WO2017092234A1 - Fibre de polyester antibactérienne contenant des nanoparticules d'argent chargée de phosphate de zirconium mésoporeux - Google Patents

Fibre de polyester antibactérienne contenant des nanoparticules d'argent chargée de phosphate de zirconium mésoporeux Download PDF

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Publication number
WO2017092234A1
WO2017092234A1 PCT/CN2016/081473 CN2016081473W WO2017092234A1 WO 2017092234 A1 WO2017092234 A1 WO 2017092234A1 CN 2016081473 W CN2016081473 W CN 2016081473W WO 2017092234 A1 WO2017092234 A1 WO 2017092234A1
Authority
WO
WIPO (PCT)
Prior art keywords
zirconium phosphate
mesoporous zirconium
silver
polyester fiber
mesoporous
Prior art date
Application number
PCT/CN2016/081473
Other languages
English (en)
Chinese (zh)
Inventor
朱美芳
周家良
陈伟
俞森龙
孙宾
周哲
Original Assignee
东华大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by 东华大学 filed Critical 东华大学
Publication of WO2017092234A1 publication Critical patent/WO2017092234A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

  • the invention belongs to the field of preparation of antibacterial fibers, in particular to a mesoporous zirconium phosphate loaded nano silver antibacterial polyester fiber and a preparation method thereof.
  • the ecological environment such as extreme environment and environmental pollution in today's society is seriously deteriorating, and the special living micro-environment such as confined space leads to the urgent demand for functional protective textiles.
  • the fibers for preparing textiles do not have antibacterial ability, and under certain conditions, the bacteria are provided with an environment for survival and reproduction, which threatens human health.
  • the main method for solving the fiber antibacterial problem is to prepare a modified fiber having an antibacterial effect by using a nanoparticle having an antibacterial effect and a polymer matrix to be compositely modified.
  • the fiber will gradually release the antibacterial component during use to achieve the purpose of antibacterial.
  • antibacterial fiber is widely used and has a large demand.
  • the main method for realizing the antibacterial function of fibers is through surface modification technology and blend modification technology.
  • the former is to make the antibacterial component adhere to the surface of the fiber or the fabric by forming a chemical bond with the surface of the fiber or the fabric by the antibacterial component, thereby achieving an antibacterial effect.
  • Patent CN101942759A is a silver nitrate which is added to an adsorption solution of a fiber in a solution containing silver nitrate, and an antibacterial fiber or fabric having a surface-attached silver obtained by reduction of the adsorbed fiber. This method does not form a uniform and stable antibacterial coating, and the antibacterial time is limited, and the antibacterial effect cannot be achieved. The whole process is too complicated and it is easy to pollute the environment.
  • the antibacterial component is directly or modified and added to the polymer, and the antibacterial masterbatch is prepared by screw extrusion, and the antibacterial fiber is prepared by melt spinning.
  • the patent CN101440533 is an antibacterial component by using nano bamboo charcoal and nano silver as an antibacterial component, and is prepared by using one of polyester or polypropylene or nylon as a carrier, and preparing antibacterial fiber by screw extrusion.
  • this method has a large addition amount and an uneven distribution of the antibacterial components, and it is difficult to achieve continuous production.
  • the object of the present invention is to provide an antibacterial polyester fiber with a small amount of antibacterial component added and uniform distribution Its preparation method.
  • the present invention provides a mesoporous zirconium phosphate-loaded nanosilver antibacterial polyester fiber characterized by comprising a polyester matrix in which Ag@ mesoporous zirconium phosphate is dispersed.
  • the Ag@ mesoporous zirconium phosphate has a size of 200 to 700 nm.
  • the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is from 0.5:99.5 to 3:97.
  • the polyester matrix is one of polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate.
  • the invention also provides the preparation method of the above-mentioned mesoporous zirconium phosphate-loaded nano silver antibacterial polyester fiber, characterized in that the specific steps include:
  • the first step treating mesoporous zirconium phosphate with fuming sulfuric acid to obtain mesoporous zirconium phosphate having a sulfonic acid group on the surface, and ultrasonically stirring the silver ion compound and the diol to obtain a sol containing silver ions, and the surface is coated a mesoporous zirconium phosphate having a sulfonic acid group is added to a sol containing silver ions, and stirred at 20 to 100 ° C for 1 to 3 hours to obtain a silver@mesoporous zirconium phosphate sol precursor;
  • Step 2 The above-mentioned silver@mesoporous zirconium phosphate sol precursor, terephthalic acid (PTA), glycol, stabilizer and catalyst are added to the polyester reactor in proportion for in-situ polymerization and redox reaction.
  • PTA terephthalic acid
  • glycol glycol
  • stabilizer catalyst
  • the specific step of treating mesoporous zirconium phosphate by using fuming sulfuric acid is: the mass fraction of fuming sulfuric acid is 50% to 98%, the reaction temperature is 40-80 ° C, and the reaction time is 20-80 min.
  • the mesoporous zirconium phosphate having a sulfonic acid group on the surface is from 60 to 90:0.5 to 5:5 to 39.5.
  • the silver ion compound is one or more of silver chloride, silver bromide, silver iodide, silver hydroxide, silver sulfide, and silver sulfate.
  • the glycol is one or more of ethylene glycol, propylene glycol, butylene glycol and isosorbide.
  • the reaction process of the in-situ polymerization and the redox reaction is 180-240 ° C, 300 Kpa, and the reaction is carried out for 2-5 h under N 2 atmosphere, and the reaction is carried out for 2-6 h under conditions of 260-285 ° C and less than 150 Pa.
  • the antibacterial fiber prepared by the invention is based on conventional polymer polymerization, using a compound containing silver as a precursor of an antibacterial component, and adding a sol to a polymerization system by using a sol to form a sol, using a sulfonated mesoporous zirconium phosphate Adsorption of pores and ionic bonding of sulfonic acid groups with silver ions to make mesoporous zirconium phosphate pores Silver ions are supported on the surface, and nano-silver is formed by in-situ oxidation reduction in the polymerization process to prepare a nano-silver antibacterial composite.
  • the mesoporous zirconium phosphate of the present invention supports silver ions, and the formation of nano silver and the formation of functional composite materials are realized in one step by using reaction heat in the polymerization process, thereby realizing good dispersion of the antibacterial functional components in the matrix.
  • the invention adopts the method of in-situ polymerization to prepare the silver-loaded zirconium phosphate antibacterial polyester chip, and the functional nanoparticles have stable performance and no discoloration in the polymerization and processing steps.
  • the method of the invention has simple operation, high efficiency, low cost, long-lasting utility and broad application prospect.
  • the antibacterial fiber prepared by the invention can be effectively applied in the fields of masks, home textiles, garments, large airplanes, high-speed rails, astronauts, military combat apparel and the like.
  • the industrialization of the antibacterial fiber of the invention can effectively fill the blank of the domestic antibacterial fiber preparation technology.
  • the mesoporous zirconium phosphate nanopowder in each of the embodiments of the present invention is a commercially available product having a particle diameter of 100 to 700 nm and a pore diameter of 10 to 60 nm.
  • a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PET polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm.
  • the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 3:97.
  • the fiber has an antibacterial rate of >95% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, and an antibacterial rate of >60% against Candida albicans.
  • the number of washable fabrics is >100 times.
  • a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PBT polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm.
  • the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 3:97.
  • the specific steps of treating mesoporous zirconium phosphate with fuming sulfuric acid are: sulphuric acid with a mass fraction of 50% The pore zirconium phosphate mass ratio was 10:1, the reaction temperature was 40 ° C, and the reaction was carried out for 80 min. .
  • the fiber has an antibacterial rate of >98% against Escherichia coli, an antibacterial rate of >91% against Staphylococcus aureus, and an antibacterial rate of >70% against Candida albicans.
  • the number of washable fabrics is >100 times.
  • a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PET polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm.
  • the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 0.5:99.5.
  • the fiber has an antibacterial rate of >90% against Escherichia coli, an antibacterial rate of >88% against Staphylococcus aureus, and an antibacterial rate of >65% against Candida albicans.
  • the number of washable fabrics is >80 times.
  • a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber including a PTT polyester matrix, said poly Ag@ mesoporous zirconium phosphate is dispersed in the ester matrix, and the Ag@ mesoporous zirconium phosphate has a size of 200 to 700 nm.
  • the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 0.5:99.5.
  • the fiber has an antibacterial rate of >90% against Escherichia coli, an antibacterial rate of >90% against Staphylococcus aureus, and an antibacterial rate of >65% against Candida albicans.
  • the number of washable fabrics is >80 times.
  • a mesoporous zirconium phosphate-loaded nano-silver antibacterial polyester fiber comprising a PET polyester matrix, wherein the polyester matrix is dispersed with Ag@ mesoporous zirconium phosphate, and the size of the Ag@ mesoporous zirconium phosphate is 200 to 700 nm.
  • the mass ratio of the Ag@ mesoporous zirconium phosphate to the polyester matrix is 2:98.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne une fibre de polyester antibactérienne contenant des nanoparticules d'argent chargée de phosphate de zirconium mésoporeux et un procédé de préparation associé. La fibre de polyester antibactérienne contenant des nanoparticules d'argent chargée de phosphate de zirconium mésoporeux comprend une matrice de polyester; à l'intérieur de ladite matrice de polyester est dispersé un phosphate de zirconium mésoporeux argent. Le procédé de préparation de la fibre de polyester antibactérienne contenant des nanoparticules d'argent chargée de phosphate de zirconium mésoporeux comprend: la préparation d'un précurseur de sol de phosphate de zirconium mésoporeux argent; le précurseur de sol de phosphate de zirconium mésoporeux argent décrit, un acide téréphtalique (PTA), un diol, un agent stabilisant et un catalyseur sont ajoutés proportionnellement à un réacteur de polyester; la réalisation d'une polymérisation in situ et d'une réaction d'oxydoréduction pour préparer un matériau composite antibactérien contenant des nanoparticules d'argent de phosphate de zirconium mésoporeux, et le séchage et la réalisation d'un filage par fusion pour réaliser une fibre de polyester antibactérienne contenant des nanoparticules d'argent chargées de phosphate de zirconium mésoporeux.
PCT/CN2016/081473 2015-12-01 2016-05-09 Fibre de polyester antibactérienne contenant des nanoparticules d'argent chargée de phosphate de zirconium mésoporeux WO2017092234A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510866954.5 2015-12-01
CN201510866954.5A CN105332087B (zh) 2015-12-01 2015-12-01 一种介孔磷酸锆负载纳米银抗菌聚酯纤维及其制备方法

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WO2017092234A1 true WO2017092234A1 (fr) 2017-06-08

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CN (1) CN105332087B (fr)
WO (1) WO2017092234A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105332078B (zh) * 2015-12-01 2018-01-02 东华大学 一种基于载银磷酸锆的抗菌聚酯纤维及其制备方法
CN105350103B (zh) * 2015-12-01 2018-10-26 东华大学 一种抗菌材料及其制备方法
CN105332087B (zh) * 2015-12-01 2017-06-30 东华大学 一种介孔磷酸锆负载纳米银抗菌聚酯纤维及其制备方法
CN112674112A (zh) * 2020-12-23 2021-04-20 深圳市世格赛思医疗科技有限公司 一种载银磷酸锆及其制备方法和应用

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JP2007077519A (ja) * 2005-09-13 2007-03-29 Mitsui Chemicals Inc 抗菌性の繊維の集合体、その製造方法および用途
CN101305735A (zh) * 2007-05-16 2008-11-19 上海松明寄存设备有限公司 载银纳米抗菌材料及其制备方法和应用
CN101363141A (zh) * 2007-08-09 2009-02-11 太仓市金辉化纤实业有限公司 全消光抗菌涤纶纤维及其制备方法和应用
CN105332085A (zh) * 2015-12-01 2016-02-17 东华大学 一种介孔磷酸锆负载纳米银抗菌纤维及其制备方法
CN105332078A (zh) * 2015-12-01 2016-02-17 东华大学 一种基于载银磷酸锆的抗菌聚酯纤维及其制备方法
CN105332087A (zh) * 2015-12-01 2016-02-17 东华大学 一种介孔磷酸锆负载纳米银抗菌聚酯纤维及其制备方法

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CN101993527B (zh) * 2010-10-20 2012-11-07 东华大学 一种含银pet基复合树脂材料的制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007077519A (ja) * 2005-09-13 2007-03-29 Mitsui Chemicals Inc 抗菌性の繊維の集合体、その製造方法および用途
CN101305735A (zh) * 2007-05-16 2008-11-19 上海松明寄存设备有限公司 载银纳米抗菌材料及其制备方法和应用
CN101363141A (zh) * 2007-08-09 2009-02-11 太仓市金辉化纤实业有限公司 全消光抗菌涤纶纤维及其制备方法和应用
CN105332085A (zh) * 2015-12-01 2016-02-17 东华大学 一种介孔磷酸锆负载纳米银抗菌纤维及其制备方法
CN105332078A (zh) * 2015-12-01 2016-02-17 东华大学 一种基于载银磷酸锆的抗菌聚酯纤维及其制备方法
CN105332087A (zh) * 2015-12-01 2016-02-17 东华大学 一种介孔磷酸锆负载纳米银抗菌聚酯纤维及其制备方法

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CN105332087A (zh) 2016-02-17
CN105332087B (zh) 2017-06-30

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