CN105602217A - Environment-friendly high-strength barrier film - Google Patents
Environment-friendly high-strength barrier film Download PDFInfo
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- CN105602217A CN105602217A CN201610145390.0A CN201610145390A CN105602217A CN 105602217 A CN105602217 A CN 105602217A CN 201610145390 A CN201610145390 A CN 201610145390A CN 105602217 A CN105602217 A CN 105602217A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention relates to a multilayer polylactic acid composite barrier high-strength film which is compounded from multiple layers. The barrier film comprises an outer polylactic acid hydrophobic film, a middle polylactic acid barrier film and a bottom polylactic acid reinforcing film. The barrier film is characterized in that a hot-melt adhesive film is respectively arranged between the outer polylactic acid hydrophobic strong film and middle polylactic acid barrier film and between the middle polylactic acid barrier film and bottom polylactic acid elastic film. The composite film has the advantages of excellent strength, excellent gas barrier property, excellent heat insulation property and environment-friendly materials, and can be used for packaging in multiple fields.
Description
Technical field
The present invention relates to a kind of preparation method of film, relate in particular to a kind of poly-breast with excellent in strength, excellent barrierThe preparation method of acid environmental protection composite membrane.
Background technology
Although plastic material has more excellent performance and applicability widely, it derives from oil product and cannot fallSeparate, in crisis of resource and environmental pollution serious all the more today, finding function admirable and reproducible substitution material becomes orderThe most important thing of front Material Field research.
At present, film consumption is increasing, although and the plastic foil extensively adopting has well as PE film, PP film, PET film etc.Mechanical property, and prepare simple and easyly, but cannot degrade, caused serious white pollution.
In degradation material, starch because of its cheap price and widely source furtherd investigate and by modification withCompound multiple life and the industrial goods prepared, as starch basement membrane, starch dishware etc. But starch has its natural defect, itPoor mechanical property, unstable properties, can only apply to the field low to mechanical property requirements. And the appearance of PLA has changed thisOne present situation. PLA (PLA) is aliphatic polyester, taking lactic acid (2 hydroxy propanoic acid) as basic structural unit. PLA can be by fermentationThe natural materials such as corn make, and also can adopt lactic acid polycondensation to make. PLA and end product thereof can naturally divide under composting conditionsSolution becomes CO2And water, reduce solid waste discharge amount, be a kind of biogenetic derivation material of environmental protection. Although PLAThere is good biodegradability, machinability, good mechanical property, but its property is crisp frangible, lacks flexibility with pliable and toughProperty, limit to a great extent the application of polylactic acid membrane. And how to improve the mechanical property of polylactic acid membrane, reach suitable applicationsDegree, meanwhile, further develops that it is functional to provide film more special-effect, will have undoubtedly extraordinary prospect.
Have chemical modification and physical modification for the modification of PLA, chemical modification is by synthesis phase molecular structureDesign carrys out the performance of controlled material, but often very high to equipment, technological requirement, cannot simple realization, also significantly improveCost. Physical modification adopts the mode of blend, and the performance of comprehensive different material, although be not a kind of basic mode, is doneWith macroscopical film application, can effectively solve functional problem. The study on the modification of a lot of PLAs is also for carrying out in this respect. AsDisclosed a kind of transparent high-toughness polylactic acid film of CN103467941B and preparation method thereof, the disclosed one of CN105199348A is highThe preparation method of strength high toughness heat-proof polylactic acid basal lamina material etc., thus be all to adopt the blend of different material to improve single filmPerformance.
Summary of the invention
The object of the invention is for polylactic acid membrane intensity difference and cannot realize the defect of barrier, providing one to there is excellenceThe preparation method of the blend film of intensity and barrier.
The object of the invention is to be achieved through the following technical solutions:
A kind of environment-friendly high-intensity Obstruct membrane, comprises polylactic resin, EVOH resin, Graphene graft, PLA-g-PVA by major ingredientCopolymer, SBS elastomer are major ingredient, and auxiliary material comprises the compositions such as antioxidant, delustering agent, UV resistant agent, processing aid. Major ingredientIn, the mass fraction of polylactic resin between 30-50%, the mass fraction of EVOH resin between 20-40%, PLA-g-The mass fraction of PVA copolymer between 8-15%, the elastomeric mass fraction of SBS between 10-15%, Graphene graftingThing mass fraction between 2-4%; In auxiliary material, the quality of antioxidant, UV resistant agent, processing aid is all between major ingredientBetween the 2-4% of quality, the consumption of delustering agent is between the 0.1-0.3% of major ingredient quality.
Further, the PLA described in the present invention is Pfansteihl, D-ALPHA-Hydroxypropionic acid or L, D-ALPHA-Hydroxypropionic acid composition, this PLA pointSon amount the best is 300000-500000g/mol, is 150000-300000g/mol again, is 80000-150000g/ againmol。
Further, described PLA-g-PVA copolymer can adopt polyvinyl alcohol and lactic acid directly under the catalysis of stannic chloride, to contractPoly-.
Concrete technology condition can bibliography " Industrial&EngineeringChemistryResearch ",2008,48 (2): the method that 788-793 records is synthetic. According to the ratio of PVA and PLA in the ratio adjustment copolymer of monomer,In PLA-g-PVA copolymer, the mass fraction of PLA is not less than 20%, preferred, the mass fraction of PLA in PLA-g-PVA copolymerBetween between 25%-35%.
Further, the PVA molecular weight of PLA-g-PVA copolymer chain is between 6000-15000.
Further, described Graphene graft is the one in Graphene grafting polyisoprene and Graphene grafted polystyreneOr both arbitrary proportions mix. The preparation method of Graphene grafting polyisoprene is the polyisoprene of: Bei perylene processed acid anhydride end-blocking,Thereby in the building-up process of polyisoprene, prepare different molecular by controlling n-BuLi from the different rate of charges of monomerThe polyisoprene of amount, under same anhydrous and oxygen-free condition, Jia Ru perylene acid anhydride molecule carries out end-blocking to polyisoprene chain; Exist, thereafterGraphene in solution environmental is Yu the polyisoprene chain of perylene acid anhydride end-blocking carries out the non-covalent combination of pi-pi bond accumulation, thus preparation instituteThe Graphene grafting polyisoprene needing. Wherein, the grafting degree of polyisoprene (adopting mass ratio to calculate) is between 0.5%-1.2%Between. The preparation method of the preparation method of Graphene grafted polystyrene and above-mentioned Graphene grafting polyisoprene is similar, onlyChange synthon into styrene monomer by isoprene.
Further, described antioxidant is antioxidant 264, BHT, one or more in 168,1010.
Further, described processing aid is the one in calcium stearate, butyl stearate.
Further, described UV resistant agent is commodity Ultraviolet Absorber UV-P.
Further, described delustering agent can be commercially available prod, as delustering agent OB-1.
Further, the processing technology of described environment-friendly high-intensity Obstruct membrane is:
(1) by all vacuum drying 24 hours under 50 degree of all raw materials, for subsequent use;
(2) by after the EVOH resin of polylactic resin, 50% quality, SBS elastomer and the blend of auxiliary material high speed, melt extrude, cutGrain obtains masterbatch A, and it melt extrudes temperature is 190-210 degree, and screw speed is 150-200rad/min, and the time of staying is 1-2Minute.
(3) by the EVOH resin high speed blend of masterbatch A and Graphene graft, PLA-g-PVA copolymer, 50% qualityAfter, to extrude by melt blending, pelletizing obtains masterbatch B, and it melt extrudes temperature is 180-200 degree, and screw speed is 100-150rad/min, the time of staying is 2-3 minute.
(4) masterbatch B is obtained to PP TYPE by blow moulding machine blown film, blow temperatures is 200-220 DEG C, and blow-up ratio is situated betweenBetween 2-4.
Detailed description of the invention
Below will describe exemplary implementation method of the present invention in detail. But these implementation methods are only exemplary object, andThe invention is not restricted to this.
Embodiment 1
A kind of environment-friendly high-intensity Obstruct membrane, comprises polylactic resin, EVOH resin, Graphene graft, PLA-g-PVA by major ingredientCopolymer, SBS elastomer are major ingredient, and auxiliary material comprises the compositions such as antioxidant, delustering agent, UV resistant agent, processing aid. Major ingredientIn, the mass fraction of polylactic resin is that the mass fraction of 42%, EVOH resin is that the quality of 32%, PLA-g-PVA copolymer is dividedNumber is that the elastomeric mass fraction of 12%, SBS is 11%, Graphene graft mass fraction be 3%; Antioxidant in auxiliary material,The quality of UV resistant agent, processing aid is all situated between for 3% of major ingredient quality, and the consumption of delustering agent is 0.2% of major ingredient quality.
Described PLA is Pfansteihl, and the molecular weight of this PLA is 80000-150000g/mol.
The PVA molecular weight of described PLA-g-PVA copolymer chain is 8000, and in copolymer, the mass fraction of PLA is 25%.
Described Graphene graft is Graphene grafting polyisoprene. Wherein, the grafting degree of polyisoprene (adopts mass ratioCalculate) be 0.8%.
Described antioxidant is antioxidant 264.
Described processing aid is calcium stearate.
Described UV resistant agent is commodity Ultraviolet Absorber UV-P.
Described delustering agent can be commercially available prod, as delustering agent OB-1.
The processing technology of described environment-friendly high-intensity Obstruct membrane is:
(1) by all vacuum drying 24 hours under 50 degree of all raw materials, for subsequent use;
(2) by after the EVOH resin of polylactic resin, 50% quality, SBS elastomer and the blend of auxiliary material high speed, melt extrude, cutGrain obtains masterbatch A, and it melt extrudes temperature is 190-210 degree, and screw speed is 180rad/min, and the time of staying is 1-2 minute;
(3) by after the EVOH resin high speed blend of masterbatch A and Graphene graft, PLA-g-PVA copolymer, 50% quality, logicalCross melting blending extrusion, pelletizing obtains masterbatch B, and it melt extrudes temperature is 180-200 degree, and screw speed is 120rad/min,The time of staying is 2-3 minute;
(4) masterbatch B is obtained to PP TYPE by blow moulding machine blown film, blow temperatures is 200-220 DEG C, and blow-up ratio is 3.5.
Embodiment 2
A kind of environment-friendly high-intensity Obstruct membrane, comprises polylactic resin, EVOH resin, Graphene graft, PLA-g-PVA by major ingredientCopolymer, SBS elastomer are major ingredient, and auxiliary material comprises the compositions such as antioxidant, delustering agent, UV resistant agent, processing aid. Major ingredientIn, the mass fraction of polylactic resin is that the mass fraction of 45%, EVOH resin is that the quality of 30%, PLA-g-PVA copolymer is dividedNumber is that the elastomeric mass fraction of 9.5%, SBS is 12%, Graphene graft mass fraction be 3.5%; Anti-oxidant in auxiliary materialThe quality of agent, UV resistant agent, processing aid is all situated between for 3% of major ingredient quality, and the consumption of delustering agent is 0.2% of major ingredient quality.
Described PLA is D-ALPHA-Hydroxypropionic acid, and the molecular weight of this PLA is 80000-150000g/mol.
The PVA molecular weight of described PLA-g-PVA copolymer chain is 10000, and in copolymer, the mass fraction of PLA is 30%.
Described Graphene graft is Graphene grafted polystyrene. Wherein, the grafting degree of polystyrene (adopts mass ratio meterCalculate) be 1.1%.
Described antioxidant is antioxidant 264.
Described processing aid is calcium stearate.
Described UV resistant agent is commodity Ultraviolet Absorber UV-P.
Described delustering agent can be commercially available prod, as delustering agent OB-1.
The processing technology of described environment-friendly high-intensity Obstruct membrane is:
(1) by all vacuum drying 24 hours under 50 degree of all raw materials, for subsequent use;
(2) by after the EVOH resin of polylactic resin, 50% quality, SBS elastomer and the blend of auxiliary material high speed, melt extrude, cutGrain obtains masterbatch A, and it melt extrudes temperature is 190-210 degree, and screw speed is 180rad/min, and the time of staying is 1-2 minute;
(3) by after the EVOH resin high speed blend of masterbatch A and Graphene graft, PLA-g-PVA copolymer, 50% quality, logicalCross melting blending extrusion, pelletizing obtains masterbatch B, and it melt extrudes temperature is 180-200 degree, and screw speed is 120rad/min,The time of staying is 2-3 minute;
(4) masterbatch B is obtained to PP TYPE by blow moulding machine blown film, blow temperatures is 200-220 DEG C, and blow-up ratio is 3.
The specific performance data of embodiment 1,2 are as follows:
Claims (4)
1. an environment-friendly high-intensity Obstruct membrane, comprises polylactic resin, EVOH resin, Graphene graft, PLA-g-by major ingredientPVA copolymer, SBS elastomer are major ingredient, and auxiliary material comprises the compositions such as antioxidant, delustering agent, UV resistant agent, processing aid.In major ingredient, the mass fraction of polylactic resin between 30-50%, the mass fraction of EVOH resin between 20-40%,The mass fraction of PLA-g-PVA copolymer between 8-15%, the elastomeric mass fraction of SBS between 10-15%, graphiteAlkene graft mass fraction between 2-4%; In auxiliary material, the quality of antioxidant, UV resistant agent, processing aid is all situated betweenBetween the 2-4% of major ingredient quality, the consumption of delustering agent is between the quality 0.1-0.3% of major ingredient.
2. a kind of environment-friendly high-intensity Obstruct membrane as claimed in claim 1, is characterized in that: described Graphene graft is graphiteOne in alkene grafting polyisoprene or Graphene grafted polystyrene or arbitrary proportion mix.
3. a kind of environment-friendly high-intensity Obstruct membrane as claimed in claim 1, is characterized in that: in described PLA-g-PVA copolymerThe mass fraction of PLA is not less than 20%.
4. a kind of environment-friendly high-intensity Obstruct membrane as claimed in claim 1, is characterized in that: its processing technology is:
(1) by all vacuum drying 24 hours under 50 degree of all raw materials, for subsequent use;
(2) by after the EVOH resin of polylactic resin, 50% quality, SBS elastomer and the blend of auxiliary material high speed, melt extrude pelletizingObtain masterbatch A, it melt extrudes temperature is 190-210 degree, and screw speed is 150-200rad/min, and the time of staying is that 1-2 dividesClock;
(3) by after the EVOH resin high speed blend of masterbatch A and Graphene graft, PLA-g-PVA copolymer, 50% quality, pass throughMelt blending is extruded, and pelletizing obtains masterbatch B, and it melt extrudes temperature is 180-200 degree, and screw speed is 100-150rad/Min, the time of staying is 2-3 minute;
(4) masterbatch B is obtained to PP TYPE by blow moulding machine blown film, blow temperatures is 200-220 DEG C, and blow-up ratio is between 2-4Between.
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| CN201610145390.0A CN105602217A (en) | 2016-03-15 | 2016-03-15 | Environment-friendly high-strength barrier film |
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| CN201610145390.0A CN105602217A (en) | 2016-03-15 | 2016-03-15 | Environment-friendly high-strength barrier film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968760A (en) * | 2016-07-01 | 2016-09-28 | 铜陵方正塑业科技有限公司 | Cyanobacteria-based biodegradable composite film material prepared by Cyanobacteria fermentation and preparation method thereof |
| CN114474650A (en) * | 2021-12-23 | 2022-05-13 | 镇江现代包装有限公司 | Preparation process of green environment-friendly packaging film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834134A (en) * | 2006-03-09 | 2006-09-20 | 四川大学 | Blend material of vinol/polylactic acid graft copolymer and starch, their prepn. and application |
| CN102993654A (en) * | 2012-11-23 | 2013-03-27 | 金发科技股份有限公司 | Biodegradable barrier thin film, as well as preparation method and application thereof |
| CN104403379A (en) * | 2014-11-30 | 2015-03-11 | 湖南科技大学 | Method for quickly functionalizing graphene with covalent polystyrene |
-
2016
- 2016-03-15 CN CN201610145390.0A patent/CN105602217A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834134A (en) * | 2006-03-09 | 2006-09-20 | 四川大学 | Blend material of vinol/polylactic acid graft copolymer and starch, their prepn. and application |
| CN102993654A (en) * | 2012-11-23 | 2013-03-27 | 金发科技股份有限公司 | Biodegradable barrier thin film, as well as preparation method and application thereof |
| CN104403379A (en) * | 2014-11-30 | 2015-03-11 | 湖南科技大学 | Method for quickly functionalizing graphene with covalent polystyrene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968760A (en) * | 2016-07-01 | 2016-09-28 | 铜陵方正塑业科技有限公司 | Cyanobacteria-based biodegradable composite film material prepared by Cyanobacteria fermentation and preparation method thereof |
| CN114474650A (en) * | 2021-12-23 | 2022-05-13 | 镇江现代包装有限公司 | Preparation process of green environment-friendly packaging film |
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Application publication date: 20160525 |