CN106702524A - Preparation method of multifunctional polyamide fiber - Google Patents
Preparation method of multifunctional polyamide fiber Download PDFInfo
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- CN106702524A CN106702524A CN201710004928.0A CN201710004928A CN106702524A CN 106702524 A CN106702524 A CN 106702524A CN 201710004928 A CN201710004928 A CN 201710004928A CN 106702524 A CN106702524 A CN 106702524A
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- Prior art keywords
- functional
- modified
- zrp
- carbon material
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Classifications
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- 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
- 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
- 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
- D01F1/103—Agents inhibiting growth of microorganisms
Abstract
Provided is a preparation method of a multifunctional polyamide fiber, and belongs to the technical field of functional materials and functional fiber preparation. The preparation method comprises the following steps that step1, functional metal ions are put in an alpha-ZrP through ion exchange to form a functional alpha-ZrP, and then using a KH550 modified functional alpha-ZrP, a carbon material is treated with acidification to obtain an acidified carbon material, an E51 epoxy modifier is used for modifying the carbon material after acidification, a modified carbon material is obtained, and the functional alpha-ZrP modified by the KH550 is added to the modified carbon material to form multifunctional nanoclusters; step 2, the multifunctional nanoclusters and a polyamide matrix are mixed and granulated at 180-270 DEG C, after being dried, and a multifunctional polyamide fiber is prepared by melt spinning. The addition of an antibacterial object component in the multifunctional polyamide fiber is few, the dispersion is even, the function is durable, and the operation is simple.
Description
Technical field
The invention belongs to functional material and functional fibre preparing technical field, and in particular to a kind of multi-functional Fypro
Preparation method.
Background technology
Current Fypro functionalization kind is more and more, different according to different function realizing methods, for example
In order to realize the functionalization of Fypro, common method is process for modifying surface and blend modification technology.However as society
Development, single function is increasingly difficult to meet multi-field, multi-functional requirement.
Patent CN101942759A is that fiber is added into silver nitrate in the solution containing silver nitrate in adsorbent solution, then
Fiber after to absorption silver nitrate carries out reducing the anti-bacterial fibre or fabric that obtain surface attachment silver.The method can not be formed
The antimicrobial coating of stable homogeneous, and antibacterial time is limited, it is impossible to reach durable antibiotic.Whole process excessively complexity is easily to environment
Produce pollution.The latter be then by antibacterial components it is direct or it is modified be added in polymer, it is female to prepare antibacterial by Screw Extrusion
Grain, then prepare anti-bacterial fibre by melt spinning technology.Patent CN103038403A is specific by carrying out after extension is processed
In the range of heat treatment without tension be prepared for wearability functional polyester fiber.Patent CN103710963A is by adding high content
Various inorganic nanometer powders it is multi-functional for polyester matrix is provided, the method addition is high to be difficult dispersion, and effect is poor.
The content of the invention
It is an object of the invention to provide a kind of preparation method of multi-functional Fypro, described multi-functional polyamide is fine
The addition of antibacterial guest component is few in dimension, be uniformly dispersed, and function is persistently, easy to operate.
In order to achieve the above object, it is the invention provides a kind of preparation method of multi-functional Fypro including following
Step：
The first step：Functional metal ion is formed into functional α-ZrP by ion exchange into α-ZrP, is then utilized
α-the ZrP of KH550 modified functions, by carbon material acidification, obtain the carbon material of acidification, epoxide modified using E51
Agent is modified to the carbon material after acidification, obtains modified carbon material, and functional α-ZrP that KH550 is modified are added to
Multifunctional nano cluster is formed in the modified carbon material；
Second step：The multifunctional nano cluster and polyamide substrate are blended granulation at 180 ~ 270 DEG C, and are dried, finally
Multi-functional Fypro is spun into through melt spinning method.
Preferably, described functional metal ion is in copper chloride, copper sulphate, copper nitrate, silver nitrate and germanium chloride
It is at least one.
Preferably, described carbon material is at least one in CNT, nanometer carbon black and nano-graphite.
Preferably, the mass ratio of described KH550 modified functional α-ZrP and the modified carbon material is 1:1-
10。
Preferably, the size of described multifunctional nano cluster is in 300 ~ 700 nm.
Preferably, described polyamide substrate is polycaprolactam, PA 66, poly- 11 lactams, poly- ten
Two lactams, polyhexamethylene sebacamide, the formyl hexamethylene diamine of poly- dodecane two, nylon 1010 or poly hexamethylene adipamide isophthalic diformazan
Amine.
Compared with prior art, beneficial effects of the present invention are as follows：
（1）Functional metal ion is entered into α-ZrP by ion exchange, α-ZrP is realized and functional metal ion is born
Carry；And be modified by KH550 and increased the compatibility of α-ZrP and polymeric matrix simultaneously, it is substantial amounts of to be that α-ZrP surfaces introduce
Amino；
（2）The nano-carbon material of acidification is modified using E51, increased the compatibility of carbon material and matrix, and be carbon materials
Material surface provides substantial amounts of epoxide group；
（3）The multifunctional nano cluster for obtaining can realize once adding various functions and addition is few, and function is lasting, and not shadow
Ring the shaping of polymer nano material；
（4）Method is simple to operate, efficient, low cost, and effectiveness persistently, has a extensive future；
（5）The multi-functional Fypro for preparing can be applied effectively in interior trims such as household textiles, clothes, big aircraft, high ferros, navigated
Its member's dress ornament, military battle-dress uniform decorations etc..The country can effectively be filled up by the industrialization of multi-functional Fypro of the invention
Multifunctional fibre technology of preparing blank.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Zirconium phosphate nano powder in various embodiments of the present invention is commercially available prod, and particle diameter is 100-700 nm, nano-carbon powder
Body is that commercially available prod length of carbon nanotube is 200-700 nm, and nanometer carbon black particle diameter is 100-500 nm, the particle diameter of nano-graphite
It is 200-700 nm.
Embodiment 1：
A kind of preparation method of multi-functional Fypro, concretely comprises the following steps：
The first step：19.5g α-ZrP are added in 100 ml tetrahydrofurans, ultrasonic and mechanical agitation, ultrasonic power is 50W,
Time is 20min；Churned mechanically rotating speed is 200r/min, and the time is 20min；1.7g copper chlorides are added in solution, react 6h；
Silane coupling agent KH550 is added dropwise to continue to react, the dripping quantity of KH550 is 0.5 with the mass ratio of α-ZrP:1；Addition mass fraction
It is 80% nitric acid treatment multi-walled carbon nano-tubes；Reaction temperature is 80 DEG C, and the time of reaction is 12 h.Addition E51 is modified acidifying
Multi-walled carbon nano-tubes；Acidifying carbon material is 1 with epoxy modifying agent E51 mol ratios:5, reaction temperature is 80 DEG C, and the reaction time is 12
h.Epoxide modified multi-walled carbon nano-tubes is 1 with the mol ratio of KH550- α-ZrP:1；High-temperature is risen to 80 DEG C, continues to react
16h；Washed 3 times using acetone, 60 DEG C of drying 12h of filtering vacuum baking oven；
Second step：By above-mentioned multifunctional nano cluster and PA6 in mass ratio 5:95 are blended granulation at 210 DEG C ~ 270 DEG C, and do
It is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA6 fibers.Multi-functional powder in fiber
Size in 300-700 nm.The fiber to the antibiotic rate ＞ 90% of Escherichia coli, to the antibiotic rate ＞ of staphylococcus aureus
85%, to the antibiotic rate ＞ 60% of Candida albicans.The water-fastness number of times ＞ of fabric 80 times.The specific insulation of the fiber is less than 108
Ω·cm。
Embodiment 2：
A kind of preparation method of multi-functional Fypro, concretely comprises the following steps：
The first step：19.5g α-ZrP are added in 100 ml DMF, ultrasonic and mechanical agitation, ultrasonic power is 35W, time
It is 60 min；Churned mechanically rotating speed is 300r/min, and the time is 15min；1.6g copper sulphate is added in solution, reacts 12 h；
Silane coupling agent KH550 is added dropwise to continue to react, the dripping quantity of KH550 is 1 with the mass ratio of α-ZrP:1；Adding mass fraction is
80% nitric acid treatment multi-walled carbon nano-tubes；Reaction temperature is 75 DEG C, and the time of reaction is 24 h.Addition E51 is modified many of acidifying
Wall carbon nano tube；Acidifying carbon material is 1 with epoxy modifying agent E51 mol ratios:5, reaction temperature is 75 DEG C, and the reaction time is 24
h.Epoxide modified multi-walled carbon nano-tubes is 1 with the mol ratio of KH550- α-ZrP:1；High-temperature is risen to 80 DEG C, continues to react
16h；Washed 3 times using acetone, 60 DEG C of drying 12h of filtering vacuum baking oven；
Second step：By above-mentioned multifunctional nano cluster and PA 66 in mass ratio 3:97 are blended granulation at 210 DEG C ~ 270 DEG C, and
Dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA66 fibers.Multi-functional powder in fiber
The size of body is in 500-700 nm.The fiber to the antibiotic rate ＞ 85% of Escherichia coli, to the antibiotic rate ＞ of staphylococcus aureus
80%, to the antibiotic rate ＞ 60% of Candida albicans.The water-fastness number of times ＞ of fabric 80 times.The specific insulation of the fiber is less than 108
Ω·cm。
Embodiment 3：
A kind of preparation method of multi-functional Fypro, concretely comprises the following steps：
The first step：19.5g α-ZrP are added in 100 ml tetrahydrofurans, ultrasonic and mechanical agitation, ultrasonic power is 50W,
Time is 30min；Churned mechanically rotating speed is 300r/min, and the time is 30min；0.85g silver nitrates are added in solution, reaction 18
h；Silane coupling agent KH550 is added dropwise to continue to react, the dripping quantity of KH550 is 1 with the mass ratio of α-ZrP:1；Addition mass fraction
It is 80% nitric acid treatment nanometer carbon black；Reaction temperature is 80 DEG C, and the time of reaction is 12 h.Addition E51 is modified the nanometer of acidifying
Carbon black；Acidifying carbon material is 1 with epoxy modifying agent E51 mol ratios:5, reaction temperature is 80 DEG C, and the reaction time is 24 h.Epoxy
Modified multi-walled carbon nano-tubes is 1 with the mol ratio of KH550- α-ZrP:1；High-temperature is risen to 80 DEG C, continues to react 16h；Utilize
Acetone is washed 3 times, 60 DEG C of 12 h of drying of filtering vacuum baking oven；
Second step：By above-mentioned multifunctional nano cluster and MXD6 in mass ratio 5:95 are blended granulation at 210 DEG C ~ 270 DEG C, and do
It is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional MXD6 fibers.Multi-functional powder in fiber
Size in 200-500 nm.The fiber to the antibiotic rate ＞ 90% of Escherichia coli, to the antibiotic rate ＞ of staphylococcus aureus
90%, to the antibiotic rate ＞ 70% of Candida albicans.The water-fastness number of times ＞ of fabric 80 times.The specific insulation of the fiber is less than 109
Ω·cm。
Embodiment 4：
A kind of preparation method of multi-functional Fypro, concretely comprises the following steps：
The first step：39g α-ZrP are added in 100 ml DMF, ultrasound and mechanical agitation, ultrasonic power is 35 W, and the time is
60min；Churned mechanically rotating speed is 300r/min, and the time is 60 min；1.35g copper chlorides and 0.11g germanium chlorides add solution
In, react 12 h；Silane coupling agent KH550 is added dropwise to continue to react, the dripping quantity of KH550 is 1 with the mass ratio of α-ZrP:1；Add
Plus the nitric acid treatment multi-walled carbon nano-tubes that mass fraction is 80%；Reaction temperature is 75 DEG C, and the time of reaction is 18 h.Addition E51
The multi-walled carbon nano-tubes of modified acidifying；Acidifying carbon material is 1 with epoxy modifying agent E51 mol ratios:10, reaction temperature is 75 DEG C,
Reaction time is 24 h.Epoxide modified multi-walled carbon nano-tubes is 1 with the mol ratio of KH550- α-ZrP:1；Rise high-temperature to 80
DEG C, continue to react 16h；Washed 3 times using acetone, 60 DEG C of drying 12h of filtering vacuum baking oven；
Second step：By above-mentioned multifunctional nano cluster and PA6 in mass ratio 2:98 are blended granulation at 210 DEG C ~ 270 DEG C, and do
It is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA6 fibers.Multi-functional powder in fiber
Size in 300-700 nm.The fiber to the antibiotic rate ＞ 90% of Escherichia coli, to the antibiotic rate ＞ of staphylococcus aureus
85%, to the antibiotic rate ＞ 60% of Candida albicans.The water-fastness number of times ＞ of fabric 80 times.The specific insulation of the fiber is less than 108
Ω·cm.Rubbing manipulation measures 400 ~ 1000 per cubic centimeter of anion yield.
Embodiment 5：
A kind of preparation method of multi-functional Fypro, concretely comprises the following steps：
The first step：39 g α-ZrP are added in 100 ml tetrahydrofurans, ultrasonic and mechanical agitation, ultrasonic power is 50W, when
Between be 30min；Churned mechanically rotating speed is 300r/min, and the time is 30min；1.7g silver nitrates and 0.2 g germanium chlorides add molten
In liquid, 12 h are reacted；Silane coupling agent KH550 is added dropwise to continue to react, the dripping quantity of KH550 is 0.5 with the mass ratio of α-ZrP:
1；Addition mass fraction is 60% nitric acid treatment nano-graphite；Reaction temperature is 80 DEG C, and the time of reaction is 24 h.Addition E51
The nano-graphite of modified acidifying；Acidifying carbon material is 1 with epoxy modifying agent E51 mol ratios:10, reaction temperature is 80 DEG C, reaction
Time is 18 h.Epoxide modified multi-walled carbon nano-tubes is 1 with the mol ratio of KH550- α-ZrP:1；High-temperature is risen to 80 DEG C, after
Continuous reaction 16h；Washed 3 times using acetone, 60 DEG C of drying 12h of filtering vacuum baking oven；
Second step：By above-mentioned multifunctional nano cluster and PA66 in mass ratio 1:99 are blended granulation at 210 DEG C ~ 270 DEG C, and do
It is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA66 fibers.Multi-functional powder in fiber
Size in 500-700 nm.The fiber to the antibiotic rate ＞ 95% of Escherichia coli, to the antibiotic rate ＞ of staphylococcus aureus
90%, to the antibiotic rate ＞ 70% of Candida albicans.The water-fastness number of times ＞ of fabric 80 times.The specific insulation of the fiber is less than 1010
Ω·cm.Rubbing manipulation measures 400 ~ 1000 per cubic centimeter of anion yield.
Claims (6)
1. a kind of preparation method of multi-functional Fypro, it is characterised in that comprise the following steps：
The first step：Functional metal ion is formed into functional α-ZrP by ion exchange into α-ZrP, is then utilized
α-the ZrP of KH550 modified functions, by carbon material acidification, obtain the carbon material of acidification, epoxide modified using E51
Agent is modified to the carbon material after acidification, obtains modified carbon material, and functional α-ZrP that KH550 is modified are added to
Multifunctional nano cluster is formed in the modified carbon material；
Second step：The multifunctional nano cluster and polyamide substrate are blended granulation at 180 ~ 270 DEG C, and are dried, finally
Multi-functional Fypro is spun into through melt spinning method.
2. a kind of preparation method of multi-functional Fypro according to claim 1, it is characterised in that described function
Property metal ion be copper chloride, copper sulphate, copper nitrate, silver nitrate and germanium chloride at least one.
3. a kind of preparation method of multi-functional Fypro according to claim 1, it is characterised in that described carbon materials
Expect to be at least one in CNT, nanometer carbon black and nano-graphite.
4. a kind of preparation method of multi-functional Fypro according to claim 1, it is characterised in that described KH550
Modified functional α-ZrP and the mass ratio of the modified carbon material are 1:1-10.
5. a kind of preparation method of multi-functional Fypro according to claim 1, it is characterised in that described many work(
The size of energy nanocluster is in 300 ~ 700 nm.
6. a kind of preparation method of multi-functional Fypro according to claim 1, it is characterised in that described polyamides
Amido body is polycaprolactam, PA 66, poly- 11 lactams, nylon 12, polyhexamethylene sebacamide, poly-
The formyl hexamethylene diamine of dodecane two, nylon 1010 or poly-meta-xylylene adipamide.
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| CN201710004928.0A CN106702524B (en) | 2017-01-04 | 2017-01-04 | A kind of preparation method of multi-functional Fypro |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618850A (en) * | 2004-10-11 | 2005-05-25 | 东华大学 | Composite material fiber based on carbon nano-tube and its preparation method |
| WO2006137893A2 (en) * | 2004-10-01 | 2006-12-28 | Board Of Regents Of The University Of Texas System | Polymer-free carbon nanotube assemblies (fibers, ropes, ribbons, films) |
| CN102617870A (en) * | 2012-03-31 | 2012-08-01 | 中国地质大学（武汉） | Method for preparing modified epoxy resin composite material |
| CN105483852A (en) * | 2015-11-30 | 2016-04-13 | 东华大学 | Preparation method of polymer-organically-modified and metal-ion-loaded alpha-ZrP composite fiber material |
-
2017
- 2017-01-04 CN CN201710004928.0A patent/CN106702524B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006137893A2 (en) * | 2004-10-01 | 2006-12-28 | Board Of Regents Of The University Of Texas System | Polymer-free carbon nanotube assemblies (fibers, ropes, ribbons, films) |
| CN1618850A (en) * | 2004-10-11 | 2005-05-25 | 东华大学 | Composite material fiber based on carbon nano-tube and its preparation method |
| CN102617870A (en) * | 2012-03-31 | 2012-08-01 | 中国地质大学（武汉） | Method for preparing modified epoxy resin composite material |
| CN105483852A (en) * | 2015-11-30 | 2016-04-13 | 东华大学 | Preparation method of polymer-organically-modified and metal-ion-loaded alpha-ZrP composite fiber material |
Non-Patent Citations (1)
| Title |
|---|
| 张娇霞等: "碳纳米管的表面功能化研究:接枝环氧基聚合物", 《航空材料学报》 * |
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