CN105400109A - Modified polyvinylalcohol foamed plastic and preparation method thereof - Google Patents
Modified polyvinylalcohol foamed plastic and preparation method thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2329/00—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
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
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Abstract
The invention discloses modified polyvinylalcohol foamed plastic and a preparation method thereof. The modified polyvinylalcohol foamed plastic is prepared from the following raw materials in parts by weight: 100 parts of modified polyvinylalcohol, 3-8 parts of microfibrillated cellulose, 4-10 parts of a pore forming agent, 5-15 parts of a surface active agent, 2-6 parts of a thickening agent, 2-8 parts of a filler and 100-150 parts of water. The preparation method of the modified polyvinylalcohol foamed plastic comprises the following steps: adding water into polyvinylalcohol, soaking, heating, stirring until dissolution is complete, adding sodium hydroxide solution, regulating pH value to be 10-11, stirring, adding a silane coupling agent, heating, stirring, adding acid to regulate pH to be 7-8, carrying out reduced pressure distillation, so that modified polyvinylalcohol foamed plastic is obtained. The prepared modified polyvinylalcohol foamed plastic has biodegradability and also can meet requirements of foamed plastic on mechanical properties and processability.
Description
Technical field
The present invention relates to foam technology field, particularly relate to a kind of modified polyvinyl alcohol porous plastics and preparation method thereof.
Background technology
Waste plastic pollutes and constantly increases a few days ago, and natural fiber and biodegradable polymers are being produced and obtained the extensive concern of people in offal treatment and replace conventional plastic gradually.Strengthen in biodegradable polymers composite foam material preparing natural fiber, fibrillation Mierocrystalline cellulose (MFC) has multiple dimensioned Fibre diameter and high length-diameter ratio, and its high strength and rigidity and the characteristic such as biodegradable more and more receive publicity.Wood pulp cellulose suspension is obtained primitive fiber by the mechanical homogenizer with High Pressure Difference, and Turbak etc. prepare first and define fibrillation Mierocrystalline cellulose.The acquisition being subject to the nanometer fibrillated fibre element (NFC) of extensive concern equally then needs chemistry or enzyme pre-treatment, need consume mass energy, only be in laboratory preparatory phase at present.
As previously mentioned, biodegradable composite foam material causes investigator and pays close attention to greatly.Green polymer is as polyvinyl alcohol, and be current commercial most popular hydrolysable polymeric, it is soluble in water and form polyvinyl alcohol hydrogel.The polyvinyl alcohol of strong polarity not only have good ion-exchange performance, physical adsorbability, solvent resistance, biocompatibility and with the advantage such as the excellent compatibility of multiple material, filter in preparation and possess outstanding advantage in sorbing material, sound and thermal insulating material and composite foam material etc.About the research work of natural fiber/polyvinyl alcohol composite foam material has been reported: Avella etc. utilize Physical to prepare and can be recycled and different multilayer carton paper pulp (the MC)/PVA-based composite foam material of content.Fiber and the good interface compatibility of polyvinyl alcohol make the expansion behavior of composite foam material, mechanical property and thermostability all be improved, and meanwhile, along with the increase of MC content, abscess-size reduces and then mechanical property improves.But the degradation temperature of polyvinyl alcohol, close to its melt temperature, therefore needs softening agent to improve processing characteristics, prevents from producing thermal destruction in the course of processing.Water or the carbonic acid gas such as Srithep have studied intermittent type temperature-raising method NFC/PVOH matrix material foaming behavior as pneumatogen.Result of study shows, only has the sample of high moisture content just to form uniform abscess under the effect of carbonic acid gas.Dry pure PVOH and MFC matrix material is when carbonic acid gas is as whipping agent, because nano-fiber composite material has very high intensity at normal temperatures, hinder air bubble growth and reduce abscess-size, therefore in stereoscan photograph, not observing foam structure.Above research work illustrates, the natural fiber/polyvinyl alcohol composite foam material using different softening agent and different molding mode to prepare all does not obtain high-foaming density and the uniform polyvinyl alcohol foam material of abscess pattern.
How improving the composite property of natural fiber and polyvinyl alcohol, obtain a kind of natural fiber/polyvinyl alcohol micro foaming composite material of high-foaming density, having great importance for enriching biodegradable composite foam material.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of modified polyvinyl alcohol porous plastics and preparation method thereof, described modified polyvinyl alcohol porous plastics has biodegradable performance, meets the requirement of porous plastics for mechanics and processing characteristics simultaneously.
A kind of modified polyvinyl alcohol porous plastics that the present invention proposes, comprises following raw material by weight:
The preparation technology of described modified polyvinyl alcohol comprises: soaked by polyvinyl alcohol, heats up, and is stirred to and dissolves completely, add sodium hydroxide solution, adjust ph is 10-11, adds silane coupling agent, heats up, and stirs, it is 7-8 that acid adding is adjusted to pH, and underpressure distillation, obtains modified polyvinyl alcohol;
Prepare described modified polyvinyl alcohol porous plastics to comprise: modified polyvinyl alcohol is added to the water, be heated to 70-80 DEG C, insulated and stirred 0.5-1h, adds fibrillation Mierocrystalline cellulose and continues to stir 0.5-1h, be cooled to 50-60 DEG C, add pore former, tensio-active agent, thickening material and filler, stir 1-2h and obtain suspension, described suspension is poured into rapidly at 20-30 DEG C of dry 56-70h in mould, send in 50-70 DEG C of vacuum drying oven after taking out, dry 40-48h, obtains plastics first product; Described plastics first product is added in intermittent type foaming autoclave, vacuumize, be 180-200 DEG C in temperature, pressure is under the condition of 10-11MPa, continuous injection supercritical carbon dioxide gas 0.5-1h, pressure release, immerses 0.2-0.5h in-10-0 DEG C of pond by described autoclave, open autoclave, obtain described modified polyvinyl alcohol porous plastics.
Preferably, the preparation technology of described modified polyvinyl alcohol comprises: by weight polyvinyl alcohol 100 parts is soaked 1-3h, be warming up to 80-100 DEG C, insulated and stirred is to dissolving completely, and add the sodium hydroxide solution of 25-30wt%, adjust ph is 10-11, stir 0.5-1h, add silane coupling agent 3-8 part, be warming up to 100-120 DEG C with the temperature rise rate of 2-3 DEG C/min, stirring reaction 1-3h, be cooled to room temperature, adding acid for adjusting pH is 7-8, and underpressure distillation, obtains described modified polyvinyl alcohol.
Preferably, described silane coupling agent is KH-560.
Preferably, described pore former is plasticized starch, prepares described plasticized starch and comprises: after being added water by starch, be heated to 70-90 DEG C, after gelatinization reaction 0.5-1h, then adds fluidizer and carries out plastics processing 0.5-1h, obtain described plasticized starch; Preferably, described starch is one or more in wheat kind of starch, potato starch, W-Gum; Described fluidizer is one or more in ethylene glycol, glycerol, dimethyl sulfoxide (DMSO), water and urea.
Preferably, described tensio-active agent is one or more in C12-C17 alkylbenzene sulfonate, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene.
Preferably, described thickening material is one or more in methylcellulose gum, Vltra tears, Xylo-Mucine, Natvosol.
Preferably, the cellulosic Fibre diameter of described fibrillation is 0.01-2 μm, and length is 0.1-1 μm.
Preferably, described filler is one or more in calcium carbonate, carbon black, silicon-dioxide, titanium dioxide, aluminium hydroxide, polynite, mica powder, talcum powder, barium sulfate, diatomite, kaolin, graphite.
In the present invention, in described modified polyvinyl alcohol porous plastics, add modified polyvinyl alcohol, reacted by polyvinyl alcohol and silane coupling agent, silane coupling agent generates silanol at hydrolysis reaction, polycondensation can be carried out at a certain temperature and generate siloxanes, produce the long flexible chain with active group thus, by reacting with the hydroxyl condensation on polyvinyl alcohol the modified polyvinyl alcohol generated with long flexible chain, substantially improve the processing characteristics of polyvinyl alcohol, utilize in polyvinyl alcohol after modification simultaneously and add fibrillation Mierocrystalline cellulose, the dispersing property of fibrillation Mierocrystalline cellulose in polyvinyl alcohol can be significantly increased, utilize fibrillation Mierocrystalline cellulose as skeleton, enhance its mechanical property as foam material and degradation property.In addition also add plasticized starch in the present invention, it both as pore former, can increase again the viscosity of solution, was conducive to obtaining poromerics, strengthened its biodegradability; Adding of the tensio-active agents such as alkylbenzene sulfonate, extraordinary steady bubble, even bubble effect can be played; The stream of thickening material then for improving modified polyvinyl alcohol foam material becomes, processing characteristics.
The preparation technology of the porous plastics of modified polyvinyl alcohol described in the present invention, by carrying out modification to polyvinyl alcohol, the fibrillation Mierocrystalline cellulose added is dispersed in modified polyvinyl alcohol matrix, and adds pore former, tensio-active agent etc., it greatly improves the foam performance of matrix material.In addition also pass through intermittent type step-down foaming forming technique in the present invention, process under the specific temperature and pressure of selection, make the foam performance of the fiber composite foam material obtained best, the highest cell density is 5.84 × 10
8cellscm
-3.Compared with pure polyvinyl alcohol foam material, modified polyvinyl alcohol porous plastics of the present invention has biodegradable performance, meets the requirement of porous plastics for mechanics and processing characteristics simultaneously.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of modified polyvinyl alcohol porous plastics, comprises following raw material: modified polyvinyl alcohol 100 parts, fibrillation Mierocrystalline cellulose 3 parts, pore former 10 parts, C12-C17 alkylbenzene sulfonate 5 parts, methylcellulose gum 6 parts, 2 parts, calcium carbonate, 150 parts, water by weight;
The preparation technology of described modified polyvinyl alcohol comprises: by weight polyvinyl alcohol 100 parts is soaked 1h, be warming up to 100 DEG C, and insulated and stirred is to dissolving completely, add the sodium hydroxide solution of 25wt%, adjust ph is 10-11, stirs 1h, adds KH-5603 part, 100 DEG C are warming up to the temperature rise rate of 3 DEG C/min, stirring reaction 3h, is cooled to room temperature, and adding acid for adjusting pH is 7-8, underpressure distillation, obtains described modified polyvinyl alcohol;
Described pore former is plasticized starch, prepares described plasticized starch and comprises: after being added water by starch, be heated to 70 DEG C, and after gelatinization reaction 1h, then add fluidizer and carry out plastics processing 0.5h, obtain described plasticized starch, wherein said starch is wheat kind of starch; Described fluidizer is ethylene glycol; The cellulosic Fibre diameter of described fibrillation is 0.01-2 μm, and staple length is 0.1-1 μm;
Prepare described modified polyvinyl alcohol porous plastics to comprise: modified polyvinyl alcohol is added to the water, be heated to 70 DEG C, insulated and stirred 1h, adds fibrillation Mierocrystalline cellulose and continues to stir 0.5h, be cooled to 60 DEG C, add pore former, tensio-active agent, thickening material and filler, stir 1h and obtain suspension, described suspension is poured into rapidly at 30 DEG C of dry 56h in mould, send in 70 DEG C of vacuum drying ovens after taking out, dry 40h, obtains plastics first product; Described plastics first product is added in intermittent type foaming autoclave, vacuumize, it is 200 DEG C in temperature, pressure is under the condition of 10MPa, continuous injection supercritical carbon dioxide gas 1h, pressure release, immerses 0.5h in-10 DEG C of ponds by described autoclave, open autoclave, obtain described modified polyvinyl alcohol porous plastics.
Embodiment 2
A kind of modified polyvinyl alcohol porous plastics, comprises following raw material: modified polyvinyl alcohol 100 parts, fibrillation Mierocrystalline cellulose 8 parts, pore former 4 parts, polyoxyethylene sorbitan fatty acid ester 15 parts, Vltra tears 2 parts, carbon black 8 parts, 100 parts, water by weight;
The preparation technology of described modified polyvinyl alcohol comprises: by weight polyvinyl alcohol 100 parts is soaked 3h, be warming up to 80 DEG C, and insulated and stirred is to dissolving completely, add the sodium hydroxide solution of 30wt%, adjust ph is 10-11, stirs 0.5h, adds KH-5608 part, 120 DEG C are warming up to the temperature rise rate of 2 DEG C/min, stirring reaction 1h, is cooled to room temperature, and adding acid for adjusting pH is 7-8, underpressure distillation, obtains described modified polyvinyl alcohol;
Described pore former is plasticized starch, prepares described plasticized starch and comprises: after being added water by starch, be heated to 90 DEG C, and after gelatinization reaction 0.5h, then add fluidizer and carry out plastics processing 1h, obtain described plasticized starch, wherein, described starch is potato starch; Described fluidizer is glycerol; The cellulosic Fibre diameter of described fibrillation is 0.01-2 μm, and staple length is 0.1-1 μm;
Prepare described modified polyvinyl alcohol porous plastics to comprise: modified polyvinyl alcohol is added to the water, be heated to 80 DEG C, insulated and stirred 0.5h, adds fibrillation Mierocrystalline cellulose and continues to stir 1h, be cooled to 50 DEG C, add pore former, tensio-active agent, thickening material and filler, stir 2h and obtain suspension, described suspension is poured into rapidly at 20 DEG C of dry 70h in mould, send in 50 DEG C of vacuum drying ovens after taking out, dry 48h, obtains plastics first product; Described plastics first product is added in intermittent type foaming autoclave, vacuumize, it is 180 DEG C in temperature, pressure is under the condition of 11MPa, continuous injection supercritical carbon dioxide gas 0.5h, pressure release, immerses 0.2h in 0 DEG C of pond by described autoclave, open autoclave, obtain described modified polyvinyl alcohol porous plastics.
Embodiment 3
A kind of modified polyvinyl alcohol porous plastics, comprises following raw material: modified polyvinyl alcohol 100 parts, fibrillation Mierocrystalline cellulose 5 parts, pore former 7 parts, alkylphenol polyoxyethylene 10 parts, Xylo-Mucine 4 parts, filler 5 parts, 125 parts, water by weight;
The preparation technology of described modified polyvinyl alcohol comprises: by weight polyvinyl alcohol 100 parts is soaked 2h, be warming up to 90 DEG C, and insulated and stirred is to dissolving completely, add the sodium hydroxide solution of 27wt%, adjust ph is 10-11, stirs 0.7h, adds KH-5605 part, 110 DEG C are warming up to the temperature rise rate of 2.5 DEG C/min, stirring reaction 2h, is cooled to room temperature, and adding acid for adjusting pH is 7-8, underpressure distillation, obtains described modified polyvinyl alcohol;
Described pore former is plasticized starch, prepares described plasticized starch and comprises: after being added water by starch, be heated to 80 DEG C, after gelatinization reaction 0.7h, then adds fluidizer and carries out plastics processing 0.7h, obtain described plasticized starch; Wherein, described starch is W-Gum; Described fluidizer is dimethyl sulfoxide (DMSO); The cellulosic Fibre diameter of described fibrillation is 0.01-2 μm, and staple length is 0.1-1 μm; Described filler is the mixture of silicon-dioxide, titanium dioxide, aluminium hydroxide, polynite and mica powder;
Prepare described modified polyvinyl alcohol porous plastics to comprise: modified polyvinyl alcohol is added to the water, be heated to 75 DEG C, insulated and stirred 0.7h, adds fibrillation Mierocrystalline cellulose and continues to stir 0.8h, be cooled to 55 DEG C, add pore former, tensio-active agent, thickening material and filler, stir 1.5h and obtain suspension, described suspension is poured into rapidly at 25 DEG C of dry 63h in mould, send in 60 DEG C of vacuum drying ovens after taking out, dry 44h, obtains plastics first product; Described plastics first product is added in intermittent type foaming autoclave, vacuumize, it is 190 DEG C in temperature, pressure is under the condition of 10.5MPa, continuous injection supercritical carbon dioxide gas 0.7h, pressure release, immerses 0.3h in-5 DEG C of ponds by described autoclave, open autoclave, obtain described modified polyvinyl alcohol porous plastics.
Embodiment 4
A kind of modified polyvinyl alcohol porous plastics, comprises following raw material: modified polyvinyl alcohol 100 parts, fibrillation Mierocrystalline cellulose 6 parts, pore former 8 parts, 12 parts, tensio-active agent, thickening material 3 parts, filler 4 parts, 130 parts, water by weight;
The preparation technology of described modified polyvinyl alcohol comprises: by weight polyvinyl alcohol 100 parts is soaked 2h, be warming up to 95 DEG C, and insulated and stirred is to dissolving completely, add the sodium hydroxide solution of 28wt%, adjust ph is 10-11, stirs 0.8h, adds KH-5606 part, 115 DEG C are warming up to the temperature rise rate of 2 DEG C/min, stirring reaction 2h, is cooled to room temperature, and adding acid for adjusting pH is 7-8, underpressure distillation, obtains described modified polyvinyl alcohol;
Described pore former is plasticized starch, prepares described plasticized starch and comprises: after being added water by starch, be heated to 75 DEG C, after gelatinization reaction 0.8h, add fluidizer again and carry out plastics processing 0.7h, obtain described plasticized starch, wherein said starch is the mixture of wheat kind of starch and potato starch; Described fluidizer is the mixture of water and urea; Described tensio-active agent is the mixture of polyoxyethylene sorbitan fatty acid ester and alkylphenol polyoxyethylene; Described thickening material is the mixture that methylcellulose gum closes Natvosol; The cellulosic Fibre diameter of described fibrillation is 0.01-2 μm, and staple length is 0.1-1 μm; Described filler is the mixture of talcum powder, barium sulfate, diatomite, kaolin and graphite.
Prepare described modified polyvinyl alcohol porous plastics to comprise: modified polyvinyl alcohol is added to the water, be heated to 76 DEG C, insulated and stirred 0.8h, adds fibrillation Mierocrystalline cellulose and continues to stir 0.7h, be cooled to 56 DEG C, add pore former, tensio-active agent, thickening material and filler, stir 1-2h and obtain suspension, described suspension is poured into rapidly at 24 DEG C of dry 60h in mould, send in 55 DEG C of vacuum drying ovens after taking out, dry 46h, obtains plastics first product; Described plastics first product is added in intermittent type foaming autoclave, vacuumize, it is 195 DEG C in temperature, pressure is under the condition of 10.3MPa, continuous injection supercritical carbon dioxide gas 0.8h, pressure release, immerses 0.4h in-6 DEG C of ponds by described autoclave, open autoclave, obtain described modified polyvinyl alcohol porous plastics.
The preparation technology of the porous plastics of modified polyvinyl alcohol described in the present invention, by carrying out modification to polyvinyl alcohol, the fibrillation Mierocrystalline cellulose added is dispersed in modified polyvinyl alcohol matrix, and adds pore former, tensio-active agent etc., it greatly improves the foam performance of matrix material.In addition also pass through intermittent type step-down foaming forming technique in the present invention, process under the specific temperature and pressure of selection, make the foam performance of the fiber composite foam material obtained best, the highest cell density is 5.84 × 10
8cellscm
-3.Compared with pure polyvinyl alcohol foam material, modified polyvinyl alcohol porous plastics of the present invention has biodegradable performance, meets the requirement of porous plastics for mechanics and processing characteristics simultaneously.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (8)
1. a modified polyvinyl alcohol porous plastics, is characterized in that, comprises following raw material by weight:
The preparation technology of described modified polyvinyl alcohol comprises: soaked by polyvinyl alcohol, heats up, and is stirred to and dissolves completely, add sodium hydroxide solution, adjust ph is 10-11, stirs, adds silane coupling agent, heats up, stir, adding acid for adjusting pH is 7-8, and underpressure distillation, obtains modified polyvinyl alcohol;
Prepare described modified polyvinyl alcohol porous plastics to comprise: modified polyvinyl alcohol is added to the water, be heated to 70-80 DEG C, insulated and stirred 0.5-1h, adds fibrillation Mierocrystalline cellulose and continues to stir 0.5-1h, be cooled to 50-60 DEG C, add pore former, tensio-active agent, thickening material and filler, stir 1-2h and obtain suspension, described suspension is poured into rapidly at 20-30 DEG C of dry 56-70h in mould, send in 50-70 DEG C of vacuum drying oven after taking out, dry 40-48h, obtains plastics first product; Described plastics first product is added in intermittent type foaming autoclave, vacuumize, be 180-200 DEG C in temperature, pressure is under the condition of 10-11MPa, continuous injection supercritical carbon dioxide gas 0.5-1h, pressure release, immerses 0.2-0.5h in-10-0 DEG C of pond by described autoclave, open autoclave, obtain described modified polyvinyl alcohol porous plastics.
2. modified polyvinyl alcohol porous plastics according to claim 1, it is characterized in that, the preparation technology of described modified polyvinyl alcohol comprises: by weight polyvinyl alcohol 100 parts is soaked 1-3h, be warming up to 80-100 DEG C, insulated and stirred is to dissolving completely, add the sodium hydroxide solution of 25-30wt%, adjust ph is 10-11, stir 0.5-1h, add silane coupling agent 3-8 part, 100-120 DEG C is warming up to the temperature rise rate of 2-3 DEG C/min, stirring reaction 1-3h, be cooled to room temperature, adding acid for adjusting pH is 7-8, underpressure distillation, obtain described modified polyvinyl alcohol.
3. modified polyvinyl alcohol porous plastics according to claim 1 and 2, is characterized in that, described silane coupling agent is KH-560.
4. the modified polyvinyl alcohol porous plastics according to any one of claim 1-3, it is characterized in that, described pore former is plasticized starch, prepare described plasticized starch to comprise: after starch is added water, be heated to 70-90 DEG C, after gelatinization reaction 0.5-1h, then add fluidizer and carry out plastics processing 0.5-1h, obtain described plasticized starch; Preferably, described starch is one or more in wheat kind of starch, potato starch, W-Gum; Described fluidizer is one or more in ethylene glycol, glycerol, dimethyl sulfoxide (DMSO), water and urea.
5. the modified polyvinyl alcohol porous plastics according to any one of claim 1-4, is characterized in that, described tensio-active agent is one or more in C12-C17 alkylbenzene sulfonate, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene.
6. the modified polyvinyl alcohol porous plastics according to any one of claim 1-5, is characterized in that, described thickening material is one or more in methylcellulose gum, Vltra tears, Xylo-Mucine, Natvosol.
7. the modified polyvinyl alcohol porous plastics according to any one of claim 1-6, is characterized in that, the cellulosic Fibre diameter of described fibrillation is 0.01-2 μm, and staple length is 0.1-1 μm.
8. the modified polyvinyl alcohol porous plastics according to any one of claim 1-7, it is characterized in that, described filler is one or more in calcium carbonate, carbon black, silicon-dioxide, titanium dioxide, aluminium hydroxide, polynite, mica powder, talcum powder, barium sulfate, diatomite, kaolin, graphite.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652464A (en) * | 2016-07-25 | 2018-02-02 | 克林纳奇（荆州）高分子科技有限公司 | A kind of polyvinyl formal sponge cloth and its preparation method and application |
| CN109762283A (en) * | 2019-01-31 | 2019-05-17 | 中国科学院理化技术研究所 | A kind of water-soluble degradation foamed material of recoverable version and preparation method thereof |
| CN111111651A (en) * | 2019-12-24 | 2020-05-08 | 四川大学 | Method for preparing foamed silver catalyst based on supercritical carbon dioxide foaming technology |
| CN113004578A (en) * | 2021-04-02 | 2021-06-22 | 江苏恒尚节能科技股份有限公司 | Waterproof heat-insulation curtain wall and preparation method thereof |
| CN113121937A (en) * | 2020-01-10 | 2021-07-16 | 宿迁嘉禾塑料金属制品有限公司 | Thermoplastic modified polyvinyl alcohol microporous foamed collodion and preparation process thereof |
| CN115558227A (en) * | 2022-09-13 | 2023-01-03 | 安徽瑞鸿新材料科技有限公司 | Thermoplastic processing method of polyvinyl alcohol composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363324A (en) * | 2001-06-04 | 2002-12-18 | Sumitomo Bakelite Co Ltd | Plastic sheet foamed in gradient manner and manufacturing method therefor |
| CN102807682A (en) * | 2012-08-24 | 2012-12-05 | 东北林业大学 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
| CN103003376A (en) * | 2010-05-12 | 2013-03-27 | 斯托拉恩索公司 | A composition comprising microfibrillated cellulose and a process for the production of a composition |
| CN104910429A (en) * | 2015-05-27 | 2015-09-16 | 铜陵方正塑业科技有限公司 | Thermoplastic full-degradable plastic film with excellent processability and preparation method thereof |
| CN104962010A (en) * | 2015-07-28 | 2015-10-07 | 苏州荣昌复合材料有限公司 | Preparation method of degradable PVC plastic |
-
2015
- 2015-11-06 CN CN201510760663.8A patent/CN105400109B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002363324A (en) * | 2001-06-04 | 2002-12-18 | Sumitomo Bakelite Co Ltd | Plastic sheet foamed in gradient manner and manufacturing method therefor |
| CN103003376A (en) * | 2010-05-12 | 2013-03-27 | 斯托拉恩索公司 | A composition comprising microfibrillated cellulose and a process for the production of a composition |
| CN102807682A (en) * | 2012-08-24 | 2012-12-05 | 东北林业大学 | Method for preparing modified single hydrophobic polyvinyl alcohol film |
| CN104910429A (en) * | 2015-05-27 | 2015-09-16 | 铜陵方正塑业科技有限公司 | Thermoplastic full-degradable plastic film with excellent processability and preparation method thereof |
| CN104962010A (en) * | 2015-07-28 | 2015-10-07 | 苏州荣昌复合材料有限公司 | Preparation method of degradable PVC plastic |
Non-Patent Citations (3)
| Title |
|---|
| JUE LU ET AL.: "Preparation and properties of microfibrillated cellulose polyvinyl alcohol composite materials", 《COMPOSITES PART A：APPLIED SCIENCE AND MANUFACTURING》 * |
| 漫沙汀: "聚乙烯醇缩甲醛（PVFM）实验性能影响因素（笔记版）", 《新浪博客》 * |
| 赵娜 等: "聚乙烯醇/微纤化纤维素复合微发泡材料的制备", 《化工学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652464A (en) * | 2016-07-25 | 2018-02-02 | 克林纳奇（荆州）高分子科技有限公司 | A kind of polyvinyl formal sponge cloth and its preparation method and application |
| CN109762283A (en) * | 2019-01-31 | 2019-05-17 | 中国科学院理化技术研究所 | A kind of water-soluble degradation foamed material of recoverable version and preparation method thereof |
| CN109762283B (en) * | 2019-01-31 | 2021-06-29 | 中国科学院理化技术研究所 | Recyclable water-soluble degradable foam material and preparation method thereof |
| CN111111651A (en) * | 2019-12-24 | 2020-05-08 | 四川大学 | Method for preparing foamed silver catalyst based on supercritical carbon dioxide foaming technology |
| CN111111651B (en) * | 2019-12-24 | 2020-12-22 | 四川大学 | Method for preparing foamed silver catalyst based on supercritical carbon dioxide foaming technology |
| CN113121937A (en) * | 2020-01-10 | 2021-07-16 | 宿迁嘉禾塑料金属制品有限公司 | Thermoplastic modified polyvinyl alcohol microporous foamed collodion and preparation process thereof |
| CN113004578A (en) * | 2021-04-02 | 2021-06-22 | 江苏恒尚节能科技股份有限公司 | Waterproof heat-insulation curtain wall and preparation method thereof |
| CN115558227A (en) * | 2022-09-13 | 2023-01-03 | 安徽瑞鸿新材料科技有限公司 | Thermoplastic processing method of polyvinyl alcohol composite material |
| CN115558227B (en) * | 2022-09-13 | 2024-01-12 | 安徽瑞鸿新材料科技有限公司 | Thermoplastic processing method of polyvinyl alcohol composite material |
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