibacterial particles has lasting antibacterial capacity;
4. the branched quaternary ammonium salt can also embed other functional guest molecules such as dye and the like, and the multifunctional performance of the polyurethane fiber is improved.
Drawings
FIG. 1 is the chemical structural formula of hyperbranched quaternary ammonium salt and the antibacterial composite material thereof.
Detailed Description
The preparation method of the polyurethane elastic fiber with excellent antibacterial performance comprises the following steps:
(1) performing prepolymerization reaction on polytetramethylene ether glycol and 4, 4-diphenylmethane diisocyanate in an N, N-dimethylacetamide solution, and performing chain extension reaction on a mixture of ethylenediamine, 1, 2-propylenediamine and diethylamine to obtain a polyurethane stock solution;
(2) synthesizing branched quaternary ammonium salt and preparing into a composite material containing coated antibacterial particles;
(3) fully mixing a branched quaternary ammonium salt antibacterial composite material, N-dimethylacetamide, an anti-ultraviolet auxiliary agent UV-320, a dyeing auxiliary agent SAS, a delustering agent titanium dioxide and a lubricant magnesium stearate with a part of the polyurethane stock solution in a grinding machine to form low-viscosity additive slurry, and adding the low-viscosity additive slurry into the polyurethane stock solution to prepare a spinning stock solution;
(4) and curing the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
The preparation method of the polyurethane elastic fiber with the multi-element functionality comprises the following steps of (1), wherein the molar ratio of polytetramethylene ether glycol to 4, 4-diphenylmethane diisocyanate is 1: 1.6-1: 2.1, the molar ratio of ethylenediamine to 1, 2-propylene diamine is 10: 1-1: 10, and the mass ratio of diethylamine to polytetramethylene ether glycol is 0.30-0.55 wt%.
The invention discloses a preparation method of polyurethane elastic fiber with excellent antibacterial performance, wherein the branched quaternary ammonium salt in the step (2) is prepared by branching polyethyleneimine methylation and modification by halogenated compounds containing amine end groups or epoxy end groups, and the chemical structural formula is as follows:
wherein in formula I
Having the conventional meaning in the art, in certain embodiments it is meant that, in addition to being the end point of a segment, there continues to be attached a repeating unit or segment,
can be represented as one or more repeats of the following structural units.
Wherein each R in formula I is independently selected from:
(1) saturated or unsaturated aliphatic hydrocarbon group containing terminal epoxy group C3-C15;
(2) containing a saturated or unsaturated aromatic hydrocarbon group having C6-C20.
The invention relates to a preparation method of polyurethane elastic fiber with excellent antibacterial performance, and the synthesis method of the branched quaternary ammonium salt in the step 2) comprises the following steps: dissolving branched polyethyleneimine in DMAC, adding a certain amount of formic acid and formaldehyde, performing aminomethylation reaction for 1-10 days at 70 ℃ to obtain methylated branched polyethyleneimine, adding halogenated compounds containing epoxy end groups or halogenated compounds containing aromatic groups, performing reaction for 1 day at 50 ℃ to obtain branched polyquaternary ammonium salt solution, adding nano antibacterial particles with a certain mass into the branched polyquaternary ammonium salt solution, and fully stirring and dispersing to obtain the branched quaternary ammonium salt composite material containing the antibacterial particles.
The preparation method of the polyurethane elastic fiber with excellent antibacterial property comprises the step (3), wherein the additive slurry comprises a part of polyurethane stock solution, branched quaternary ammonium salt containing antibacterial particles, UTP (ultraviolet resistance additive), HAS (dye assistant), titanium dioxide as a delustering agent, hydrotalcite as a chlorine-resistant additive and the like, the addition mode is that a slurry technology and mechanical stirring are adopted, namely, the branched quaternary ammonium salt containing the antibacterial particles and the additive solution are firstly added into the part of the polyurethane stock solution to form low-viscosity uniformly mixed additive slurry, and then the uniformly mixed additive slurry is added into the polyurethane stock solution to be fully mixed to form spinning stock solution, wherein the addition amount of the branched quaternary ammonium salt containing the antibacterial particles is 0.1-3 wt% of the solid content of the polyurethane stock solution.
The preparation method of the polyurethane elastic fiber with excellent antibacterial property comprises the steps of filtering spinning solution, extruding the spinning solution by a spinneret plate, passing through a high-temperature channel, false twisting, oiling and winding to prepare the polyurethane elastic fiber with excellent antibacterial property in the dry spinning in the step (4).
To further illustrate the present invention, the following examples are provided to describe the specific procedures of the present invention in detail, but these examples should not be construed as limiting the invention in any way. It should also be understood that various modifications of the invention can be made by those skilled in the art after reading the teachings herein, and that such equivalents are within the scope of the invention as defined by the claims.
Example 1
Step 1, (1) 1kg of branched polyethyleneimine is dissolved in water, 0.046kg of formic acid and 0.015kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at the temperature of 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, adding 0.0293kg of glycidyl bromoacetate, and reacting at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; adding 10g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 0.1362kg of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Example 2
Step 1, (1) 1kg of branched polyethyleneimine is dissolved in water, 0.046kg of formic acid and 0.015kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at the temperature of 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, adding 0.0293kg of glycidyl bromoacetate, and reacting at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; adding 10g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 0.6809kg of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Example 3
Step 1, (1) 3kg of branched polyethyleneimine is dissolved in water, 0.092kg of formic acid and 0.045kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, and reacting 0.0878kg of glycidyl bromoacetate at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; and adding 30g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 1.3617kg of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Example 4
Step 1, (1) 5kg of branched polyethyleneimine is dissolved in water, 0.23kg of formic acid and 0.075kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at the temperature of 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, reacting 0.146kg of glycidyl bromoacetate at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; adding 50g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 4.0852kg of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Example 5
Step 1, (1) 1kg of branched polyethyleneimine is dissolved in water, 0.046kg of formic acid and 0.015kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at the temperature of 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, adding 0.0153kg of glycidyl bromoacetate, and reacting at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; adding 10g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 0.2723kg of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Example 6
Step 1, (1) 2kg of branched polyethyleneimine is dissolved in water, 0.092kg of formic acid and 0.030kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at the temperature of 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, adding 0.0426kg of epoxy-terminated undecylenic alkyl bromoacetate, and reacting at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; adding 20g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 0.6809kg of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Example 7
Step 1, (1) 2kg of branched polyethyleneimine is dissolved in water, 0.092kg of formic acid and 0.030kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at the temperature of 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, adding 0.0426kg of epoxy-terminated undecylenic alkyl bromoacetate, and reacting at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; adding 20g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 1.3617kg of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Example 8
Step 1, (1) 5kg of branched polyethyleneimine is dissolved in water, 0.23kg of formic acid and 0.075kg of formaldehyde are added, and aminomethylation reaction is carried out for 1 day at the temperature of 70 ℃ to obtain methylated branched polyethyleneimine; (2) dissolving the methylated branched polyethylene obtained in the step (1) in a DMAC solution, adding 0.0852kg of epoxy-terminated undecylenic alkyl bromoacetate, and reacting at 50 ℃ for 1 day to obtain a branched polyquaternary ammonium salt solution; adding 50g of nano silver into the prepared branched quaternary ammonium salt solution, and fully stirring and mixing to obtain the branched quaternary ammonium salt composite material containing the inorganic antibacterial particles.
Step 2, simultaneously adding 10.8kg of polytetramethylene ether glycol (with the molecular weight of 1810) and 2.535kg of 4, 4-diphenylmethane diisocyanate into an RA1 reactor, and reacting at the temperature of 65 ℃ for 2 hours to obtain a-NCO-terminated prepolymer PP with a certain mass fraction; adding 20.1kg of DMAC (dimethylacetamide), and diluting the prepolymer PP into a PPs solution; 5.2143kg of mixed amine DMAC solution (comprising 0.0147kg of propane diamine, 0.2267kg of ethylene diamine and 0.401kg of diethylamine) is subjected to chain extension reaction in a dropwise manner to obtain RA2 stock solution; finally adding 0.175kg of SAS, 0.0366kg of UV-320, 0.0812kg of titanium dioxide, 0.4005kg of magnesium stearate and 4.0852g of branched quaternary ammonium salt composite material containing inorganic antibacterial particles to obtain spinning solution.
And 3, dry spinning of the spinning solution: and (3) curing, filtering and defoaming the spinning solution, and then carrying out dry spinning to obtain the polyurethane elastic fiber.
Comparative example 1
Polyurethane elastic fiber was prepared according to the same method as described in example 1, except that the branched quaternary ammonium salt composite containing inorganic antibacterial particles was not added to the spinning dope.
The obtained spandex filament with the antibacterial function is subjected to an antibacterial test, and the antibacterial test is carried out according to a test method of antibacterial performance of a product of national standard GB1759-2002 of the people's republic of China, "hygienic Standard for Disposable sanitary articles", wherein test strains are staphylococcus aureus (ATCC 6538) and escherichia coli (ATCC 25922) for bacteria and candida albicans (ATCC 10231) for fungi.
From the test results, the bacteriostatic rates of the three bacteria can be more than 99% in 0 washing, 10 washing, 20 washing and 50 washing of the fiber, which shows that the spandex filament with the antibacterial function prepared by the invention has good antibacterial property.
The above description is provided for the embodiments of the present invention, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical scheme of the present invention shall be equivalent substitution ways, so long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention as long as the technical principle and the inventive concept of the preparation method of the antibacterial spandex filament of the present invention are not departed.
Claims (5)
1. A polyurethane elastic fiber having excellent antibacterial properties, characterized in that: the polyurethane elastic fiber comprises functional branched quaternary ammonium salt and a polyurethane elastomer, and is obtained by dry spinning, wherein the functional branched quaternary ammonium salt is prepared from branched quaternary ammonium salt and antibacterial particles, and the addition amount of the branched quaternary ammonium salt is 0.1-3 wt% of the solid content of a polyurethane stock solution for preparing the polyurethane elastic fiber with excellent antibacterial performance;
the branched quaternary ammonium salt is prepared by reacting branched polyethyleneimine with a halogenated compound, and has the following chemical structural formula:
in the formula I
Having the conventional meaning in the art means that it is not the end point of a segment here, but continues to have a repeating unit or segment attached;
the above-mentioned
Represented as one or more repetitions of the structure of the following structural units;
wherein each R in the formula I is independently selected from saturated or unsaturated aliphatic hydrocarbon groups containing end epoxy groups C3-C15;
the polyurethane elastomer is any one of polyether polyurethane, polyester polyurethane and polyether-polyester polyurethane.
2. A method for preparing the polyurethane elastic fiber having excellent antibacterial properties as claimed in claim 1, comprising the steps of:
1) performing prepolymerization reaction on polytetramethylene ether glycol and 4, 4-diphenylmethane diisocyanate in an N, N-dimethylacetamide solution, and performing chain extension reaction on a mixture of ethylenediamine, 1, 2-propylenediamine and diethylamine to obtain a polyurethane stock solution;
2) synthesizing branched quaternary ammonium salt and preparing a functional branched quaternary ammonium salt composite material containing antibacterial particles;
3) fully mixing a functional branched quaternary ammonium salt composite material, N-dimethylacetamide, an anti-ultraviolet auxiliary agent UV-320, a delustering agent titanium dioxide and a lubricant magnesium stearate with a part of the polyurethane stock solution in a grinding machine to form low-viscosity additive slurry, and adding the low-viscosity additive slurry into the polyurethane stock solution to prepare a spinning stock solution;
4) curing the spinning stock solution, and then carrying out dry spinning to obtain polyurethane elastic fiber;
wherein the content of the first and second substances,
in the step 1), the molar ratio of the polytetramethylene ether glycol to the 4, 4-diphenylmethane diisocyanate is 1: 1.6-1: 2.1, and the molar ratio of the ethylenediamine to the 1, 2-propylenediamine is 10: 1-1: 10.
3. The method for preparing polyurethane elastic fiber having excellent antibacterial property according to claim 2, characterized in that: the method for synthesizing the branched quaternary ammonium salt in the step 2) comprises the following steps:
(1) dissolving branched polyethyleneimine in water, adding formic acid and formaldehyde, and performing aminomethylation reaction for 1-10 days at 70-100 ℃ to obtain methylated branched polyethyleneimine;
(2) dissolving the methylated branched polyethyleneimine obtained in the step (1) in a DMAC solution, adding a certain amount of halogenated compound containing epoxy end groups, and reacting at 50-80 ℃ for 1-10 days to obtain the branched quaternary ammonium salt.
4. The method for preparing polyurethane elastic fiber having excellent antibacterial property according to claim 2, characterized in that: in the synthesis of the branched quaternary ammonium salt, the molar ratio of the branched polyethyleneimine to the formic acid to the formaldehyde is 1: 20-50: 10-30, wherein the amount of the halogenated compound containing the epoxy end group is 1.5-3 times of the molar amount of the branched polyethyleneimine.
5. The method for preparing polyurethane elastic fiber having excellent antibacterial property according to claim 2, characterized in that: in the preparation of the functional branched quaternary ammonium salt, the weight ratio of the branched quaternary ammonium salt to the antibacterial particles is 1: 0.1-1.
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| CN110528142B (en) * | 2019-08-21 | 2021-08-10 | 江苏大毛牛新材料有限公司 | Natural mosquito-repellent fabric product |
| CN110565201B (en) * | 2019-10-30 | 2021-05-04 | 华峰化学股份有限公司 | Preparation method of antibacterial and deodorant spandex |
| CN111485299A (en) * | 2020-04-28 | 2020-08-04 | 连云港杜钟新奥神氨纶有限公司 | Preparation method and application of Ag (III) -PHMB/ZrP and antibacterial spandex |
| CN111334879A (en) * | 2020-04-28 | 2020-06-26 | 连云港杜钟新奥神氨纶有限公司 | Preparation method and application of polyhexamethylene biguanide intercalated α -zirconium phosphate and antibacterial spandex |
| CN112779626A (en) * | 2020-12-29 | 2021-05-11 | 宁夏宁东泰和新材有限公司 | Preparation method of photocatalytic composite antibacterial spandex |
| CN114892294B (en) * | 2022-05-09 | 2023-08-29 | 西南大学 | Multifunctional polyurethane fiber and preparation method and application thereof |
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