WO2017214742A1 - Method for preparing magnetic polyamide acid nano-composite fibre - Google Patents

Method for preparing magnetic polyamide acid nano-composite fibre Download PDF

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Publication number
WO2017214742A1
WO2017214742A1 PCT/CN2016/000326 CN2016000326W WO2017214742A1 WO 2017214742 A1 WO2017214742 A1 WO 2017214742A1 CN 2016000326 W CN2016000326 W CN 2016000326W WO 2017214742 A1 WO2017214742 A1 WO 2017214742A1
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Prior art keywords
polyamic acid
diaminodiphenyl ether
polyamide acid
mixed solution
pyromellitic anhydride
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PCT/CN2016/000326
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French (fr)
Chinese (zh)
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杨磊
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杨磊
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Publication of WO2017214742A1 publication Critical patent/WO2017214742A1/en

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F6/90—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 polyamides
    • 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
    • D01F6/94—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 other polycondensation products

Definitions

  • the invention relates to the technical field of preparation of polyamic acid, in particular to a preparation process of a polyamic acid magnetic nano composite fiber.
  • Polyamide commonly known as nylon (Nylon), is a generic term for polymers containing amide groups in the repeating units of macromolecular backbones.
  • the polyamic acid can be obtained by ring-opening polymerization of a caprolactam, or the polyamic acid obtained by polycondensation of a diamine and a dibasic acid, etc., which is a kind of free shuttle group derived from an aromatic diamine and an aromatic amine.
  • the linear polymer with the main chain of acid amine structure has good comprehensive properties, including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricity, and has low friction coefficient and certain resistance. It is flammable, easy to process, and can be restored to its original shape after being pulled.
  • the present invention provides a preparation process of a polyamic acid magnetic nanocomposite fiber, which is obtained by combining a polyamic acid with Fe 3 O 4 to obtain a magnetic nanocomposite fiber, which has good electrical conductivity and is easy to obtain raw materials;
  • the fiber length can be freely controlled, and the strength is large and the gas permeability is good, which can effectively solve the problems in the background art.
  • a preparation process of a polyamic acid magnetic nano composite fiber comprising the following steps:
  • the pyromellitic anhydride and diaminodiphenyl ether are weighed according to the molar mass ratio, the pyromellitic anhydride is 40g-50g, the diaminodiphenyl ether is 80g-100g;
  • the receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
  • the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
  • the N,N-dimethylacetamide and the nano Fe 3 O 4 are of analytical grade.
  • the diaminodiphenyl ether in the step (4) is added to the three-necked bottle five times, and the amount of each addition is equal, and each is 20 g to 25 g.
  • the metal needle of the syringe has a model number of 12 # and 15 cm.
  • the distance between the spinneret and the collecting plate in the step (7) is 16-18 cm, and the spinning time is 5 h-6 h.
  • the invention combines polyamic acid with Fe 3 O 4 to obtain magnetic nano-composite fiber, has good electrical conductivity, and the raw material is simple and easy to obtain; the generated fiber length can be adjusted by adjusting the distance between the spinneret and the distance between the collecting plates. Fibers of different lengths are obtained, and the length of the fiber can be freely controlled to meet different needs; the fiber produced by the invention has high strength and good gas permeability, and the joint is smooth and not easy to break.
  • a preparation process of a polyamic acid magnetic nano composite fiber comprising the following steps:
  • the pyromellitic anhydride and diaminodiphenyl ether are weighed according to the molar mass ratio, the tetrazoic acid anhydride is 45 g, and the diaminodiphenyl ether is 90 g;
  • the diaminodiphenyl ether is gradually added to the mixed solution several times to obtain a polyamic acid solution
  • the receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
  • the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
  • the N,N-dimethylacetamide and the nano Fe 3 O 4 are of analytical grade.
  • the diaminodiphenyl ether in the step (4) is added to the three-necked bottle 5 times, and the amount of each addition is equal, both being 18 g.
  • the metal needle of the syringe has a model number of 12 # and 15 cm.
  • the distance between the spinneret and the collecting plate in the step (7) is 16-18 cm, and the spinning time is 5 h-6 h.
  • a preparation process of a polyamic acid magnetic nano composite fiber comprising the following steps:
  • the pyromellitic anhydride and diaminodiphenyl ether are weighed according to the molar mass ratio, the pyromellitic anhydride is 40g-50g, the diaminodiphenyl ether is 80g-100g;
  • the diaminodiphenyl ether is gradually added to the mixed solution several times to obtain a polyamic acid solution
  • the receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
  • the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
  • the N, N- dimethylacetamide and Fe 3 O 4 nano analytical grade According to the above aspect, the N, N- dimethylacetamide and Fe 3 O 4 nano analytical grade.
  • the diaminodiphenyl ether in the step (4) is added to the three-necked bottle five times, and the amount of each addition is equal, and each is 20 g to 25 g.
  • the metal needle of the syringe has a model number of 12 # and 15 cm.
  • the distance between the spinneret and the collecting plate in the step (7) is 17 cm, and the spinning time is 5.5.
  • a preparation process of a polyamic acid magnetic nano composite fiber comprising the following steps:
  • the pyromellitic anhydride and diaminodiphenyl ether are weighed in a molar ratio, the pyromellitic anhydride is 40g-50g, and the diaminodiphenyl ether is 80g-100g;
  • the diaminodiphenyl ether is gradually added to the mixed solution several times to obtain a polyamic acid solution
  • the receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
  • the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
  • the N,N-dimethylacetamide and the nano Fe 3 O 4 are of analytical grade.
  • the diaminodiphenyl ether in the step (4) is added to the three-necked bottle five times, and the amount of each addition is equal, and each is 20 g to 25 g.
  • the temperature of the water bath heating in the step (2) is 45 °C.
  • the distance between the spinneret and the collecting plate in the step (7) is 17 cm, and the spinning time is 6 h.
  • an advantage of the present invention is that the present invention combines a polyamic acid with Fe 3 O 4 to obtain a magnetic nanocomposite fiber, which has good electrical conductivity, and the raw material is simple and easy to obtain; the length of the produced fiber can be adjusted by adjusting the spinneret and collecting The distance between the distances between the plates is obtained to obtain fibers of different lengths, and the length of the fibers can be freely controlled to meet different needs; the fibers obtained by the invention have high strength and good gas permeability, and the joints are smooth and not easy to break.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

Disclosed is a method for preparing a magnetic polyamide acid nano-composite fibre, comprising the following steps: at a temperature below 10ºC, weighing pyromellitic dianhydride and diaminodiphenyl ether at an equal molar mass ratio, adding the weighed pyromellitic dianhydride to a 250 ml three-necked flask, adding 12 g to 15 g of N,N-dimethylformamide, and introducing protective nitrogen; after the pyromellitic dianhydride is completely dissolved, gradually adding the diaminodiphenyl ether to the mixed solution in five portions to obtain a polyamide acid solution; adding 16 g to 20 g of nano Fe3O4 particles to the polyamide acid solution, and stirring same constantly using a stirring rod so as to obtain a thick black polyamide acid/Fe3O4 mixed solution; charging the resulting polyamide acid/Fe3O4 mixed solution into an injector having a volume of 20 mL in portions, and fixing the injector onto a high-voltage static spinning device, wherein the metal needle head of the injector is kept in connection with one pole of a high-voltage power source; and cladding a receiving plate with a layer of an aluminium foil, the receiving plate being in connection with the other pole of the high-voltage power source, adjusting the distance between a spinneret and the receiving plate, and setting the spinning time, and turning on the power for spinning.

Description

一种聚酰胺酸磁性纳米复合纤维的制备工艺Preparation process of polyamic acid magnetic nano composite fiber 技术领域Technical field
本发明涉及聚酰胺酸制备技术领域，具体涉及一种聚酰胺酸磁性纳米复合纤维的制备工艺。The invention relates to the technical field of preparation of polyamic acid, in particular to a preparation process of a polyamic acid magnetic nano composite fiber.
背景技术Background technique
聚酰胺俗称尼龙(Nylon)，它是大分子主链重复单元中含有酰胺基团的高聚物的总称。聚酰胺酸可由内酸胺开环聚合制得，也可由二元胺与二元酸缩聚等得到的聚酰胺酸是由芳族二元胺与芳族缩胺而成的一类含游离梭基、主链为酸胺结构的线型聚合物，具有良好的综合性能，包括力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性，且摩擦系数低，有一定的阻燃性，易于加工，在被拉扯后可恢复原形，可洗、快干、吸水少、防虫，是一种制作手套的常见材料。但普通的手套仅用普通的聚酯胺制成，没有导电性能，对于现在习惯使用智能手机的用户来说，冬天带上手套时因为手套不能导电，传递人体电流，隔着手套就无法进行操作，必须脱掉手套忍受寒冷进行操作。Polyamide, commonly known as nylon (Nylon), is a generic term for polymers containing amide groups in the repeating units of macromolecular backbones. The polyamic acid can be obtained by ring-opening polymerization of a caprolactam, or the polyamic acid obtained by polycondensation of a diamine and a dibasic acid, etc., which is a kind of free shuttle group derived from an aromatic diamine and an aromatic amine. The linear polymer with the main chain of acid amine structure has good comprehensive properties, including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricity, and has low friction coefficient and certain resistance. It is flammable, easy to process, and can be restored to its original shape after being pulled. It can be washed, dried quickly, absorbs less water, and is insect-proof. It is a common material for making gloves. However, ordinary gloves are made only of ordinary polyesteramine, and have no conductive properties. For users who are now accustomed to using smart phones, when gloves are worn in winter, because gloves cannot conduct electricity, the body current is transmitted, and it is impossible to operate through gloves. Must take off the gloves and endure the cold to operate.
发明内容Summary of the invention
针对以上问题，本发明提供了一种聚酰胺酸磁性纳米复合纤维的制备工艺，将聚酰胺酸与Fe3O4复合得到磁性纳米复合纤维，具有良好的导电性能，原料简单易得；产生的纤维长度可以自由控制，且强度大透气性好，可以有效解决背景技术中的问题。In view of the above problems, the present invention provides a preparation process of a polyamic acid magnetic nanocomposite fiber, which is obtained by combining a polyamic acid with Fe 3 O 4 to obtain a magnetic nanocomposite fiber, which has good electrical conductivity and is easy to obtain raw materials; The fiber length can be freely controlled, and the strength is large and the gas permeability is good, which can effectively solve the problems in the background art.
为了实现上述目的，本发明采用的技术方案如下：一种聚酰胺酸磁性纳米复合纤维的制备工艺，包括如下步骤：In order to achieve the above object, the technical scheme adopted by the present invention is as follows: a preparation process of a polyamic acid magnetic nano composite fiber, comprising the following steps:
(1)在10摄氏度以下，将均苯四甲酸酐与二氨基二苯醚按照摩尔质量等比例称重，均苯四甲酸酐为40g-50g，二氨基二苯醚为80g-100g；(1) at 10 ° C or less, the pyromellitic anhydride and diaminodiphenyl ether are weighed according to the molar mass ratio, the pyromellitic anhydride is 40g-50g, the diaminodiphenyl ether is 80g-100g;
(2)在250ml的三口瓶中，加入步骤(1)中称好的均苯四甲酸酐，并加入12g-15g的N，N-二甲基甲酰胺；(2) In a 250 ml three-necked flask, the weighed pyromellitic anhydride in the step (1) is added, and 12 g to 15 g of N,N-dimethylformamide is added;
(3)在三口瓶中通入保护氮气；(3) Passing protective nitrogen gas into the three-neck bottle;
(4)均苯四甲酸酐完全溶解后，将二氨基二苯醚分多次逐步加入到混 合液中，得到聚酰胺酸溶液；(4) After the complete dissolution of the pyromellitic anhydride, the diaminodiphenyl ether is gradually added to the mixture in multiple steps. In the liquid mixture, a polyamic acid solution is obtained;
(5)在聚酰胺酸溶液中加入16g-20g的纳米Fe3O4颗粒，并利用搅拌棒不断搅拌，得到黑色粘稠状的聚酰胺酸/Fe3O4混合溶液；(5) adding 16 g to 20 g of nano-Fe 3 O 4 particles to the polyamic acid solution, and continuously stirring with a stir bar to obtain a black viscous polyamic acid/Fe 3 O 4 mixed solution;
(6)将得到的黑色粘稠状的聚酰胺酸/Fe3O4混合溶液分次装入的20ml的注射器中，固定于高压静电纺丝装置上，注射器的金属针头与高压电源的一极相连；(6) The obtained black viscous polyamic acid/Fe 3 O 4 mixed solution was placed in a 20 ml syringe, and fixed on a high-voltage electrospinning device, the metal needle of the syringe and the pole of the high-voltage power source. Connected
(7)在接收板上覆上一层铝箔接收板与高压电源的另一极相连，调整喷丝头与收集板之间的距离，并设置纺丝时间，打开电源，开始纺丝。(7) The receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
根据上述技术方案，所述均苯四甲酸酐、二氨基二苯醚均为化学纯。According to the above technical solution, the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
根据上述技术方案，所述N，N-二甲基乙酰胺和纳米Fe3O4为分析纯。According to the above technical solution, the N,N-dimethylacetamide and the nano Fe 3 O 4 are of analytical grade.
根据上述技术方案，所述步骤(4)中的二氨基二苯醚分5次加入三口瓶中，且每次加入的量相等，均为20g-25g。According to the above technical solution, the diaminodiphenyl ether in the step (4) is added to the three-necked bottle five times, and the amount of each addition is equal, and each is 20 g to 25 g.
根据上述技术方案，所述注射器的金属针头的型号为12#、15cm。According to the above technical solution, the metal needle of the syringe has a model number of 12 # and 15 cm.
根据上述技术方案，所述步骤(7)中的喷丝头与收集板之间的距离为16-18cm，纺丝时间为5h-6h。According to the above technical solution, the distance between the spinneret and the collecting plate in the step (7) is 16-18 cm, and the spinning time is 5 h-6 h.
本发明的有益效果：The beneficial effects of the invention:
本发明将聚酰胺酸与Fe3O4复合得到磁性纳米复合纤维，具有良好的导电性能，原料简单易得；产生的纤维长度可以通过调节喷丝头与收集板之间的距离之间的距离得到不同长度的纤维，实现自由控制纤维长度，以适应不同的需要；本发明制取的纤维强度大透气性好，节点光滑不易断裂。The invention combines polyamic acid with Fe 3 O 4 to obtain magnetic nano-composite fiber, has good electrical conductivity, and the raw material is simple and easy to obtain; the generated fiber length can be adjusted by adjusting the distance between the spinneret and the distance between the collecting plates. Fibers of different lengths are obtained, and the length of the fiber can be freely controlled to meet different needs; the fiber produced by the invention has high strength and good gas permeability, and the joint is smooth and not easy to break.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
实施例1：Example 1:
一种聚酰胺酸磁性纳米复合纤维的制备工艺，包括如下步骤：A preparation process of a polyamic acid magnetic nano composite fiber, comprising the following steps:
(1)在10摄氏度以下，将均苯四甲酸酐与二氨基二苯醚按照摩尔质量等比例称重，均苯四甲酸酐为45g，二氨基二苯醚为90g； (1) at 10 ° C or less, the pyromellitic anhydride and diaminodiphenyl ether are weighed according to the molar mass ratio, the tetrazoic acid anhydride is 45 g, and the diaminodiphenyl ether is 90 g;
(2)在250ml的三口瓶中，加入步骤(1)中称好的均苯四甲酸酐，并加入13g的N，N-二甲基甲酰胺；(2) In a 250 ml three-necked flask, the pyromellitic anhydride referred to in the step (1) is added, and 13 g of N,N-dimethylformamide is added;
(3)在三口瓶中通入保护氮气；(3) Passing protective nitrogen gas into the three-neck bottle;
(4)均苯四甲酸酐完全溶解后，将二氨基二苯醚分多次逐步加入到混合液中，得到聚酰胺酸溶液；(4) after the complete dissolution of the pyromellitic anhydride, the diaminodiphenyl ether is gradually added to the mixed solution several times to obtain a polyamic acid solution;
(5)在聚酰胺酸溶液中加入17g的纳米Fe3O4颗粒，并利用搅拌棒不断搅拌，得到黑色粘稠状的聚酰胺酸/Fe3O4混合溶液；(5) adding 17 g of nano-Fe 3 O 4 particles to the polyamic acid solution, and continuously stirring with a stir bar to obtain a black viscous polyamic acid/Fe 3 O 4 mixed solution;
(6)将得到的黑色粘稠状的聚酰胺酸/Fe3O4混合溶液分次装入的20ml的注射器中，固定于高压静电纺丝装置上，注射器的金属针头与高压电源的一极相连；(6) The obtained black viscous polyamic acid/Fe 3 O 4 mixed solution was placed in a 20 ml syringe, and fixed on a high-voltage electrospinning device, the metal needle of the syringe and the pole of the high-voltage power source. Connected
(7)在接收板上覆上一层铝箔接收板与高压电源的另一极相连，调整喷丝头与收集板之间的距离，并设置纺丝时间，打开电源，开始纺丝。(7) The receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
根据上述技术方案，所述均苯四甲酸酐、二氨基二苯醚均为化学纯。According to the above technical solution, the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
根据上述技术方案，所述N，N-二甲基乙酰胺和纳米Fe3O4为分析纯。According to the above technical solution, the N,N-dimethylacetamide and the nano Fe 3 O 4 are of analytical grade.
根据上述技术方案，所述步骤(4)中的二氨基二苯醚分5次加入三口瓶中，且每次加入的量相等，均为18g。According to the above technical solution, the diaminodiphenyl ether in the step (4) is added to the three-necked bottle 5 times, and the amount of each addition is equal, both being 18 g.
根据上述技术方案，所述注射器的金属针头的型号为12#、15cm。According to the above technical solution, the metal needle of the syringe has a model number of 12 # and 15 cm.
根据上述技术方案，所述步骤(7)中的喷丝头与收集板之间的距离为16-18cm，纺丝时间为5h-6h。According to the above technical solution, the distance between the spinneret and the collecting plate in the step (7) is 16-18 cm, and the spinning time is 5 h-6 h.
实施例2：Example 2:
一种聚酰胺酸磁性纳米复合纤维的制备工艺，包括如下步骤：A preparation process of a polyamic acid magnetic nano composite fiber, comprising the following steps:
(1)在10摄氏度以下，将均苯四甲酸酐与二氨基二苯醚按照摩尔质量等比例称重，均苯四甲酸酐为40g-50g，二氨基二苯醚为80g-100g；(1) at 10 ° C or less, the pyromellitic anhydride and diaminodiphenyl ether are weighed according to the molar mass ratio, the pyromellitic anhydride is 40g-50g, the diaminodiphenyl ether is 80g-100g;
(2)在250ml的三口瓶中，加入步骤(1)中称好的均苯四甲酸酐，并加入12g-15g的N，N-二甲基甲酰胺；(2) In a 250 ml three-necked flask, the weighed pyromellitic anhydride in the step (1) is added, and 12 g to 15 g of N,N-dimethylformamide is added;
(3)在三口瓶中通入保护氮气；(3) Passing protective nitrogen gas into the three-neck bottle;
(4)均苯四甲酸酐完全溶解后，将二氨基二苯醚分多次逐步加入到混合液中，得到聚酰胺酸溶液； (4) after the complete dissolution of the pyromellitic anhydride, the diaminodiphenyl ether is gradually added to the mixed solution several times to obtain a polyamic acid solution;
(5)在聚酰胺酸溶液中加入18g的纳米Fe3O4颗粒，并利用搅拌棒不断搅拌，得到黑色粘稠状的聚酰胺酸/Fe3O4混合溶液；(5) adding 18 g of nano-Fe 3 O 4 particles to the polyamic acid solution, and continuously stirring with a stir bar to obtain a black viscous polyamic acid/Fe 3 O 4 mixed solution;
(6)将得到的黑色粘稠状的聚酰胺酸/Fe3O4混合溶液分次装入的20ml的注射器中，固定于高压静电纺丝装置上，注射器的金属针头与高压电源的一极相连；(6) The obtained black viscous polyamic acid/Fe 3 O 4 mixed solution was placed in a 20 ml syringe, and fixed on a high-voltage electrospinning device, the metal needle of the syringe and the pole of the high-voltage power source. Connected
(7)在接收板上覆上一层铝箔接收板与高压电源的另一极相连，调整喷丝头与收集板之间的距离，并设置纺丝时间，打开电源，开始纺丝。(7) The receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
根据上述技术方案，所述均苯四甲酸酐、二氨基二苯醚均为化学纯。According to the above technical solution, the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
根据上述技术方案，所述N，N-二甲基乙酰胺和纳米Fe3O4为分析纯。According to the above aspect, the N, N- dimethylacetamide and Fe 3 O 4 nano analytical grade.
根据上述技术方案，所述步骤(4)中的二氨基二苯醚分5次加入三口瓶中，且每次加入的量相等，均为20g-25g。According to the above technical solution, the diaminodiphenyl ether in the step (4) is added to the three-necked bottle five times, and the amount of each addition is equal, and each is 20 g to 25 g.
根据上述技术方案，所述注射器的金属针头的型号为12#、15cm。According to the above technical solution, the metal needle of the syringe has a model number of 12 # and 15 cm.
根据上述技术方案，所述步骤(7)中的喷丝头与收集板之间的距离为17cm，纺丝时间为5.5。According to the above technical solution, the distance between the spinneret and the collecting plate in the step (7) is 17 cm, and the spinning time is 5.5.
实施例3：Example 3:
一种聚酰胺酸磁性纳米复合纤维的制备工艺，包括如下步骤：A preparation process of a polyamic acid magnetic nano composite fiber, comprising the following steps:
((1)在10摄氏度以下，将均苯四甲酸酐与二氨基二苯醚按照摩尔质量等比例称重，均苯四甲酸酐为40g-50g，二氨基二苯醚为80g-100g；(1) at 10 degrees Celsius or less, the pyromellitic anhydride and diaminodiphenyl ether are weighed in a molar ratio, the pyromellitic anhydride is 40g-50g, and the diaminodiphenyl ether is 80g-100g;
(2)在250ml的三口瓶中，加入步骤(1)中称好的均苯四甲酸酐，并加入12g-15g的N，N-二甲基甲酰胺；(2) In a 250 ml three-necked flask, the weighed pyromellitic anhydride in the step (1) is added, and 12 g to 15 g of N,N-dimethylformamide is added;
(3)在三口瓶中通入保护氮气；(3) Passing protective nitrogen gas into the three-neck bottle;
(4)均苯四甲酸酐完全溶解后，将二氨基二苯醚分多次逐步加入到混合液中，得到聚酰胺酸溶液；(4) after the complete dissolution of the pyromellitic anhydride, the diaminodiphenyl ether is gradually added to the mixed solution several times to obtain a polyamic acid solution;
(5)将16g-20g的纳米Fe3O4颗粒在N，N-二甲基甲酰胺溶液中进行超声震荡处理，得到纳米Fe3O4溶液；(5) 16g-20g of nano Fe 3 O 4 particles in an N, N-dimethylformamide solution for ultrasonic vibration treatment to obtain a nano Fe 3 O 4 solution;
(6)在聚酰胺酸溶液中加入步骤(5)中制取的纳米Fe3O4溶液，并利用搅拌棒不断搅拌，得到黑色粘稠状的聚酰胺酸/Fe3O4混合溶液；(6) adding the nano Fe 3 O 4 solution prepared in the step (5) to the polyamic acid solution, and continuously stirring with a stirring bar to obtain a black viscous polyamic acid/Fe 3 O 4 mixed solution;
(7)将得到的黑色粘稠状的聚酰胺酸/Fe3O4混合溶液分次装入的20ml 的注射器中，固定于高压静电纺丝装置上，注射器的金属针头与高压电源的一极相连；(7) The obtained black viscous polyamic acid/Fe 3 O 4 mixed solution was placed in a 20 ml syringe, and fixed on a high-voltage electrospinning device, the metal needle of the syringe and the pole of the high-voltage power source. Connected
(8)在接收板上覆上一层铝箔接收板与高压电源的另一极相连，调整喷丝头与收集板之间的距离，并设置纺丝时间，打开电源，开始纺丝。(8) The receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
根据上述技术方案，所述均苯四甲酸酐、二氨基二苯醚均为化学纯。According to the above technical solution, the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
根据上述技术方案，所述N，N-二甲基乙酰胺和纳米Fe3O4为分析纯。According to the above technical solution, the N,N-dimethylacetamide and the nano Fe 3 O 4 are of analytical grade.
根据上述技术方案，所述步骤(4)中的二氨基二苯醚分5次加入三口瓶中，且每次加入的量相等，均为20g-25g。According to the above technical solution, the diaminodiphenyl ether in the step (4) is added to the three-necked bottle five times, and the amount of each addition is equal, and each is 20 g to 25 g.
根据上述技术方案，所述步骤(2)中水浴加热的温度为45℃。According to the above technical solution, the temperature of the water bath heating in the step (2) is 45 °C.
根据上述技术方案，所述步骤(7)中的喷丝头与收集板之间的距离为17cm，纺丝时间为6h。According to the above technical solution, the distance between the spinneret and the collecting plate in the step (7) is 17 cm, and the spinning time is 6 h.
基于上述，本发明的优点在于，本发明将聚酰胺酸与Fe3O4复合得到磁性纳米复合纤维，具有良好的导电性能，原料简单易得；产生的纤维长度可以通过调节喷丝头与收集板之间的距离之间的距离得到不同长度的纤维，实现自由控制纤维长度，以适应不同的需要；本发明制取的纤维强度大透气性好，节点光滑不易断裂。Based on the above, an advantage of the present invention is that the present invention combines a polyamic acid with Fe 3 O 4 to obtain a magnetic nanocomposite fiber, which has good electrical conductivity, and the raw material is simple and easy to obtain; the length of the produced fiber can be adjusted by adjusting the spinneret and collecting The distance between the distances between the plates is obtained to obtain fibers of different lengths, and the length of the fibers can be freely controlled to meet different needs; the fibers obtained by the invention have high strength and good gas permeability, and the joints are smooth and not easy to break.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。 The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (6)

  1. 一种聚酰胺酸磁性纳米复合纤维的制备工艺，其特征在于，包括如下步骤：A preparation process of a polyamic acid magnetic nano composite fiber, comprising the steps of:
    (1)在10摄氏度以下，将均苯四甲酸酐与二氨基二苯醚按照摩尔质量等比例称重，均苯四甲酸酐为40g-50g，二氨基二苯醚为80g-100g；(1) at 10 ° C or less, the pyromellitic anhydride and diaminodiphenyl ether are weighed according to the molar mass ratio, the pyromellitic anhydride is 40g-50g, the diaminodiphenyl ether is 80g-100g;
    (2)在250ml的三口瓶中，加入步骤(1)中称好的均苯四甲酸酐，并加入12g-15g的N，N-二甲基甲酰胺；(2) In a 250 ml three-necked flask, the weighed pyromellitic anhydride in the step (1) is added, and 12 g to 15 g of N,N-dimethylformamide is added;
    (3)在三口瓶中通入保护氮气；(3) Passing protective nitrogen gas into the three-neck bottle;
    (4)均苯四甲酸酐完全溶解后，将二氨基二苯醚分多次逐步加入到混合液中，得到聚酰胺酸溶液；(4) after the complete dissolution of the pyromellitic anhydride, the diaminodiphenyl ether is gradually added to the mixed solution several times to obtain a polyamic acid solution;
    (5)在聚酰胺酸溶液中加入16g-20g的纳米Fe3O4颗粒，并利用搅拌棒不断搅拌，得到黑色粘稠状的聚酰胺酸/Fe3O4混合溶液；(5) adding 16 g to 20 g of nano-Fe 3 O 4 particles to the polyamic acid solution, and continuously stirring with a stir bar to obtain a black viscous polyamic acid/Fe 3 O 4 mixed solution;
    (6)将得到的黑色粘稠状的聚酰胺酸/Fe3O4混合溶液分次装入的20ml的注射器中，固定于高压静电纺丝装置上，注射器的金属针头与高压电源的一极相连；(6) The obtained black viscous polyamic acid/Fe 3 O 4 mixed solution was placed in a 20 ml syringe, and fixed on a high-voltage electrospinning device, the metal needle of the syringe and the pole of the high-voltage power source. Connected
    (7)在接收板上覆上一层铝箔接收板与高压电源的另一极相连，调整喷丝头与收集板之间的距离，并设置纺丝时间，打开电源，开始纺丝。(7) The receiving plate is covered with a layer of aluminum foil receiving plate and connected to the other pole of the high voltage power supply, the distance between the spinneret and the collecting plate is adjusted, the spinning time is set, the power is turned on, and the spinning is started.
  2. 根据权利要求1所述的一种聚酰胺酸磁性纳米复合纤维的制备工艺，其特征在于，所述均苯四甲酸酐、二氨基二苯醚均为化学纯。The process for preparing a polyamic acid magnetic nanocomposite fiber according to claim 1, wherein the pyromellitic anhydride and the diaminodiphenyl ether are all chemically pure.
  3. 根据权利要求1所述的一种聚酰胺酸磁性纳米复合纤维的制备工艺，其特征在于，所述N，N-二甲基乙酰胺和纳米Fe3O4颗粒为分析纯。The process for preparing a polyamic acid magnetic nanocomposite fiber according to claim 1, wherein the N,N-dimethylacetamide and the nano Fe 3 O 4 particles are of analytical grade.
  4. 根据权利要求1所述的一种聚酰胺酸磁性纳米复合纤维的制备工艺，其特征在于，所述步骤(4)中的二氨基二苯醚分5次加入三口瓶中，且每次加入的量相等，均为20g-25g。The process for preparing a polyamic acid magnetic nanocomposite fiber according to claim 1, wherein the diaminodiphenyl ether in the step (4) is added to the three-necked bottle five times, and each time The amount is equal, both are 20g-25g.
  5. 根据权利要求2所述的一种聚酰胺酸磁性纳米复合纤维的制备工艺，其特征在于，所述注射器的金属针头的型号为12#、15cm。The process for preparing a polyamic acid magnetic nanocomposite fiber according to claim 2, wherein the metal needle of the syringe has a model number of 12 # and 15 cm.
  6. 根据权利要求1所述的一种聚酰胺酸磁性纳米复合纤维的制备工艺，其特征在于，所述步骤(7)中的喷丝头与收集板之间的距离为16-18cm，纺丝时间为5h-6h。 The process for preparing a polyamic acid magnetic nanocomposite fiber according to claim 1, wherein the distance between the spinneret and the collecting plate in the step (7) is 16-18 cm, and the spinning time is It is 5h-6h.
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* Cited by examiner, † Cited by third party
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CN101603213A (en) * 2008-11-12 2009-12-16 苏州大学 Polyimide nano-fiber and preparation method thereof
CN102277648A (en) * 2011-05-30 2011-12-14 中国科学院青岛生物能源与过程研究所 Inorganic/organic composite polyimide nanometer fibrous film, preparation method thereof and application thereof
CN104752665A (en) * 2015-03-31 2015-07-01 渤海大学 Method for preparing polyimide porous nanofiber electrode diaphragm
CN105062047A (en) * 2015-07-29 2015-11-18 苏州荣昌复合材料有限公司 Preparation method of magnetic adsorption nylon material

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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101603213A (en) * 2008-11-12 2009-12-16 苏州大学 Polyimide nano-fiber and preparation method thereof
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CN104752665A (en) * 2015-03-31 2015-07-01 渤海大学 Method for preparing polyimide porous nanofiber electrode diaphragm
CN105062047A (en) * 2015-07-29 2015-11-18 苏州荣昌复合材料有限公司 Preparation method of magnetic adsorption nylon material

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