CN108410144A - A kind of fruits and vegetables anti-bacterial refreshing nano fibrous membrane and preparation method thereof - Google Patents
A kind of fruits and vegetables anti-bacterial refreshing nano fibrous membrane and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of fruits and vegetables anti-bacterial refreshing nano fibrous membranes 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 anti-bacterial refreshing nano fibrous membrane.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.By showing good fresh-keeping bacteriostatic effect compared with the control group, therefore, nano fibrous membrane produced by the present invention is with a wide range of applications in field of food preservation.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of fruits and vegetables anti-bacterial refreshing nano fibrous membrane and its system
Preparation Method.
Background technology
Moisture in fruit is high, and especially for the fruit of mechanical damage, microorganism is easy to grow above, draws
Rotting for fruit is played, fruit freshness preserving is to maintain the fresh major issue of fruit.Preservative film is that a kind of holding food is fresh
Film, preservative film mainly prevent food from occurring in transporting procedures by preventing the migration of dust, moisture, gas and solute etc.
The variation of flavor, texture etc., and then ensure the quality of food, extend Food Shelf-life.
For the fruit-vegetable food of high moisture content, the sucting wet air permeability of preservative film be the key that the fresh-keeping film quality of evaluation because
Element.In recent years, functional form preservative film rapidly develops, wherein the research using micro/nano fibrous membrane material as preservative film increasingly increases,
Nano-fiber material can effectively barrier filters out dust and is harmful to micro- life under the premise of ensureing that proper amount of gas and moisture penetrate
Object shows good development prospect.However existing nano fibrous membrane mechanical performance is poor, and antibiotic property also needs into one
Step improves.
Invention content
Above of the existing technology in order to solve the problems, such as, the purpose of the present invention is to provide a kind of fruits and vegetables anti-bacterial refreshings to receive
Rice tunica fibrosa and preparation method thereof, to improve the anti-bacterial refreshing performance of nano fibrous membrane.
To achieve the goals above, the present invention provides following technical scheme：
A kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
To the m-cresol solution that 5-10 times of parts by weight are added in 80-100 parts of poly terephthalic acid class raw material, 10-25 is then added
The modifying agent of part, 45-60min is stirred to react at a temperature of 30-45 DEG C, and modified poly terephthalic acid class raw material is made；
（2）The preparation of fiber film master batch
By 25-50 parts of steps（1）It is 1 that volume ratio, which is added, in modified poly terephthalic acid class raw material obtained: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 10-18%；
The aqueous solution of 10-20 times of parts by weight is added in 30-50 parts of the nano-powder coated to carboxymethyl cellulose, is sufficiently stirred simultaneously
It is heated to 70-80 DEG C, initiator is added under the action of nitrogen protection after stirring 20-30min, continues to be stirred to react 8-15min
After add modified poly terephthalic acid class material solution, the reaction was continued 2-4h obtains mixture A；
By mixture A, 10-18 parts of Poly(D,L-lactide-co-glycolide, 4-8 parts of polyvinyl alcohol, 3-6 parts of gliadin, amino
Sour modification of chitosan 4-8 parts, 5-12 parts of polyvinylpyrrolidone, 4-7 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, polyhexamethylene
3-7 parts of guanidine phosphate, 4-8 parts of tea polyphenols are sufficiently mixed in high mixer, then through double screw extruder fusion plastification, squeeze
Go out, filter membrane；
（3）The preparation of modified film material
By 10-16 parts of the high density polyethylene (HDPE) and step of maleic anhydride grafting（2）The fiber film master batch of preparation is high in high mixer
Speed is uniformly mixed, spare；
（4）The preparation of anti-bacterial refreshing nano fibrous membrane
By step（3）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 95-120 DEG C, and the linear velocity of first roller is 12-28m/min,
Draw ratio is 1.0-4.0；The split pin density of the fine porcupine roller used of the mechanical membrane is 60-100 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 60-
85°。
Further, the heat setting temperature is 95-125 DEG C.
Preferably, the modified poly terephthalic acid class raw material includes modified polyethylene terephthalate, is modified and gathers
The one or more combination of propylene glycol ester terephthalate or modified polybutylene terephthalate (PBT).
Preferably, the modifying agent used in the modified poly terephthalic acid class raw material is maleic anhydride, polyethylene glycol, gathers
The one or more combination of propylene glycol.
Preferably, the nano-powder is nano zine oxide, nano-titanium dioxide, nanometer basic zirconium phosphate load silver or nanometer
CaCO3One or more combination.
Preferably, the initiator is potassium peroxydisulfate.
Preferably, the melt index of the modified poly terephthalic acid class raw material is 5-8g/10min.
Preferably, the amino-acid modified chitin is one kind of lysine modified chitosan or arginine modification of chitosan
Or it is several.
Fruits and vegetables anti-bacterial refreshing nano fibrous membrane made from preparation method of the present invention.
Advantageous effect：The present invention provides a kind of fruits and vegetables anti-bacterial refreshing nano fibrous membrane and preparation method thereof, systems of the present invention
The nano fibrous membrane obtained contains modified poly terephthalic acid class raw material, and the product being made from it has good intensity, impact resistance, resists and answer
The advantages such as power is strong, are modified poly terephthalic acid class raw material by using modifying agent the water-wet behavior for improving raw material, improve
The problem of poly terephthalic acid class raw material hydrophily difference；The nano-powder of carboxymethyl cellulose cladding makes the dispersion of nano-powder
Property improve, while carboxymethyl cellulose is grafted to modified poly terephthalic acid class raw material surface, improves the moisture absorption of nano fibrous membrane
Property, the addition of nano-powder improves the antibiotic property and mechanical strength of nano fibrous membrane；Poly(D,L-lactide-co-glycolide is good
Biocompatibility, absorbability, film forming and biological degradability to improve material fiber film comprehensive performance have it is important
Effect；The addition of polyvinyl alcohol and gliadin plays an important role the film forming of tunica fibrosa；Polyvinylpyrrolidone,
Sodium sulfate of polyethenoxy ether of fatty alcohol plays an important role the stability for improving system；Polyhexamethylene guanide phosphate and tea
The addition of polyphenol improves the antibiotic property of nano fibrous membrane.
It is obtained by performance test, the fracture strength of nano fibrous membrane prepared by the present invention is not less than 17.6g/d, and fracture is stretched
Long rate is not less than 62.3%, and film surface contact angle is less than 75 °, while being reached to the bacteriostasis rate of Escherichia coli and staphylococcus aureus
To 95% or more, weight-loss ratio is not higher than 6.8%, and Decayed rate is not higher than 4.4%, therefore nano fibrous membrane mechanics produced by the present invention is strong
Degree is higher, and hydrophilicity is good, has good inhibition to Escherichia coli and staphylococcus aureus, compared with the control group
It shows good fresh-keeping bacteriostatic effect, is with a wide range of applications in field of food preservation.
Specific implementation mode
The invention will now be further described with reference to specific embodiments, but examples are merely exemplary, not to this hair
Bright range constitutes 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.
Embodiment 1
A kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
It is 1 to mass ratio:5 times of weight are added in 1 polyethylene terephthalate, 80 parts of polypropylene terephthalate
Then the m-cresol solution of part is added 10 parts of maleic anhydride, 45min is stirred to react at a temperature of 30 DEG C, be made modified poly-
The melt index of terephthaldehyde's acids raw material, the modified poly terephthalic acid class raw material is 5g/10min；
（2）The preparation of fiber film master batch
By 25 parts of steps（1）It is 1 that volume ratio, which is added, in modified poly terephthalic acid class raw material obtained: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
The solution that number is 10%；
The aqueous solution of 10 times of parts by weight is added in 30 parts of the nano-powder coated to carboxymethyl cellulose, is sufficiently stirred and is heated to
70 DEG C, potassium peroxydisulfate initiator is added under the action of nitrogen protection after stirring 20min, continues to add after being stirred to react 8min
Modified poly terephthalic acid class material solution, the reaction was continued 2h obtain mixture A, the nano-powder is mass ratio 1:1 receives
Rice zinc oxide and nano-titanium dioxide；
By mixture A, 10 parts of Poly(D,L-lactide-co-glycolide, 4 parts of polyvinyl alcohol, 3 parts of gliadin, lysine modified
4 parts of chitosan, 5 parts of polyvinylpyrrolidone, 4 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, 3 parts of polyhexamethylene guanide phosphate,
4 parts of tea polyphenols are sufficiently mixed in high mixer, then through double screw extruder fusion plastification, extrusion, filter membrane；
（3）The preparation of modified film material
By 10 parts of the high density polyethylene (HDPE) and step of maleic anhydride grafting（2）The fiber film master batch of preparation is mixed in high mixer high speed
It closes uniformly, it is spare；
（4）The preparation of anti-bacterial refreshing nano fibrous membrane
By step（3）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 95 DEG C, and the linear velocity of first roller is 12m/min, is stretched again
Number is 1.0；The split pin density of the fine porcupine roller used of the mechanical membrane 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 95 DEG C.
Embodiment 2
A kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane, 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, poly terephthalic acid fourth
The m-cresol solution of 8 times of parts by weight is added in 90 parts of diol ester, 18 parts of mass ratio 1 is then added:1:1 maleic anhydride gathers
The modifying agent that ethylene glycol 2000, polypropylene glycol 1000 form, 52min is stirred to react at a temperature of 38 DEG C, is made modified poly- pair
The melt index of Phthalic acids raw material, the modified poly terephthalic acid class raw material is 7g/10min；
（2）The preparation of fiber film master batch
By 32 parts of steps（1）It is 1 that volume ratio, which is added, in modified poly terephthalic acid class raw material obtained:4 dichloromethane and trifluoro
In acetic acid mixed solution, 1.5h is dissolved under the action of magnetic agitation, modified poly terephthalic acid class raw material is configured to quality
The solution that score is 14%；
The aqueous solution of 15 times of parts by weight is added in 40 parts of the nano-powder coated to carboxymethyl cellulose, is sufficiently stirred and is heated to
75 DEG C, potassium peroxydisulfate initiator is added under the action of nitrogen protection after stirring 25min, continue to be stirred to react after 13min again plus
Enter modified poly terephthalic acid class material solution, the reaction was continued 3h obtains mixture A, and the nano-powder is mass ratio 1:1:
1:1 nano zine oxide, nano-titanium dioxide, nanometer basic zirconium phosphate load silver and Nano-meter CaCO33；
By mixture A, 14 parts of Poly(D,L-lactide-co-glycolide, 6 parts of polyvinyl alcohol, 5 parts of gliadin, mass ratio 1:1
Lysine modified chitosan and 6 parts of arginine modification of chitosan, 9 parts of polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether sulfuric acid
6 parts of sodium, 5 parts of polyhexamethylene guanide phosphate, 6 parts of tea polyphenols are sufficiently mixed in high mixer, then through double screw extruder
Fusion plastification, extrusion, filter membrane；
（3）The preparation of modified film material
By 13 parts of the high density polyethylene (HDPE) and step of maleic anhydride grafting（2）The fiber film master batch of preparation is mixed in high mixer high speed
It closes uniformly, it is spare；
（4）The preparation of anti-bacterial refreshing nano fibrous membrane
By step（3）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 107 DEG C, and the linear velocity of first roller is 20m/min, is stretched again
Number is 2.5；The split pin density of the fine porcupine roller used of the mechanical membrane is 80 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 72 °.
Further, the heat setting temperature is 110 DEG C.
Embodiment 3
A kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
It is 1 to mass ratio:6 times of weights are added in 1 85 parts of polyethylene terephthalate and polybutylene terephthalate (PBT)
The m-cresol solution of part is measured, 12 parts of cetomacrogol 1000 is then added, 50min is stirred to react at a temperature of 35 DEG C, is made
The melt index of modified poly terephthalic acid class raw material, the modified poly terephthalic acid class raw material is 6g/10min；
（2）The preparation of fiber film master batch
By 30 parts of steps（1）It is 1 that volume ratio, which is added, in modified poly terephthalic acid class raw material obtained: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
The solution that score is 12%；
The aqueous solution of 15 times of parts by weight is added in 35 parts of the nano-powder coated to carboxymethyl cellulose, is sufficiently stirred and is heated to
72 DEG C, potassium peroxydisulfate initiator is added under the action of nitrogen protection after stirring 22min, continue to be stirred to react after 10min again plus
Enter modified poly terephthalic acid class material solution, the reaction was continued 2.5h obtains mixture A, and the nano-powder is mass ratio 1:1
Nano zine oxide and nanometer basic zirconium phosphate carry silver；
By mixture A, 12 parts of Poly(D,L-lactide-co-glycolide, 5 parts of polyvinyl alcohol, 4 parts of gliadin, mass ratio 1:1
Lysine modified chitosan or 5 parts of arginine modification of chitosan, 7 parts of polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether sulfuric acid
5 parts of sodium, 4 parts of polyhexamethylene guanide phosphate, 5 parts of tea polyphenols are sufficiently mixed in high mixer, then through double screw extruder
Fusion plastification, extrusion, filter membrane；
（3）The preparation of modified film material
By 12 parts of the high density polyethylene (HDPE) and step of maleic anhydride grafting（2）The fiber film master batch of preparation is mixed in high mixer high speed
It closes uniformly, it is spare；
（4）The preparation of anti-bacterial refreshing nano fibrous membrane
By step（3）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 15m/min, is stretched again
Number is 2.0；The split pin density of the fine porcupine roller used of the mechanical membrane is 70 needles/cm.
Further, the split angle of fine all needles using porcupine roller and film traffic direction of the mechanical membrane is 75 °.
Further, the heat setting temperature is 105 DEG C.
Embodiment 4
A kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane, includes the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
To the m-cresol solution that 10 times of parts by weight are added in 100 parts of polyethylene terephthalate, 25 parts of matter is then added
Amount is stirred to react 60min than polypropylene glycol 4000 at a temperature of 45 DEG C, and modified poly terephthalic acid class raw material is made, described
The melt index of modified poly terephthalic acid class raw material is 8g/10min；
（2）The preparation of fiber film master batch
By 50 parts of steps（1）It is 1 that volume ratio, which is added, in modified poly terephthalic acid class raw material obtained: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
The solution that number is 18%；
The aqueous solution of 20 times of parts by weight is added in 50 parts of the nano-powder coated to carboxymethyl cellulose, is sufficiently stirred and is heated to
80 DEG C, potassium peroxydisulfate initiator is added under the action of nitrogen protection after stirring 30min, continue to be stirred to react after 15min again plus
Enter modified poly terephthalic acid class material solution, the reaction was continued 4h obtains mixture A, and the nano-powder is mass ratio 1:1:1
Nano-titanium dioxide, nanometer basic zirconium phosphate carry silver and Nano-meter CaCO33；
Mixture A, 18 parts of Poly(D,L-lactide-co-glycolide, 8 parts of polyvinyl alcohol, 6 parts of gliadin, arginine are modified
8 parts of chitosan, 12 parts of polyvinylpyrrolidone, 7 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, 7 parts of polyhexamethylene guanide phosphate,
8 parts of tea polyphenols are sufficiently mixed in high mixer, then through double screw extruder fusion plastification, extrusion, filter membrane；
（3）The preparation of modified film material
By 16 parts of the high density polyethylene (HDPE) and step of maleic anhydride grafting（2）The fiber film master batch of preparation is mixed in high mixer high speed
It closes uniformly, it is spare；
（4）The preparation of anti-bacterial refreshing nano fibrous membrane
By step（3）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 28m/min, is stretched again
Number is 4.0；The split pin density of the fine porcupine roller used of the mechanical membrane 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
Comparative example 1 the difference from example 2 is that poly terephthalic acid class raw material without modification.
Comparative example 2
Comparative example 2 is the difference from example 2 is that nano-powder is coated without carboxymethyl cellulose.
Embodiment 1-4 and comparative example 1-2 the fruits and vegetables anti-bacterial refreshing nano fibrous membrane prepared are carried out to the test of following performance,
Test result is as 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 of ps hollow fiber uf membrane is studied, engineering plastics application, and 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.
Embodiment 1-4 and comparative example the 1-2 nano fibrous membrane prepared coat the strawberry of fresh picking, while with
The strawberry of uncoated nano fibrous membrane as a control group, measures the mistake for being placed in the nano fibrous membrane strawberry after 30 days of cladding at room temperature
Rate and Decayed rate again.
It is obtained by table 1, the fracture strength of nano fibrous membrane prepared by the present invention is not less than 17.6g/d, elongation at break
Not less than 62.3%, film surface contact angle is less than 75 °, while reaching 95% to the bacteriostasis rate of Escherichia coli and staphylococcus aureus
More than, weight-loss ratio be not higher than 6.8%, Decayed rate be not higher than 4.4%, therefore nano fibrous membrane mechanical strength produced by the present invention compared with
Height, hydrophilicity is good, has good inhibition to Escherichia coli and staphylococcus aureus, shows compared with the control group
Go out good fresh-keeping bacteriostatic effect.
Table 1
Claims (8)
1. a kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane, which is characterized in that include the following steps：
（1）The preparation of modified poly terephthalic acid class raw material
To the m-cresol solution that 5-10 times of parts by weight are added in 80-100 parts of poly terephthalic acid class raw material, 10-25 is then added
The modifying agent of part, 45-60min is stirred to react at a temperature of 30-45 DEG C, and modified poly terephthalic acid class raw material is made；
（2）The preparation of fiber film master batch
By 25-50 parts of steps（1）It is 1 that volume ratio, which is added, in modified poly terephthalic acid class raw material obtained: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 10-18%；
The aqueous solution of 10-20 times of parts by weight is added in 30-50 parts of the nano-powder coated to carboxymethyl cellulose, is sufficiently stirred simultaneously
It is heated to 70-80 DEG C, initiator is added under the action of nitrogen protection after stirring 20-30min, continues to be stirred to react 8-15min
After add modified poly terephthalic acid class material solution, the reaction was continued 2-4h obtains mixture A；
By mixture A, 10-18 parts of Poly(D,L-lactide-co-glycolide, 4-8 parts of polyvinyl alcohol, 3-6 parts of gliadin, amino
Sour modification of chitosan 4-8 parts, 5-12 parts of polyvinylpyrrolidone, 4-7 parts of sodium sulfate of polyethenoxy ether of fatty alcohol, polyhexamethylene
3-7 parts of guanidine phosphate, 4-8 parts of tea polyphenols are sufficiently mixed in high mixer, then through double screw extruder fusion plastification, squeeze
Go out, filter membrane；
（3）The preparation of modified film material
By 10-16 parts of the high density polyethylene (HDPE) and step of maleic anhydride grafting（2）The fiber film master batch of preparation is high in high mixer
Speed is uniformly mixed, spare；
（4）The preparation of anti-bacterial refreshing nano fibrous membrane
By step（3）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
Anti-bacterial refreshing nano fibrous membrane is made in heating, second of multiple roll hot-stretch, mechanical membrane fine, thermal finalization of splitting.
2. a kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane according to claim 1, which is characterized in that described
Modified poly terephthalic acid class raw material include modified polyethylene terephthalate, modified polypropylene terephthalate or
The one or more combination of modified polybutylene terephthalate (PBT).
3. a kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane according to claim 1, which is characterized in that described
Modifying agent used in modified poly terephthalic acid class raw material is the one or more of maleic anhydride, polyethylene glycol, polypropylene glycol
Combination.
4. a kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane according to claim 1, which is characterized in that described
Nano-powder is nano zine oxide, nano-titanium dioxide, nanometer basic zirconium phosphate load silver or Nano-meter CaCO33One or more combination.
5. a kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane according to claim 1, which is characterized in that described
Initiator is potassium peroxydisulfate.
6. a kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane according to claim 1, which is characterized in that described
The melt index of modified poly terephthalic acid class raw material is 5-8g/10min.
7. a kind of preparation method of fruits and vegetables anti-bacterial refreshing nano fibrous membrane according to claim 1, which is characterized in that described
Amino-acid modified chitin is the one or more of lysine modified chitosan or arginine modification of chitosan.
8. fruits and vegetables anti-bacterial refreshing nano fibrous membrane made from claim 1-7 any one of them preparation methods.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867824A (en) * | 2019-01-29 | 2019-06-11 | 华中科技大学 | A kind of method of low melting point chitosan microball plasticising biomass composite |
| CN111394890A (en) * | 2020-03-02 | 2020-07-10 | 浙江农林大学 | Preparation method and application of alcohol soluble protein slow-release antioxidant membrane |
| CN111567717A (en) * | 2020-05-27 | 2020-08-25 | 河南大学 | Chinese yam mucilage-nano zinc oxide solution and preparation method and application thereof |
| CN113897786A (en) * | 2020-10-09 | 2022-01-07 | 单中妹 | Anti-static wear-resistant non-woven fabric |
| CN114409936A (en) * | 2021-12-29 | 2022-04-29 | 太原理工大学 | Preparation method of composite film added with arginine chitosan and zinc oxide nanoparticles |
| CN116875004A (en) * | 2023-08-23 | 2023-10-13 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008145828A1 (en) * | 2007-06-01 | 2008-12-04 | Oy Keskuslaboratorio - Centrallaboratorium Ab | Novel dispersions and method for the production thereof |
| CN101469144A (en) * | 2007-12-29 | 2009-07-01 | 比亚迪股份有限公司 | Composite nano titanium dioxide and preparation thereof |
| CN102408687A (en) * | 2011-10-24 | 2012-04-11 | 广州市信联智通实业有限公司 | PP-PET-nano-silver antimicrobial packaging material and preparation method thereof |
| CN104497222A (en) * | 2014-12-18 | 2015-04-08 | 桐乡中欣化纤有限公司 | Hygroscopic deep-dyeable low-melting point polyester chip and preparation method thereof |
-
2018
- 2018-02-28 CN CN201810165683.4A patent/CN108410144A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008145828A1 (en) * | 2007-06-01 | 2008-12-04 | Oy Keskuslaboratorio - Centrallaboratorium Ab | Novel dispersions and method for the production thereof |
| CN101469144A (en) * | 2007-12-29 | 2009-07-01 | 比亚迪股份有限公司 | Composite nano titanium dioxide and preparation thereof |
| CN102408687A (en) * | 2011-10-24 | 2012-04-11 | 广州市信联智通实业有限公司 | PP-PET-nano-silver antimicrobial packaging material and preparation method thereof |
| CN104497222A (en) * | 2014-12-18 | 2015-04-08 | 桐乡中欣化纤有限公司 | Hygroscopic deep-dyeable low-melting point polyester chip and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867824A (en) * | 2019-01-29 | 2019-06-11 | 华中科技大学 | A kind of method of low melting point chitosan microball plasticising biomass composite |
| CN109867824B (en) * | 2019-01-29 | 2020-10-02 | 华中科技大学 | Method for plasticizing biomass composite material by using low-melting-point chitosan microspheres |
| CN111394890A (en) * | 2020-03-02 | 2020-07-10 | 浙江农林大学 | Preparation method and application of alcohol soluble protein slow-release antioxidant membrane |
| CN111567717A (en) * | 2020-05-27 | 2020-08-25 | 河南大学 | Chinese yam mucilage-nano zinc oxide solution and preparation method and application thereof |
| CN113897786A (en) * | 2020-10-09 | 2022-01-07 | 单中妹 | Anti-static wear-resistant non-woven fabric |
| CN114409936A (en) * | 2021-12-29 | 2022-04-29 | 太原理工大学 | Preparation method of composite film added with arginine chitosan and zinc oxide nanoparticles |
| CN116875004A (en) * | 2023-08-23 | 2023-10-13 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
| CN116875004B (en) * | 2023-08-23 | 2024-03-26 | 青岛周氏塑料包装有限公司 | PBAT master batch, preparation method thereof and PBAT preservative film |
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