CN106397841A - High-barrier biomaterial and preparation method thereof - Google Patents
High-barrier biomaterial and preparation method thereof Download PDFInfo
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- CN106397841A CN106397841A CN201610779083.8A CN201610779083A CN106397841A CN 106397841 A CN106397841 A CN 106397841A CN 201610779083 A CN201610779083 A CN 201610779083A CN 106397841 A CN106397841 A CN 106397841A
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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
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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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
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a high-barrier biomaterial and a preparation method thereof and belongs to the technical field of modification of barrier materials. The high-barrier biomaterial provided by the invention is prepared from starch, an addition reaction plasticizer, an antioxidant, polyvinyl alcohol, plant cellulose, an antimicrobial agent, an intercalation modifier, an intercalation modifier dispersant and auxiliaries, which serve as raw materials, through dry-process melt extrusion, wherein the intercalation modifier is graphene, graphene oxide, hydrophobic modified graphene or bio-graphene. The high-barrier biomaterial provided by the invention can be completely biodegraded and has excellent water resistance, strength and gas barrier; the invention simultaneously provides the easy and feasible preparation method which facilitates industrial production.
Description
Technical field
The present invention relates to a kind of bio-based high barrier material and preparation method thereof, belong to barrier material technical field of modification.
Background technology
Plastic flexible package is increasingly widely used in people's life, just the speed development to make rapid progress, in people
It is desirable to feature of environmental protection packaging just seems increasingly important in the case that environmental consciousness improves, and there is the high-barrier material of biological degradability
Material is also immature.
Existing barrier material has aluminum platinum film, aluminizer, ethylene-vinyl alcohol copolymer, polyvinylidene chloride etc..Aluminum platinum
Film, aluminizer have high temperature resistant, thermally-stabilised, high barrier, the function such as uvioresistant, but it invests big, unit cost
High.Ethylene-vinyl alcohol copolymer (EVOH) is the reasonable material of current plastic flexible package barrier, but price is extremely high
Expensive, ten thousand yuan/ton of resin 4-8, material all relies on Japanese import.Polyvinylidene chloride (PVDC) is also current plastic flexible package
The reasonable material of barrier, but it produces harmful gass at high temperature using high-frequency welding in use, thus dirty
Dye food, burns and produces a large amount of harmful gass, because in China's packaging for foodstuff in addition to co-extrusion or dry type are combined, being mainly used in Petaso
Intestinal is packed.
For the application of Graphene, graphene oxide, oneself has pertinent literature to report at present, and the Ma Tiantian of such as University Of Tianjin exists
Have been introduced in academic dissertation " performance study of polymolecularity graphene composite material ", be not difficult to find out its effort done and answer
With there being good effect.But in actual applications, have the shortcomings that processed complex, processing cost are higher, yield poorly, solution mode
Film will remove nearly more than 80% moisture content, and therefore efficiency is low, and industrialization is difficult.Xi'an University of Technology hereby continue person of outstanding talent " polyethylene/
PET/GO/PVA coating combination process system is described in the graphene oxide preparation containing thin film and performance structure research again " paper
Standby, but because of complex process, high expensive, promote difficulty big.
CN105778373A discloses a kind of preparation side of the modified polyvinylalcohol-graphene composite material of melt-processable
Method is although this patent is melt extruded using polyvinyl alcohol and Graphene, but it adopts wet process fusion to extrude, and first will change
Property polyvinyl alcohol and Graphene preparation be in liquid form, then by ultrasonic disperse or churned mechanically mode, both are mixed,
Then it is then exhausted from the liquid in mixed liquor, it is especially difficult, especially using super in industry that this method wants real industrialization
The scattered method of sound, poor feasibility.This patent also discloses the " modified polyvinylalcohol-stone of the melt-processable of described high filling
Black alkene composite also as masterbatch, can be added to the polymeric matrix of melt-processable, such as nylon, EVOH, and polyvinyl alcohol gathers
Urethane, polyformaldehyde, polysilane, PET, polyester, polycaprolactone, polylactic acid, polrvinyl chloride, acrylate copolymer, polystyrene,
ABS, Merlon, polyvinyl butyral resin, polyvinyl acetate, in polysulfones etc., prepare Graphene excellent dispersion further
Polymer composites." in fact, in material recited above only have nylon, EVOH, polyvinyl alcohol these three can be special with this
The composite of profit preparation carry out compatible, and other material and composite be cannot blended melting it is impossible to solution is compatible
Sex chromosome mosaicism, in addition the cost of pla-pcl is also very high.
Content of the invention
It is an object of the invention to provide a kind of bio-based high barrier material, its not only can complete biodegradable, and have
Excellent resistance to water, intensity and barrier properties for gases；Invention also provides simple preparation method, beneficial to industrial metaplasia
Produce.
Bio-based high barrier material of the present invention, be with starch, additive reaction plasticiser, antioxidant, polyvinyl alcohol,
Plant cellulose, antibacterial, intercalation modifying agent, intercalation modifying agent dispersant and auxiliary agent are raw material, melt extrude system by dry method
Obtain bio-based high barrier material；Described intercalation modifying agent is Graphene, graphene oxide, hydrophobically modified Graphene or biological foundation stone
Black alkene.
Described starch is the ative starch in tapioca, corn starch, potato starch or sweet potato starch, starch granuless >=
100 mesh, water content≤13%.
Described additive reaction plasticiser is additive reaction product and one of glycerol, ethylene glycol or ethyl acetate or many
The compounding mixture planted；Described additive reaction product is an acetoglyceride, two acetoglycerides or triacetyl glycerine with sweet
Oil carries out the product of additive reaction.
Described antioxidant is the multiple mixture in antioxidant 300, antioxidant 1010 or antioxidant TNP.
Alcoholysis degree >=88 of described polyvinyl alcohol, the degree of polymerization is 1700-2600, and grain graininess is 80-100 mesh.
Described antibacterial is nano-silver ionic fluorite, sodium alginate, shitosan, trimethyl, triethyl group or three normal-butyl seasons
Ammonium salt.
Described intercalation modifying agent dispersant is sodium dodecylbenzene, PVP, sodium cholate, Tween 80, oxygen
Change the multiple mixture in dibutyl tin, polyacrylamide or polyethylene glycol 200-600.
Described auxiliary agent is oleamide, erucyl amide, OPE, zinc stearate, nano silicon, nano-sized carbon
Multiple mixture in sour calcium, Pulvis Talci or titanium dioxide.
Described bio-based high barrier material, by the Material synthesis of following parts by weight：
The preparation method of described bio-based high barrier material, is to put into raw material in high speed mixer to be mixed,
Stir 30-60min at 30-120 DEG C, then carry out melt extruding pelletize by mixed material.
In big kind synthesis macromolecular material, polyvinyl alcohol is the material uniquely with biodegradability, polyethylene
Great amount of hydroxy group, mainly elementary composition by tri- kinds of C, H, O is contained on alcohol molecule, be hydrolyzable, degraded, high-barrier, no electrostatic, do not inhale
The environment-friendly material of dirt.Show through authoritative department detection, food bag, pesticide bag, medical protection can be prepared with polyvinyl alcohol
Film, the fresh-keeping packaging of milk product.Polyvinyl alcohol is hydrophilic polymer, but itself does not have plasticity and melt processable.
The present invention is making full use of the high barrier of polyvinyl alcohol, is protecting fragrant guarantor's taste, uvioresistant, tool biodegradable
On the basis of, introduce graphite alkenes material, make use of its specific surface area big and advantage that density is high, be conducive to polyvinyl alcohol with
Other stock dispersion evenly, thus effectively improve polyvinyl alcohol resistance to water；The graphite alkenes material introducing is for product
Physical property be greatly improved, such as superelevation barrier, intensity, resistance to water, product strength can improve 100-500%, be conducive to
Various uses needs, in addition, with the increase of Graphene consumption, barrier is greatly improved, and intensity is also improved largely.
The present invention melts one-step method by dry method and prepares described bio-based high barrier material, that is, avoid employing public affairs
Open the wet process fusion mentioned in patent, the loaded down with trivial details technique of ultrasonic disperse and drain, simple energy-conserving and environment-protective need not be carried out, and be
Improve the barrier of material and to be realized using 5 layers, 7 layers, 9 layers or 13 layers of coextrusion or dry type composite algorithm.Described bio-based
High barrier material, can substitute the flexible packing materials such as aluminum platinum film, aluminizer, polyvinylidene chloride, ethylene-vinyl alcohol copolymer.
The invention has the advantages that：
(1) the bio-based high barrier material described in, not only can complete biodegradable, and there is excellent resistance to water, strong
Degree and barrier properties for gases；
(2) preparation method of the bio-based high barrier material described in, without special equipment, is set using traditional plastic processing
The standby techniques such as blown film sheet material, injection of can realizing are processed, simple, beneficial to industrialized production.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the enforcement of the present invention.
Raw material used below is parts by weight.
Embodiment 1
Prepare raw material：
Described starch is tapioca, and starch granuless are 100 mesh, and water content is 10%.
Described additive reaction plasticiser is the compounding mixture of additive reaction product and glycerol, and mixing quality ratio is for 2:3；
Described additive reaction product is the product that an acetoglyceride and glycerol carry out additive reaction.
The alcoholysis degree of described polyvinyl alcohol is 110, and the degree of polymerization is 1700, and grain graininess is 80 mesh.
The preparation method of described bio-based high barrier material, is to put into raw material in high speed mixer to be mixed,
Stir 60min at 30 DEG C, then carry out melt extruding pelletize by mixed material.
Embodiment 2
Prepare raw material：
Described starch is corn starch, and starch granuless are 500 mesh, and water content is 13%.
Described additive reaction plasticiser is the compounding mixture of additive reaction product and glycerol and ethyl acetate, mixes matter
Amount ratio is 1:2:1；Described additive reaction product is the product that two acetoglycerides and glycerol carry out additive reaction.
The alcoholysis degree of described polyvinyl alcohol is 88, and the degree of polymerization is 2600, and grain graininess is 100 mesh.
The preparation method of described bio-based high barrier material, is to put into raw material in high speed mixer to be mixed,
Stir 30min at 120 DEG C, then carry out melt extruding pelletize by mixed material.
Embodiment 3
Prepare raw material：
Described starch is potato starch, and starch granuless are 1000 mesh, and water content is 8%.
Described additive reaction plasticiser is mixed with the compounding of glycerol, ethylene glycol and ethyl acetate for additive reaction product
Thing, mixing quality is than for 2:1:5:7；Described additive reaction product is the product that triacetyl glycerine and glycerol carry out additive reaction
Thing.
The alcoholysis degree of described polyvinyl alcohol is 160, and the degree of polymerization is 2000, and grain graininess is 100 mesh.
The preparation method of described bio-based high barrier material, is to put into raw material in high speed mixer to be mixed,
Stir 40min at 60 DEG C, then carry out melt extruding pelletize by mixed material.
Embodiment 4
Prepare raw material：
Described starch is sweet potato starch, and starch granuless are 400 mesh, and water content is 13%.
Described additive reaction plasticiser is the compounding mixture of additive reaction product and ethylene glycol, and mixing quality ratio is for 3:5；
Described additive reaction product is the product that an acetoglyceride and glycerol carry out additive reaction.
The alcoholysis degree of described polyvinyl alcohol is 223, and the degree of polymerization is 2200, and grain graininess is 90 mesh.
The preparation method of described bio-based high barrier material, is to put into raw material in high speed mixer to be mixed,
Stir 45min at 90 DEG C, then carry out melt extruding pelletize by mixed material.
Claims (10)
1. a kind of bio-based high barrier material it is characterised in that：With starch, additive reaction plasticiser, antioxidant, polyvinyl alcohol,
Plant cellulose, antibacterial, intercalation modifying agent, intercalation modifying agent dispersant and auxiliary agent are raw material, melt extrude system by dry method
Obtain bio-based high barrier material；Described intercalation modifying agent is Graphene, graphene oxide, hydrophobically modified Graphene or biological foundation stone
Black alkene.
2. bio-based high barrier material according to claim 1 it is characterised in that：Starch be tapioca, corn starch,
Ative starch in potato starch or sweet potato starch, starch granuless >=100 mesh, water content≤13%.
3. bio-based high barrier material according to claim 1 it is characterised in that：Additive reaction plasticiser is additive reaction
The compounding mixture of one or more of product and glycerol, ethylene glycol or ethyl acetate；Described additive reaction product is one
Acetoglyceride, two acetoglycerides or triacetyl glycerine and glycerol carry out the product of additive reaction.
4. bio-based high barrier material according to claim 1 it is characterised in that：Antioxidant is antioxidant 300, antioxidant
1010 or antioxidant TNP in multiple mixture.
5. bio-based high barrier material according to claim 1 it is characterised in that：Alcoholysis degree >=88 of polyvinyl alcohol, gather
Right for 1700-2600, grain graininess is 80-100 mesh.
6. bio-based high barrier material according to claim 1 it is characterised in that：Antibacterial be nano-silver ionic fluorite,
Sodium alginate, shitosan, trimethyl, triethyl group or three normal-butyl quaternary ammonium salts.
7. bio-based high barrier material according to claim 1 it is characterised in that：Intercalation modifying agent dispersant is dodecane
Phenylpropenoic acid sodium, PVP, sodium cholate, Tween 80, dibutyltin oxide, polyacrylamide or polyethylene glycol 200-
Multiple mixture in 600.
8. bio-based high barrier material according to claim 1 it is characterised in that：Auxiliary agent be oleamide, erucyl amide,
Multiple mixing in OPE, zinc stearate, nano silicon, nano-calcium carbonate, Pulvis Talci or titanium dioxide
Thing.
9. bio-based high barrier material according to claim 1 is it is characterised in that Material synthesis by following parts by weight：
10. a kind of arbitrary described bio-based high barrier material of claim 1-9 preparation method it is characterised in that：By raw material
Put in high speed mixer and mixed, stir 30-60min at 30-120 DEG C, then mixed material is melted
Extruding pelletization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610779083.8A CN106397841A (en) | 2016-08-31 | 2016-08-31 | High-barrier biomaterial and preparation method thereof |
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| CN201610779083.8A CN106397841A (en) | 2016-08-31 | 2016-08-31 | High-barrier biomaterial and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163379A (en) * | 2017-05-22 | 2017-09-15 | 台州市苏达山新材料有限公司 | Bio-based composite material and preparation method thereof, application |
| CN108314804A (en) * | 2018-01-28 | 2018-07-24 | 朱春英 | The preparation method of graphene modified PVA composite material |
| CN108314805A (en) * | 2018-01-28 | 2018-07-24 | 朱春英 | Degradable gas phase fruit-vegetable plastic wrap and preparation method thereof |
| CN108384161A (en) * | 2018-01-28 | 2018-08-10 | 朱春英 | Graphene modified starch multifunctional composite and preparation method thereof |
| CN108530690A (en) * | 2018-05-02 | 2018-09-14 | 合肥市晨雷思建筑材料科技有限公司 | A kind of high molecular film material and preparation method thereof |
| CN108610579A (en) * | 2018-05-22 | 2018-10-02 | 安徽申科塑业有限公司 | A kind of fragrance environmentally-friendly plastic thin-film material |
| CN108659267A (en) * | 2018-06-04 | 2018-10-16 | 天津科技大学 | A kind of ultraviolet protection method |
| CN110079891A (en) * | 2019-05-05 | 2019-08-02 | 苏州回蓝环保科技有限公司 | A kind of biodegradable PVA melt spinning resin and its application |
| CN110129917A (en) * | 2019-05-05 | 2019-08-16 | 苏州回蓝环保科技有限公司 | A kind of antibacterial starch base melt spinning resin and its application |
| CN112455043A (en) * | 2020-11-05 | 2021-03-09 | 苏州市雄林新材料科技有限公司 | Super-barrier TPU film and preparation method thereof |
| CN113846419A (en) * | 2021-10-14 | 2021-12-28 | 北京化工大学 | Antibacterial and disinfectant nanofiber medical dressing and preparation method thereof |
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| CN102372858A (en) * | 2010-08-18 | 2012-03-14 | 陈天云 | Preparation method for starch-based biodegradable plastic |
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| CN102372858A (en) * | 2010-08-18 | 2012-03-14 | 陈天云 | Preparation method for starch-based biodegradable plastic |
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| TIANTIAN MA等: "The composites based on plasticized starch and graphene oxide/reduced graphene oxide", 《CARBOHYDRATE POLYMERS》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163379A (en) * | 2017-05-22 | 2017-09-15 | 台州市苏达山新材料有限公司 | Bio-based composite material and preparation method thereof, application |
| CN107163379B (en) * | 2017-05-22 | 2019-12-17 | 浙江苏达山新材料有限公司 | bio-based composite material and preparation method and application thereof |
| CN108314804A (en) * | 2018-01-28 | 2018-07-24 | 朱春英 | The preparation method of graphene modified PVA composite material |
| CN108314805A (en) * | 2018-01-28 | 2018-07-24 | 朱春英 | Degradable gas phase fruit-vegetable plastic wrap and preparation method thereof |
| CN108384161A (en) * | 2018-01-28 | 2018-08-10 | 朱春英 | Graphene modified starch multifunctional composite and preparation method thereof |
| CN108530690A (en) * | 2018-05-02 | 2018-09-14 | 合肥市晨雷思建筑材料科技有限公司 | A kind of high molecular film material and preparation method thereof |
| CN108610579A (en) * | 2018-05-22 | 2018-10-02 | 安徽申科塑业有限公司 | A kind of fragrance environmentally-friendly plastic thin-film material |
| CN108659267A (en) * | 2018-06-04 | 2018-10-16 | 天津科技大学 | A kind of ultraviolet protection method |
| CN110079891A (en) * | 2019-05-05 | 2019-08-02 | 苏州回蓝环保科技有限公司 | A kind of biodegradable PVA melt spinning resin and its application |
| CN110129917A (en) * | 2019-05-05 | 2019-08-16 | 苏州回蓝环保科技有限公司 | A kind of antibacterial starch base melt spinning resin and its application |
| CN112455043A (en) * | 2020-11-05 | 2021-03-09 | 苏州市雄林新材料科技有限公司 | Super-barrier TPU film and preparation method thereof |
| CN113846419A (en) * | 2021-10-14 | 2021-12-28 | 北京化工大学 | Antibacterial and disinfectant nanofiber medical dressing and preparation method thereof |
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Application publication date: 20170215 |