CN102350844A - Polymer film and preparation method thereof - Google Patents
Polymer film and preparation method thereof Download PDFInfo
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- CN102350844A CN102350844A CN2011101938843A CN201110193884A CN102350844A CN 102350844 A CN102350844 A CN 102350844A CN 2011101938843 A CN2011101938843 A CN 2011101938843A CN 201110193884 A CN201110193884 A CN 201110193884A CN 102350844 A CN102350844 A CN 102350844A
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Abstract
The invention provides a polymer film. The polymer film comprises a support layer and a barrier layer. The barrier layer comprises high-molecular weight poly(1,2-propylene carbonate) or high-molecular weight nano-montmorillonite-modified poly(1,2-propylene carbonate). The support layer comprises one or more fully biodegradable polyesters, has good oxygen barrier properties and mechanical properties, and can be degraded fully. The invention also provides a preparation method of the polymer film.
Description
Technical field
The present invention relates to polymer processing field, relate in particular to a kind of thin polymer film and preparation method thereof.
Background technology
Agricultural film plays enormous function to agricultural production and income, yet the present employed agricultural film overwhelming majority is non-degraded or light degradation plastic sheeting for farm use (polyethylene).According to reports, the residual 3.9kg/ mu of plastic sheeting for farm use, corn underproduction 11%-23%, wheat yield 9%-16%, soybean underproduction 5.5%-9%, vegetables underproduction 14.6%-59.2%; The plastic sheeting for farm use relic that is wrapped on the crops will cause the livestock M & M to improve (research and development forward position, 16 (21), 30-31,2008).The good complete biodegradable plastic sheeting for farm use of the exploitation transparency is one of important channel that solves above-mentioned agricultural film defective.
Food package film requires this film to have oxygen-barrier property preferably except that requiring to have the good transparency usually, so that prolong the shelf life of the food of pack.Commercially available food package film mainly is that employing PVDC, EVOH, PAN, PEN, PA66, PA6 and PET are the packaging film (plastics package of barrier layer at present; 18 (1); 42-44.; 2008), because these are as the difficult degradation of the material utmost point and the recovery of barrier layer, the good complete biodegradable packaging film of the development transparency also is one of means that solve " white pollution ".
The full-biodegradable material of large-scale production has poly-succinic fourth diester (PBS), polytetramethylene glycol-succinic acid/adipic acid copolyesters (PBSA), PLA (PLA), polycaprolactone (PCL), polyglycolic acid (PGA), gathers adipic acid/butylene terephthalate (PBAT) and polyhydroxyalkanoate (PHA) (plastics science and technology up to now; 35 (7); 92～97,2007; Polyester industrial, 21 (3), 3～8,2008) etc., it is extremely strong to remove fragility, separately gathering outside the beta-hydroxy-butanoic acid acid esters of film forming, all exists oxygen barrier performance poor, can not hinder membrane material as oxygen and use.
High-molecular-weight poly carbonic acid 1,2-propylene diester (PPC) is (Macromolecular Research, 16 (5), 473～480,2008 except that having the complete biodegradable performance; P olymer Reviews, 48,192～219,2008), have oxygen barrier performance (J.Appl.Polym.Symp, 26,257,1975 concurrently; Chemtech, 6,588,1976; The chemistry circular, 10,29～34,1997).
It is base material that Chinese patent publication number CN1884371A adopts PBAT or PLA, has prepared the complete biodegradable transparent membrane through the method that adds antifoggant and surfactant, it is said that this transparent membrane can be used for agricultural film and packaging material for food.Because this transparent membrane is to be the film of matrix with the PBAT or the PLA that do not have oxygen-barrier property, its film is used for packaging for foodstuff will exist the short problem of shelf life.
The method that Japan Patent JP2000177072 then is employed in the polyvinyl alcohol of polylactic acid membrane surface-coated saponification number＞95% prepares the good film with oxygen barrier performance of transparency; Because the coated polyvinyl alcohol in this film surface is typical water soluble polymer, and polyvinyl alcohol only could degrade in specific environment, and in natural environment, being difficult to be degraded, (biotechnology is circulated a notice of; 6; 51-54,2007), therefore limited his application.
Though it is the film that the transparency is good, have oxygen barrier performance that Chinese patent CN1006944, CN1736812 and CN101016099 all declare prepared film; But it has used prodegradant; Promptly used make that disintegration takes place non-biodegradable material (PE, PP, PET etc.) collapse broken dose, therefore can not be called the complete biodegradable film.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of thin polymer film, has both had good oxygen-barrier property and mechanical performance, can high-fallly separate again.
In order to solve the prior art problem; The invention provides a kind of thin polymer film, comprising: one deck supporting layer and one deck barrier layer at least at least, said barrier layer comprises high-molecular-weight poly carbonic acid 1; 2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1, the 2-propylene diester; Said supporting layer comprises the complete biodegradable polyester.
Preferably, said barrier layer comprises high-molecular-weight poly carbonic acid 1, and 2-propylene diester number-average molecular weight is 40000～300000g/mol, and molecular weight distribution is 2.0～7.0; The nano montmorillonite modified carbonic acid 1 that gathers, the nano imvite that the 2-propylene diester adopts is the modified Nano imvite of interlamellar spacing more than or equal to 2nm, the weight percent amount is 0.2～5%.
Preferably, the material selected for use of said supporting layer comprises: poly butylene succinate, polyethylene glycol succinate, polyethylene glycol adipate, PPA, poly adipate succinic acid ester, gather adipic acid hexylene glycol ester, poly-succinic/adipic acid-butanediol ester, gather (butylene terephthalate ester-co-tetramethylene adipate), gather (butylene terephthalate ester-co-succinic acid-butanediol ester) and gather in (butylene terephthalate ester-co-succinic acid propylene glycol ester) one or more.
Preferably, the number-average molecular weight of the material that said supporting layer is selected for use is 40000～200000g/mol, and molecular weight distribution is 1.5～6.0.
Preferably, the gross thickness of said thin polymer film is 10 μ m～150 μ m.
Preferably, the thickness of said barrier layer is 5～50 μ m; Said supporting layer thickness is 5-50 μ m.
Preferably, said barrier layer also comprises plasticizer, heat stabilizer and anticaking agent.
The present invention also provides a kind of preparation method of thin polymer film, comprising:
With complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester are respectively as in the layering screw rod casting machine;
Said complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester melting mixing, curtain coating respectively form thin polymer film;
Wherein said complete biodegradable polyester forms one deck supporting layer at least; Said high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1, the 2-propylene diester forms one deck barrier layer at least.
Preferably, said high-molecular-weight poly carbonic acid 1, the preparation method of 2-propylene diester is:
With percentage by weight is the high-molecular-weight poly carbonic acid 1 of 91-97%; 2-propylene diester, percentage by weight are anticaking agent blend 3～10min in high-speed mixer that the plasticizer of 1-5%, heat stabilizer that percentage by weight is 1-2% and percentage by weight are 1%-2%, obtain mixture;
With said mixture melting mixing in extruder, extrude the back granulation, obtain gathering carbonic acid 1, the 2-propylene diester.
Preferably, said plasticizer is: molecular weight smaller or equal to 2000 polyethylene glycol (PEG), molecular weight less than in 10000 polyester plasticizer, ATBC, tributyl 2-acetylcitrate, glyceryl triacetate, diallyl phthalate and the dibutyl succinate one or more;
Heat stabilizer is: one or more in maleic anhydride, phthalic anhydride, succinyl oxide, THPA, HHPA, carbodiimides, polycarbodiimide and the stearic acid;
Anticaking agent is: one kind of multiple in gas phase nano white carbon, the precipitated silica.
The invention provides a kind of thin polymer film, comprise one deck supporting layer and one deck barrier layer at least at least, said barrier layer comprises high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester; Said supporting layer comprises the complete biodegradable polyester, and thin polymer film provided by the invention comprises barrier layer and supporting layer, comprises high-molecular-weight poly carbonic acid 1 in the barrier layer; 2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1, the 2-propylene diester, these two kinds of materials all have good oxygen-barrier property; And this oxygen-barrier property is not with whole oxygen obstructions; But use the difference in field according to film, have different barrier layers, so that oxygen-barrier property is thought is controlled.Again can complete biodegradable, comprise the polyester of complete biodegradable in the said supporting layer, good mechanical performance can be provided, intensity and toughness all meet the demands, and can complete biodegradable.So thin polymer film provided by the invention had both had good oxygen-barrier property and mechanical performance, can high-fallly separate again.Be applicable to agricultural film or food product packing film.
The present invention also provides a kind of preparation method of thin polymer film, comprising: with complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester are respectively as in the layering screw rod casting machine; Said complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester melting mixing, curtain coating respectively form thin polymer film; Wherein said complete biodegradable polyester forms one deck supporting layer at least; Said high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1, the 2-propylene diester forms one deck barrier layer at least.Preparation method's operation provided by the invention is few, simple to operation, and the adhesion between every layer of the curtain coating thin films is tight, and the transparency is good.Be fit to large-scale industrial production.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that these just restriction for further specifying feature and advantage of the present invention rather than patent of the present invention being required is described.
The invention provides a kind of thin polymer film, comprising: one deck supporting layer and one deck barrier layer at least at least, said barrier layer comprises high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester; Said supporting layer comprises the complete biodegradable polyester,
The present invention seeks to for a kind of good oxygen-barrier property and mechanical performance of both having had, the film that can high-fallly separate again are provided.In view of the thin polymer film major part is used for agricultural film and packaging for foodstuff field, so properties of transparency is also had certain requirement.According to barrier layer according to the invention is high-molecular-weight poly carbonic acid 1; 2-propylene diester or nano montmorillonite modified HMW high-molecular-weight poly carbonic acid 1; The 2-propylene diester: gather carbonic acid 1,2-propylene diester number-average molecular weight is preferably 40000～300000g/mol, more preferably 80000～250000g/mol; Molecular weight distribution is 2.0～7.0, and the best is 2.5～5.0; The nano montmorillonite modified carbonic acid 1 that gathers gathers carbonic acid 1 in the 2-propylene diester, and 2-malonic acid number-average molecular weight is 40000～300000g/mol, and the optimum number average molecular weight is 80000～250000g/mol, and molecular weight distribution is 2.0～7.0, and the best is 2.5～5.0; Nano imvite is the modified Nano imvite of interlamellar spacing more than or equal to 2nm, and weight percentage is 0.2～5%, and optimum content is 0.5～3%.
According to the present invention; The material that said supporting layer is selected for use preferably includes the good polymer of toughness; More preferably good-toughness and polyester material that can high-fallly separate, most preferably be poly butylene succinate (PB S), polyethylene glycol succinate (PES), polyethylene glycol adipate (PEA), PPA (PPA), poly adipate succinic acid ester (PBA), gather adipic acid hexylene glycol ester (PHA), poly-succinic/adipic acid-butanediol ester (PB SA), gather (butylene terephthalate ester-co-tetramethylene adipate) (PBAT), gather (butylene terephthalate ester-co-succinic acid-butanediol ester) (PB ST) and gather in (butylene terephthalate ester-co-succinic acid propylene glycol ester) (PB SPS) one or more.
The number-average molecular weight of the material that said supporting layer is selected for use is preferably 20000～150000g/mol, 40000～100000g/mol more preferably, and molecular weight distribution is preferably 1.5～6.0, and more preferably 2.0～4.0.
The prior art of comparing; Thin polymer film provided by the invention can have sandwich construction; Comprise multilayer barrier layer and supporting layer, according to the present invention, the structure of said thin polymer film can be supporting layer/barrier layer/supporting layer, supporting layer/barrier layer/supporting layer/barrier layer/supporting layer or supporting layer/supporting layer/barrier layer/supporting layer/supporting layer; When adjacent two layers was all supporting layer, two-layer supporting layer used the material different preparation.
According to the present invention, the thickness of said barrier layer is preferably 5～50 μ m, more preferably 10～40 μ m.The thickness of said supporting layer is preferred 5-50 μ m, more preferably 10-40 μ m.The film gross thickness is preferably 10 μ m～150 μ m, more preferably 25 μ m～100 μ m.
The present invention also provides a kind of preparation method of thin polymer film, comprising: with complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester are respectively as in the layering screw rod casting machine;
Said complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester melting mixing, curtain coating respectively form thin polymer film;
Wherein said complete biodegradable polyester forms one deck supporting layer at least; Said high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1, the 2-propylene diester forms one deck barrier layer at least.
Gather carbonic acid 1,2-dipropyl pellet can be bought or preparation voluntarily, and the present invention preferably uses preparation voluntarily.
With percentage by weight is the high-molecular-weight poly carbonic acid 1 of 91-97%; 2-propylene diester and percentage by weight are anticaking agent blend 3～10 minutes (800-1500r/min) in high-speed mixer that the plasticizer of 1-5%, heat stabilizer that percentage by weight is 1-2% and percentage by weight are 1%-2%; Mixture is 20-50 through draw ratio then; The best is extruded at 100-180 ℃ of following melt blending for the double screw extruder of 35-42, adopts water-cooled tie rod pelletizing or granulation underwater, and the gained particle is through 40 ℃ of-50 ℃ of air-flows or after vacuum drying 2-10 hour; Obtain and gather carbonic acid 1,2-dipropyl pellet.
According to the present invention, plasticizer is preferably: molecular weight is smaller or equal to 2000 polyethylene glycol (PEG), molecular weight one or more mixtures less than 10000 polyester plasticizer, ATBC, tributyl 2-acetylcitrate, glyceryl triacetate, diallyl phthalate and dibutyl succinate.
Heat stabilizer is preferably: maleic anhydride, phthalic anhydride, succinyl oxide, THPA, HHPA, carbodiimides, polycarbodiimide, stearic one or more mixtures.
Anticaking agent is preferably: one or both mixtures of gas phase nano white carbon, precipitated silica.
Nanometer is covered holder land reform property and is gathered carbonic acid 1, the preparation method of 2-dipropyl pellet:
With percentage by weight is 86-96.8%; The interlamellar spacing that anticaking agent that percentage by weight is the plasticizer of 1-5%, heat stabilizer that percentage by weight is 1-2%, percentage by weight is 1%-2% and percentage by weight are 0.2-5% is more than or equal to nano imvite blend 3-10 minute (1000-1500r/min) in high-speed mixer of 2 nanometers; Mixture is 20-50 through draw ratio then; Best extrude at 100～160 ℃ of following melt blendings for the double screw extruder of 35-42, employing water-cooled tie rod pelletizing or granulation underwater, gained particle are through 40 ℃ of air-flows or vacuum drying after 2～10 hours; Obtain nanometer illiteracy holder land reform property and gather carbonic acid 1,2-dipropyl pellet.
Plasticizer is preferably: molecular weight is smaller or equal to 2000 polyethylene glycol (PEG), molecular weight one or more mixtures less than 10000 polyester plasticizer, ATBC, tributyl 2-acetylcitrate, glyceryl triacetate, diallyl phthalate and dibutyl succinate.
Heat stabilizer is preferably: maleic anhydride, phthalic anhydride, succinyl oxide, THPA, HHPA, carbodiimides, polycarbodiimide, stearic one or more mixtures.
Anticaking agent is preferably: one or both mixtures of gas phase nano white carbon, precipitated silica.
According to the present invention, the method for making of thin polymer film is following:
Multi-layer co-extruded casting apparatus is with the multi-layer co-extruded casting apparatus of single screw rod, different complete biodegradable polyester dropped into respectively in the different single screw extrusion machines of three layers or five-layer co-squeezing casting apparatus, and wherein the control of each section of single screw extrusion machine temperature and head temperature is as follows:
Extruder one district: 100～160 ℃
Extruder two districts: 140～200 ℃
Extruder three districts: 140～200 ℃
Die head temperature: 180～200 ℃
Thickness ratio through different each layers of rate of feeding adjustment; Through hauling speed adjustment overall film thickness; Used single screw extrusion machine is a gradual change type; Compression ratio is controlled between 2.8～3.2, and extruder reduces acute angle and dead angle as far as possible with a mouthful mould runner, prevents that material from causing the thermal degradation of material because of long-time the delay.
Thin polymer film provided by the present invention has suitable oxygen barrier performance film, has the good transparency, can directly contact with food, and the oxygen transit dose of its film and PEN, PA66 are suitable, belongs to better-than-average level oxygen Obstruct membrane; In full accord or the slightly raising of physical and mechanical properties and commercially available biodegradable film, this film can be used for agricultural lining film, and prevents to cause white pollution; Also can be applicable to packaging for foodstuff, help prolonging the shelf life of food.
Below will set forth the present invention program with specific embodiment:
Embodiment 1:
With percentage by weight 96% PPC; Percentage by weight is that 2% diallyl phthalate, percentage by weight are that 1% stearic acid and percentage by weight are gas-phase silica blend 5 minutes (1000r/min) in high-speed mixer of 1%; Mixture is that 35 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then, adopts the pelletizing of water-cooled tie rod, and the gained particle is through 40 ℃ of vacuum drying after 10 hours; Obtain and gather carbonic acid 1,2-dipropyl pellet (PPC pellet).
Respectively with PBAT/PPC pellet/PB S as outer, in, internal layer drops in three layers of single screw rod curtain coating unit, three sections temperature of ectonexine screw rod are respectively: 150 ℃, 190 ℃ and 190 ℃.The intermediate layer temperature is: 110 ℃, 180 ℃, 100 ℃. 190 ℃ of head temperatures.Start three simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 15 μ m, and each layer thickness is 5 μ m, 5 μ m, 5 μ m, and film performance is seen attached list.
Embodiment 2:
With percentage by weight 91.5% PPC; Percentage by weight is that 3% PEG400, percentage by weight are that 1% stearic acid, percentage by weight are that 1% maleic anhydride, percentage by weight are that 1.5% white carbon and percentage by weight are nano imvite (the Zhejiang Feng Hong DK-2 of company) blend 10 minutes (1500r/min) in high-speed mixer of 2%; Mixture is that 42 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then; Adopt the pelletizing of water-cooled tie rod; The gained particle after 5 hours, obtains the nano montmorillonite modified carbonic acid 1 that gathers through 45 ℃ of heated-air dryings, 2-dipropyl pellet (nano montmorillonite modified PPC pellet).
Respectively with the nano montmorillonite modified PPC/PBS/PBAT of PBAT/PBS/ respectively as the 1-5 layer, drop in five layers of single screw rod curtain coating unit, PB S and PBAT layer temperature are: 140 ℃, 190 ℃ and 185 ℃.Nano montmorillonite modified PPC layer temperature is: 110 ℃, 180 ℃, 180 ℃. 195 ℃ of head temperatures.Start five simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 40 μ m, each layer thickness is 10 μ m, 5 μ m, 10 μ m, 5 μ m, 10 μ m film performances are seen attached list.
Embodiment 3:
With percentage by weight 95% PPC; Percentage by weight is that 2% adjacent glyceryl triacetate, percentage by weight are that 1% polycarbodiimide and percentage by weight are gas-phase silica blend 8 minutes (1000r/min) in high-speed mixer of 2%; Mixture is that 27 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then, adopts underwater cutpellet, and the gained particle is through 40 ℃ of vacuum drying after 10 hours; Obtain and gather carbonic acid 1,2-dipropyl pellet (PPC pellet).
Respectively PBAT/PPC pellet/PBAT/PPC pellet/PBAT is dropped in five layers of single screw rod curtain coating unit as the 1-5 layer, three sections temperature of PBAT layer screw rod are respectively: 160 ℃, 190 ℃ and 200 ℃.PPC layer temperature is: 120 ℃, 180 ℃, 190 ℃. 190 ℃ of head temperatures.Start three simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 50 μ m, and each layer thickness is 10 μ m, 10 μ m, 10 μ m, and 10 μ m, 10 μ m film performances are seen attached list.
Embodiment 4:
With percentage by weight 95.5% PPC; Percentage by weight is that 1% cetomacrogol 1000, percentage by weight are that 1% stearic acid, percentage by weight are that 1% phthalic anhydride, percentage by weight are that 1% white carbon and percentage by weight are 0.5% nano imvite (softex kw modified montmorillonoid; Interlamellar spacing is 2nm) blend 10 minutes (1000r/min) in high-speed mixer; Mixture is that 35 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then; Adopt the pelletizing of water-cooled tie rod; The gained particle after 4 hours, obtains the nano montmorillonite modified carbonic acid 1 that gathers through 40 ℃ of heated-air dryings, 2-dipropyl pellet (nano montmorillonite modified PPC pellet).
Respectively with the nano montmorillonite modified PPC/PBS of the nano montmorillonite modified PPC/PBAT/ of PBS/ respectively as the 1-5 layer, drop in five layers of single screw rod curtain coating unit, PB S and PBAT layer temperature are: 140 ℃, 190 ℃ and 185 ℃.Nano montmorillonite modified PPC layer temperature is: 110 ℃, 180 ℃, 180 ℃. 195 ℃ of head temperatures.Start five simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 130 μ m, each layer thickness is 10 μ m, 30 μ m, 50 μ m, 30 μ m, 10 μ m film performances are seen attached list.
Embodiment 5:
With percentage by weight 91% PPC; Percentage by weight is that 1% ATBC, percentage by weight are that 2% glyceryl triacetate, percentage by weight are that 1% THPA, percentage by weight are that 1% gas-phase silica and percentage by weight are nano imvite (U.S. south clay cloisite 20A of company) blend 7 minutes (1500r/min) in high-speed mixer of 4%; Mixture is that 42 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then; Adopt the pelletizing of water-cooled tie rod; The gained particle is through 40 ℃ of heated-air dryings after 2 hours; Obtain the nano montmorillonite modified carbonic acid 1 that gathers, 2-dipropyl pellet (nano montmorillonite modified PPC pellet).
Respectively with the nano montmorillonite modified PPC/PBAT/ of PBAT/ respectively as the 1-3 layer, drop in three layers of single screw rod curtain coating unit, PB S and PBAT layer temperature are: 140 ℃, 190 ℃ and 200 ℃.Nano montmorillonite modified PPC layer temperature is: 110 ℃, 180 ℃, 190 ℃. 195 ℃ of head temperatures.Start three simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 90 μ m, and each layer thickness is 30 μ m, 30 μ m, 30 μ m, and film performance is seen attached list.
Embodiment 6:
With percentage by weight 91.5% PPC; Percentage by weight is that 3% PEG400, percentage by weight are that 1% stearic acid, percentage by weight are that 1% maleic anhydride, percentage by weight are that 1.5% white carbon and percentage by weight are nano imvite (the Zhejiang Feng Hong DK-2 of company) blend 10 minutes (1500r/min) in high-speed mixer of 2%; Mixture is that 42 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then; Adopt the pelletizing of water-cooled tie rod; The gained particle after 5 hours, obtains the nano montmorillonite modified carbonic acid 1 that gathers through 45 ℃ of heated-air dryings, 2-dipropyl pellet (nano montmorillonite modified PPC pellet).
Respectively with the nano montmorillonite modified PPC/PEA/PBAT of PBAT/PES/ respectively as the 1-5 layer, drop in five layers of single screw rod curtain coating unit, the supporting layer temperature is: 140 ℃, 190 ℃ and 185 ℃.Nano montmorillonite modified PPC layer temperature is: 110 ℃, 180 ℃, 180 ℃. 195 ℃ of head temperatures.Start five simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 40 μ m, each layer thickness is 10 μ m, 5 μ m, 10 μ m, 5 μ m, 10 μ m film performances are seen attached list.
Embodiment 7:
With percentage by weight 95.5% PPC; Percentage by weight is that 1% cetomacrogol 1000, percentage by weight are that 1% stearic acid, percentage by weight are that 1% phthalic anhydride, percentage by weight are that 1% white carbon and percentage by weight are 0.5% nano imvite (softex kw modified montmorillonoid; Interlamellar spacing is 2nm) blend 10 minutes (1000r/min) in high-speed mixer; Mixture is that 35 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then; Adopt the pelletizing of water-cooled tie rod; The gained particle after 4 hours, obtains the nano montmorillonite modified carbonic acid 1 that gathers through 40 ℃ of heated-air dryings, 2-dipropyl pellet (nano montmorillonite modified PPC pellet).
Respectively with the nano montmorillonite modified PPC/PBSA of the nano montmorillonite modified PPC/PBST/ of PBSA/ respectively as the 1-5 layer, drop in five layers of single screw rod curtain coating unit, the supporting layer temperature is: 140 ℃, 190 ℃ and 185 ℃.Nano montmorillonite modified PPC layer temperature is: 110 ℃, 180 ℃, 180 ℃. 195 ℃ of head temperatures.Start five simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 130 μ m, each layer thickness is 10 μ m, 30 μ m, 50 μ m, 30 μ m, 10 μ m film performances are seen attached list.
Embodiment 8:
With percentage by weight 95% PPC; Percentage by weight is that 2% adjacent glyceryl triacetate, percentage by weight are that 1% polycarbodiimide and percentage by weight are gas-phase silica blend 8 minutes (1000r/min) in high-speed mixer of 2%; Mixture is that 27 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then, adopts underwater cutpellet, and the gained particle is through 40 ℃ of vacuum drying after 10 hours; Obtain and gather carbonic acid 1,2-dipropyl pellet (PPC pellet).
Respectively PHA/PPC pellet/PBST/PPC pellet/PHA is dropped in five layers of single screw rod curtain coating unit as the 1-5 layer, three sections temperature of supporting layer screw rod are respectively: 160 ℃, 190 ℃ and 200 ℃.PPC layer temperature is: 120 ℃, 180 ℃, 190 ℃. 190 ℃ of head temperatures.Start three simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 50 μ m, and each layer thickness is 10 μ m, 10 μ m, 10 μ m, and 10 μ m, 10 μ m film performances are seen attached list.
Embodiment 9:
With percentage by weight 91% PPC; Percentage by weight is that 1% ATBC, percentage by weight are that 2% glyceryl triacetate, percentage by weight are that 1% THPA, percentage by weight are that 1% gas-phase silica and percentage by weight are nano imvite (U.S. south clay cloisite 20A of company) blend 7 minutes (1500r/min) in high-speed mixer of 4%; Mixture is that 42 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then; Adopt the pelletizing of water-cooled tie rod; The gained particle is through 40 ℃ of heated-air dryings after 2 hours; Obtain the nano montmorillonite modified carbonic acid 1 that gathers, 2-dipropyl pellet (nano montmorillonite modified PPC pellet).
Respectively with the nano montmorillonite modified PPC/PBSPS/ of PPA/ respectively as the 1-3 layer, drop in three layers of single screw rod curtain coating unit, the supporting layer temperature is: 140 ℃, 190 ℃ and 200 ℃.Nano montmorillonite modified PPC layer temperature is: 110 ℃, 180 ℃, 190 ℃. 195 ℃ of head temperatures.Start three simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 90 μ m, and each layer thickness is 30 μ m, 30 μ m, 30 μ m, and film performance is seen attached list.
Embodiment 10:
With percentage by weight 96% PPC; Percentage by weight is that 2% diallyl phthalate, percentage by weight are that 1% stearic acid and percentage by weight are gas-phase silica blend 5 minutes (1000r/min) in high-speed mixer of 1%; Mixture is that 35 double screw extruder is extruded at 100～160 ℃ of following melt blendings through draw ratio then, adopts the pelletizing of water-cooled tie rod, and the gained particle is through 40 ℃ of vacuum drying after 10 hours; Obtain and gather carbonic acid 1,2-dipropyl pellet (PPC pellet).
Respectively with PBST/PPC pellet/PHA as outer, in, internal layer drops in three layers of single screw rod curtain coating unit, three sections temperature of ectonexine screw rod are respectively: 150 ℃, 190 ℃ and 190 ℃.The intermediate layer temperature is: 110 ℃, 180 ℃, 100 ℃. 190 ℃ of head temperatures.Start three simultaneously and extrude unit, preparation composite oxygen barrier film, film thickness is 15 μ m, and each layer thickness is 5 μ m, 5 μ m, 5 μ m, and film performance is seen attached list.
The thin polymer film mechanical performance of table 1 embodiment 1～10 preparation
More than a kind of thin polymer film provided by the invention and preparation method thereof has been carried out detailed introduction; Having used concrete example among this paper sets forth principle of the present invention and embodiment; The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a thin polymer film is characterized in that, comprising: one deck supporting layer and one deck barrier layer at least at least, and said barrier layer comprises high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester; Said supporting layer comprises the complete biodegradable polyester.
2. thin polymer film according to claim 1 is characterized in that said barrier layer comprises high-molecular-weight poly carbonic acid 1, and 2-propylene diester number-average molecular weight is 40000～300000g/mol, and molecular weight distribution is 2.0～7.0; The nano montmorillonite modified carbonic acid 1 that gathers, the nano imvite that the 2-propylene diester adopts is the modified Nano imvite of interlamellar spacing more than or equal to 2nm, the weight percent amount is 0.2～5%.
3. thin polymer film according to claim 1; It is characterized in that the material that said supporting layer is selected for use comprises: poly butylene succinate, polyethylene glycol succinate, polyethylene glycol adipate, PPA, poly adipate succinic acid ester, gather adipic acid hexylene glycol ester, poly-succinic/adipic acid-butanediol ester, gather (butylene terephthalate ester-co-tetramethylene adipate), gather (butylene terephthalate ester-co-succinic acid-butanediol ester) and gather in (butylene terephthalate ester-co-succinic acid propylene glycol ester) one or more.
4. thin polymer film according to claim 3 is characterized in that, the number-average molecular weight of the material that said supporting layer is selected for use is 40000～200000g/mol, and molecular weight distribution is 1.5～6.0.
5. thin polymer film according to claim 1 is characterized in that, the gross thickness of said thin polymer film is 10 μ m～150 μ m.
6. thin polymer film according to claim 1 is characterized in that, the thickness of said barrier layer is 5～50 μ m; Said supporting layer thickness is 5-50 μ m.
7. thin polymer film according to claim 1 is characterized in that said barrier layer also comprises plasticizer, heat stabilizer and anticaking agent.
8. the preparation method of a thin polymer film is characterized in that, comprising:
With complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester are respectively as in the layering screw rod casting machine;
Said complete biodegradable polyester and high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1,2-propylene diester melting mixing, curtain coating respectively form thin polymer film;
Wherein said complete biodegradable polyester forms one deck supporting layer at least; Said high-molecular-weight poly carbonic acid 1,2-propylene diester or nano montmorillonite modified high-molecular-weight poly carbonic acid 1, the 2-propylene diester forms one deck barrier layer at least.
9. preparation method according to claim 8 is characterized in that, said high-molecular-weight poly carbonic acid 1, and the preparation method of 2-propylene diester is:
With percentage by weight is the high-molecular-weight poly carbonic acid 1 of 91-97%; 2-propylene diester, percentage by weight are anticaking agent blend 3～10min in high-speed mixer that the plasticizer of 1-5%, heat stabilizer that percentage by weight is 1-2% and percentage by weight are 1%-2%, obtain mixture;
With said mixture melting mixing in extruder, extrude the back granulation, obtain gathering carbonic acid 1, the 2-propylene diester.
10. preparation method according to claim 8; It is characterized in that said plasticizer is: molecular weight smaller or equal to 2000 polyethylene glycol (PEG), molecular weight less than in 10000 polyester plasticizer, ATBC, tributyl 2-acetylcitrate, glyceryl triacetate, diallyl phthalate and the dibutyl succinate one or more;
Heat stabilizer is: one or more in maleic anhydride, phthalic anhydride, succinyl oxide, THPA, HHPA, carbodiimides, polycarbodiimide and the stearic acid;
Anticaking agent is: one kind of multiple in gas phase nano white carbon, the precipitated silica.
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| CN103568244A (en) * | 2013-10-23 | 2014-02-12 | 巨石集团有限公司 | Method for improving plasticizing effect of casting wrapping film |
| CN103640290A (en) * | 2013-12-13 | 2014-03-19 | 山东汇盈新材料科技有限公司 | Completely biodegradable composite membrane with high barrier property |
| CN104691067A (en) * | 2015-03-06 | 2015-06-10 | 北京工商大学 | Biodegradable multilayer material with adjustable gas transmission rate and preparation method and applications thereof |
| CN105482385A (en) * | 2016-01-20 | 2016-04-13 | 中国科学院长春应用化学研究所 | Biodegradable agricultural mulching film and preparation method thereof |
| CN110643153A (en) * | 2017-10-20 | 2020-01-03 | 福建恒安卫生材料有限公司 | Preparation method of nano-silver antibacterial biodegradable film |
| CN113650382A (en) * | 2021-08-27 | 2021-11-16 | 厦门艾美森新材料科技股份有限公司 | Film with ultra-long shelf life and capable of being completely degraded for air cushion and preparation method of film |
| CN114007841A (en) * | 2019-03-28 | 2022-02-01 | 卡比奥利司公司 | Multilayer article comprising an enzyme |
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| CN102007001A (en) * | 2009-06-19 | 2011-04-06 | 中国海洋石油总公司 | Biodegradable composite oxygen-barrier film and use thereof |
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Patent Citations (1)
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| CN102007001A (en) * | 2009-06-19 | 2011-04-06 | 中国海洋石油总公司 | Biodegradable composite oxygen-barrier film and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103568244A (en) * | 2013-10-23 | 2014-02-12 | 巨石集团有限公司 | Method for improving plasticizing effect of casting wrapping film |
| CN103568244B (en) * | 2013-10-23 | 2016-01-20 | 巨石集团有限公司 | A kind of method improving curtain coating winding film plasticizing effect |
| CN103640290A (en) * | 2013-12-13 | 2014-03-19 | 山东汇盈新材料科技有限公司 | Completely biodegradable composite membrane with high barrier property |
| CN104691067A (en) * | 2015-03-06 | 2015-06-10 | 北京工商大学 | Biodegradable multilayer material with adjustable gas transmission rate and preparation method and applications thereof |
| CN105482385A (en) * | 2016-01-20 | 2016-04-13 | 中国科学院长春应用化学研究所 | Biodegradable agricultural mulching film and preparation method thereof |
| CN110643153A (en) * | 2017-10-20 | 2020-01-03 | 福建恒安卫生材料有限公司 | Preparation method of nano-silver antibacterial biodegradable film |
| CN110643153B (en) * | 2017-10-20 | 2022-02-15 | 福建恒安卫生材料有限公司 | Preparation method of nano-silver antibacterial biodegradable film |
| CN114007841A (en) * | 2019-03-28 | 2022-02-01 | 卡比奥利司公司 | Multilayer article comprising an enzyme |
| CN114007841B (en) * | 2019-03-28 | 2024-04-09 | 卡比奥利司公司 | Multilayer article comprising enzymes |
| CN113650382A (en) * | 2021-08-27 | 2021-11-16 | 厦门艾美森新材料科技股份有限公司 | Film with ultra-long shelf life and capable of being completely degraded for air cushion and preparation method of film |
| CN113650382B (en) * | 2021-08-27 | 2023-02-10 | 厦门艾美森新材料科技股份有限公司 | Film with ultra-long shelf life and capable of being completely degraded for air cushion and preparation method of film |
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