CN106702524B - A kind of preparation method of multi-functional Fypro - Google Patents
A kind of preparation method of multi-functional Fypro Download PDFInfo
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- CN106702524B CN106702524B CN201710004928.0A CN201710004928A CN106702524B CN 106702524 B CN106702524 B CN 106702524B CN 201710004928 A CN201710004928 A CN 201710004928A CN 106702524 B CN106702524 B CN 106702524B
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- functional
- zrp
- carbon material
- fypro
- modified
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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
A kind of preparation method of multi-functional Fypro, belongs to functional material and functional fibre preparing technical field.Comprise the following steps：The first step：Functional metal ion is formed into functional α ZrP by ion exchange into α ZrP, then the α ZrP of KH550 modified functions are utilized, by carbon material acidification, obtain the carbon material of acidification, the carbon material after acidification is modified using E51 epoxy modifying agents, modified carbon material is obtained, the KH550 functional α ZrP being modified are added to formation multifunctional nano cluster in the carbon material of the modification；Second step：The multifunctional nano cluster and polyamide substrate are blended to granulation at 180 ~ 270 DEG C, and it is dry, most multi-functional Fypro is spun into through melt spinning method afterwards.The additive amount of antibacterial guest component is few in the multi-functional Fypro, is uniformly dispersed, and function is lasting, easy to operate.
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
Fypro functionalization kind is more and more at present, different according to different function realizing methods, such as
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 to silver nitrate in the solution containing silver nitrate in adsorbent solution, then
By being reduced to obtain the anti-bacterial fibre or fabric of surface attachment silver to the fiber after absorption silver nitrate.This method cannot 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, passing through Screw Extrusion, to prepare antibacterial female
Grain, then prepare anti-bacterial fibre by melt spinning technology.Patent CN103038403A is specific by being carried out after extension is handled
In the range of heat treatment without tension be prepared for wearability functional polyester fiber.Patent CN103710963A is by adding high-content
A variety of inorganic nanometer powders provided for polyester matrix multi-functional, this method additive amount height is not easy to disperse, and effect is poor.
The content of the invention
The object of the present invention is to provide a kind of preparation method of multi-functional Fypro, the multi-functional polyamide are fine
The additive amount of antibacterial guest component is few in dimension, is uniformly dispersed, and function is lasting, easy to operate.
In order to achieve the above object, the present invention provides a kind of preparation method of multi-functional Fypro, including it is following
Step：
The first step：Functional metal ion is formed into functional α-ZrP, Ran Houli by ion exchange into α-ZrP
With the α-ZrP of KH550 modified functions, by carbon material acidification, the carbon material of acidification is obtained, is changed using E51 epoxies
Property agent to after acidification carbon material be modified, obtain modified carbon material, by KH550 be modified functional α-ZrP add
Multifunctional nano cluster is formed into the carbon material of the modification；
Second step：The multifunctional nano cluster and polyamide substrate are blended to granulation at 180 ~ 270 DEG C, and it is dry,
Most multi-functional Fypro is spun into through melt spinning method afterwards.
Preferably, the functional metal ion is in copper chloride, copper sulphate, copper nitrate, silver nitrate and germanium chloride
It is at least one.
Preferably, the carbon material is at least one of carbon nanotubes, nanometer carbon black and nano-graphite.
Preferably, the functional α-ZrP and the mass ratio of the carbon material of the modification that the KH550 is modified are 1:1-
10。
Preferably, the size of the multifunctional nano cluster is in 300 ~ 700 nm.
Preferably, the polyamide substrate is polycaprolactam, PA 66, poly- 11 lactams, poly- ten
Two lactams, polyhexamethylene sebacamide, two formyl hexamethylene diamine of poly- dodecane, 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, realizes α-ZrP to functional metal ion
Load；And be modified by KH550 and add the compatibility of α-ZrP and polymeric matrix at the same time, introduced greatly for α-ZrP surfaces
The amino of amount；
（2）The nano-carbon material of acidification is modified using E51, adds the compatibility of carbon material and matrix, and be
Carbon material surface provides substantial amounts of epoxide group；
（3）Obtained multifunctional nano cluster can realize once addition multiple functions and additive amount is few, and function is lasting, and
The shaping of polymer nano material is not influenced；
（4）Method is easy to operate, efficient, and cost is low, and effectiveness is lasting, has a extensive future；
（5）The multi-functional Fypro prepared can be applied effectively in household textiles, clothes, big aircraft, high ferro etc.
Decorations, spacefarer's dress ornament, military battle-dress uniform decorations etc..State can effectively be filled up by the industrialization of the multi-functional Fypro of the present invention
Interior multifunctional fibre technology of preparing blank.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Scope.
Zirconium phosphate nano powder in various embodiments of the present invention is commercial product, and particle diameter is 100-700 nm, nano-carbon powder
Body is that commercial product length of carbon nanotube is 200-700 nm, and nanometer carbon black particle diameter is 100-500 nm, the particle diameter of nano-graphite
For 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, ultrasound and mechanical agitation, ultrasonic power is
50W, time 20min；Churned mechanically rotating speed is 200r/min, time 20min；1.7g copper chlorides are added in solution, instead
Answer 6h；Silane coupling agent KH550 is added dropwise, and the reaction was continued, and the dripping quantity of KH550 is 0.5 with the mass ratio of α-ZrP:1；Add quality
Fraction is 80% nitric acid treatment multi-walled carbon nanotube；Reaction temperature is 80 DEG C, and the time of reaction is 12 h.Add E51 acid modifieds
The multi-walled carbon nanotube of change；It is 1 that carbon material, which is acidified, with epoxy modifying agent E51 molar ratios:5, reaction temperature is 80 DEG C, the reaction time
For 12 h.The molar ratio of epoxide modified multi-walled carbon nanotube and KH550- α-ZrP are 1:1；Temperature is raised to 80 DEG C, is continued anti-
Answer 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 it is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA6 fibers.It is multi-functional in fiber
The size of powder is in 300-700 nm.The fiber is 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 fabric 80 times.The volume resistivity of the fiber is less than
108Ω·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, ultrasound and mechanical agitation, ultrasonic power 35W,
Time is 60 min；Churned mechanically rotating speed is 300r/min, time 15min；1.6g copper sulphate is added in solution, reaction
12 h；Silane coupling agent KH550 is added dropwise, and the reaction was continued, and the dripping quantity of KH550 is 1 with the mass ratio of α-ZrP:1；Add quality point
Number is 80% nitric acid treatment multi-walled carbon nanotube；Reaction temperature is 75 DEG C, and the time of reaction is 24 h.Add E51 and be modified acidifying
Multi-walled carbon nanotube；It is 1 that carbon material, which is acidified, with epoxy modifying agent E51 molar ratios:5, reaction temperature is 75 DEG C, and the reaction time is
24 h.The molar ratio of epoxide modified multi-walled carbon nanotube and KH550- α-ZrP are 1:1；Temperature is raised to 80 DEG C, the reaction was continued
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 at 210 DEG C ~ 270 DEG C and make
Grain, and it is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA66 fibers.It is more in fiber
The size of function powder is in 500-700 nm.The fiber resists staphylococcus aureus the antibiotic rate ＞ 85% of Escherichia coli
Bacterium rate ＞ 80%, to the antibiotic rate ＞ 60% of Candida albicans.The water-fastness number ＞ of fabric 80 times.The volume resistivity of the fiber is small
In 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, ultrasound and mechanical agitation, ultrasonic power is
50W, time 30min；Churned mechanically rotating speed is 300r/min, time 30min；0.85g silver nitrates are added in solution, instead
Answer 18 h；Silane coupling agent KH550 is added dropwise, and the reaction was continued, and the dripping quantity of KH550 is 1 with the mass ratio of α-ZrP:1；Add quality
Fraction is 80% nitric acid treatment nanometer carbon black；Reaction temperature is 80 DEG C, and the time of reaction is 12 h.Add E51 and be modified acidifying
Nanometer carbon black；It is 1 that carbon material, which is acidified, with epoxy modifying agent E51 molar ratios:5, reaction temperature is 80 DEG C, and the reaction time is 24 h.
The molar ratio of epoxide modified multi-walled carbon nanotube and KH550- α-ZrP are 1:1；Temperature is raised to 80 DEG C, the reaction was continued 16h；
Washed 3 times using acetone, 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 it is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional MXD6 fibers.It is multi-functional in fiber
The size of powder is in 200-500 nm.The fiber is 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 fabric 80 times.The volume resistivity of the fiber is less than
109Ω·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, when
Between be 60min；Churned mechanically rotating speed is 300r/min, and the time is 60 min；1.35g copper chlorides and 0.11g germanium chlorides add
In solution, 12 h are reacted；Silane coupling agent KH550 is added dropwise, and the reaction was continued, and the dripping quantity of KH550 is 1 with the mass ratio of α-ZrP:
1；Add the nitric acid treatment multi-walled carbon nanotube that mass fraction is 80%；Reaction temperature is 75 DEG C, and the time of reaction is 18 h.Add
E51 is added to be modified the multi-walled carbon nanotube of acidifying；It is 1 that carbon material, which is acidified, with epoxy modifying agent E51 molar ratios:10, reaction temperature is
75 DEG C, the reaction time is 24 h.The molar ratio of epoxide modified multi-walled carbon nanotube and KH550- α-ZrP are 1:1；Raise temperature
To 80 DEG C, the reaction was continued 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 it is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA6 fibers.It is multi-functional in fiber
The size of powder is in 300-700 nm.The fiber is 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 fabric 80 times.The volume resistivity 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, ultrasound and mechanical agitation, ultrasonic power is
50W, time 30min；Churned mechanically rotating speed is 300r/min, time 30min；1.7g silver nitrates and 0.2 g germanium chlorides
Add in solution, react 12 h；Silane coupling agent KH550 is added dropwise, and the reaction was continued, the dripping quantity of KH550 and the mass ratio of α-ZrP
For 0.5:1；Add the nitric acid treatment nano-graphite that mass fraction is 60%；Reaction temperature is 80 DEG C, and the time of reaction is 24 h.
Add the nano-graphite that E51 is modified acidifying；It is 1 that carbon material, which is acidified, with epoxy modifying agent E51 molar ratios:10, reaction temperature 80
DEG C, the reaction time is 18 h.The molar ratio of epoxide modified multi-walled carbon nanotube and KH550- α-ZrP are 1:1；Raise temperature extremely
80 DEG C, the reaction was continued 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 it is dry, most afterwards through melt spinning method（Spinning temperature is 230 ~ 290 DEG C）It is spun into multi-functional PA66 fibers.It is multi-functional in fiber
The size of powder is in 500-700 nm.The fiber is 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 fabric 80 times.The volume resistivity 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 into α-ZrP by ion exchange, 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 the carbon material after acidification, obtains modified carbon material, and the KH550 functional α-ZrP being modified are added to
Multifunctional nano cluster is formed in the carbon material of the modification；
Second step：The multifunctional nano cluster and polyamide substrate are blended to granulation at 180 ~ 270 DEG C, and it is dry, finally
Multi-functional Fypro is spun into through melt spinning method.
A kind of 2. preparation method of multi-functional Fypro according to claim 1, it is characterised in that the function
Property metal ion at least one of for copper chloride, copper sulphate, copper nitrate, silver nitrate and germanium chloride.
A kind of 3. preparation method of multi-functional Fypro according to claim 1, it is characterised in that the carbon materials
Expect at least one of carbon nanotubes, nanometer carbon black and nano-graphite.
A kind of 4. preparation method of multi-functional Fypro according to claim 1, it is characterised in that the KH550
Modified functional α-ZrP and the mass ratio of the carbon material of the modification are 1:1-10.
A kind of 5. preparation method of multi-functional Fypro according to claim 1, it is characterised in that more work(
The size of energy nanocluster is in 300 ~ 700 nm.
A kind of 6. preparation method of multi-functional Fypro according to claim 1, it is characterised in that the polyamides
Amido body is polycaprolactam, PA 66, poly- 11 lactams, nylon 12, polyhexamethylene sebacamide, poly-
Two formyl hexamethylene diamine of dodecane, 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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| US7938996B2 (en) * | 2004-10-01 | 2011-05-10 | Board Of Regents, The University Of Texas System | Polymer-free carbon nanotube assemblies (fibers, ropes, ribbons, films) |
| CN1241979C (en) * | 2004-10-11 | 2006-02-15 | 东华大学 | Composite material fiber based on carbon nano-tube and its preparation method |
| CN102617870B (en) * | 2012-03-31 | 2014-05-28 | 中国地质大学（武汉） | Method for preparing modified epoxy resin composite material |
| CN105483852B (en) * | 2015-11-30 | 2018-05-25 | 东华大学 | A kind of polymer-organically-modified and loaded metal ion α-ZrP complex fiber materials preparation method |
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