CN101983986A - Transparent and toughening polylactic acid resin and method for preparing the same - Google Patents
Transparent and toughening polylactic acid resin and method for preparing the same Download PDFInfo
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Abstract
The invention provides a transparent and toughening polylactic acid resin and method for preparing the same. The polylactic acid resin consists of polylactic acid, methyl methacrylate-butyl acrylate copolymer as the flexibilizer, citrate plasticizer, pentaerythritol toltetranitrate (Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-) as the antioxidant and tris (2,4-ditert-butylphenyl) phosphate. First, premix is prepared by mixing polylactic acid, flexibilizer, plasticizer and antioxidant mechanically. Then the premix is subject to melt extrusion and granulation by utilizing double-screw extruder. The above method has the advantages of increasing the anti-impact strength, tensile strength and elongation at break of polylactic acid and maintaining the transparency thereof. In addition, the viscosity of the blends is decreased, thereby remedying the defects of brittleness of polylactic acid and improving the rheological behavior of materials obviously. The impact strength is up to 60.1KJ/M2.The light transmittance and the haze of the products are 89% and 8.5% respectively when the thickness thereof is 0.04mm.The above polylactic acid resin, instead of PE and PVC, is applicable to the preparation of films, plates, sheet materials, foamings and injection moulding plastics.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of transparent and toughness reinforcing polylactic resin and preparation method thereof.
Background technology
Different with traditional petroleum-based plastics, poly(lactic acid) is that the lactic acid polymerizes that is got by the plant amylum fermentation forms, and this is a kind of renewable resources.Under the situation that is becoming tight petroleum-based energy day, it is particularly important that the development research polylactic resin seems.The performance classes of poly(lactic acid) itself is similar to the general-purpose plastics polypropylene, as the modulus height, tensile strength is big and processability good.But the fragility of poly(lactic acid) is serious, and resistance to impact shock is less than 5KJ/m
2, serious restriction its widespread use.
Poly(lactic acid) also has the better machining property and the transparency, can be applicable to traditional extrude, working method such as injection moulding, blowing.
Therefore, fragility important disadvantages at poly(lactic acid) is being carried out study on the modification both at home and abroad energetically, adopting the toughness of the method raising poly(lactic acid) of polycomponent blending and modifying is present major technique means, but poly(lactic acid) generally is difficult to keep the transparency of polylactic resin behind blending toughening, how to obtain existing high tenacity, the polylactic resin that has the transparency again is product requirements such as preparation food product packing film and beverage bottle.
The blending and modifying research of transparent high-toughness polylactic acid is less, and poly(lactic acid)/softening agent blending and modifying with poly(lactic acid) and small molecules or simple plasticizer blend, reaches polylactic acid plasticize even toughness reinforcing purpose, keeps the transparency of poly(lactic acid) simultaneously.Citric acid ester type (citrate plasticization and modification poly(lactic acid). (polymer material science and engineering, (2008), 24 (1): 151-154.), research (Polymer Bulletin, (2009), 62 (1): 91-98.) of Plasticizer Epoxidized Soybean Oil blend.
Component blend such as poly(lactic acid) and vanay, lubricant prepare polylactic resin, are used to prepare anti tear, high transparent polylactic acid film (CN1304471C).
Application number is that 200910066621 Chinese invention patent has been studied a kind of transparent biodegradable polylactic acid nano composite and preparation method thereof.This nano composite material composition comprises poly(lactic acid), nano silicon, softening agent, oxidation inhibitor and lubricant; The complete biology of this nano composite material falls, and compares with pure poly(lactic acid), and thermostability obviously improves, and the good transparency and tensile strength and elongation at break are arranged.Can be in aspect widespread uses such as product for agriculture, food product pack and articles for daily use.
Application number is that 200710023106 Chinese invention patent discloses a kind of polylactic acid blend and uses thereof.This blend mainly is made up of poly(lactic acid), nano silicon, amides.This blend is compared with poly(lactic acid) when keeping the poly(lactic acid) transparency, has higher fusion-crystallization and lower cold crystallization temperature.
Application number provides the method for producing transparent poly-lactic acid material for 200510067228 Chinese invention patent, mediates poly(lactic acid) and have the monomer of two or more pairs key in its molecule; Molding is mediated product to obtain moulded parts under the temperature of the fusing point to 200 of poly(lactic acid) ℃; This moulded parts quenches behind molding; And the moulded parts that will quench carries out crosslinking Treatment, carries out recrystallize so that prevent the molecule of poly(lactic acid), makes transparent poly-lactic acid material.
Application number is that 200710023108 Chinese invention patent discloses a kind of poly(lactic acid) and modified cellulose blend and preparation method and heat-proof macromolecule material, and blend is mainly formed by 70～100 weight part poly(lactic acid) and 30～90 weight part modified-cellulose blend.The thickness that this poly(lactic acid)/modified cellulose blend is obtained after fusion, moulding is heat-resisting moulding product 0.02～5mm, that have certain transparency.The heat-proof macromolecule material that is made by poly(lactic acid) and modified cellulose blend has good heat resistance and certain transparency.
Application number is that 200510049546 Chinese invention patent discloses a kind of poly(lactic acid) environmental protection complete degradable plastic and production method thereof.Poly(lactic acid) and polyvinyl alcohol, epoxy soybean wet goods auxiliary agent are through high-speed mixing, and the poly(lactic acid) complete degradable plastic is made in the granulation oven dry.Product is transparent, soft, and the physical strength height is moistureproof, anticorrosion, and barrier properties for gases is good.
Below,, all do not study the method that improves its polylactic resin resistance to impact shock, and the fragility of polylactic resin seriously is the subject matter that influences the poly(lactic acid) widespread use though can keep the transparency of polylactic resin both at home and abroad to the transparent modified research of poly(lactic acid).Keep high-clarity, have high impact strength simultaneously, can make not easy fracture of goods, the film article anti tear is to satisfy the very important performance that polylactic resin is extruded at injection-molded item, beverage bottle, film and sheet material, blown film pushes and rolling processing requires.
Summary of the invention
In order to solve the problem that prior art exists, the invention provides a kind of transparent and toughness reinforcing polylactic resin and preparation method thereof.
The invention provides a kind of transparent and toughness reinforcing polylactic resin, the moiety of its prescription and mass fraction proportioning are: 100 parts of poly(lactic acid), toughner 10-22 part, softening agent 2-15 part, oxidation inhibitor 0.1-1 part;
The number-average molecular weight of described poly(lactic acid) is 5-20 ten thousand dalton;
Described toughner is the methyl methacrylate-butyl acrylate multipolymer, and wherein, the mass percentage content of methyl methacrylate is 10-25%, and the mass percentage content of butyl acrylate is 90-75%;
Softening agent is ATBC, tri-n-butyl citrate, triethyl citrate or acetyl triethyl citrate;
Oxidation inhibitor is the mixture of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, and both quality proportionings are 1: 2.
A kind of preparation method of transparent and toughness reinforcing polylactic resin is as follows:
By said ratio, exsiccant poly(lactic acid), toughner and softening agent, oxidation inhibitor are carried out mechanical blending, 3-10 minute blend time, preferred 5 minutes, then mixed material is joined and melt extrude granulation in the twin screw extruder, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.
Beneficial effect: a kind of transparent and toughness reinforcing polylactic resin provided by the invention and preparation method thereof, use the toughner of methyl methacrylate-butyl acrylate multipolymer as poly(lactic acid), and use citric acid ester plasticizer, can effectively improve the tension fracture elongation rate and the resistance to impact shock of poly(lactic acid), and blend viscosity degradation, softening agent is nonpoisonous and tasteless, compliance with environmental protection requirements, and shock strength is up to 60.1KJ/m
2, having solved the serious defective of poly(lactic acid) fragility, and kept the transparency of poly(lactic acid), softening agent can obviously improve the rheological behaviour of material, improves the processing characteristics of poly(lactic acid), is fit to multiple process requirements.The refractive index of poly(lactic acid) is 1.454, and the refractive index of methyl methacrylate-butyl acrylate multipolymer and poly(lactic acid) are very approaching, can keep the poly(lactic acid) transparency, when thickness 0.04mm, and transmittance 89%, mist degree 8.5%.This blending modification method equipment is simple, technology advanced person.The transparent high-toughness polylactic acid resin product applications is extensive, and alternative PE, PVC etc. make various environmentally-friendly transparent plastics, and especially in the food product packing film field, market outlook are wide.Can be used for preparing film, sheet material, sheet material, foaming and injection-molded plastic spare, have the anti-aging and anti-uv-ray of goods.The industrialization of poly(lactic acid) helps the needs of the energy and material resources long term growth, promotes deep processing of farm products, reduces the dependence to oil, solves white pollution, promotes the development of novel environment friendly material industry, has great economy and social effect.
Embodiment
Embodiment 1: the invention provides a kind of transparent and toughness reinforcing polylactic resin, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate was 17% during copolymerization was formed, the mass percentage content of butyl acrylate is 83%;
8 parts of softening agent ATBC;
Oxidation inhibitor is 0.5 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 5 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.
The mechanical property that obtains transparent and toughness reinforcing polylactic resin is as follows: tensile strength is 41.5MPa, elongation at break 82%, and notched Izod impact strength is 37.3KJ/m
2, during thickness 0.04mm, transmittance 88%, mist degree 8.8%.
Embodiment 2: the invention provides a kind of transparent and toughness reinforcing polylactic resin, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
22 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
5 parts of softening agent ATBC;
Oxidation inhibitor is 0.3 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 5 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 36.6MPa, elongation at break 95%, and notched Izod impact strength is 60.1KJ/m
2, during thickness 0.04mm, transmittance 88%, mist degree 8.8%.
Embodiment 3: take by weighing each component by following prescription and quality:
200,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 15% in the multipolymer, the mass percentage content of butyl acrylate is 85%;
8 parts of softening agent ATBC;
Oxidation inhibitor is 0.3 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 5 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 26.2MPa, elongation at break 88%, and notched Izod impact strength is 29.0KJ/m
2, during thickness 0.04mm, transmittance 89%, mist degree 8.5%.
Embodiment 4: take by weighing each component by following prescription and quality:
200,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 25% in the multipolymer, the mass percentage content of butyl acrylate is 75%;
5 parts of softening agent tri-n-butyl citrates;
Oxidation inhibitor is 0.8 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 3 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 51.3MPa, elongation at break 31%, and notched Izod impact strength is 8.7KJ/m
2, during thickness 0.04mm, transmittance 89%, mist degree 8.7%.
Embodiment 5: take by weighing each component by following prescription and quality:
50,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
Described methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 10% in the multipolymer, the mass percentage content of butyl acrylate is 90%;
2 parts of softening agent ATBC;
Oxidation inhibitor is 1 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 10 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 49.8MPa, elongation at break 29%, and notched Izod impact strength is 8.1KJ/m
2, during thickness 0.04mm, transmittance 89%, mist degree 8.7%.
Embodiment 6: take by weighing each component by following prescription and quality:
50,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
2 parts of softening agent ATBC;
Oxidation inhibitor is 0.1 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 5 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 52.4MPa, elongation at break 30%, and notched Izod impact strength is 8.4KJ/m
2, during thickness 0.04mm, transmittance 88%, mist degree 8.9%.
Embodiment 7: take by weighing each component by following prescription and quality:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
11 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
10 parts of softening agent acetyl triethyl citrate;
Oxidation inhibitor is 0.5 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 3 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-145 ℃, two districts: 160-170 ℃, three districts: 170-180 ℃, four districts: 175-185 ℃, five districts: 175-185 ℃, six districts: 180-190 ℃, seven districts: 180-190 ℃, head: 175-185 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 45.6MPa, elongation at break 47%, and notched Izod impact strength is 10.3KJ/m
2, during thickness 0.04mm, transmittance 88%, mist degree 8.9%.
Embodiment 8: take by weighing each component by following prescription and quality:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 15% in the multipolymer, the mass percentage content of butyl acrylate is 85%;
15 parts of softening agent ATBC;
Oxidation inhibitor is 0.5 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 5 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-145 ℃, two districts: 160-170 ℃, three districts: 170-180 ℃, four districts: 175-185 ℃, five districts: 175-185 ℃, six districts: 180-190 ℃, seven districts: 180-190 ℃, head: 175-185 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 35.2MPa, elongation at break 91%, and notched Izod impact strength is 29.7KJ/m
2, during thickness 0.04mm, transmittance 88%, mist degree 8.7%.
Embodiment 9: the invention provides a kind of transparent and toughness reinforcing polylactic resin, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
22 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
8 parts of softening agent acetyl triethyl citrate;
Oxidation inhibitor is 0.3 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 5 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 33.5MPa, elongation at break 112%, and notched Izod impact strength is 52.6KJ/m
2, during thickness 0.04mm, transmittance 88%, mist degree 8.8%.
Embodiment 10: the invention provides a kind of transparent and toughness reinforcing polylactic resin, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
22 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
5 parts of softening agent triethyl citrates;
Oxidation inhibitor is 0.3 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Take by weighing each component by above prescription, each component was carried out mechanical blending 5 minutes, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-150 ℃, two districts: 160-180 ℃, three districts: 170-190 ℃, four districts: 175-195 ℃, five districts: 175-195 ℃, six districts: 180-200 ℃, seven districts: 180-200 ℃, head: 175-195 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 35.3MPa, elongation at break 89%, and notched Izod impact strength is 54.3KJ/m
2, during thickness 0.04mm, transmittance 88%, mist degree 8.8%.
Reference examples 1 takes by weighing each component by following prescription and quality:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
Described toughner copolymer of methyl methacrylate-styrene-butadiene, the mass percentage content of methyl methacrylate is 17% in the multipolymer, and the quality of butadiene degree is 73%, and cinnamic mass percentage content is 10%;
15 parts of softening agent ATBC;
Oxidation inhibitor is 0.5 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
Each above-mentioned component is carried out mechanical blending 5 minutes, then mixed material is joined extruding pelletization in the twin screw extruder, obtain polylactic resin.The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-145 ℃, two districts: 160-170 ℃, three districts: 170-180 ℃, four districts: 175-185 ℃, five districts: 175-185 ℃, six districts: 180-190 ℃, seven districts: 180-190 ℃, head: 175-185 ℃, screw speed: 100-300rpm.Resulting target material mechanical property is as follows: tensile strength is 28.9MPa, elongation at break 160%, and notched Izod impact strength is 61.9KJ/m
2, during thickness 0.04mm, transmittance 86.8%, mist degree 15.2%.
Claims (11)
1. a transparent and toughness reinforcing polylactic resin is characterized in that, the moiety of its prescription and mass fraction proportioning are: 100 parts of poly(lactic acid), toughner 10-22 part, softening agent 2-15 part, oxidation inhibitor 0.1-1 part;
The number-average molecular weight of described poly(lactic acid) is 5-20 ten thousand dalton;
Described toughner is the methyl methacrylate-butyl acrylate multipolymer, and wherein, the mass percentage content of methyl methacrylate is 10-25%, and the mass percentage content of butyl acrylate is 90-75%;
Softening agent is ATBC, tri-n-butyl citrate, triethyl citrate or acetyl triethyl citrate;
Oxidation inhibitor is the mixture of four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, and both quality proportionings are 1: 2.
2. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate was 17% during copolymerization was formed, the mass percentage content of butyl acrylate is 83%;
8 parts of softening agent ATBC;
Oxidation inhibitor is 0.5 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
3. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
22 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
5 parts of softening agent ATBC;
Oxidation inhibitor is 0.3 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
4. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
200,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 15% in the multipolymer, the mass percentage content of butyl acrylate is 85%;
8 parts of softening agent ATBC;
Oxidation inhibitor is 0.3 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
5. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
200,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 25% in the multipolymer, the mass percentage content of butyl acrylate is 75%;
5 parts of softening agent tri-n-butyl citrates;
Oxidation inhibitor is 0.8 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
6. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
50,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
Described methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 10% in the multipolymer, the mass percentage content of butyl acrylate is 90%;
2 parts of softening agent ATBC;
Oxidation inhibitor is 1 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
7. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
50,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
2 parts of softening agent ATBC;
Oxidation inhibitor is 0.1 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
8. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
11 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 17% in the multipolymer, the mass percentage content of butyl acrylate is 83%;
10 parts of softening agent acetyl triethyl citrate;
Oxidation inhibitor is 0.5 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
9. a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that, the moiety of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
Described toughner methyl methacrylate-butyl acrylate multipolymer, the mass percentage content of methyl methacrylate is 15% in the multipolymer, the mass percentage content of butyl acrylate is 85%;
15 parts of softening agent ATBC;
Oxidation inhibitor is 0.5 part in the mixture of 1: 2 four (β-(3,5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
10. the method for making of a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 1 is characterized in that step and condition are as follows; Take by weighing each component by described prescription, each component was carried out mechanical blending 3-10 minute, mixed material is joined melt extrude granulation in the twin screw extruder then, obtain transparent and toughness reinforcing polylactic resin; The condition of extruding pelletization is: the design temperature of twin screw extruder is: a district: 130-145 ℃, two districts: 160-170 ℃, three districts: 170-180 ℃, four districts: 175-185 ℃, five districts: 175-185 ℃, six districts: 180-190 ℃, seven districts: 180-190 ℃, head: 175-185 ℃, screw speed: 100-300rpm.
11. the method for making of a kind of transparent and toughness reinforcing polylactic resin as claimed in claim 10 is characterized in that it is 5 minutes that described each component is carried out the mechanical blending time.
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| CN2010105190095A CN101983986B (en) | 2010-10-26 | 2010-10-26 | Transparent and toughening polylactic acid resin and method for preparing the same |
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| CN2010105190095A CN101983986B (en) | 2010-10-26 | 2010-10-26 | Transparent and toughening polylactic acid resin and method for preparing the same |
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| CN103146164A (en) * | 2013-04-07 | 2013-06-12 | 苏州聚复高分子材料有限公司 | Nano-toughened polylactic acid material for rapid prototyping and preparation method thereof |
| CN103232689A (en) * | 2013-04-03 | 2013-08-07 | 西安理工大学 | Preparation method for polylactic acid film with toughness |
| US9102782B2 (en) | 2011-08-12 | 2015-08-11 | China Petroleum & Chemical Corporation | Transparent copolyester, preparing method thereof and articles made from the same |
| CN110305435A (en) * | 2019-07-31 | 2019-10-08 | 金旸（厦门）新材料科技有限公司 | A kind of transparent plasticizing polylactic acid/acrylic alloy material and its prepare raw material and preparation method |
| CN112457639A (en) * | 2020-11-17 | 2021-03-09 | 杨勇 | Polylactic resin prepared from corn and preparation method thereof |
| CN114181501A (en) * | 2021-11-08 | 2022-03-15 | 广东众塑降解材料有限公司 | Fully-degradable transparent seafood packaging film material and preparation method thereof |
| CN114211664A (en) * | 2021-11-15 | 2022-03-22 | 吉安创德精密电子有限公司 | Preparation method of toughened thermoplastic plastic |
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| CN101412842A (en) * | 2007-10-19 | 2009-04-22 | 奇钛科技股份有限公司 | Preparation of composition containing polylactic resin and polyacrylacid ester compounds |
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| US9102782B2 (en) | 2011-08-12 | 2015-08-11 | China Petroleum & Chemical Corporation | Transparent copolyester, preparing method thereof and articles made from the same |
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| CN103146164A (en) * | 2013-04-07 | 2013-06-12 | 苏州聚复高分子材料有限公司 | Nano-toughened polylactic acid material for rapid prototyping and preparation method thereof |
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| CN110305435B (en) * | 2019-07-31 | 2022-01-25 | 金旸（厦门）新材料科技有限公司 | Transparent toughened polylactic acid/acrylic alloy material and preparation raw materials and preparation method thereof |
| CN112457639A (en) * | 2020-11-17 | 2021-03-09 | 杨勇 | Polylactic resin prepared from corn and preparation method thereof |
| CN114181501A (en) * | 2021-11-08 | 2022-03-15 | 广东众塑降解材料有限公司 | Fully-degradable transparent seafood packaging film material and preparation method thereof |
| CN114211664A (en) * | 2021-11-15 | 2022-03-22 | 吉安创德精密电子有限公司 | Preparation method of toughened thermoplastic plastic |
| CN114211664B (en) * | 2021-11-15 | 2024-09-06 | 吉安创德精密电子有限公司 | Preparation method of toughened thermoplastic plastic |
| CN114410085A (en) * | 2022-01-13 | 2022-04-29 | 江苏斯尔邦石化有限公司 | Full-biodegradable toughened plasticized polyglycolic acid material and preparation method thereof |
| CN114410085B (en) * | 2022-01-13 | 2023-08-15 | 江苏斯尔邦石化有限公司 | Full-biodegradation toughened plasticized polyglycolic acid material and preparation method thereof |
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| CN101983986B (en) | 2012-05-23 |
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