CN102241862A - Preparation of water resistant polyvinyl alcohol biodegradable film through melt extrusion method - Google Patents
Preparation of water resistant polyvinyl alcohol biodegradable film through melt extrusion method Download PDFInfo
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- CN102241862A CN102241862A CN2010101719983A CN201010171998A CN102241862A CN 102241862 A CN102241862 A CN 102241862A CN 2010101719983 A CN2010101719983 A CN 2010101719983A CN 201010171998 A CN201010171998 A CN 201010171998A CN 102241862 A CN102241862 A CN 102241862A
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- polyvinyl alcohol
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Abstract
The invention relates to a formula and a process for preparing water resistant polyvinyl alcohol biodegradable film through a melt extrusion and blow molding processing method. The process is characterized by: uniformly mixing polyvinyl alcohol and various assistants through a specific mixing method; carrying out extruding and granulating through a twin-screw extruder; carrying out melt extrusion through a single screw extruder to prepare the water resistant polyvinyl alcohol biodegradable film. The preparation process for the water resistant polyvinyl alcohol biodegradable film has the following advantages that: the melt extrusion and blow molding processing method is adopted; compared to the traditional tape casting method, the process provided by the present invention has high continuous degree, short production period, stable process, and the prepared water resistant polyvinyl alcohol biodegradable film has adjustable thickness and folding diameter; the water resistance and processability of the polyvinyl alcohol film are improved through adding a crosslinking agent, a processing modifier and the like, such that each performance of the prepared film provided by the present invention are excellent, and the prepared water resistant polyvinyl alcohol biodegradable film can be widely applicable for packaging industries such as food, daily chemical products, pharmaceutical electronic components and the like.
Description
One, technical field
The present invention relates to the prescription and the technology of a kind of water-resistant polyvinyl alcohol (PVA) Biodegradable film, adopt to melt extrude the blow moulding preparation, belong to field of high polymer material processing.
Two, background technology
PVA has the characteristic of water-soluble and safety non-toxic, as the packaging film material, is applied in industries such as food, daily use chemicals, medicine, packing electronic component widely.The PVA film is as wrapping material, and more general wrapping material all are better than polyolefin film at aspects such as transparency, static resistance, oil-proofness organic solvent resistance, printings.In recent years because bio-degradable plastics for water-proof particular requirement, makes the development of PVA film that new direction arranged.
Owing to contain great amount of hydroxy group in the PVA molecule, make PVA intramolecularly and the very strong hydrogen bond of intermolecular existence, the degree of crystallinity height makes its melt temperature be higher than decomposition temperature, is difficult to thermoplastic shaping, so work in-process need add softening agent.The adding of softening agent can reduce melt temperature and the melt viscosity thereof of PVA, improves its stability in the course of processing.As in air, PVA is heated to more than 100 ℃, it is variable color at leisure; More than 150 ℃, can fully soften and fusion; Be heated to more than 160 ℃, it is very dark that color can become; More than 170 ℃, color is darker; Be heated to more than 220 ℃, the very fast decomposition of PVA generates acetic acid, acetaldehyde, butylene alcohol and water; Then become the polymkeric substance that contains conjugated double bond to the PVA that has little time to decompose more than 250 ℃.PVA is owing to the ratio difference of vinyl alcohol in the chemical structure, and decomposition temperature has certain difference, and its temperature contrast that begins to decompose can reach 80 ℃.Select suitable softening agent to make processing temperature be lower than decomposition temperature, can make PVA under molten state, extrude processing.
Because the existence of hydroxyl makes PVA that very high water-absorbent and biological degradability be arranged, in prescription, add the starch based degradation material and can reduce the goods cost simultaneously, do not lose biodegradation character again.Yet the film that PVA and starch/PVA are mixed and made into very easily absorbs water, and causes strength degradation, has limited in a lot of fields the application of particularly daily wrapping material aspect.The a lot of scholars in the whole nation improve the water-proof method of starch/PVA in searching at present, mainly contain following several method and improve water tolerance: water-proof coating method, blending method, crosslinking etc.
Begin in recent years at starch plastics film surface coating indissoluble or water insoluble and have the superpolymer of complete biodegradable, thereby can when guaranteeing the material completely biodegradable, obviously improve the water tolerance of material.By having water-proof polymer blending, can significantly improve the water tolerance of starch/PVA with some.And can also add different polymkeric substance at different performance requirements by blend.Discover at present and in system, add the water tolerance that small amount of fibers element, poly(lactic acid) etc. can obviously improve material.Owing to contain hydroxyl in starch/PVA molecule, have stronger wetting ability, be not suitable in the environment that water or high humidity are arranged, using, so people adopt crosslinked method to reduce the content of hydroxyl, thereby improve the water tolerance of material.Linking agent commonly used at present has: aldehydes, tolylene diisocyanate (TDI), boric acid, urea, Resins, epoxy etc.Also have some additive methods to improve the water tolerance of starch/PVA plastics film, improve water tolerance as using modified starch.
Three, summary of the invention
The objective of the invention is to adopt the method that melt extrudes blow molding, production water tolerance PVA Biodegradable film.Be characterized in having solved PVA film poor water resistance, the difficult problem of poor processability has improved the water tolerance of PVA film.
The objective of the invention is to realize that by following technical measures wherein said umber does not have outside the specified otherwise, is parts by weight.The technology that extrusion by melting prepares water tolerance PVA Biodegradable film comprises subordinate's processing step:
(1) PVA is put into homogenizer, stir and be warming up to the slow and evenly adding with softening agent between 70 ℃-80 ℃;
(2) stirring at low speed 10min-120min temperature is controlled between 80 ℃-110 ℃, treats that PVA fully absorbs softening agent;
(3) processing aids such as plasticising PVA and starch, poly(lactic acid), thermoplastic polyurethane, linking agent are mixed;
(4) the PVA mixture that mixes is carried out granulation by exhaust twin screw extruder or single screw extrusion machine;
(5) particle that will make prepares water tolerance PVA Biodegradable film by the single screw extrusion machine blow molding, also film can be steeped after the further two-way stretch dryness finalization again, can obtain that water tolerance is strong, intensity good, the film of high-clarity;
(6) cooling of the film after will finalizing the design rolling is water tolerance PVA Biodegradable film finished product.
The present invention compared with prior art has following characteristics:
1, the present invention's method of adopting single screw rod to melt extrude blow molding prepares film, by add formaldehyde, oxalic dialdehyde, linking agents such as boric acid, TDI, can produce the PVA film that has excellent water-resistance.
2, the present invention's method of adopting single screw rod to melt extrude blow molding prepares film, by adding auxiliary agents such as poly(lactic acid), thermoplastic polyurethane, can not only obtain the good PVA film of processing characteristics, can also improve mechanical properties in films.
It is PVA raw material more than 88% that PVA among the present invention can use multiple alcoholysis degree, and auxiliary agent can use usual auxiliaries of the prior art.Can use in glycerine, ethylene glycol, low molecular poly, hexanolactam, the tetramethylolmethane one or more as softening agent, addition is at 5～80 parts.Linking agent can select for use formaldehyde, oxalic dialdehyde, in the boric acid, TDI one or more, addition is at 0.1～5 part.Can in prescription, add auxiliary agents such as starch in addition as required.
Four, concrete embodiment
Below by embodiment the present invention is specifically described.It is important to point out that embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment one:
In 100 parts of PVA, add 40 parts of glycerine, 20 parts of poly(lactic acid), at first 100 parts of PVA are put into homogenizer, make PVA resin powder be warming up to 80 ℃, then softening agent glycerine slowly and is evenly added, stirring at low speed 60min temperature is controlled between 80 ℃-110 ℃, treats that PVA fully absorbs glycerine, discharging after sneaking into poly(lactic acid), place slaking 24h, then mixture is passed through the twin screw extruder extruding pelletization.The particle of making is melt extruded blow molding by single screw extrusion machine prepare water tolerance PVA Biodegradable film.The folding footpath 500mm of blown film, thickness 40 μ m tensile strengths are 20.4Mpa, and tear strength is 50.4Mpa, and taking out behind the water logging bubble 24h and recording tensile strength is 13.4Mpa.
Embodiment two:
In 100 parts of PVA, add 40 parts of glycerine, 20 parts of poly(lactic acid), 1 part of TDI, at first 100 parts of PVA are put into homogenizer, make PVA resin powder be warming up to 70 ℃, then softening agent glycerine slowly and is evenly added, stirring at low speed 60min temperature is controlled between 80 ℃-110 ℃, treats that PVA fully absorbs glycerine, discharging after sneaking into poly(lactic acid) and TDI, place slaking 24h, then with mixture by exhaust single screw extrusion machine extruding pelletization.The particle of making is melt extruded blow molding by single screw extrusion machine prepare water tolerance PVA Biodegradable film.The folding footpath 500mm of blown film, thickness 40 μ m tensile strengths are 21.6Mpa, and tear strength is 61.3Mpa, and taking out behind the water logging bubble 24h and recording tensile strength is 20.3Mpa.
Claims (4)
1. water tolerance biodegradable films, it is characterized in that this film is by twin screw extruder or single screw extrusion machine extruding pelletization by a kind of mixture, single screw extrusion machine melt extrudes blowing and the product that forms, and described mixture contains PVA, softening agent, contains or not starch-containing.
2. film according to claim 1, wherein, the described PVA intermediate value polymerization degree is 1700～3000, alcoholysis degree is 88～99%; Described starch is one or more in W-Gum, tapioca (flour), the modified starch, and its addition is 0～150 part; Described softening agent is one or more in glycerine, ethylene glycol, low molecular poly, hexanolactam, the tetramethylolmethane, and its addition is 5～80 parts.
3. film according to claim 1 wherein, also contains in poly(lactic acid), thermoplastic polyurethane, the polyester one or more in the described mixture, its addition is 5～100 parts.
4. film according to claim 1, wherein, also contain in the described mixture formaldehyde, oxalic dialdehyde, in the boric acid, tolylene diisocyanate one or more, its addition is 0.1～5 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101719983A CN102241862A (en) | 2010-05-14 | 2010-05-14 | Preparation of water resistant polyvinyl alcohol biodegradable film through melt extrusion method |
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|---|---|---|---|
| CN2010101719983A CN102241862A (en) | 2010-05-14 | 2010-05-14 | Preparation of water resistant polyvinyl alcohol biodegradable film through melt extrusion method |
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| CN102241862A true CN102241862A (en) | 2011-11-16 |
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| CN2010101719983A Pending CN102241862A (en) | 2010-05-14 | 2010-05-14 | Preparation of water resistant polyvinyl alcohol biodegradable film through melt extrusion method |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214695A (en) * | 2013-05-08 | 2013-07-24 | 方卫国 | Chaff starch completely-biodegradable environmental protection material |
| CN103409837A (en) * | 2013-08-02 | 2013-11-27 | 东华大学 | Method for preparing water soluble polyvinyl alcohol fiber through melt spinning |
| CN103435985A (en) * | 2013-07-24 | 2013-12-11 | 吴江龙硕金属制品有限公司 | Low-moisture-penetrability biodegradable plastic |
| CN105524383A (en) * | 2014-09-29 | 2016-04-27 | 中国石化集团四川维尼纶厂 | Thermoplastic polyvinyl alcohol composition and preparation method thereof |
| CN106189013A (en) * | 2016-07-15 | 2016-12-07 | 怀化学院 | Thermoplastic polyvinyl alcohol material and preparation method thereof |
| CN106496895A (en) * | 2016-10-27 | 2017-03-15 | 重庆云天化瀚恩新材料开发有限公司 | A kind of preparation method of polyvinyl alcohol film |
| CN106700362A (en) * | 2017-01-18 | 2017-05-24 | 彭先彧 | Polyvinyl alcohol full-biodegradation film having water resistance and preparation method thereof |
| CN107379585A (en) * | 2017-08-21 | 2017-11-24 | 怀化学院 | High-temperature water-soluble polyvinyl alcohol film and preparation method thereof |
| CN107471694A (en) * | 2017-09-13 | 2017-12-15 | 安徽鼎正包装材料有限公司 | A kind of film forming preparation technology of PVA film |
| CN107936430A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof |
| CN108219168A (en) * | 2016-12-21 | 2018-06-29 | 中国石化集团四川维尼纶厂 | A kind of polyvinyl alcohol water soluble film and preparation method thereof |
| CN109456555A (en) * | 2018-12-03 | 2019-03-12 | 广东省生物工程研究所（广州甘蔗糖业研究所） | A kind of water-soluble polyvinyl alcohol film of blow molding and its preparation method and application |
| CN109825016A (en) * | 2019-01-24 | 2019-05-31 | 安徽鼎洋生物基材料有限公司 | A kind of biodegrade PVA stretch wrap film and preparation method thereof |
| CN109844018A (en) * | 2016-10-31 | 2019-06-04 | 金伯利-克拉克环球有限公司 | Soft thermoplastic injection can break up material |
| CN110540725A (en) * | 2018-05-29 | 2019-12-06 | 合肥杰事杰新材料股份有限公司 | degradable halogen-free flame-retardant foaming material and preparation method thereof |
| CN110734625A (en) * | 2019-10-24 | 2020-01-31 | 樊刚 | plastic film materials and preparation method thereof |
| CN111303463A (en) * | 2020-04-13 | 2020-06-19 | 中国石化长城能源化工（宁夏）有限公司 | Preparation method of thermoplastic processing formed high-strength high-water-resistance PVA hydrogel film |
| CN111808391A (en) * | 2019-04-10 | 2020-10-23 | 西安昊锐电子科技有限公司 | Preparation method and application of polyvinyl alcohol plastic |
| CN113480751A (en) * | 2021-07-15 | 2021-10-08 | 江南大学 | Spinnable polyvinyl alcohol master batch for sea-island fiber and preparation method thereof |
| CN113801419A (en) * | 2021-10-27 | 2021-12-17 | 浙江宏南精密工业有限公司 | Production and processing technology of degradable plastic product |
| CN114573933A (en) * | 2022-03-31 | 2022-06-03 | 郑州轻工业大学 | Polyvinyl alcohol film and preparation method thereof |
| CN115011052A (en) * | 2022-04-30 | 2022-09-06 | 冯艳梅 | Modified packaging material |
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2010
- 2010-05-14 CN CN2010101719983A patent/CN102241862A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214695B (en) * | 2013-05-08 | 2017-02-01 | 肇庆市威盛环保新材料科技有限公司 | Chaff starch completely-biodegradable environmental protection material |
| CN103214695A (en) * | 2013-05-08 | 2013-07-24 | 方卫国 | Chaff starch completely-biodegradable environmental protection material |
| CN103435985A (en) * | 2013-07-24 | 2013-12-11 | 吴江龙硕金属制品有限公司 | Low-moisture-penetrability biodegradable plastic |
| CN103409837A (en) * | 2013-08-02 | 2013-11-27 | 东华大学 | Method for preparing water soluble polyvinyl alcohol fiber through melt spinning |
| CN103409837B (en) * | 2013-08-02 | 2015-10-28 | 东华大学 | The method of water-soluble polyvinyl alcohol fibers prepared by a kind of melt spinning |
| CN105524383A (en) * | 2014-09-29 | 2016-04-27 | 中国石化集团四川维尼纶厂 | Thermoplastic polyvinyl alcohol composition and preparation method thereof |
| CN106189013B (en) * | 2016-07-15 | 2017-09-22 | 怀化学院 | Thermoplastic polyvinyl alcohol material and preparation method thereof |
| CN106189013A (en) * | 2016-07-15 | 2016-12-07 | 怀化学院 | Thermoplastic polyvinyl alcohol material and preparation method thereof |
| CN107936430A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof |
| CN106496895A (en) * | 2016-10-27 | 2017-03-15 | 重庆云天化瀚恩新材料开发有限公司 | A kind of preparation method of polyvinyl alcohol film |
| CN109844018A (en) * | 2016-10-31 | 2019-06-04 | 金伯利-克拉克环球有限公司 | Soft thermoplastic injection can break up material |
| CN108219168A (en) * | 2016-12-21 | 2018-06-29 | 中国石化集团四川维尼纶厂 | A kind of polyvinyl alcohol water soluble film and preparation method thereof |
| CN106700362A (en) * | 2017-01-18 | 2017-05-24 | 彭先彧 | Polyvinyl alcohol full-biodegradation film having water resistance and preparation method thereof |
| CN107379585A (en) * | 2017-08-21 | 2017-11-24 | 怀化学院 | High-temperature water-soluble polyvinyl alcohol film and preparation method thereof |
| CN107471694A (en) * | 2017-09-13 | 2017-12-15 | 安徽鼎正包装材料有限公司 | A kind of film forming preparation technology of PVA film |
| CN110540725A (en) * | 2018-05-29 | 2019-12-06 | 合肥杰事杰新材料股份有限公司 | degradable halogen-free flame-retardant foaming material and preparation method thereof |
| CN109456555A (en) * | 2018-12-03 | 2019-03-12 | 广东省生物工程研究所（广州甘蔗糖业研究所） | A kind of water-soluble polyvinyl alcohol film of blow molding and its preparation method and application |
| CN109456555B (en) * | 2018-12-03 | 2021-01-29 | 广东省科学院生物工程研究所 | Blow molding water-soluble polyvinyl alcohol film and preparation method and application thereof |
| CN109825016A (en) * | 2019-01-24 | 2019-05-31 | 安徽鼎洋生物基材料有限公司 | A kind of biodegrade PVA stretch wrap film and preparation method thereof |
| CN111808391A (en) * | 2019-04-10 | 2020-10-23 | 西安昊锐电子科技有限公司 | Preparation method and application of polyvinyl alcohol plastic |
| CN110734625A (en) * | 2019-10-24 | 2020-01-31 | 樊刚 | plastic film materials and preparation method thereof |
| CN111303463A (en) * | 2020-04-13 | 2020-06-19 | 中国石化长城能源化工（宁夏）有限公司 | Preparation method of thermoplastic processing formed high-strength high-water-resistance PVA hydrogel film |
| CN113480751A (en) * | 2021-07-15 | 2021-10-08 | 江南大学 | Spinnable polyvinyl alcohol master batch for sea-island fiber and preparation method thereof |
| CN113801419A (en) * | 2021-10-27 | 2021-12-17 | 浙江宏南精密工业有限公司 | Production and processing technology of degradable plastic product |
| CN114573933A (en) * | 2022-03-31 | 2022-06-03 | 郑州轻工业大学 | Polyvinyl alcohol film and preparation method thereof |
| CN115011052A (en) * | 2022-04-30 | 2022-09-06 | 冯艳梅 | Modified packaging material |
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Application publication date: 20111116 |