CN106009051A - Nanometer propolis-gamma-polyglutamic acid grafted pineapple leaf fiber packaging film and preparation method for same - Google Patents
Nanometer propolis-gamma-polyglutamic acid grafted pineapple leaf fiber packaging film and preparation method for same Download PDFInfo
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- CN106009051A CN106009051A CN201610516160.0A CN201610516160A CN106009051A CN 106009051 A CN106009051 A CN 106009051A CN 201610516160 A CN201610516160 A CN 201610516160A CN 106009051 A CN106009051 A CN 106009051A
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- polyglutamic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Jellies, Jams, And Syrups (AREA)
- General Preparation And Processing Of Foods (AREA)
Abstract
The invention discloses a nanometer propolis-gamma-polyglutamic acid grafted pineapple leaf fiber packaging film, which is prepared from the following components in parts by weight: 110 to 112 parts of pineapple leaf fibers, 6 to 7 parts of cellobiohydrolase, 4.3 to 4.5 parts of nanometer attapulgite, 4.8 to 5 parts of citric acid, 505 to 2 parts of gamma-polyglutamic acid, 6.5 to 7 parts of zinc dioxide nanoparticles, 8 to 9 parts of nanometer propolis, 5 to 6 parts of acetylated konjac glucomannan, 3.5 to 4 parts of hydroxymethyl cellulose, 2.5 to 3 parts of xylitol, 3 to 4 parts of sucrose ester, a proper amount of de-ionized water and a proper amount of glycerin. The packaging film is prepared by grafting pineapple leaf cellulose with the nanometer propolis and the modified gamma-polyglutamic acid, and the high film-forming performance of the modified gamma-polyglutamic acid coacts with the nanometer pineapple leaf fibers, so that the film is stable in structure and fine in texture; the nanometer propolis is adopted as one of main components of a film material, so that the preservation, anti-oxidation and nutritional performance of the film is improved, and the uniformity and the stability of the film material are improved.
Description
Technical field
The present invention relates to arghan packaging film technical field, particularly relate to a kind of nanometer propolis-gamma-polyglutamic acid-and connect
Branch arghan packaging film and preparation method thereof.
Background technology
With cellulose as raw material, the different macromolecule member material of processability is at necks such as medical science, biology and food medicine
Territory plays an important role, and has become as the focus of current research.China often produces substantial amounts of Fructus Ananadis comosi per year, and arghan has
The health-care effecies such as antibacterial, smelly eliminating, utilize arghan to prepare macromolecule member material and have huge development prospect.Pineapple leaves is fine
The fiber macromolecular alignment of dimension crystallization song is neat, regular, and the polyhydroxy structure of fiber molecule and strong hydrogen bonding effect make it clean
Cleanliness and the degree of orientation are higher, and chemical reactivity is low, thus cause its application to be restricted." the agriculture in south such as Wei Xiaoyi, Yang Qin
Journal ", 2016,47(1): 101-106 " arghan element film preparation process optimization " utilizes emulsifying cut mode to make pineapple leaves
Cellulose dissolution improves the chemical reactivity of arghan in ionic liquid, it is achieved the preparation of cellulose membrane, specifically does
Method is: be ground into cotton shape with Universalpulverizer after first being dried by arghan element, and alkali processes and acid treatment realizes it respectively
Purification process, is then being placed in together with ionic liquid in mulser, is carrying out shear treatment, acquisition prepare the cellulose of film from
Sub-liquid homogeneous phase solution, is layered on homogeneous phase solution on the carrier scribbling politef afterwards, through casting solution (glycerol, second
Alcohol) etc. soak drying and forming-film；This process technique improves the chemical reaction activity of arghan element, improves the equal of coating solution
Phase, but operate and employ substantial amounts of acidizer and alkali inorganic agent, adds somewhat to pollute, add Fructus Ananadis comosi
Leaf fibre element film preparation cost, the cellulose membrane function singleness simultaneously prepared.Nano-cellulose have high-crystallinity, high intensity,
The excellent properties such as high-specific surface area, environmental friendliness and low cost, also exist substantial amounts of-OH in its molecular structure, with other skies
So macromole is easily formed intermolecular and intramolecular hydrogen bond when being blended, and when being used for making membrane material, can make the formation of intermingling material
Membrane structure more stable.Gamma-polyglutamic acid-(γ-PGA) is the homopolymer of glutamic acid, is a kind of water soluble polymer, by D-
Glutamic acid or Pidolidone form, by alpha-amido and γ-carboxyl, the anionic polymer that γ-amido link is combined into, and have
The feature features such as good biocompatibility, good water solubility, degradable, edible, film property, as the life of a kind of new green environment protection
Thing material receives much concern, but readily soluble because meeting water, and certain degree limits its application.Micro-nano bubble refers to that diameter is between micron
Bubble (bubble of a diameter of 10-50um in water body) and nano bubble (a diameter of bubble less than 200nm in water body) it
Between bubble, have big specific surface area, can in water body the time of staying long, and micro-nano bubble is when shrinking, it is possible to
Producing substantial amounts of hydroxyl radical free radical, these substantial amounts of hydroxyl radical free radicals can attract the hydrogen in arghan element to a certain extent
Key, plays equivalent acidifying alkalization and destroys the effect that hydrogen bond is identical, the nanorize promoting arghan is improved its chemical reaction
Activity has certain facilitation.
The fibrous membrane that arghan based on modified gamma-polyglutamic acid-and high chemical reactivity combines is to improving Fructus Ananadis comosi
Comprehensive utilization and the abundant packaging film kind of leaf are significant.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that a kind of nanometer propolis-gamma-polyglutamic acid-grafting
Arghan packaging film and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of nanometer propolis-gamma-polyglutamic acid-grafting arghan packaging film, including following parts by weight of component: pineapple leaves is fine
Tie up 110-112, exocellulase 6-7, nano-attapulgite 4.3-4.5, citric acid 4.8-5, gamma-polyglutamic acid-505-2, receive
Rice zinc oxide particle 6.5-7, nanometer propolis 8-9, acetylation Konjac glucomannan 5-6, hydroxymethyl cellulose 3.5-4, xylitol 2.5-
3, sucrose ester 3-4, appropriate deionized water, appropriate water, appropriate glycerol.
A kind of nanometer propolis-gamma-polyglutamic acid-grafting arghan packaging film preparation method, comprises the following steps:
(1), will arghan dry after become cotton shape by pulverization process 30min in Universalpulverizer, afterwards with citric acid with
And the water mixing and stirring of gross weight 2-3 times to obtain slurry standby；By nano-attapulgite, exocellulase and gross weight
The water mixing and stirring of 1-2 times, be spray-dried modified, high temperature resistant exocellulase is standby；Slurry is heated to 80 DEG C,
And it is continuously added into modified, high temperature resistant exocellulase mix and blend enzymolysis 40min, after 100 DEG C of enzyme denaturing, use funnel sucking filtration to dry
Dry, obtain modified arghan element standby；
(2), the deionized water of nanometer titanium dioxide zinc particles, acetylation Konjac glucomannan and gross weight 2-3 times is mixed, add at 40 DEG C
After thermal agitation uniformly, adding gamma-polyglutamic acid-and continue heated and stirred 1h at 80 DEG C, the least fire literary composition boils 1-1.2h and obtains nothing
The nanometer particle-modified hydrophobic gamma-polyglutamic acid-of machine is standby；
(3), by hydrophobic gamma-polyglutamic acid-plain for modification arghan, inorganic nano particle modified, nanometer propolis, methylol fibre
Stir after the deionized water mixing of dimension element, xylitol, sucrose ester and gross weight 3-4 times, be then placed in the most ultrasonic
The mulser of ripple carries out ultrasonic assistant emulsifying shear treatment 40min and obtains homogeneous membrane solution for standby, wherein ultrasonic power
1000W, emulsifying shear rate 15000r/min；
(4), the deionized water coagulating bath of homogeneous membrane solution is solidified, take out after film water is washed again with the glycerol liquor of concentration 28%-30%
Solution soaks 2h at 40 DEG C and carries out plastics processing, afterwards dried 2h and get final product under 45 DEG C of constant temperature.
The invention have the advantage that
The present invention uses nanometer propolis, modified gamma-polyglutamic acid-graft modification arghan element to prepare packaging film, and modified γ-
The high film build synergic nano arghan of polyglutamic acid so that membrane structure is stable, exquisite quality；Nanometer propolis is as film
One of main component of material, on the one hand adds fresh-keeping antioxidation and the nutritional properties of film, on the other hand improves film material
The uniform and stable property of material；By the modification to gamma-polyglutamic acid-of the Nano zinc dioxide impact-resistant particulate inorganic nanoparticle, it is achieved that hydrophobic
Modified and special effect of nanometer titanium dioxide zinc particles strengthens, it is achieved that the gamma-polyglutamic acid-extensive application in packaging film.This
Invention, in preparation process, by means of the enzyme that nano-attapulgite is modified, decreases traditional fibre element soda acid purification process and causes
Pollution and expense cost, it is achieved that environmental protection produce, meanwhile, nano-attapulgite synergic nano arghan element work in coordination with
Enhance the barrier property of film, improve the toughness of film；In preparation process, ultrasonic assistant emulsifying shear treatment one step realizes
The further nanorize of arghan and coating solution homogeneous, the micro-nano bubble that intense ultrasonic wave effect produces is molten at film
Existence in liquid, promotes the nanorize of arghan, increases its dissolubility, improves the homogeneous degree of coating solution, for fibre
Dimension element the uniform and stable of membrane structure provides guarantee, and this physical treatment method decreases conventional homogeneous liquid preparation process intermediate ion
The use of liquid.
Detailed description of the invention
A kind of nanometer propolis γ polyglutamic acid grafting arghan packaging film, including following parts by weight of component: pineapple leaves
Fiber 110, exocellulase 6, nano-attapulgite 4.3, citric acid 4.8, γ polyglutamic acid 505, nanometer titanium dioxide zinc granule
Son 6.5, nanometer propolis 8, acetylation Konjac glucomannan 5, hydroxymethyl cellulose 3.5, xylitol 2.5, sucrose ester 3, appropriate deionization
Water, appropriate water, appropriate glycerol.
A kind of nanometer propolis γ polyglutamic acid grafting arghan packaging film preparation method, comprises the following steps:
(1), will arghan dry after become cotton shape by pulverization process 30min in Universalpulverizer, afterwards with citric acid with
And the water mixing and stirring of gross weight 2 times to obtain slurry standby；By nano-attapulgite, exocellulase and gross weight 1
Times water mixing and stirring, be spray-dried modified, high temperature resistant exocellulase is standby；Slurry is heated to 80 DEG C, and holds
Continuous addition modified, high temperature resistant exocellulase mix and blend enzymolysis 40min, after 100 DEG C of enzyme denaturing, uses funnel sucking filtration to dry,
Modified arghan element is standby；
(2), the deionized water of nanometer titanium dioxide zinc particles, acetylation Konjac glucomannan and gross weight 2 times is mixed, 40 DEG C of heating
After stirring, adding γ polyglutamic acid and continue heated and stirred 1h at 80 DEG C, the least fire literary composition boils 1h and obtains inorganic nano
Particle modified hydrophobic γ polyglutamic acid is standby；
(3), by hydrophobic γ polyglutamic acid plain for modification arghan, inorganic nano particle modified, nanometer propolis, hydroxylmethyl cellulose
Stir after the deionized water mixing of element, xylitol, sucrose ester and gross weight 3 times, be then placed in intense ultrasonic wave
Mulser carries out ultrasonic assistant emulsifying shear treatment 40min and obtains homogeneous membrane solution for standby, wherein ultrasonic power 1000W,
Emulsifying shear rate 15000r/min；
(4), the deionized water coagulating bath of homogeneous membrane solution is solidified, take out after film water is washed again with the glycerine water solution of concentration 28%%
Soak 2h at 40 DEG C and carry out plastics processing, afterwards dried 2h and get final product under 45 DEG C of constant temperature.
After tested, the maximum tensile strength of this packaging film is 18.5MPa, and now elongation at break is 23.2%；The minimum of film
OTR oxygen transmission rate is reached for 2.1 × 10-5cm3/(m2D Pa), the Fructus Vitis viniferae coccobacillus is had good antibacterial effect, for fresh
When spending fresh-keeping, fresh-keeping effect is up to 10d, and after soil buries 150d, its biological degradation rate reaches 96%, demonstrates excellent biological degradability.
Claims (2)
1. nanometer propolis-gamma-polyglutamic acid-grafting arghan packaging film, it is characterised in that include following weight portion
Component: arghan 110-112, exocellulase 6-7, nano-attapulgite 4.3-4.5, citric acid 4.8-5, γ-poly-
Glutamic acid 505-2, nanometer titanium dioxide zinc particles 6.5-7, nanometer propolis 8-9, acetylation Konjac glucomannan 5-6, hydroxymethyl cellulose
3.5-4, xylitol 2.5-3, sucrose ester 3-4, appropriate deionized water, appropriate water, appropriate glycerol.
2. a nanometer propolis-gamma-polyglutamic acid-grafting arghan packaging film preparation method, it is characterised in that include with
Lower step:
(1), will arghan dry after become cotton shape by pulverization process 30min in Universalpulverizer, afterwards with citric acid with
And the water mixing and stirring of gross weight 2-3 times to obtain slurry standby；By nano-attapulgite, exocellulase and gross weight
The water mixing and stirring of 1-2 times, be spray-dried modified, high temperature resistant exocellulase is standby；Slurry is heated to 80 DEG C,
And it is continuously added into modified, high temperature resistant exocellulase mix and blend enzymolysis 40min, after 100 DEG C of enzyme denaturing, use funnel sucking filtration to dry
Dry, obtain modified arghan element standby；
(2), the deionized water of nanometer titanium dioxide zinc particles, acetylation Konjac glucomannan and gross weight 2-3 times is mixed, add at 40 DEG C
After thermal agitation uniformly, adding gamma-polyglutamic acid-and continue heated and stirred 1h at 80 DEG C, the least fire literary composition boils 1-1.2h and obtains nothing
The nanometer particle-modified hydrophobic gamma-polyglutamic acid-of machine is standby；
(3), by hydrophobic gamma-polyglutamic acid-plain for modification arghan, inorganic nano particle modified, nanometer propolis, methylol fibre
Stir after the deionized water mixing of dimension element, xylitol, sucrose ester and gross weight 3-4 times, be then placed in the most ultrasonic
The mulser of ripple carries out ultrasonic assistant emulsifying shear treatment 40min and obtains homogeneous membrane solution for standby, wherein ultrasonic power
1000W, emulsifying shear rate 15000r/min；
(4), the deionized water coagulating bath of homogeneous membrane solution is solidified, take out after film water is washed again with the glycerol liquor of concentration 28%-30%
Solution soaks 2h at 40 DEG C and carries out plastics processing, afterwards dried 2h and get final product under 45 DEG C of constant temperature.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610516160.0A CN106009051A (en) | 2016-07-04 | 2016-07-04 | Nanometer propolis-gamma-polyglutamic acid grafted pineapple leaf fiber packaging film and preparation method for same |
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| CN201610516160.0A CN106009051A (en) | 2016-07-04 | 2016-07-04 | Nanometer propolis-gamma-polyglutamic acid grafted pineapple leaf fiber packaging film and preparation method for same |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219348A (en) * | 2007-09-12 | 2008-07-16 | 昆山华科生物高分子材料研究所有限公司 | Gama-polyglutamic acid compound film producing method |
| CN103102419A (en) * | 2013-01-25 | 2013-05-15 | 浙江理工大学 | Method for preparing nano microcrystalline cellulose by hydrolyzing phyllostachys edulis fiber with cellulase |
| CN103254469A (en) * | 2013-06-08 | 2013-08-21 | 中国国旅贸易有限责任公司 | Edible film material containing nanocellulose, edible film and preparation method of edible film |
-
2016
- 2016-07-04 CN CN201610516160.0A patent/CN106009051A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219348A (en) * | 2007-09-12 | 2008-07-16 | 昆山华科生物高分子材料研究所有限公司 | Gama-polyglutamic acid compound film producing method |
| CN103102419A (en) * | 2013-01-25 | 2013-05-15 | 浙江理工大学 | Method for preparing nano microcrystalline cellulose by hydrolyzing phyllostachys edulis fiber with cellulase |
| CN103254469A (en) * | 2013-06-08 | 2013-08-21 | 中国国旅贸易有限责任公司 | Edible film material containing nanocellulose, edible film and preparation method of edible film |
Non-Patent Citations (3)
| Title |
|---|
| 唐春红主编: "《天然防腐剂与抗氧化剂》", 31 May 2010, 中国轻工业出版社 * |
| 张莉等: ""纤维素纳米改性技术及其性能研究"", 《中国印刷与包装研究》 * |
| 魏晓奕等: ""菠萝叶纤维素膜制备工艺优化"", 《南方农业学报》 * |
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Application publication date: 20161012 |