CN103073738A - Polyvinyl alcohol/xylan biodegradable composite membrane and preparation method and application thereof - Google Patents
Polyvinyl alcohol/xylan biodegradable composite membrane and preparation method and application thereof Download PDFInfo
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- CN103073738A CN103073738A CN201310023993XA CN201310023993A CN103073738A CN 103073738 A CN103073738 A CN 103073738A CN 201310023993X A CN201310023993X A CN 201310023993XA CN 201310023993 A CN201310023993 A CN 201310023993A CN 103073738 A CN103073738 A CN 103073738A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention discloses a polyvinyl alcohol/xylan biodegradable composite membrane and a preparation method and an application thereof. The preparation method comprises the following steps: adding polyvinyl alcohol into water, dissolving for 1-4 hours at a temperature of 80-100 DEG C, adding and uniformly mixing xylan and citric acid and controlling the mass ratio of the xylan to the citric acid to be 1:1-4:1; and agitating obtained mixed solution for 2-6 hours at a temperature of 50-80 DEG C, standing, casting on a horizontally-arranged clean polyfluortetraethylene plate and vacuum-drying to obtain the polyvinyl alcohol/xylan biodegradable composite membrane. The polyvinyl alcohol/xylan biodegradable composite membrane and the preparation method and the application thereof have the benefits that the composite membrane has a tensile strength of 7.58-37.42 MPa and an elongation at break of 13.67-249.50 percent; the process is simple, the reaction conditions are easy to control, no environmental pollution is generated in the production process, and the industrialization is easy; and the composite membrane is innocuous, has good biodegradability and higher strength and can be applied to food packaging materials.
Description
Technical field
The present invention relates to the preparation method of a kind of polyvinyl alcohol for packaging material for food/xylan biodegradable composite membrane, belong to agricultural waste utilization and food product pack field.
Background technology
Along with the needs of exhaustion and the Sustainable development of petrochemical industry resource, the Recent study Biodegradable material becomes hot issue.Polyvinyl alcohol is as biodegradable synthetic superpolymer, and the film of its preparation has good oxygen barrier, oil resistance performance, has water-solublely under certain condition, is widely used in packaging material for food.
It is good to obtain consistency from agricultural-forestry biomass, and the research of degradable polymeric membrane has caused people's interest.The xylan hemicellulose becomes the main raw material source of making film as the major portion of hemicellulose.But exist in a large amount of molecules in the xylan and intermolecular hydrogen bonding, film forming properties is poor, water absorbability by force, easily crisp.Therefore add the small molecules softening agent, or introduce other high molecular component and replace the hydrogen bond of self, improve film forming properties.But the small molecules such as glycerine have been the effect of plasticising as softening agent, when the preparation composite membrane, can have free glycerine during too high levels, cause easily and leak.
Prior art has bibliographical information (Wang SY, Li HL, RenJL, Liu CF, PengF, Sun RC.Preparation of xylan citrate-A potential adsorbent for industrial wastewater treatment.Carbohydrate polymers, 2013,92 (2), 1960-1965): with Citrin ester innovation wood glycan, the citric acid xylan ester that generates, but this product is water insoluble, therefore is difficult to the above-mentioned product that makes of recycling and produces the degradable membrane compound with polyvinyl alcohol.
Summary of the invention
The object of the present invention is to provide a kind of small molecules softening agent such as glycerine leak contaminated food products and biodegradable composite membrane of polyvinyl alcohol/xylan of snappiness and intensity excellent combination property avoided.
Another object of the present invention is to provide the preparation method of above-mentioned film, the method is a kind of cleaning, simple, free of contamination friendly process, is fit to scale operation.
The present invention also has a purpose to be to provide the application of the biodegradable composite membrane of above-mentioned polyvinyl alcohol/xylan as packaging material for food.
Citric acid is generally as traditional food, drink additive, also contains hydroxyl owing to it and carboxyl functional group has crosslinked action, and it is used as linking agent in the Polymer materialspreparation process.The present invention utilizes the citric acid small molecules with polyvinyl alcohol and xylan macromolecules cross-linking, between citric acid self existence and two macromole, plays bridge, so in the composite membrane of the present invention's preparation, the small molecules citric acid is difficult for leaking out.Simultaneously, the present invention is for fear of the generation of the citric acid xylan ester of insoluble in water, and directly with citric acid as linking agent, add in polyvinyl alcohol and the xylan solution, adopting the synthetic macromolecule polyvinyl alcohol is template, obtain polyvinyl alcohol and the good Biodegradable film of xylan consistency by solution blended process, utilize the macromolecular interaction of citric acid small molecules and polyvinyl alcohol and xylan, citric acid plays bridge between macromole, preparation polyvinyl alcohol/xylan composite membrane, effectively reduce in the macromole molecule and intermolecular hydrogen bonded, improve sub-chain motion and relatively sliding between macromole, obtained comparatively soft mould material.
Purpose of the present invention is achieved by the following technical programs:
The preparation method of the biodegradable composite membrane of a kind of polyvinyl alcohol/xylan comprises the steps:
(1) polyvinyl alcohol is added to the water, in 80～100 ℃ of lower dissolving 1～4h, adds xylan and citric acid and mix, the mass ratio of polyvinyl alcohol and xylan is 1: 1～4: 1; Citric acid accounts for 5～50% of polyvinyl alcohol and xylan total mass;
(2) mixing solutions with step (1) gained stirs 2～6h under 50～80 ℃, leave standstill, and curtain coating on the clean polyfluortetraethylene plate of horizontal positioned, vacuum-drying obtains polyvinyl alcohol/xylan film.
Preferably, first wiring solution-forming added again before described citric acid added.
The polyvinyl alcohol molecule amount is 14～180,000 described in the step (1), uses before without purifying.Described xylan extracts from beech, and molecular weight is 10～130,000, uses before without purifying.
Vacuum drying condition is described in the step (2): temperature is 30～60 ℃, time of drying 12～24h.
The biodegradable composite membrane of a kind of polyvinyl alcohol/xylan is prepared by aforesaid method; This composite film material tensile strength is 7.58～37.42MPa, and elongation at break is 13.67～249.50%
The biodegradable composite membrane of a kind of polyvinyl alcohol/xylan is as the application of packaging material for food.
The embrane method that is blended into polyvinyl alcohol of the present invention and xylan had both reduced the consumption of petroleum base synthetic macromolecule, again xylan-agricultural waste material was fully used, and economized on resources.The used plasticising of the present invention, linking agent are citric acid, and it can improve the taste of beverage, food as foodstuff additive.As linking agent, also avoided traditional small molecules softening agent to leak so that in the food product pack process contaminated food products, reduce the quality of food.Up to the present yet there are no and use citric acid to do the relevant report that linking agent prepares polyvinyl alcohol/xylan composite film material.
The present invention compared with prior art has following advantage and beneficial effect:
(1) to adopt the citric acid foodstuff additive be the plasticising linking agent in the present invention, avoided in the food product pack process, and traditional small molecules softening agent (glycerine) leaks contaminated food products.
(2) the prepared polyvinyl alcohol of the present invention/xylan laminated film, its snappiness is high more a lot of than other polymer-based composite membrane of polyvinyl alcohol, and keeps certain intensity.This composite film material is nontoxic, biodegradable, can be applied to the aspects such as food product pack, food fresh keeping.
(3) the present invention has that preparation is simple, and the pollution-free the production of material of preparation process is suitable for suitability for industrialized production, and prepared composite film material has good performance.
Embodiment
The invention will be further described below in conjunction with embodiment, but embodiments of the present invention are not limited to this, below embodiment 1～3 used polyvinyl alcohol molecule amount be 14～180,000, alcoholysis degree is 〉=99%, before using without purifying; The xylan that uses extracts from beech, and molecular weight is 10～130,000, uses before without purifying.
Embodiment 1
Take by weighing 3.0g, molecular weight is the polyvinyl alcohol of 162801g/mol, dissolves 2h in 90 ℃ of hot water, add 1.0g, molecular weight is 12,3011g/mol xylan and 1.0g citric acid (being made in advance 10mL solution), 90 ℃ stir half an hour after, be put in 65 ℃ of water-baths, fully stir 4h.Leave standstill, curtain coating on the clean polyfluortetraethylene plate of horizontal positioned, 50 ℃ of vacuum-dryings are taken off film and are got the biodegradable composite membrane of polyvinyl alcohol/xylan behind the 20h.This film thickness is 88.3 μ m, and size is 15 * 15cm
2The film of preparation places thermostatic constant wet chamber to be detected.Obtain through measurer for pulling force, tensile strength is 11.58MPa, and elongation at break is 249.50%.(Limpan N.ProdpranT.Benjakul S.Prasarpran S.Influences of degree of hydrolysis and molecular weight of poly (vinyl alcohol) is on properties of fish myofibrillar protein/PVA blend films.Food Hydrocolloids (PVA) for the prior art bibliographical information, 2012,29 (1), 226-233. hero Tan, Liang Yurong, Yuan Ding. the preparation and property research of starch base/polyvinyl alcohol compound film. Northcentral University's journal (natural science edition), 2012,33 (3), 304-308), the tensile strength of the composite membrane that polyvinyl alcohol and the blend of fish parapeptone make is 10.65MPa, and elongation at break is 150.21%; The tensile strength of starch base/polyvinyl alcohol compound film is 11.3MPa, and elongation at break is 110%.As seen with respect to prior art, the snappiness of the composite membrane that present embodiment makes is better, can be used for the fresh-keeping of fruit, vegetables.Present embodiment utilizes the citric acid small molecules with polyvinyl alcohol and xylan macromolecules cross-linking, between citric acid self existence and two macromole, play bridge, therefore in the composite membrane of present embodiment preparation, the small molecules citric acid is difficult for leaking out, by detecting, do not find that the free state citric acid exists yet.
Embodiment 2
Take by weighing 3.0g, molecular weight is 17,9687g/mol polyvinyl alcohol, 1h in 100 ℃ of hot water, add 1.0g, molecular weight is 13,1463g/mol xylan and 0.2g citric acid (being made in advance 1mL solution), 100 ℃ stir half an hour after, be put in 80 ℃ of water-baths, fully stir 2h.Leave standstill, curtain coating on the clean polyfluortetraethylene plate of horizontal positioned, 60 ℃ of vacuum-dryings are taken off film and are got the biodegradable composite membrane of polyvinyl alcohol/xylan behind the 12h.This film thickness is 60.2 μ m, and size is 15 * 15cm
2The film of preparation places thermostatic constant wet chamber to be detected.
Obtain through measurer for pulling force, tensile strength is 37.42MPa, and elongation at break is 13.67%.Bibliographical information is arranged, and the tensile strength of the composite membrane that polyvinyl alcohol and the blend of fish parapeptone make is 10.65MPa, and elongation at break is 150.21%; The tensile strength of starch base/polyvinyl alcohol compound film is 11.3MPa, and elongation at break is 110%.The composite membrane tensile strength that present embodiment makes is large, good rigidly, and anti-pressure for public use is good, can be used for the outer packaging of food, makes it in transportation, avoids pushing the detrimentally affects such as food distortion that bring.
Embodiment 3
Take by weighing 3.2g, molecular weight is 14,0203g/mol polyvinyl alcohol, dissolves 4h in 80 ℃ of hot water, add 0.8g, molecular weight is 10,1024g/mol xylan and 2.0g citric acid (being made in advance 5mL solution), 80 ℃ stir half an hour after, be put in 50 ℃ of water-baths, fully stir 6h.Leave standstill, curtain coating on the clean polyfluortetraethylene plate of horizontal positioned, 30 ℃ of vacuum-dryings are taken off film and are got the biodegradable composite membrane of polyvinyl alcohol/xylan behind the 24h.This film thickness is 110.5 μ m, and size is 15 * 15cm
2The film of preparation places thermostatic constant wet chamber to be detected.
Obtain through measurer for pulling force, tensile strength is 15.16MPa, and elongation at break is 136.73%.Bibliographical information is arranged, and the tensile strength of the composite membrane that polyvinyl alcohol and the blend of fish parapeptone make is 10.65MPa, and elongation at break is 150.21%; The tensile strength of starch base/polyvinyl alcohol compound film is 11.3MPa, and elongation at break is 110%.Therefore the composite membrane that makes of present embodiment is all making moderate progress than other composite membranes aspect rigidity and the flexibility, has good prospects for the food product pack aspect.
Claims (7)
1. the preparation method of the biodegradable composite membrane of polyvinyl alcohol/xylan is characterized in that comprising the steps:
(1) polyvinyl alcohol is added to the water, in 80～100 ℃ of lower dissolving 1～4h, adds xylan and citric acid and mix, the mass ratio of polyvinyl alcohol and xylan is 1: 1～4: 1; Citric acid accounts for 5～50% of polyvinyl alcohol and xylan total mass;
(2) mixing solutions with step (1) gained stirs 2～6h under 50～80 ℃, leave standstill, and curtain coating on the clean polyfluortetraethylene plate of horizontal positioned, vacuum-drying obtains polyvinyl alcohol/xylan film.
2. method according to claim 1 is characterized in that, first wiring solution-forming added again before described citric acid added.
3. method according to claim 1 is characterized in that, the polyvinyl alcohol molecule amount is 14～180,000 described in the step (1), uses before without purifying.
4. method according to claim 1 is characterized in that, xylan extracts from beech described in the step (1), and molecular weight is 10～130,000, uses before without purifying.
5. method according to claim 1 is characterized in that, vacuum drying condition is described in the step (2): temperature is 30～60 ℃, time of drying 12～24h.
6. the biodegradable composite membrane of polyvinyl alcohol/xylan is characterized in that, it is by the described method preparation of claim 1～5 any one; This composite film material tensile strength is 7.58～37.42MPa, and elongation at break is 13.67～249.50%.
7. the biodegradable composite membrane of the described a kind of polyvinyl alcohol/xylan of claim 6 is as the application of packaging material for food.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250415A (en) * | 2014-09-18 | 2014-12-31 | 华南理工大学 | Uvioresistant polyving alcohol-xylan composite membrane as well as preparation method and application thereof |
| CN107082946A (en) * | 2017-06-12 | 2017-08-22 | 太仓雅奥塑业有限公司 | A kind of environmentally friendly food grade film |
| CN107266775A (en) * | 2017-06-12 | 2017-10-20 | 太仓雅奥塑业有限公司 | A kind of environment-protection food package bag |
| CN110791047A (en) * | 2019-07-15 | 2020-02-14 | 华南理工大学 | Nontoxic harmless high-strength high-heat-resistance hemicellulose foam composite material and preparation method thereof |
| CN110903579A (en) * | 2019-11-25 | 2020-03-24 | 华南理工大学 | Nontoxic harmless high-mechanical-strength high-elasticity hemicellulose foam composite material and preparation method thereof |
| CN111057336A (en) * | 2019-12-30 | 2020-04-24 | 武汉轻工大学 | Composite film for food and preparation method thereof |
| CN113896956A (en) * | 2021-09-14 | 2022-01-07 | 福建农林大学 | Xylan-based composite preservative film and preparation method thereof |
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| CN101631838A (en) * | 2007-02-19 | 2010-01-20 | 西洛芬股份公司 | The polymeric film or the coating that comprise hemicellulose |
| CN102775525A (en) * | 2012-07-16 | 2012-11-14 | 华南理工大学 | Preparation method and application of cross-linking type hemicellulose |
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2013
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| CN101631838A (en) * | 2007-02-19 | 2010-01-20 | 西洛芬股份公司 | The polymeric film or the coating that comprise hemicellulose |
| CN102775525A (en) * | 2012-07-16 | 2012-11-14 | 华南理工大学 | Preparation method and application of cross-linking type hemicellulose |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250415A (en) * | 2014-09-18 | 2014-12-31 | 华南理工大学 | Uvioresistant polyving alcohol-xylan composite membrane as well as preparation method and application thereof |
| CN107082946A (en) * | 2017-06-12 | 2017-08-22 | 太仓雅奥塑业有限公司 | A kind of environmentally friendly food grade film |
| CN107266775A (en) * | 2017-06-12 | 2017-10-20 | 太仓雅奥塑业有限公司 | A kind of environment-protection food package bag |
| CN110791047A (en) * | 2019-07-15 | 2020-02-14 | 华南理工大学 | Nontoxic harmless high-strength high-heat-resistance hemicellulose foam composite material and preparation method thereof |
| CN110791047B (en) * | 2019-07-15 | 2022-03-29 | 华南理工大学 | Nontoxic harmless high-strength high-heat-resistance hemicellulose foam composite material and preparation method thereof |
| CN110903579A (en) * | 2019-11-25 | 2020-03-24 | 华南理工大学 | Nontoxic harmless high-mechanical-strength high-elasticity hemicellulose foam composite material and preparation method thereof |
| CN110903579B (en) * | 2019-11-25 | 2022-03-25 | 华南理工大学 | Nontoxic harmless high-mechanical-strength high-elasticity hemicellulose foam composite material and preparation method thereof |
| CN111057336A (en) * | 2019-12-30 | 2020-04-24 | 武汉轻工大学 | Composite film for food and preparation method thereof |
| CN111057336B (en) * | 2019-12-30 | 2023-02-03 | 武汉轻工大学 | Composite film for food and preparation method thereof |
| CN113896956A (en) * | 2021-09-14 | 2022-01-07 | 福建农林大学 | Xylan-based composite preservative film and preparation method thereof |
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Application publication date: 20130501 |