CN103232689A - Preparation method for polylactic acid film with toughness - Google Patents
Preparation method for polylactic acid film with toughness Download PDFInfo
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- CN103232689A CN103232689A CN2013101163247A CN201310116324A CN103232689A CN 103232689 A CN103232689 A CN 103232689A CN 2013101163247 A CN2013101163247 A CN 2013101163247A CN 201310116324 A CN201310116324 A CN 201310116324A CN 103232689 A CN103232689 A CN 103232689A
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a preparation method for a polylactic acid film with toughness. The preparation method comprises the following steps: 1, weighing, by weight, 80 to 90% of polylactic acid and 10 to 20% of two plasticizers, wherein the total weight of the polylactic acid and the plasticizers is 100%, then weighing 0.5 to 5 parts of montmorillonite and 0.5 to 3 parts of an anti-oxidant on the basis of each 100 parts of a mixture of the polylactic acid and the plasticizers and drying the polylactic acid and the montmorillonite in a drying box; 2, mixing the two plasticizers with the polylactic acid, the montmorillonite and the anti-oxidant to prepare a master batch; and 3, subjecting the master batch to reactive extrusion with a double-screw extruder, carrying out cooling in a cooling water bath, granulation and drying after extrusion of a material so as to obtain a composite material and preparing the polylactic acid film with the composite material used as a master batch. The polylactic acid film provided by the invention can be completely degraded in a natural environment after the polylactic acid film is used and discarded, and the polylactic acid film belongs to environmental protection materials.
Description
Technical field
The invention belongs to field of polymer material preparing technology, relate to a kind of preparation method of toughness polylactic acid film.
Background technology
The continuous aggravation of problems such as the environmental pollution that faces along with human society, shortage of resources, green is capable of circulation, resources sustainable development worldwide receives much concern, under such background, have degradable, reproducible bioabsorbable polymer material just arises at the historic moment, poly(lactic acid) is wherein a kind of, because it has nontoxic, good biocompatibility and tissue absorption, can be degraded into carbonic acid gas and water fully simultaneously.Poly(lactic acid) has plurality of advantages as a kind of degradable material, has good biodegradability and consistency as poly(lactic acid), and good glossiness and transparency are arranged.But poly(lactic acid) also has some to restrict the shortcoming of its application, and matter is crisp, does not have enough snappinesies, and intensity and thermostability also need to improve, so synthetic, the processing of poly(lactic acid), application and study on the modification are big focuses.
At present, improve its toughness under the prerequisite that guarantees the existing use properties of poly(lactic acid), the method that mechanical property and thermostability mainly adopt is the method for physics melt blending modification.Mentioned a kind of full-degradation natural fibre among the Chinese patent CN101200578A: polynite: the preparation method of lactic acid composite material, this matrix material is made up of natural fiber, poly(lactic acid), polynite, oxidation inhibitor and solubilizing agent, this matrix material is than pure poly(lactic acid), all increasing aspect mechanical property, flame retardant resistance and the thermal characteristics, be applicable to the engineering plastics of preparation condition requirement harshness.This matrix material is degraded fully faster under field conditions (factors) after use is discarded.But this material is still and belongs to hard brittle material, therefore, adopts the material of this method preparation to be very restricted in the application of film.
Be this defective of fragility in order to overcome poly(lactic acid) itself, usually the method that adopts is added softening agent exactly, poly(lactic acid) and softening agent melt blending are obtained polydactyl acid, increase along with plasticizer loading, the most tangible change of poly(lactic acid) is exactly that elongation at break obviously improves, and makes the use range of polylactic acid film obtain widening.But the interpolation of general softening agent can make the second-order transition temperature of poly(lactic acid) reduce, and plasticizer loading is more many, second-order transition temperature reduces more obvious, after softening agent is increased to a certain degree, the elongation at break of polylactic acid film has improved a lot, but second-order transition temperature is too low, has dropped to below the room temperature, and this has limited the use range of polylactic acid film again from another aspect.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of toughness polylactic acid film has solved the elongation at break of the polylactic acid film that exists in the prior art and the problem that two performance index of second-order transition temperature can not be taken into account simultaneously.
The technical solution adopted in the present invention is that a kind of preparation method of toughness polylactic acid film may further comprise the steps:
Step 1, take by weighing each component according to following weight percent: poly(lactic acid) is 80%-90%, and two kinds of softening agent add up to 10%-20%, and gross weight is 100%; In addition, again according to per 100 parts of poly(lactic acid): the compound of two kinds of softening agent takes by weighing the polynite of 0.5-5 part and 0.5-3 part antioxidant;
With poly(lactic acid) and polynite in 55-75 ℃ of loft drier drying treatment 8-16 hour, remove moisture;
Two kinds of softening agent mix in step 2, elder generation, mix the back and mix with poly(lactic acid) and polynite, mix with antioxidant more at last, make masterbatch;
Step 3, the masterbatch that step 2 is obtained, utilizing twin screw extruder to react extrudes, material is extruded by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, again matrix material is made polylactic acid film as masterbatch.
The invention has the beneficial effects as follows, can effectively improve the flexibility of polylactic acid film behind the interpolation softening agent, improve its elongation at break, the adding of polynite has not only improved the barrier of polylactic acid film, and the mechanical property of polylactic acid film also is improved; This preparation method is simply effective, has snappiness, mechanical property and high glass transition preferably, is beneficial to suitability for industrialized production.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
The preparation method of toughness polylactic acid film of the present invention, implement according to following concrete steps:
Step 1, take by weighing each component according to following weight percent: poly(lactic acid) is 80%-90%, and two kinds of softening agent add up to 10%-20%, and gross weight is 100%;
In addition, again according to per 100 parts of poly(lactic acid): the compound of two kinds of softening agent takes by weighing the polynite of 0.5-5 part and 0.5-3 part antioxidant;
With poly(lactic acid) and polynite in 55-75 ℃ of loft drier drying treatment 8-16 hour, remove moisture;
Two kinds of softening agent mix in step 2, elder generation, mix the back and mix with poly(lactic acid) and polynite, mix with antioxidant more at last, make masterbatch;
Step 3, the masterbatch that step 2 is obtained, utilizing twin screw extruder to react extrudes, the processing parameter of twin screw extruder is respectively: screw speed is 50-150rpm, the feeding rotating speed is 10-40rpm, forcing machine is respectively distinguished temperature and is respectively a district 135-150 ℃, two district 150-165 ℃, three district 165-175 ℃, four district 170-185 ℃, five district 175-190 ℃, six district 175-190 ℃, seven district 175-190 ℃, eight district 175-185 ℃, head 170-185 ℃, material is extruded by cooling trough and is cooled off, pelletizing, obtain poly(lactic acid)-polynite-two kind of softening agent matrix material after the drying; Again poly(lactic acid)-polynite-two kind of softening agent matrix material is made as masterbatch and have toughness polylactic acid film preferably.
Poly(lactic acid) is selected crystallization type polylactic acid for use, and degree of crystallinity is 30%-90%, is the fragility poly(lactic acid) without any modification.
The organic nano modified montmorillonoid is selected in polynite for use, is a kind of nano material that can be used for the poly-lactic acid material modification.
Softening agent is selected triethyl citrate, acetyl triethyl citrate, tributyl citrate, tributyl acetylcitrate, hexanaphthene 1 for use, in the 2-dioctyl phthalate dinonyl any two kinds.
The optimum ratio of two kinds of softening agent is tributyl citrate and hexanaphthene 1, and the summation of 2-dioctyl phthalate dinonyl is 16%, and wherein the content of tributyl citrate is 5%-11%, hexanaphthene 1, and the content of 2-dioctyl phthalate dinonyl is 5%-11%.
Antioxidant is selected any one in triphenyl phosphite, the β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, four [methyl-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester for use.
Embodiment 1
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 84%:16%, two kinds of softening agent wherein 12%:4% are by weight percentage selected tributyl citrate and hexanaphthene 1 for use, 2-dioctyl phthalate dinonyl, polynite is 0.5 part, antioxidant is 0.5 part, antioxidant is β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid;
With poly(lactic acid) and polynite in 55 ℃ of loft drier dry 16 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 50rpm, the feeding rotating speed is 10prm, and forcing machine is respectively distinguished temperature and is respectively 140 ℃ in a district, 160 ℃ in two districts, 170 ℃ in three districts, 175 ℃ in four districts, 180 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 185 ℃ in eight districts, 182 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 2
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 86%:14%, two kinds of softening agent 10%:4% are by weight percentage selected tributyl citrate for use: hexanaphthene 1,2-dioctyl phthalate dinonyl, polynite is 1 part, antioxidant is 1 part, and antioxidant is triphenyl phosphite;
With poly(lactic acid) and polynite in 60 ℃ of loft drier dry 12 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 60rpm, the feeding rotating speed is 15prm, and forcing machine is respectively distinguished temperature and is respectively 140 ℃ in a district, 160 ℃ in two districts, 170 ℃ in three districts, 175 ℃ in four districts, 180 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 180 ℃ in eight districts, 182 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 3
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 84%:16%, two kinds of softening agent are tributyl citrate and hexanaphthene 1,2-dioctyl phthalate dinonyl is 8%:8% by weight percentage, 2.0 parts of polynites, antioxidant is 2.0 parts, antioxidant is β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid;
With poly(lactic acid) and polynite in 65 ℃ of loft drier dry 10 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 70rpm, the feeding rotating speed is 20prm, and forcing machine is respectively distinguished temperature and is respectively 135 ℃ in a district, 155 ℃ in two districts, 165 ℃ in three districts, 175 ℃ in four districts, 180 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 180 ℃ in eight districts, 178 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 4
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 84%:16%, two kinds of softening agent are tributyl citrate and hexanaphthene 1,2-dioctyl phthalate dinonyl is 6%:10% by weight percentage, 4 parts of polynites, antioxidant is 1.5 parts, antioxidant is β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid;
With poly(lactic acid) and polynite in 75 ℃ of loft drier dry 8 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 80rpm, the feeding rotating speed is 26prm, and forcing machine is respectively distinguished temperature and is respectively 145 ℃ in a district, 155 ℃ in two districts, 165 ℃ in three districts, 170 ℃ in four districts, 175 ℃ in five districts, 180 ℃ in six districts, 185 ℃ in seven districts, 180 ℃ in eight districts, 182 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 5
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 84%:16%, two kinds of softening agent are tributyl citrate and hexanaphthene 1,2-dioctyl phthalate dinonyl is 4%:12% by weight percentage, 4 parts of polynites, antioxidant is 2.5 parts, and antioxidant is triphenyl phosphite;
With poly(lactic acid) and polynite in 70 ℃ of loft drier dry 10 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 90rpm, the feeding rotating speed is 30prm, and forcing machine is respectively distinguished temperature and is respectively 135 ℃ in a district, 155 ℃ in two districts, 165 ℃ in three districts, 175 ℃ in four districts, 185 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 175 ℃ in eight districts, 178 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 6
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 84%:16%, two kinds of softening agent are tributyl citrate and hexanaphthene 1,2-dioctyl phthalate dinonyl is 11%:5% by weight percentage, 4.5 parts of polynites, antioxidant is 2.0 parts, antioxidant is β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid;
With poly(lactic acid) and polynite in 65 ℃ of loft drier dry 9 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 140rpm, the feeding rotating speed is 40prm, and forcing machine is respectively distinguished temperature and is respectively 150 ℃ in a district, 155 ℃ in two districts, 170 ℃ in three districts, 175 ℃ in four districts, 180 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 180 ℃ in eight districts, 185 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 7
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 80%:20%, two kinds of softening agent are acetyl triethyl citrate and tributyl citrate 10%:10% by weight percentage, 5 parts of polynites, antioxidant is 3 parts, and antioxidant is triphenyl phosphite;
With poly(lactic acid) and polynite in 60 ℃ of loft drier dry 11 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 150rpm, the feeding rotating speed is 35prm, and forcing machine is respectively distinguished temperature and is respectively 150 ℃ in a district, 155 ℃ in two districts, 170 ℃ in three districts, 175 ℃ in four districts, 180 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 180 ℃ in eight districts, 185 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 8
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 90%:10%, two kinds of softening agent are triethyl citrate and tributyl acetylcitrate 5%:5% by weight percentage, 2.5 parts of polynites, antioxidant is 1.5 parts, antioxidant is β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid;
With poly(lactic acid) and polynite in 70 ℃ of loft drier dry 9 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 130rpm, the feeding rotating speed is 30prm, and forcing machine is respectively distinguished temperature and is respectively 150 ℃ in a district, 155 ℃ in two districts, 170 ℃ in three districts, 175 ℃ in four districts, 180 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 180 ℃ in eight districts, 185 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Embodiment 9
Step 1, elder generation take by weighing each component according to following weight percent: wherein poly(lactic acid) and two kinds of softening agent weight percents are 85%:15%, two kinds of softening agent are triethyl citrate and tributyl citrate 10%:5% by weight percentage, 1.5 parts of polynites, antioxidant is 2.5 parts, antioxidant is four [methyl-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
With poly(lactic acid) and polynite in 55 ℃ of loft drier dry 12 hours, remove moisture again.
Step 2, two kinds of softening agent and dried poly(lactic acid), polynite and antioxidant are mixed in drying receptacle, make masterbatch.
Step 3, with the masterbatch of making twin screw extruder melt blending, react and extrude, screw speed is 120rpm, the feeding rotating speed is 20prm, and forcing machine is respectively distinguished temperature and is respectively 150 ℃ in a district, 155 ℃ in two districts, 170 ℃ in three districts, 175 ℃ in four districts, 180 ℃ in five districts, 185 ℃ in six districts, 185 ℃ in seven districts, 180 ℃ in eight districts, 185 ℃ of heads.Material extrudes by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, matrix material made as masterbatch to have toughness polylactic acid film preferably again.
Adopt method of the present invention, when the softening agent that adds 16%, the elongation at break of polylactic acid film can improve about 50 times, and when plasticizer loading brings up to 20%, the elongation at break of polylactic acid film can improve 60 times.Polylactic acid film reduces along with the increase of polynite content in the lactic acid composite material the perviousness of oxygen, and when polynite content was 1.5 parts, with respect to pure polylactic acid film, lactic acid composite material had reduced about 35% the perviousness of oxygen.The second-order transition temperature of the lactic acid composite material for preparing by method provided by the invention is at 40-50 ℃.
Claims (7)
1. the preparation method of a toughness polylactic acid film is characterized in that, may further comprise the steps:
Step 1, take by weighing each component according to following weight percent: poly(lactic acid) is 80%-90%, and two kinds of softening agent add up to 10%-20%, and gross weight is 100%; In addition, again according to per 100 parts of poly(lactic acid): the compound of two kinds of softening agent takes by weighing the polynite of 0.5-5 part and 0.5-3 part antioxidant;
With poly(lactic acid) and polynite in 55-75 ℃ of loft drier drying treatment 8-16 hour, remove moisture;
Two kinds of softening agent mix in step 2, elder generation, mix the back and mix with poly(lactic acid) and polynite, mix with antioxidant more at last, make masterbatch;
Step 3, the masterbatch that step 2 is obtained, utilizing twin screw extruder to react extrudes, material is extruded by obtaining poly(lactic acid)-polynite-two kind of softening agent matrix material after cooling trough cooling, pelletizing, the drying, again matrix material is made polylactic acid film as masterbatch.
2. the preparation method of toughness polylactic acid film according to claim 1, it is characterized in that: described poly(lactic acid) is crystallization type polylactic acid, degree of crystallinity is 30%-90%.
3. the preparation method of toughness polylactic acid film according to claim 1, it is characterized in that: described polynite is the organic nano modified montmorillonoid.
4. the preparation method of toughness polylactic acid film according to claim 1, it is characterized in that: described antioxidant is selected triphenyl phosphite, β-(3 for use, the 5-di-tert-butyl-hydroxy phenyl) a kind of in the positive octadecanol ester of propionic acid, four [methyl-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
5. the preparation method of toughness polylactic acid film according to claim 1, it is characterized in that: described softening agent is selected triethyl citrate, acetyl triethyl citrate, tributyl citrate, tributyl acetylcitrate, hexanaphthene 1 for use, in the 2-dioctyl phthalate dinonyl two kinds.
6. the preparation method of toughness polylactic acid film according to claim 5, it is characterized in that: described softening agent is selected tributyl citrate and hexanaphthene 1 for use, 2-dioctyl phthalate dinonyl, summation is 16%, wherein the content of tributyl citrate is 5%-11%, hexanaphthene 1, the content of 2-dioctyl phthalate dinonyl is 5%-11%.
7. the preparation method of toughness polylactic acid film according to claim 1, it is characterized in that: in the described step 3, the processing parameter of twin screw extruder is, screw speed is 50-150rpm, the feeding rotating speed is 10-40rpm, and forcing machine is respectively distinguished temperature and is respectively a district 135-150 ℃, two district 150-165 ℃, three district 165-175 ℃, four district 170-185 ℃, five district 175-190 ℃, six district 175-190 ℃, seven district 175-190 ℃, eight district 175-185 ℃, head 170-185 ℃.
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