CN106117617A - A kind of high-strength, high temperature resistant, high-barrier composite membrane - Google Patents
A kind of high-strength, high temperature resistant, high-barrier composite membrane Download PDFInfo
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- CN106117617A CN106117617A CN201610458070.0A CN201610458070A CN106117617A CN 106117617 A CN106117617 A CN 106117617A CN 201610458070 A CN201610458070 A CN 201610458070A CN 106117617 A CN106117617 A CN 106117617A
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- Prior art keywords
- composite membrane
- polyvinyl alcohol
- barrier composite
- barrier
- starch crystal
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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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2429/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high-strength, high temperature resistant, high-barrier composite membrane.It includes the raw material of following weight portion: polyvinyl alcohol 80%～99%, nanometer starch crystal 1%～20%, plasticizer consumption is the 1%～80% of polyvinyl alcohol quality, solution blending casting film-forming.Compared with pure polyvinyl alcohol material, this composite membrane increases substantially at the aspect such as barrier property, mechanical property.This preparation technology is simple, and preparation process green non-pollution, low production cost, the end product obtained can use at the aspect such as packaging for foodstuff, articles of biodegradable plastics material in a large number, have broad application prospects, be expected to substitute synthetic plastic, effectively save petroleum resources, alleviate environmental pollution, and provide new approach for the utilization of resources of native starch raw material and the expansion of polyvinyl alcohol film application.
Description
Technical field
The present invention relates to a kind of high-strength, high temperature resistant, high-barrier composite membrane, particularly relate to one and utilize natural polymer to be former
The preparation method of high-performance and low-cost high-barrier composite membrane prepared by material.
Background technology
Polyvinyl alcohol is a kind of biodegradable synthesis macromolecular material, can be broken down into carbon dioxide and water, the most dirty
Dye environment, has again the performance of some uniquenesses simultaneously, such as barrier properties for gases, the transparency, antistatic behaviour, obdurability, resistance to organic molten
Agent etc., in packaging material field, tool has been widely used.But, at some high-barrier fields, polyvinyl alcohol film barrier
Can be not ideal enough with mechanical property.Therefore, the barrier property improving polyvinyl alcohol the most further becomes focus of concern.
Summary of the invention
It is an object of the invention to provide a kind of high-strength, high temperature resistant, high-barrier composite membrane, improve polyvinyl alcohol film further
Barrier and mechanical property, widen its application.
For achieving the above object, the one that the present invention provides is high-strength, high temperature resistant, high-barrier composite membrane, mainly comprises the following steps:
1) acidolysis: joined by starch in acid solution, is warming up to 30 DEG C～40 DEG C, stirs 4～8 days；
2) washing: with distilled water cyclic washing until pH value is 7.0, obtain nanometer starch crystal suspension；
3) polyvinyl alcohol, water and plasticizer being mixed, be warming up to 80 DEG C～90 DEG C, stir to obtain poly-vinyl alcohol solution；
4) nanometer starch crystal suspension is joined in poly-vinyl alcohol solution, stir, casting film-forming at 50 DEG C.
Wherein:
High-barrier composite membrane weight/mass percentage composition is polyvinyl alcohol 80%～99%, nanometer starch crystal 1%～20%；Described
Plasticizer consumption is polyvinyl alcohol quality 1%～80%.
In the preparation method of described nanometer starch crystal polyvinyl alcohol high-barrier composite membrane, used starch-containing former in step 1
Material derives from one or more in Rhizoma Solani tuber osi, Semen Maydis, potato starch.
In the preparation method of described nanometer starch crystal polyvinyl alcohol high-barrier composite membrane, in step 1, acid used is
3.16mol/L concentrated sulphuric acid.
In the preparation method of described nanometer starch crystal polyvinyl alcohol high-barrier composite membrane, in step 3, plasticizer used is
Refer to containing-OH or-NH2The micromolecular compound of isopolarity group, is specifically chosen as glycerol, Methanamide, acetamide, diethanol
One or more in amine, triethanolamine, sorbitol, carbamide, sucrose, ethylene glycol, Polyethylene Glycol.
Compared with prior art, the present invention has the following advantages:
1) present invention utilizes on nanometer starch crystal on-OH polar group and PVA the high-affinity between-OH and strong hydrogen bonding phase
Interaction, the high-barrier composite membrane prepared has good intensity and toughness.
2) present invention utilizes the specific surface area and the barrier good to gas that plate-like nanometer starch crystal is high, increases gas
Little molecule, by path during thin film, improves the barrier property of polyvinyl alcohol film further.
3) simple and environmentally-friendly (all material is green environmental protection degradable material to present invention process, and preparation process is without having simultaneously
Machine solvent, has no side effect), low production cost, the end product obtained can be in a large number at packaging for foodstuff, biodegradable plastic
The aspects such as goods use, and have broad application prospects, it is desirable to substitute synthetic plastic, effectively save petroleum resources, alleviate ring
Environment pollution.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme and application are described further, but the present invention's is interior
Hold and be not limited solely to the following examples.
Embodiment 1
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
4 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 27.8g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, and 50 DEG C dirty
Prolong film forming.
Embodiment 2
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
5 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 27.8g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, and 50 DEG C dirty
Prolong film forming.
Embodiment 3
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
6 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 27.8g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, and 50 DEG C dirty
Prolong film forming.
Embodiment 4
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
7 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 27.8g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, and 50 DEG C dirty
Prolong film forming.
Embodiment 5
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
8 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 27.8g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, and 50 DEG C dirty
Prolong film forming.
Embodiment 6
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
6 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 13.2g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, at 50 DEG C
Casting film-forming.
Embodiment 7
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
6 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 44.1g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, and 50 DEG C dirty
Prolong film forming.
Embodiment 8
Reaction vessel adds 25g corn starch and the concentrated sulphuric acid of 200ml3.16mol/L, is warming up to 40 DEG C, continuous stirring
6 days；With distilled water cyclic washing until pH value is 7.0, obtain the nanometer starch crystal suspension that concentration is 2%.By 5g polyvinyl alcohol,
0.5g glycerol and 95g water and 62.5g nanometer starch crystal suspension, 100 turns/min stirs 30min, stirs, and 50 DEG C dirty
Prolong film forming.
Comparative example
By 5g polyvinyl alcohol, 0.5g glycerol and 95g water, 100 turns/min stirs 30min, stirs, is cast at 50 DEG C
Film.
As shown in table 1, add acidolysis time different nanometer starch crystal (embodiment 1-5), the permeability of composite membrane with
Pure polyvinyl alcohol film (comparative example) is compared and is improved a lot, and demonstrates the oxygen barrier property of excellence.
When adding the nanometer starch crystal suspension that the acidolysis time is 6 days, the mechanical property of composite membrane and blocking oxygen
Can be greatly improved (table 2), and reaches maximum when nanometer starch crystal content is 10%, illustrates that rigidity, plate-like are formed sediment
The nanocrystalline ability of powder increases substantially obstruct and the mechanical property of matrix.
Each embodiment and the experimental result of comparative example
Table 1:
Table 2:
Claims (6)
1. high-strength, high temperature resistant a, high-barrier composite membrane, it is characterised in that: described high-barrier composite membrane is by polyvinyl alcohol and shallow lake
The nanocrystalline composition of powder.
High-barrier composite membrane the most according to claim 1, it is characterised in that described high-barrier composite membrane weight/mass percentage composition
For polyvinyl alcohol 80%～99%, nanometer starch crystal 1%～20%.
High-barrier composite membrane the most according to claim 1, it is characterised in that plasticizer can be added in composite membrane.
High-barrier composite membrane the most according to claim 3, it is characterised in that described plasticizer refers to containing-OH or-NH2
The micromolecular compound of isopolarity group, is specifically chosen as glycerol, Methanamide, acetamide, diethanolamine, triethanolamine, Pyrusussuriensis
One or more in alcohol, carbamide, sucrose, ethylene glycol, Polyethylene Glycol.
High-barrier composite membrane the most according to claim 4, it is characterised in that described plasticizer consumption is polyvinyl alcohol matter
The 1%～80% of amount, preferably 30%～50%.
High-barrier composite membrane the most according to claim 1, it is characterised in that described nanometer starch crystal derives from Rhizoma Solani tuber osi, jade
One or more in rice, potato starch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610458070.0A CN106117617A (en) | 2016-06-22 | 2016-06-22 | A kind of high-strength, high temperature resistant, high-barrier composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610458070.0A CN106117617A (en) | 2016-06-22 | 2016-06-22 | A kind of high-strength, high temperature resistant, high-barrier composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106117617A true CN106117617A (en) | 2016-11-16 |
Family
ID=57267941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610458070.0A Pending CN106117617A (en) | 2016-06-22 | 2016-06-22 | A kind of high-strength, high temperature resistant, high-barrier composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106117617A (en) |
-
2016
- 2016-06-22 CN CN201610458070.0A patent/CN106117617A/en active Pending
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