CN101220161B - Molecular sieve filling degradable polyalcohol group compound film and method for producing the same - Google Patents
Molecular sieve filling degradable polyalcohol group compound film and method for producing the same Download PDFInfo
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- CN101220161B CN101220161B CN2007101509377A CN200710150937A CN101220161B CN 101220161 B CN101220161 B CN 101220161B CN 2007101509377 A CN2007101509377 A CN 2007101509377A CN 200710150937 A CN200710150937 A CN 200710150937A CN 101220161 B CN101220161 B CN 101220161B
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Abstract
The invention discloses a degradable polymer-based composite membrane filled with molecular sieve and a preparation method thereof, aiming at providing a composite membrane that not only has high strength but also has good permeability and a preparation method thereof. The composite membrane consists of 45-98.5 percent of degradable material, 1.5-50 percent of molecular sieve after coupling agent treatment and 0-5.0 percent of plasticizer according to weight percentage. The preparation method of the composite membrane comprises the following steps that: the coupling agent is added to the molecular sieve after baking for surface treatment, the molecular sieve is added to degradable high polymer material solution that has the mass fraction of 0.5-1 percent, then other degradable high polymer materials are added in sequence and the plasticizer is added as well, and casting solution is prepared after evenly stirring; the solution is kept standing for deaeration and is casted into membrane. The composite membrane of the invention not only has higher strength but also has good permeability. The processing process and casting preparation technique of the invention are simple, thus being easy to realize industrial production; besides, abundant raw materials are available, thus having low cost.
Description
Technical field
The present invention relates to hybrid inorganic-organic polymer-based carbon laminated film technology of preparing, in particular, relating to a kind of is base material with the degradable high polymer material, is composite membrane of active inorganic particulate and preparation method thereof with molecular sieve.
Background technology
At present, serious day by day by the problem of environmental pollution that oil synthetic plastics are caused, petroleum resources are becoming tight especially day simultaneously, therefore are subject to people's attention just day by day based on the natural macromolecular material of renewable resources and the research and development and the application of other degradable macromolecule.These materials comprise chitosan, sodium alginate, diatomite, gelatin, starch, zein, soybean protein isolate, polyvinyl alcohol etc.Existing degradable membrane directly adopts degradation material to add softening agent mostly or common plastics is prepared from, since the shortcoming on its physical and chemical performance of these degradation materials and the processing characteristics, the mechanical property requirements when usually being difficult to satisfy the mould material practical application.Poor as pure soybean protein isolate flexibility of operation, its thin-film material is high fragility.Though general plasticising has solved the problem of machine-shaping difficulty, but produced the low shortcoming of tensile strength again.Therefore the physical and chemical modified of degradable high polymer material becomes the important topic of this class investigation of materials exploitation.Report is arranged, utilize carbon nanotube, polynite, tired hunchbacked stone and nano-silicon dioxide particle carry out modification to soybean protein, obtain the hot pressing product or the extrusion sheet of improved performance.Also have in addition and utilize the modification report of mordenite, but the hybridized film that is obtained in the above-mentioned technology shows lower medium osmosis performance, and film relates to complicated curtain coating preparation process the chitosan liquid separating film.
Summary of the invention
The present invention is in order to overcome weak point of the prior art, a kind of higher intensity that both had to be provided, having molecular sieve filling degradable polyalcohol group compound film of good penetrating quality and preparation method thereof again.
The present invention is achieved through the following technical solutions:
Composite membrane of the present invention is base material with the degradable high polymer material, is active inorganic particulate with molecular sieve, and adds a certain amount of coupling agent and softening agent, and curtain coating is prepared new type of polymer base inorganic-organic hybridization composite material film.Concrete technical scheme is as follows:
A kind of molecular sieve filling degradable polyalcohol group compound film, it is characterized in that, made by following component by weight percentage: degradation material is 45%-98.5%, molecular sieve after the coupling agent treatment is 1.5-50%, the percentage composition of softening agent is 0-5.0%, and the coupling agent consumption is the 3-10% of molecular sieve by weight percentage.
Described degradation material is the matrix material of chitosan, sodium alginate, diatomite, starch, protein such as zein, soybean protein isolate and gelatin etc., polyvinyl alcohol and above-mentioned these superpolymer; Described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve, the carbonaceous molecular sieve; Described softening agent is any in polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and the stearic acid; Described coupling agent is a silane compound.
A kind of preparation method of molecular sieve filling degradable polyalcohol group compound film is characterized in that, comprises the steps:
(1) at first with after the molecular sieve baking, adds coupling agent and carry out surface treatment.Filtration washing then, drying.The coupling agent consumption is the 3-10% of molecular sieve by weight percentage.The surface treatment of coupling agent adopts ordinary method to carry out; The storing temperature of molecular sieve is preferably 250 ℃.
(2) molecular sieve after the above-mentioned processing is joined in the degradable high polymer material solution that massfraction is 0.5-1%, be stirred to abundant dissolving, make macromolecular chain on the molecular sieve surface attachment; Then add remaining degradable high polymer material one by one, be stirred to abundant dissolving, add softening agent again, stirring and evenly mixing obtains film-casting liquid; Add remaining degradable high polymer material one by one and be beneficial to molecular sieve inorganic particle uniform distribution in polymer, and be not easy to assemble follow-up membrane prepare of agglomerating influence and mill performance, thereby bring into play the effectiveness of molecular sieve better.
(3) with above-mentioned film-casting liquid standing and defoaming, casting film-forming on flat board then, final drying obtains film.
In the film by weight percentage degradation material be 45%-98.5%, the molecular sieve after the coupling agent treatment is 1.5-50%, the percentage composition of softening agent is 0-5.0%.
Described degradation material is the matrix material of chitosan, sodium alginate, diatomite, starch, protein such as zein, soybean protein isolate and gelatin etc., polyvinyl alcohol and above-mentioned these superpolymer.Described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve and the carbonaceous molecular sieve.Described softening agent is any in polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and the stearic acid.Described coupling agent is a silane compound, as vinyltriethoxysilane, vinyltrimethoxy silane, γ-(methacryloxy) propyl trimethoxy silicane, γ-glycidyl ether propyl trimethoxy silicane, β-(3,4 oxirane ring hexene methyl) ethyl trimethoxy silane etc.
Molecular sieve filling degradable polyalcohol group compound film of the present invention, have higher intensity and good permselective property, can be used as Freshkeeping Packaging film and other various packaging films for food products of fresh and alive food such as vegetable and fruit, or be used for the gas separation membrane and the liquid separating film in fields such as chemical and environmental protection.
The present invention has following technique effect:
The present invention utilizes molecular sieve for active inorganic particulate and carry out the intensity that the coupling agent surface treatment strengthens polymer thin-film material, utilizes the pore passage structure feature of molecular sieve self and adsorption and diffusion characteristics effectively to regulate the film permeation performance.By matching optimization and optimization of preparation to each component in the film formulation, make film of the present invention both have higher intensity, have good penetrating quality again.The course of processing of the present invention and curtain coating preparation technology are simple, are convenient to realize suitability for industrialized production; And it is raw materials used abundant, with low cost.
Embodiment
Below in conjunction with specific embodiment to the detailed description of the invention.
Embodiment 1
After 250 ℃ of bakings of zeolite molecular sieve beta are removed moisture, take by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 1.5 gram vinyltriethoxysilanes room temperature reaction under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve is collected and is put in the loft drier preservation 110 ℃ of vacuum-dryings 1 hour.Molecular sieve 50.0 grams after weighing polyvinyl alcohol powder 45.0 grams and the above-mentioned processing, earlier preparing massfractions with the polyvinyl alcohol of 5.0 grams and 495.0 gram deionized waters in beaker is 1% polyvinyl alcohol water solution, then the stearic acid of the molecular sieve of weighing and 5 grams are added in this solution with mechanical stirring at least 1 hour, then add remaining polyvinyl alcohol one by one, stir 3 hours to fully dissolving, obtain film-casting liquid.After above-mentioned film-casting liquid standing and defoaming, slowly be poured on the clean sheet glass and carry out casting film-forming with special-purpose scraper, drying, skinning obtains polyvinyl alcohol-molecular sieve beta laminated film.The thickness of film is 36 μ m, and tensile strength can reach 46Mpa, and tearing toughness reaches 40kN/m, and visible light transmittance rate is 88%, and rate of perviousness is 1000g/m
2Day, N
2Rate of permeation is 470ml/m
2Day.
Embodiment 2
After 250 ℃ of bakings of carbonaceous molecular sieve are removed moisture, take by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 0.75 gram γ-(methacryloxy) propyl trimethoxy silicane room temperature reaction under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve is collected and is put in the loft drier preservation 110 ℃ of vacuum-dryings 1 hour.The molecular sieve 1.5 that takes by weighing after sodium alginate powder 98.5 gram and the above-mentioned processing restrains, earlier preparing massfractions with the sodium alginates of 3.0 grams and 397.0 gram deionized waters in beaker is 0.75% sodium alginate aqueous solution, then the molecular sieve of weighing is added in this solution with mechanical stirring at least 1 hour, then add remaining sodium alginate one by one, stir 3 hours to fully dissolving, obtain film-casting liquid.After above-mentioned film-casting liquid standing and defoaming, slowly be poured on the clean sheet glass and carry out casting film-forming with special-purpose scraper, drying, skinning obtains sodium alginate-carbonaceous molecular sieve laminated film.The thickness of film is 25 μ m, and tensile strength can reach 72Mpa, and tearing toughness reaches 30kN/m, and visible light transmittance rate is 86%, and rate of perviousness is 4200g/m
2Day, N
2Rate of permeation is 600ml/m
2Day.
Embodiment 3
Mesoporous molecular sieve SBA-15 after moisture is removed in 250 ℃ of bakings, is taken by weighing 25 grams rapidly, put into 500 milliliters of toluene, and add 2.5 gram γ-glycidyl ether propyl trimethoxy silicanes room temperature reactions under nitrogen protection and carried out surface treatment in 24 hours.Filter then, and wash successively with 500 milliliters of toluene, 250 ml methanol, the gained molecular sieve is collected and is put in the loft drier preservation 110 ℃ of vacuum-dryings 1 hour.The molecular sieve 16.0 that takes by weighing after soybean protein powder 80.0 gram and the above-mentioned processing restrains, earlier preparing massfractions with the soybean protein powder of 2.0 grams and 320.0 gram deionized waters in beaker is 0.5% the soybean protein aqueous solution, then the glycerine of the molecular sieve of weighing and 4 grams are added in this solution with mechanical stirring at least 1 hour, then add remaining polyvinyl alcohol one by one, stir 3 hours to fully dissolving, obtain film-casting liquid.After above-mentioned film-casting liquid standing and defoaming, slowly be poured on the clean sheet glass and carry out casting film-forming with special-purpose scraper, drying, skinning obtains soybean protein-molecular sieve laminated film.The thickness of film is 25 μ m, and tensile strength can reach 36Mpa, and tearing toughness reaches 26kN/m, and visible light transmittance rate is 80%, and rate of perviousness is 4500g/m
2Day, N
2Rate of permeation is 120ml/m
2Day.
Claims (2)
1. molecular sieve filling degradable polyalcohol group compound film, it is characterized in that, made by following component by weight percentage: degradation material is 45-98.5%, molecular sieve after the coupling agent treatment is 1.5-50%, softening agent is 0-5.0%, and the coupling agent consumption is the 3-10% of molecular sieve by weight percentage; Described degradation material is the matrix material of chitosan, sodium alginate, diatomite, starch, protein, polyvinyl alcohol and above-mentioned these superpolymer; Described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve, the carbonaceous molecular sieve; Described softening agent is any in polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and the stearic acid; Described coupling agent is a silane compound.
2. the preparation method of the described molecular sieve filling degradable polyalcohol group compound film of claim 1 is characterized in that, comprises the steps:
(1) at first moisture is removed in molecular sieve baking after, add coupling agent and carry out surface treatment; Filter then, washing, drying, the coupling agent consumption is the 3-10% of molecular sieve by weight percentage;
(2) molecular sieve after the above-mentioned processing is joined in the degradable high polymer material solution that massfraction is 0.5-1%, be stirred to abundant dissolving, then add remaining degradable high polymer material one by one, be stirred to abundant dissolving, when needs use softening agent, add softening agent again, stirring and evenly mixing obtains film-casting liquid;
(3) with above-mentioned film-casting liquid standing and defoaming, casting film-forming on flat board then, final drying obtains film; In the gained film by weight percentage degradation material be 45%-98.5%, the molecular sieve after the processing is 1.5-50%, the percentage composition of softening agent is 0-5.0%; Described degradation material is the matrix material of chitosan, sodium alginate, diatomite, starch, protein, polyvinyl alcohol and above-mentioned these superpolymer; Described molecular sieve is any in zeolite molecular sieve, mesopore molecular sieve, the carbonaceous molecular sieve; Described softening agent is any in polyoxyethylene glycol, ethylene glycol, Sorbitol Powder, glycerine and the stearic acid; Described coupling agent is a silane compound.
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| CN2007101509377A CN101220161B (en) | 2007-12-11 | 2007-12-11 | Molecular sieve filling degradable polyalcohol group compound film and method for producing the same |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101962306B (en) * | 2010-07-13 | 2013-03-06 | 北京市农林科学院 | Photodegradable mulch resin coated fertilizer and preparation method thereof |
| CN103434236B (en) * | 2013-08-30 | 2015-06-17 | 广州凯恒特种电线电缆有限公司 | Polyimide/polytetrafluoroethylene composite membrane for insulation of electric wire and cable and preparation method thereof |
| CN104874300B (en) * | 2015-04-30 | 2017-11-21 | 天津大学 | Chitosan sulfonation carbon molecular sieve hybridization compounding film and preparation and application |
| CN104945686A (en) * | 2015-07-10 | 2015-09-30 | 常州市南飞机械有限公司 | Easily-degradable type chitosan-based covering film for sensitive pesticide and preparing method |
| CN105694479A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Soybean protein biodegradable plastic |
| CN105694481A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Wheat-protein biodegradable plastic |
| CN105694480A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Corn protein biodegradable plastics |
| CN109401150B (en) * | 2017-08-16 | 2021-05-11 | 中国石油化工股份有限公司 | Non-sour polyvinyl alcohol composition, cast film and preparation method thereof |
| CN112011161A (en) * | 2020-09-07 | 2020-12-01 | 河南应用技术职业学院 | Composite biodegradable synthetic polymer material and processing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1770503A (en) * | 2005-09-30 | 2006-05-10 | 清华大学 | Proton exchange composite membrane for all vanadium redox flow battery and its preparing method |
| CN1861667A (en) * | 2006-06-09 | 2006-11-15 | 清华大学 | Preparation process of composite hydrogen type proton exchaning membrane for fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1770503A (en) * | 2005-09-30 | 2006-05-10 | 清华大学 | Proton exchange composite membrane for all vanadium redox flow battery and its preparing method |
| CN1861667A (en) * | 2006-06-09 | 2006-11-15 | 清华大学 | Preparation process of composite hydrogen type proton exchaning membrane for fuel cell |
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| JP平8-041216A 1996.02.13 |
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