CN115787129B - Preparation method of antibacterial deodorizing polyurethane elastic fiber - Google Patents

Preparation method of antibacterial deodorizing polyurethane elastic fiber Download PDF

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CN115787129B
CN115787129B CN202211613272.XA CN202211613272A CN115787129B CN 115787129 B CN115787129 B CN 115787129B CN 202211613272 A CN202211613272 A CN 202211613272A CN 115787129 B CN115787129 B CN 115787129B
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antibacterial
zirconium phosphate
polyethyleneimine
elastic fiber
polyurethane
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CN115787129A (en
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薛士壮
杨晓印
晋中成
于志立
周志伟
孙乐乐
钱锦
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Huafon Chongqing Spandex Co ltd
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Huafon Chongqing Spandex Co ltd
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    • Y02P70/62Manufacturing 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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Abstract

The invention relates to a preparation method of antibacterial and deodorant polyurethane elastic fiber, which is prepared from antibacterial and deodorant modified polyurethane elastic fiber and comprises the following steps: 1) Preparing an antibacterial deodorant: mixing nano zirconium phosphate, polyethyleneimine and ethanol, and uniformly stirring to obtain polyethyleneimine modified zirconium phosphate; 2) Preparing a polyurethane urea stock solution: the modified polytetrahydrofuran ether glycol PTMG is prepared by carrying out polymerization reaction on a mixed solution of polytetrahydrofuran ether glycol PTMG, 4' -diphenylmethane diisocyanate MDI and small molecular amine; 3) Preparing antibacterial deodorizing polyurethane elastic fiber: adding the polyethyleneimine modified zirconium phosphate into polyurethane urea stock solution, stirring and curing, and producing the antibacterial deodorizing fiber through dry spinning. The invention has excellent deodorizing performance and antibacterial performance, and overcomes the defect that the existing polyurethane elastic fiber has single performance; meanwhile, the antibacterial deodorant is firmly combined with the polyurethane polymer matrix, and has the advantages of water resistance and durability.

Description

Preparation method of antibacterial deodorizing polyurethane elastic fiber
Technical Field
The invention belongs to the technical field of textile processing, and particularly relates to a preparation method of antibacterial and deodorant polyurethane elastic fiber.
Background
The polyurethane elastic fiber is a multi-block copolymer with alternating soft and hard segments, is often interwoven with terylene, chinlon, cotton, viscose fiber and the like, and is applied to the field of clothing fabrics such as underwear, socks, swimwear, panty hose, sportswear, tights and the like.
In daily life, people inevitably contact with various microorganisms such as bacteria and mold, and metabolism and reproduction of the microorganisms easily cause odor generation and disease transmission. The polyurethane fiber is used as an important component of the textile, and the main polyurethane component of the polyurethane fiber has no antibacterial and deodorizing functions; meanwhile, as the proportion of the spandex fiber in the fabric is continuously increased, the antibacterial and deodorant effects of the spandex fiber are good and bad, and the antibacterial and deodorant effects of the spandex fiber on the whole fabric are increasingly important.
Related patents have been reported for the antibacterial and deodorant properties of polyurethane elastic fibers. Patent CN201210078915.5 discloses an antibacterial spandex fiber and a preparation method thereof, wherein the antibacterial agent consists of nano silver and polyurethane, but the nano silver easily discolors the fiber. Patent CN201880005926.6 discloses a deodorizing spandex and a preparation method thereof, mainly by adding 1.0wt% to 10wt% of at least one of zirconium-containing metal phosphate, or metal oxide, or composite metal oxide to the fiber, but when the addition amount is less than 1.0wt%, the deodorizing performance does not reach the standard, and at the same time the technology does not show antibacterial performance. Patent CN202010349782.5 discloses that the antibacterial spandex prepared by adopting polyhexamethylene biguanide intercalated alpha-zirconium phosphate as an antibacterial agent has antibacterial performance meeting the standard requirements, but does not involve the influence of deodorization performance, and the antibacterial agent has the defect of easy loss caused by water washing from fibers. Patent CN202111217533. X discloses a deodorizing spandex and a preparation method thereof, which can rapidly adsorb ammonia gas by introducing phenyl-ammonium carboxylate groups on the molecular chain of the spandex, solves the problem of deodorizing the spandex, but has complicated preparation process and is not beneficial to industrial production. Patent CN201310127211.7 reports a health care spandex consisting of a skin layer and a core layer, wherein the core layer contains bamboo charcoal powder, polyhexamethylene biguanide hydrochloride, perfume, fiber-forming polymer. The spinneret plate assembly is adopted, the core layer melt spinning body and the sheath layer spinning stock solution are respectively extruded from the hollow needle and the extrusion hole of the spinneret plate assembly, so that the health-care spandex with the functions of resisting bacteria and eliminating peculiar smell is prepared, but the fiber is not white, and the production process is complicated, so that the application in the downstream field is limited.
Disclosure of Invention
Technical problems: aiming at the defects of the prior art, the invention provides a preparation method of antibacterial and deodorant polyurethane elastic fiber, and in particular aims to simultaneously realize the antibacterial property and the deodorant property of spandex fiber by a simple technical means. Compared with the prior art, the antibacterial deodorant has the advantages of small addition amount, firm combination with fiber by chemical bonds, water washing resistance, difficult loss and the like.
The technical scheme is as follows: the invention realizes the antibacterial property and the deodorizing property of the polyurethane elastic fiber simultaneously by a simple and easy technical means; meanwhile, the antibacterial deodorant is uniformly dispersed in the fiber, can be firmly chemically bonded with the fiber, and realizes excellent washability.
The fiber is prepared by taking polyethyleneimine modified zirconium phosphate as an antibacterial deodorant, blending the antibacterial deodorant with polyurethane urea stock solution and spinning. Compared with the common polyurethane elastic fiber, the polyurethane elastic fiber has excellent antibacterial property and deodorizing property, and meanwhile, the antibacterial deodorizing agent can be combined with polymers through chemical bonds, and has excellent water washing resistance.
In order to achieve the aim, the preparation method of the antibacterial deodorizing polyurethane elastic fiber adopts the following technical scheme,
Step 1, preparing an antibacterial deodorant: mixing nano zirconium phosphate, polyethyleneimine and ethanol, and uniformly stirring to obtain polyethyleneimine modified zirconium phosphate;
step 2, preparing a polyurethane urea stock solution: the modified polytetrahydrofuran ether glycol PTMG is prepared by carrying out polymerization reaction on a mixed solution of polytetrahydrofuran ether glycol PTMG, 4' -diphenylmethane diisocyanate MDI and small molecular amine;
step 3, preparing the antibacterial deodorizing polyurethane elastic fiber: adding the polyethyleneimine modified zirconium phosphate into polyurethane urea stock solution, stirring and curing to obtain spinning stock solution, and performing dry spinning to obtain the antibacterial deodorizing fiber.
Wherein,
The polyethyleneimine modified zirconium phosphate in the step 1 is obtained by dispersing nano zirconium phosphate in ethanol by ultrasonic, adding polyethyleneimine, reacting for 2-4 hours at 60-80 ℃, and separating precipitate, wherein the mass percentage of the nano zirconium phosphate is 5-25%, the mass percentage of the polyethyleneimine is 1-5%, and the balance is ethanol.
The molecular weight of the polyethyleneimine is 300-1800.
In the polyurethane urea stock solution in the step 2, the polytetrahydrofuran ether glycol PTMG accounts for 75-83% by mass of the solid polymer composition, the 4,4' -diphenylmethane diisocyanate MDI accounts for 15-21% by mass, and the small molecular amine accounts for 2-4% by mass.
In the antibacterial deodorizing fiber in the step 3, the weight percentage of the polyethyleneimine modified zirconium phosphate is 0.2-1 percent, and the weight percentage of the polyurethane urea solid polymer is 99-99.8 percent.
The curing time in the step 3 is 40-50 h.
The polyurethane elastic fiber has 20 to 55meq/kg of terminal amine.
The beneficial effects are that: the invention provides an antibacterial deodorizing polyurethane elastic fiber and a preparation method thereof. The polyethyleneimine modified zirconium phosphate is adopted, so that the problem of dispersion of inorganic nano particles in stock solution is solved, and the method has the advantages of small addition amount and low cost; the antibacterial deodorant polyethylenimine modified zirconium phosphate is combined with the polyurethane fiber matrix in a chemical bond mode, so that the water washing process is not easy to run off; meanwhile, the polyethyleneimine and zirconium phosphate play a synergistic effect, and the deodorizing and antibacterial properties of the fiber can be obviously improved.
Detailed Description
In order to make the technical solution and advantages of the present invention more apparent, the technical solution of the present invention will be clearly and completely described in conjunction with the following examples, which should not be construed as limiting the present invention in any sense.
Example 1:
(1) Preparation of antibacterial deodorant
Dispersing 5 parts of nano zirconium phosphate in 94 parts of ethanol by ultrasonic, slowly adding 1 part of polyethyleneimine while stirring, heating to 60 ℃ under the condition of strong stirring, continuously reacting for 2 hours, standing, separating precipitate, washing with ethanol, and drying to obtain the polyethyleneimine modified zirconium phosphate antibacterial deodorant.
(2) Preparation of polyurethane urea stock solution
Polytetrahydrofuran ether glycol PTMG (molecular weight 1810) 238.64Kg and 4,4' -diphenylmethane diisocyanate MDI 55.09Kg were reacted at 80℃for 2 hours to give an isocyanate group-terminated polyurethane prepolymer, and 438.11Kg of N, N-dimethylacetamide solvent was added to dissolve the prepolymer in a polar solvent. Then, a mixed amine solution composed of 4.685Kg of ethylenediamine, 0.642Kg of propylenediamine, 0.938Kg of diethylamine and 119.041Kg of N, N-dimethylacetamide solvent was added to carry out a chain extension reaction and a chain termination reaction to prepare a polyurethaneurea stock solution.
(3) Preparation of antibacterial deodorizing polyurethane elastic fiber
Adding the antibacterial deodorant polyethylenimine modified zirconium phosphate of the (1) into the polyurethane urea stock solution of the (2), wherein the polyethylenimine modified zirconium phosphate is 0.2% and the polyurethane urea solid polymer is 99.8%, curing the stock solution for 40 hours, and then adopting a dry spinning technology to produce 44 dtex/3-hole antibacterial deodorant polyurethane elastic fiber, wherein the amine end group of the polyurethane elastic fiber is 20meq/kg.
Example 2:
(1) Preparation of antibacterial deodorant
Dispersing 10 parts of nano zirconium phosphate in 87 parts of ethanol by ultrasonic, slowly adding 3 parts of polyethyleneimine while stirring, heating to 70 ℃ under the condition of strong stirring, continuing to react for 3 hours, standing to separate precipitate, washing with ethanol, and drying to obtain the polyethyleneimine modified zirconium phosphate antibacterial deodorant.
(2) Preparation of polyurethane urea stock solution
Polytetrahydrofuran ether glycol PTMG (molecular weight 1810) 238.64Kg and 4,4' -diphenylmethane diisocyanate MDI 55.09Kg were reacted at 80℃for 2 hours to give an isocyanate group-terminated polyurethane prepolymer, and 438.11Kg of N, N-dimethylacetamide solvent was added to dissolve the prepolymer in a polar solvent. Then, a mixed amine solution composed of 4.685Kg of ethylenediamine, 0.642Kg of propylenediamine, 0.938Kg of diethylamine and 119.041Kg of N, N-dimethylacetamide solvent was added to carry out a chain extension reaction and a chain termination reaction to prepare a polyurethaneurea stock solution.
(3) Preparation of antibacterial deodorizing polyurethane elastic fiber
Adding the antibacterial deodorant polyethylenimine modified zirconium phosphate of the (1) into the polyurethane urea stock solution of the (2), wherein the polyethylenimine modified zirconium phosphate is 0.5% and the polyurethane urea solid polymer is 99.5%, curing the stock solution for 45 hours, and then producing the 44 dtex/3-hole antibacterial deodorant polyurethane elastic fiber by adopting a dry spinning technology, wherein the amine end group of the polyurethane elastic fiber is 40meq/kg.
Example 3:
(1) Preparation of antibacterial deodorant
Dispersing 25 parts of nano zirconium phosphate in 70 parts of ethanol by ultrasonic, slowly adding 5 parts of polyethyleneimine while stirring, heating to 80 ℃ under the condition of strong stirring, continuing to react for 4 hours, standing to separate precipitate, washing with ethanol, and drying to obtain the polyethyleneimine modified zirconium phosphate antibacterial deodorant.
(2) Preparation of polyurethane urea stock solution
Polytetrahydrofuran ether glycol PTMG (molecular weight 1810) 238.64Kg and 4,4' -diphenylmethane diisocyanate MDI 55.09Kg were reacted at 80℃for 2 hours to give an isocyanate group-terminated polyurethane prepolymer, and 438.11Kg of N, N-dimethylacetamide solvent was added to dissolve the prepolymer in a polar solvent. Then, a mixed amine solution composed of 4.685Kg of ethylenediamine, 0.642Kg of propylenediamine, 0.938Kg of diethylamine and 119.041Kg of N, N-dimethylacetamide solvent was added to carry out a chain extension reaction and a chain termination reaction to prepare a polyurethaneurea stock solution.
(3) Preparation of antibacterial deodorizing polyurethane elastic fiber
Adding the antibacterial deodorant polyethylenimine modified zirconium phosphate of the (1) into the polyurethane urea stock solution of the (2), wherein the polyethylenimine modified zirconium phosphate is 1% and the polyurethane urea solid polymer is 99%, curing the stock solution for 50 hours, and then producing the 44 dtex/3-hole antibacterial deodorant polyurethane elastic fiber by adopting a dry spinning technology, wherein the amine end group of the polyurethane elastic fiber is 55meq/kg.
Comparative example 1:
(1) Preparation of polyurethane urea stock solution
The preparation method is the same as in example 1.
(2) Preparation of polyurethane elastic fiber
The preparation method is the same as in example 1, except that the polyurethane elastic fiber prepared does not contain the antibacterial deodorant polyethylenimine modified zirconium phosphate.
The antibacterial deodorizing properties of the spandex fiber mentioned in the following examples and comparative examples were examined in the following manner.
(1) Antibacterial property
The polyurethane elastic fiber is subjected to antibacterial performance test after 50 times (AAA grade) water washing. Quantitative tests were carried out according to the standard FZ/T73023-2006 "antibacterial knitwear", using the shaking method.
(2) Deodorizing ability
Determination of textile deodorizing Properties according to Standard GB/T33610.2-2017, section 2: detecting ammonia and acetic acid reduction rate of polyurethane elastic fiber in detection tube method; determination of textile deodorizing Properties according to GB/T33610.3-2019 section 3: gas chromatography was used to determine the reduction rate of isovaleric acid and 2-nonenal. The antibacterial and deodorant test results are shown below:
TABLE 1 antibacterial Properties of polyurethane elastic fiber
TABLE 2 deodorization performance of polyurethane elastic fiber
As can be seen from the above table, the spandex fiber produced by the present technique has excellent antibacterial and deodorizing properties.

Claims (2)

1. The preparation method of the antibacterial deodorizing polyurethane elastic fiber is characterized by comprising the following steps:
step 1, preparing an antibacterial deodorant: mixing nano zirconium phosphate, polyethyleneimine and ethanol, and uniformly stirring to obtain polyethyleneimine modified zirconium phosphate;
step 2, preparing a polyurethane urea stock solution: the modified polytetrahydrofuran ether glycol PTMG is prepared by carrying out polymerization reaction on a mixed solution of polytetrahydrofuran ether glycol PTMG, 4' -diphenylmethane diisocyanate MDI and small molecular amine;
Step 3, preparing the antibacterial deodorizing polyurethane elastic fiber: adding polyethyleneimine modified zirconium phosphate into polyurethane urea stock solution, stirring and curing to obtain spinning stock solution, and performing dry spinning to obtain antibacterial deodorizing fiber;
The polyethyleneimine modified zirconium phosphate in the step 1 is prepared by dispersing nano zirconium phosphate in ethanol by ultrasonic, adding polyethyleneimine, reacting for 2-4 hours at 60-80 ℃, and separating precipitate to obtain polyethyleneimine zirconium phosphate, wherein the nano zirconium phosphate accounts for 5-25% by mass, the polyethyleneimine accounts for 1-5% by mass, and the balance is ethanol; the molecular weight of the polyethyleneimine is 300-1800;
In the polyurethane urea stock solution in the step 2, the polytetrahydrofuran ether glycol PTMG accounts for 75-83% by mass percent of the solid polymer, the 4,4' -diphenylmethane diisocyanate MDI accounts for 15-21% by mass percent, and the micromolecular amine accounts for 2-4% by mass percent; polytetrahydrofuran ether glycol PTMG molecular weight is 1810;
In the antibacterial deodorizing fiber in the step 3, the weight percentage of the polyethyleneimine modified zirconium phosphate is 0.2-1%, and the weight percentage of the polyurethane urea solid polymer is 99-99.8%; the curing time is 40-50 h.
2. The method for producing an antibacterial deodorizing polyurethane elastic fiber according to claim 1, characterized in that said polyurethane elastic fiber has 20 to 55meq/kg of terminal amine.
CN202211613272.XA 2022-12-15 2022-12-15 Preparation method of antibacterial deodorizing polyurethane elastic fiber Active CN115787129B (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006028453A (en) * 2004-07-21 2006-02-02 Nisshinbo Ind Inc Polyurethane elastomer and elastic fiber
CN101126181A (en) * 2006-07-11 2008-02-20 泰光产业株式会社 Polyurethaneurea elastic fiber and method for preparation thereof
JP2012127015A (en) * 2010-12-14 2012-07-05 Toray Opelontex Co Ltd Polyurethane elastic yarn
JP2015038261A (en) * 2013-07-19 2015-02-26 東レ・オペロンテックス株式会社 Polyurethane elastic yarn and method of producing the same
JP2018178313A (en) * 2017-04-14 2018-11-15 東亞合成株式会社 Fine particle deodorant for fibers
CN110591294A (en) * 2019-09-30 2019-12-20 华南理工大学 Modified zirconium phosphate-epoxy nanocomposite and preparation method thereof
CN111363380A (en) * 2020-03-14 2020-07-03 武汉工程大学 Nano zirconium phosphate coated modified ammonium polyphosphate and intumescent fire retardant coating prepared from same
CN113279077A (en) * 2021-05-20 2021-08-20 晋大纳米科技(厦门)有限公司 Efficient zirconium phosphate deodorant and deodorization spandex

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006028453A (en) * 2004-07-21 2006-02-02 Nisshinbo Ind Inc Polyurethane elastomer and elastic fiber
CN101126181A (en) * 2006-07-11 2008-02-20 泰光产业株式会社 Polyurethaneurea elastic fiber and method for preparation thereof
JP2012127015A (en) * 2010-12-14 2012-07-05 Toray Opelontex Co Ltd Polyurethane elastic yarn
JP2015038261A (en) * 2013-07-19 2015-02-26 東レ・オペロンテックス株式会社 Polyurethane elastic yarn and method of producing the same
JP2018178313A (en) * 2017-04-14 2018-11-15 東亞合成株式会社 Fine particle deodorant for fibers
CN110591294A (en) * 2019-09-30 2019-12-20 华南理工大学 Modified zirconium phosphate-epoxy nanocomposite and preparation method thereof
CN111363380A (en) * 2020-03-14 2020-07-03 武汉工程大学 Nano zirconium phosphate coated modified ammonium polyphosphate and intumescent fire retardant coating prepared from same
CN113279077A (en) * 2021-05-20 2021-08-20 晋大纳米科技(厦门)有限公司 Efficient zirconium phosphate deodorant and deodorization spandex

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