CN108211824A - A kind of antibacterial hydrophilic tunica fibrosa and preparation method thereof - Google Patents
A kind of antibacterial hydrophilic tunica fibrosa and preparation method thereof Download PDFInfo
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- CN108211824A CN108211824A CN201810127886.4A CN201810127886A CN108211824A CN 108211824 A CN108211824 A CN 108211824A CN 201810127886 A CN201810127886 A CN 201810127886A CN 108211824 A CN108211824 A CN 108211824A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/48—Polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Abstract
The present invention provides a kind of antibacterial hydrophilic tunica fibrosas and preparation method thereof, and preparation method includes the following steps：（1）The preparation of modified poly terephthalic acid class raw material,（2）The preparation of fiber film master batch,（3）The preparation of modified film material,（4）The preparation of antimicrobial filtering tunica fibrosa.Nano fibrous membrane mechanical strength produced by the present invention is higher, and hydrophilicity is good, has good inhibition to Escherichia coli and staphylococcus aureus.Therefore nano fibrous membrane produced by the present invention is suitable for a kind of filter membrane applied to sewage disposal or the purification of pure water, is with a wide range of applications in terms of water process.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of antibacterial hydrophilic tunica fibrosa and its preparation side
Method.
Background technology
In human lives' production process, such as manufacture, biology, medicine, the industries such as electronics, must generate airborne contaminant,
Harmful life
Object preparation, anaphylactogen, aerosol particle etc..Environmental protection is always the popular subject under discussion of modern, in recent years, due to nanometer
Section
The huge progress of technology, particularly nanometer technology and environmental protection, the further combination of environmental improvement so that make
Nano material for its basis and guide is greatly improved the ability of mankind's environmental protection, to solve the problems, such as field of environment protection such as
Harmful substance monitoring, sewage disposal, the processing of water body oil slick etc. provide possibility.Membrane technology is since it is efficient, low energy consumption and investment
The advantages that cost is small is widely applied in water process.
Membrane for water treatment is prepared mostly by polyester material, however the hydrophily of polyester is poor, therefore reduces to water-soluble
The filter effect of liquid.Meanwhile as the fouling membrane caused by concentration polarization and Pore Blocking, lead to the reduction of film device reliability, greatly
Its development is limited greatly, and it is the effective means for mitigating fouling membrane to improve the hydrophily of film and anti-microbial property.In in the prior art
Through disclosing the preparation method being improved to film, however the hydrophilic layer mechanical strength of the film prepared is poor, therefore, it is necessary to right
The membrane material of high comprehensive performance is further developed.
Invention content
In order to of the existing technology more than solving the problems, such as, the purpose of the present invention is to provide a kind of antibacterial hydrophilic fibres
Film and preparation method thereof is tieed up, so as to improve the filter efficiency of membrane material and anti-microbial property.
To achieve these goals, the present invention provides following technical scheme：
A kind of preparation method of antibacterial hydrophilic tunica fibrosa, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
Into the m-cresol solution of poly terephthalic acid class raw material 5-10 times of parts by weight of 50-80 parts of additions, 15-30 parts are then added in
Modifying agent, 30-60min is stirred to react at a temperature of 25-40 DEG C, modified poly terephthalic acid class raw material is made；
（2）The preparation of fiber film master batch
By 30-60 parts of steps（1）It is 1 that modified poly terephthalic acid class raw material obtained, which adds in volume ratio,:4 dichloromethane and three
In fluoroacetic acid mixed solution, 1-2h is dissolved under the action of magnetic agitation, modified poly terephthalic acid class raw material is configured to matter
Measure the solution that score is 8-15%；
Nano-powder is added in the DMF solution for the silane coupling agent that 3-5 times of mass fraction is 10-20% for 15-30 parts, in 50-70
40-80min is stirred to react at a temperature of DEG C, then cools the temperature to 30-50 DEG C, it is even to extract the excessive silane of removal using ethyl alcohol
Join agent, collect modified nano powder；
Poly terephthalic acid class material solution, modified nano powder and 10-18 parts of poly butyric ester base co-polymer, matter will be modified
Measure 5-10 parts of 6-12 parts of polyvinyl alcohol, amino-acid modified chitin, the sodium polyphosphate 7- for the carboxyl modified that score is 10-15%
14 parts, 3-6 parts of dispersant, 4-9 parts of antiseptic, 5-10 parts of stabilizer be sufficiently mixed in high mixer, then squeezed through twin-screw
Go out machine fusion plastification, extrusion, filter membrane；
The preparation method of the polyvinyl alcohol of the carboxyl modified is：Succinic acid glycosides method is used first in the surface modification of polyvinyl alcohol
Carboxyl, then using carbodlimide method by the polyvinyl alcohol of the PEG2000 of Amino End Group one end carboxyl and above-mentioned carboxyl modified into
Row reaction, obtains the polyvinyl alcohol that carboxyl PEG is contained on surface；
（3）The preparation of modified film material
By 9-17 parts of high density polyethylene (HDPE) and step（1）The fiber film master batch of preparation is uniformly mixed in high mixer high speed, spare；
（4）The preparation of antimicrobial filtering tunica fibrosa
By step（2）The modified film material of preparation fusion plastification in single screw extrusion machine, pass sequentially through metering pump, filter and
Melt distributor co-extrusion for laminated film, then successively through supercooling, cut into item, first time multiple roll hot-stretch, infrared baking oven
Antimicrobial filtering tunica fibrosa is made in heating, second of multiple roll hot-stretch, mechanical membrane fine, thermal finalization of splitting.
Further, the multiple roll hot-stretch temperature is 100-120 DEG C, and the linear velocity of first roller is 10-30m/
Min, draw ratio 1.0-5.0；The mechanical membrane fine pin density of porcupine roller used that splits is 50-100 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 50-
85°。
Further, the heat setting temperature is 90-125 DEG C.
Preferably, the poly butyric ester base co-polymer includes poly butyric ester -3- aminopropyl trimethoxysilanes
The mixture of copolymer and poly butyric ester-ethylene glycol copolymer, the mass ratio of the two are（1-3）：1.
Preferably, the modified poly terephthalic acid class raw material includes modified polyethylene terephthalate, is modified and gathers
Propylene glycol ester terephthalate or the one or more combination of modified polybutylene terephthalate (PBT).
Preferably, the modifying agent used in the modified poly terephthalic acid class raw material is bulking agent, and the bulking agent is third
One or more combinations of olefin(e) acid ethylene oxidic ester, maleic anhydride, isocyanates.
Preferably, the nano-powder is silica, titanium dioxide, multi-walled carbon nanotube, nano aluminium oxide are a kind of or
Several combinations, the nano-powder carry out hydroxylating pretreatment first before being modified with silane coupling agent.
Preferably, the dispersant is polyvinylpyrrolidone, tetramethylammonium hydroxide, cetyl trimethyl bromination
A kind of several combinations of ammonium, neopelex or triethanolamine.
Preferably, the antiseptic is oleoresin modified sodium alginate.
Preferably, the melt index of the modified poly terephthalic acid class raw material is 3-6g/10min.
Preferably, the one kind of the amino-acid modified chitin for lysine modified chitosan or arginine modification of chitosan
It is or several.
Preferably, the stabilizer is sodium carboxymethylcellulose.
Antibacterial hydrophilic tunica fibrosa made from preparation method of the present invention.
Advantageous effect：The present invention provides a kind of antibacterial hydrophilic tunica fibrosa and preparation method thereof, by poly- terephthaldehyde
Product made of acids feedstocks has the advantages such as intensity is good, impact resistance, resistance to stress are strong, however its poor hydrophily limits it
As the application of water filtration film, poly terephthalic acid class raw material, which is modified, by using bulking agent can improve the hydrophilic of raw material
Characteristic；The dispersibility of silane coupler modified nano-powder improves, then is blended with modified poly terephthalic acid class raw material
Improving toughness and impact to improving tunica fibrosa has good important role；Poly butyric ester base co-polymer has good
Biocompatibility improves the stability of amino-acid modified chitin with the compounding of amino-acid modified chitin, maintains amino
The sour good absorption property of modification of chitosan, while improve the tensile strength and elongation at break of tunica fibrosa；Sodium polyphosphate
Addition and the compounding of amino-acid modified chitin the absorption of heavy metal ion is played an important role；Polyvinyl alcohol has good
Good film forming, by modifying carboxylic group on polyvinyl alcohol surface, improves the biocompatibility of polyvinyl alcohol, carries simultaneously
The high biological degradability of polyvinyl alcohol, the polyvinyl alcohol of carboxyl PEG modifications play an important role the stability of system；
The addition of dispersant plays an important role the uniformity of raw material, and antiseptic improves the anti-microbial property of tunica fibrosa, stabilizer
Improve the stability of tunica fibrosa.
Use of the invention show that the fracture strength of nano fibrous membrane prepared by the present invention is not less than by performance test
16.5g/d, elongation at break are not less than 60.4%, and film surface contact angle is less than 78 °, and pure water flux is more than 324 [L（m2•h-1）],
Reach more than 95%, therefore nano fibrous membrane produced by the present invention to the bacteriostasis rate of Escherichia coli and staphylococcus aureus simultaneously
Mechanical strength is higher, and hydrophilicity is good, has good inhibition to Escherichia coli and staphylococcus aureus.And this
Invention raw material used is environment-friendly materials, meets demand of the current people to environmentally protective.Therefore nanometer produced by the present invention
Tunica fibrosa is suitable for a kind of filter membrane applied to sewage disposal or the purification of pure water, has in terms of water process and widely should
Use prospect.
Specific embodiment
The invention will now be further described with reference to specific embodiments, but embodiment is only exemplary, not to this hair
Bright range forms any restrictions.It will be understood by those skilled in the art that without departing from the spirit and scope of the invention
Can the details and form of technical solution of the present invention be modified or be replaced, but these modifications and replacement each fall within the present invention's
In protection domain.
The preparation method of the polyvinyl alcohol of carboxyl modified described in following embodiment is：First using succinic acid glycosides method in poly- second
Then the surface modification carboxyl of enol is repaiied the PEG2000 of Amino End Group one end carboxyl with above-mentioned carboxyl using carbodlimide method
The polyvinyl alcohol of decorations is reacted, and obtains the polyvinyl alcohol that carboxyl PEG is contained on surface.
Embodiment 1
A kind of preparation method of antibacterial hydrophilic tunica fibrosa, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
It is 1 to mass ratio:5 times of weights are added in 1 50 parts of polyethylene terephthalate and polypropylene terephthalate
In the m-cresol solution for measuring part, 15 parts of glycidyl acrylate is then added in, is stirred to react at a temperature of 25 DEG C
Modified poly terephthalic acid class raw material is made in 30min, and the melt index of the modified poly terephthalic acid class raw material is 3g/
10min；
（2）The preparation of fiber film master batch
By 30 parts of steps（1）It is 1 that modified poly terephthalic acid class raw material obtained, which adds in volume ratio,:4 dichloromethane and trifluoro
In acetic acid mixed solution, 1h is dissolved under the action of magnetic agitation, modified poly terephthalic acid class raw material is configured to quality point
Solution of the number for 8-15%；
Nano-powder is added in the DMF solution for the silane coupling agent that 3 times of mass fractions are 10% for 15 parts, at a temperature of 50 DEG C
40min is stirred to react, then cools the temperature to 30 DEG C, the excessive silane coupling agent of removal is extracted using ethyl alcohol, collects modification and receive
Rice flour body；
Poly terephthalic acid class material solution, modified nano powder and 10 parts of poly butyric ester base co-polymer, quality will be modified
Score is 7 parts of 5 parts of 6 parts of polyvinyl alcohol, lysine modified chitosan, sodium polyphosphate, the carboxymethyl cellulose of 10% carboxyl modified
Plain 3 parts of sodium, 4 parts of oleoresin modified sodium alginate, 5 parts of stabilizer are sufficiently mixed in high mixer, then through twin-screw extrusion
Machine fusion plastification, extrusion, filter membrane；
Wherein, it is 1 that the poly butyric ester base co-polymer, which is mass ratio,：1 poly butyric ester -3- aminopropyl trimethoxies
The mixture of silane copolymer and poly butyric ester-ethylene glycol copolymer.
Wherein, it is 1 that the nano-powder, which is mass ratio,：2 silica and titanium dioxide, the nano-powder is with silane
Coupling agent carries out hydroxylating pretreatment first before being modified.
Wherein, it is 1 that the dispersant, which is mass ratio,:3:2 polyvinylpyrrolidone, tetramethylammonium hydroxide and hexadecane
Base trimethylammonium bromide.
（3）The preparation of modified film material
By 9 parts of high density polyethylene (HDPE) and step（1）The fiber film master batch of preparation is uniformly mixed in high mixer high speed, spare；
（4）The preparation of antimicrobial filtering tunica fibrosa
By step（2）The modified film material of preparation fusion plastification in single screw extrusion machine, pass sequentially through metering pump, filter and
Melt distributor co-extrusion for laminated film, then successively through supercooling, cut into item, first time multiple roll hot-stretch, infrared baking oven
Antimicrobial filtering tunica fibrosa is made in heating, second of multiple roll hot-stretch, mechanical membrane fine, thermal finalization of splitting.
Further, the multiple roll hot-stretch temperature is 100 DEG C, and the linear velocity of first roller is 10m/min, is stretched again
Number is 1.0；The mechanical membrane fine pin density of porcupine roller used that splits is 50 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 50 °.
Further, the heat setting temperature is 90 DEG C.
Embodiment 2
A kind of preparation method of antibacterial hydrophilic tunica fibrosa, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
It is 1 to mass ratio:1:1 polyethylene terephthalate, polypropylene terephthalate and poly terephthalic acid
It is added in the m-cresol solution of 8 times of parts by weight in 65 parts of butanediol ester, the mass ratio for then adding in 23 parts is 1:2:1 acrylic acid
The modifying agent of ethylene oxidic ester, maleic anhydride and isocyanates composition, 45min is stirred to react at a temperature of 33 DEG C, is made and is changed
Property poly terephthalic acid class raw material, the melt index of the modified poly terephthalic acid class raw material is 5g/10min；
（2）The preparation of fiber film master batch
By 45 parts of steps（1）It is 1 that modified poly terephthalic acid class raw material obtained, which adds in volume ratio,:4 dichloromethane and trifluoro
In acetic acid mixed solution, 1-2h is dissolved under the action of magnetic agitation, modified poly terephthalic acid class raw material is configured to quality
Score is 12% solution；
Nano-powder is added in the DMF solution for the silane coupling agent that 4 times of mass fractions are 15% for 22 parts, at a temperature of 60 DEG C
60min is stirred to react, then cools the temperature to 40 DEG C, the excessive silane coupling agent of removal is extracted using ethyl alcohol, collects modification and receive
Rice flour body；
Poly terephthalic acid class material solution, modified nano powder and 14 parts of poly butyric ester base co-polymer, quality will be modified
9 parts of polyvinyl alcohol, the mass ratio 1 for the carboxyl modified that score is 13%:2 lysine modified chitosan and arginine is modified shell
8 parts of glycan, 10 parts of sodium polyphosphate, 5 parts of dispersant, 7 parts of oleoresin modified sodium alginate, 8 parts of sodium carboxymethylcellulose are in height
Mixed machine is sufficiently mixed, then through double screw extruder fusion plastification, extrusion, filter membrane；
Wherein, the poly butyric ester base co-polymer includes poly butyric ester -3- aminopropyl trimethoxysilane copolymers
With the mixture of poly butyric ester-ethylene glycol copolymer, the mass ratio of the two is 2：1.
Wherein, it is 1 that the nano-powder, which is mass ratio,:1:2:1 silica, titanium dioxide, multi-walled carbon nanotube and
Nano aluminium oxide, the nano-powder carry out hydroxylating pretreatment first before being modified with silane coupling agent.
Wherein, it is 1 that the dispersant, which is mass ratio,:1:1:1 polyvinylpyrrolidone, cetyl trimethyl bromination
Ammonium, neopelex and triethanolamine.
（3）The preparation of modified film material
By 13 parts of high density polyethylene (HDPE) and step（1）The fiber film master batch of preparation is uniformly mixed in high mixer high speed, spare；
（4）The preparation of antimicrobial filtering tunica fibrosa
By step（2）The modified film material of preparation fusion plastification in single screw extrusion machine, pass sequentially through metering pump, filter and
Melt distributor co-extrusion for laminated film, then successively through supercooling, cut into item, first time multiple roll hot-stretch, infrared baking oven
Antimicrobial filtering tunica fibrosa is made in heating, second of multiple roll hot-stretch, mechanical membrane fine, thermal finalization of splitting.
Further, the multiple roll hot-stretch temperature is 110 DEG C, and the linear velocity of first roller is 20m/min, is stretched again
Number is 3.0；The mechanical membrane fine pin density of porcupine roller used that splits is 75 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 70 °.
Further, the heat setting temperature is 108 DEG C.
Embodiment 3
A kind of preparation method of antibacterial hydrophilic tunica fibrosa, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
Into the m-cresol solution of polyethylene terephthalate 60 parts of additions, 6 times of parts by weight, 20 parts of quality is then added in
Than 1:The modifying agent of 1 maleic anhydride and isocyanates composition, 40min is stirred to react at a temperature of 30 DEG C, is made modified poly-
Terephthaldehyde's acids raw material, the melt index of the modified poly terephthalic acid class raw material is 4g/10min；
（2）The preparation of fiber film master batch
By 40 parts of steps（1）It is 1 that modified poly terephthalic acid class raw material obtained, which adds in volume ratio,:4 dichloromethane and trifluoro
In acetic acid mixed solution, 1.2h is dissolved under the action of magnetic agitation, modified poly terephthalic acid class raw material is configured to quality
Score is 10% solution；
Nano-powder is added in the DMF solution for the silane coupling agent that 4 times of mass fractions are 12% for 20 parts, at a temperature of 55 DEG C
50min is stirred to react, then cools the temperature to 35 DEG C, the excessive silane coupling agent of removal is extracted using ethyl alcohol, collects modification and receive
Rice flour body；
Poly terephthalic acid class material solution, modified nano powder and 12 parts of poly butyric ester base co-polymer, quality will be modified
Score be 12% carboxyl modified 4 parts of 8 parts of 6 parts of 8 parts of polyvinyl alcohol, arginine modification of chitosan, sodium polyphosphate, dispersant,
5 parts of oleoresin modified sodium alginate, 6 parts of sodium carboxymethylcellulose are sufficiently mixed in high mixer, then through twin-screw extrusion
Machine fusion plastification, extrusion, filter membrane；
Wherein, it is 1.5 that the poly butyric ester base co-polymer, which is mass ratio,：1 poly butyric ester -3- aminopropyl trimethoxies
The mixture of base silane copolymer and poly butyric ester-ethylene glycol copolymer.
Wherein, it is 1 that the nano-powder, which is mass ratio,:1 multi-walled carbon nanotube and nano aluminium oxide one or more group
It closes, the nano-powder carries out hydroxylating pretreatment first before being modified with silane coupling agent.
Wherein, it is 3 that the dispersant, which is mass ratio,:1 tetramethylammonium hydroxide and cetyl trimethylammonium bromide.
（3）The preparation of modified film material
By 12 parts of high density polyethylene (HDPE) and step（1）The fiber film master batch of preparation is uniformly mixed in high mixer high speed, spare；
（4）The preparation of antimicrobial filtering tunica fibrosa
By step（2）The modified film material of preparation fusion plastification in single screw extrusion machine, pass sequentially through metering pump, filter and
Melt distributor co-extrusion for laminated film, then successively through supercooling, cut into item, first time multiple roll hot-stretch, infrared baking oven
Antimicrobial filtering tunica fibrosa is made in heating, second of multiple roll hot-stretch, mechanical membrane fine, thermal finalization of splitting.
Further, the multiple roll hot-stretch temperature is 105 DEG C, and the linear velocity of first roller is 15m/min, is stretched again
Number is 2.0；The mechanical membrane fine pin density of porcupine roller used that splits is 60 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 60 °.
Further, the heat setting temperature is 100 DEG C.
Embodiment 4
A kind of preparation method of antibacterial hydrophilic tunica fibrosa, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
It is 1 to mass ratio:10 times of weights are added in 1 80 parts of polypropylene terephthalate and polybutylene terephthalate (PBT)
In the m-cresol solution for measuring part, 30 parts of isocyanates is then added in, 60min is stirred to react at a temperature of 40 DEG C, is made and changes
Property poly terephthalic acid class raw material, the melt index of the modified poly terephthalic acid class raw material is 6g/10min；
（2）The preparation of fiber film master batch
By 60 parts of steps（1）It is 1 that modified poly terephthalic acid class raw material obtained, which adds in volume ratio,:4 dichloromethane and trifluoro
In acetic acid mixed solution, 2h is dissolved under the action of magnetic agitation, modified poly terephthalic acid class raw material is configured to quality point
Number is 15% solution；
Nano-powder is added in the DMF solution for the silane coupling agent that 5 times of mass fractions are 20% for 30 parts, at a temperature of 70 DEG C
80min is stirred to react, then cools the temperature to 50 DEG C, the excessive silane coupling agent of removal is extracted using ethyl alcohol, collects modification and receive
Rice flour body；
Poly terephthalic acid class material solution, modified nano powder and 18 parts of poly butyric ester base co-polymer, quality will be modified
Score is 12 parts of polyvinyl alcohol, the mass ratio 1 of 15% carboxyl modified:1 lysine modified chitosan and arginine is modified shell and gathers
10 parts of sugar, 14 parts of sodium polyphosphate, 6 parts of sodium carboxymethylcellulose, 9 parts of oleoresin modified sodium alginate, 10 parts of stabilizer are in height
Mixed machine is sufficiently mixed, then through double screw extruder fusion plastification, extrusion, filter membrane；
Wherein, it is 3 that the poly butyric ester base co-polymer, which is mass ratio,：1 poly butyric ester -3- aminopropyl trimethoxies
The mixture of silane copolymer and poly butyric ester-ethylene glycol copolymer.
Wherein, it is silica and multi-walled carbon nanotube that the nano-powder, which is mass ratio, and the nano-powder is with silicon
Alkane coupling agent carries out hydroxylating pretreatment first before being modified.
Wherein, it is 1 that the dispersant, which is mass ratio,:1 neopelex and triethanolamine.
（3）The preparation of modified film material
By 17 parts of high density polyethylene (HDPE) and step（1）The fiber film master batch of preparation is uniformly mixed in high mixer high speed, spare；
（4）The preparation of antimicrobial filtering tunica fibrosa
By step（2）The modified film material of preparation fusion plastification in single screw extrusion machine, pass sequentially through metering pump, filter and
Melt distributor co-extrusion for laminated film, then successively through supercooling, cut into item, first time multiple roll hot-stretch, infrared baking oven
Antimicrobial filtering tunica fibrosa is made in heating, second of multiple roll hot-stretch, mechanical membrane fine, thermal finalization of splitting.
Further, the multiple roll hot-stretch temperature is 120 DEG C, and the linear velocity of first roller is 30m/min, is stretched again
Number is 5.0；The mechanical membrane fine pin density of porcupine roller used that splits is 100 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 85 °.
Further, the heat setting temperature is 125 DEG C.
Comparative example 1
Documents 1 are with embodiment 2 difference lies in poly terephthalic acid class raw material without modification.
Comparative example 2
Documents 2 are modified with embodiment 2 difference lies in nano-powder without silane coupling agent.
Antibacterial hydrophilic tunica fibrosa prepared by embodiment 1-4 and comparative example 1-2 carries out the test of following performance, test
The results are shown in Table 1.Fracture strength and elongation at break are measured according to the testing standard of ASTM D2256-2002.
Film surface contact angle is measured by contact angle tester, pure water by by method disclosed in the prior art into
Row measures（The hydrophilic modifying research of ps hollow fiber uf membrane, engineering plastics application, 12（43）, 2015）.With reference to GB/
The method of T20094.3-2008 tests the bacteriostasis property of Escherichia coli and Staphylococcus aureus.Test result such as 1 institute of table
Show.
It is obtained by table 1, the fracture strength of nano fibrous membrane prepared by the present invention is not less than 16.5g/d, elongation at break
Not less than 60.4%, film surface contact angle is less than 78 °, and pure water flux is more than 324 [L（m2•h-1）], while to Escherichia coli and gold
The bacteriostasis rate of staphylococcus aureus reaches more than 95%, therefore nano fibrous membrane mechanical strength produced by the present invention is higher, hydrophily
Can be good, there is good inhibition to Escherichia coli and staphylococcus aureus.
Table 1
Claims (10)
1. a kind of preparation method of antibacterial hydrophilic tunica fibrosa, which is characterized in that include the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
Into the m-cresol solution of poly terephthalic acid class raw material 5-10 times of parts by weight of 50-80 parts of additions, 15-30 parts are then added in
Modifying agent, 30-60min is stirred to react at a temperature of 25-40 DEG C, modified poly terephthalic acid class raw material is made；
（2）The preparation of fiber film master batch
By 30-60 parts of steps（1）It is 1 that modified poly terephthalic acid class raw material obtained, which adds in volume ratio,:4 dichloromethane and three
In fluoroacetic acid mixed solution, 1-2h is dissolved under the action of magnetic agitation, modified poly terephthalic acid class raw material is configured to matter
Measure the solution that score is 8-15%；
Nano-powder is added in the DMF solution for the silane coupling agent that 3-5 times of mass fraction is 10-20% for 15-30 parts, in 50-70
40-80min is stirred to react at a temperature of DEG C, then cools the temperature to 30-50 DEG C, it is even to extract the excessive silane of removal using ethyl alcohol
Join agent, collect modified nano powder；
Poly terephthalic acid class material solution, modified nano powder and 10-18 parts of poly butyric ester base co-polymer, matter will be modified
Measure 5-10 parts of 6-12 parts of polyvinyl alcohol, amino-acid modified chitin, the sodium polyphosphate 7- for the carboxyl modified that score is 10-15%
14 parts, 3-6 parts of dispersant, 4-9 parts of antiseptic, 5-10 parts of stabilizer be sufficiently mixed in high mixer, then squeezed through twin-screw
Go out machine fusion plastification, extrusion, filter membrane；
（3）The preparation of modified film material
By 9-17 parts of high density polyethylene (HDPE) and step（1）The fiber film master batch of preparation is uniformly mixed in high mixer high speed, spare；
（4）The preparation of antimicrobial filtering tunica fibrosa
By step（2）The modified film material of preparation fusion plastification in single screw extrusion machine, pass sequentially through metering pump, filter and
Melt distributor co-extrusion for laminated film, then successively through supercooling, cut into item, first time multiple roll hot-stretch, infrared baking oven
Antimicrobial filtering tunica fibrosa is made in heating, second of multiple roll hot-stretch, mechanical membrane fine, thermal finalization of splitting.
A kind of 2. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the poly- hydroxyl
Base butyrate base co-polymer includes poly butyric ester -3- aminopropyl trimethoxysilanes copolymer and poly butyric ester-poly-
The mixture of glycol copolymer, the mass ratio of the two are（1-3）：1.
A kind of 3. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the modification
Poly terephthalic acid class raw material includes modified polyethylene terephthalate, modified polypropylene terephthalate or modification
The one or more combination of polybutylene terephthalate (PBT).
A kind of 4. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the modification
Modifying agent used in poly terephthalic acid class raw material is bulking agent, the bulking agent is glycidyl acrylate, maleic anhydride,
One or more combinations of isocyanates.
A kind of 5. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the nanometer
Powder is silica, titanium dioxide, multi-walled carbon nanotube, nano aluminium oxide one or more combination, and the nano-powder exists
Hydroxylating pretreatment is carried out before being modified with silane coupling agent first.
A kind of 6. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the dispersion
Agent is polyvinylpyrrolidone, tetramethylammonium hydroxide, cetyl trimethylammonium bromide, neopelex or three second
A kind of several combinations of hydramine.
A kind of 7. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the antibacterial
Agent is oleoresin modified sodium alginate.
A kind of 8. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the modification
The melt index of poly terephthalic acid class raw material is 3-6g/10min.
A kind of 9. preparation method of antibacterial hydrophilic tunica fibrosa according to claim 1, which is characterized in that the amino
One or more of the sour modification of chitosan for lysine modified chitosan or arginine modification of chitosan.
10. antibacterial hydrophilic tunica fibrosa made from claim 1-9 any one of them preparation methods.
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