CN101875763A - High-toughness polylactic acid resin and preparation method thereof - Google Patents
High-toughness polylactic acid resin and preparation method thereof Download PDFInfo
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- CN101875763A CN101875763A CN2010102053062A CN201010205306A CN101875763A CN 101875763 A CN101875763 A CN 101875763A CN 2010102053062 A CN2010102053062 A CN 2010102053062A CN 201010205306 A CN201010205306 A CN 201010205306A CN 101875763 A CN101875763 A CN 101875763A
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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
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
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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
- B29C2948/92895—Barrel or housing
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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
- B29C2948/92904—Die; Nozzle zone
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Abstract
The invention provides a high-toughness polylactic acid resin and a preparation method thereof. The high-toughness polylactic acid resin is prepared from polylactic acid, methyl methacrylate-butadiene-styrol copolymer as toughener, citrate plasticizer and a mixture of pentaerythrite tetra[beta-(3,5-di-tert-butyl-4-hydroxy)propionate) and tris(2,4-di-tert-butylphenyl)phosphite as antioxidant. The preparation method comprises the following steps: mechanically mixing the polylactic acid, the toughener, the plasticizer and the antioxidant, and melting and processing by using a double screw extruder. The invention has the advantages of simple process and easy acquisition of materials, and obviously overcomes serious defects of the toughness and brittleness of polylactic acid. Compared with the material prepared on the basis of pure polylactic acid, the breaking elongation of the material of the invention is increased form 5.7% to 315%, and the impact strength is increased from 4.7KJ/m<2> to 104.2KJ/m<2>. The prepared high-toughness polylactic acid resin can be used for preparing films, plates, sheets and foam and injection molding parts and used in automobiles, writing materials, toys, household appliances and the like.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of high-toughness polylactic acid resin and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) be a kind of be raw material with the cereal starch, obtain lactic acid through biological fermentation, again through polyreaction, finally obtain polylactic resin.It has two big advantages: the first, and biodegradable, in soil, be decomposed into carbonic acid gas and water easily, can be by plant absorbing, recycle.The second, for the non-petroleum base plastics, derive from renewable resourcess such as plant, 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.
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, it is simple to have technology, the outstanding effect advantage, be convenient to suitability for industrialized production, blending and modifying is broadly divided into the following aspects:
1, poly(lactic acid)/softening agent blending and modifying.With poly(lactic acid) and small molecules or simple plasticizer blend, or add the 3rd component again, reach polylactic acid plasticize even toughness reinforcing purpose.As poly(lactic acid) and polypropylene glycol or poly(propylene oxide), polyethylene oxide (WO2007/004906), polyvinyl alcohol or POLYPROPYLENE GLYCOL (Journal of AppliedPolymer Science, (2009), 114 (4): 2481-2487; Polimery, (2009), 54 (2): 83-90.), poly-(vinyl alcohol-vinylcarbinol) multipolymer (Journal of Applied Polymer Science, (2009), 114 (2): 1105-1117.), polyester-glycol blends (European Polymer Journal, (2009), 45 (8): 2304-2312.), citric acid ester type (citrate plasticization and modification poly(lactic acid)) (polymer material science and engineering, (2008), 24 (1): 151-154.) or Plasticizer Epoxidized Soybean Oil blending and modifying (Polymer Bulletin, (2009), 62 (1): 91-98.).
2, poly(lactic acid)/biodegradable polymers blend.As poly(lactic acid) and poly-epsilon-caprolactone blend (PCL) (Polymer Engineering Science, (2006), 46:1299～1308; Polymer, (2008), 49:599-609; Journal ofApplied Polymer Science, (2009), 112:345-352.), poly(lactic acid) and poly butylene succinate (PBS) (CN1475530; European Polymer Journal, (2008), 44 (3): 677-685.), poly-(3-butyric ester) (PHB) (European Polymer Journal, (2006), 42:764-775.) or poly-(butyleneglycol adipic acid ester-butyleneglycol terephthalate) multipolymer (PBAT) (trade(brand)name Ecoflex) blend (Polymer Degradation and Stability, (2009), 94 (1): 74-82.).
3, poly(lactic acid)/polarity is contained the soft segment polymer blending, and poly(lactic acid) and polymeric amide (Polymer, (2009), 50:1311-1315.), urethane (Polymers for Advanced Technologies, (2006), 17:439-443; Polymer Bulletin, (1998), 40:485-490.), hyperbranched polymer (CN1962714), hyperbranched poly esteramides (Iranian Polymer Journal, (2008), 17 (12): 891-898.) or polyethers-b-acid amides thermoplastic elastomer (PEBA) blend (CN101392814; CN101392093).
4, poly(lactic acid)/non-polar polyolefinic blending toughening adopts synthetic block or graft copolymer expanding material toughness reinforcing to the poly(lactic acid) increasing reaction.(the Joumal ofMacromolecular Science Part B-Physics of graft glycidyl methacrylate or epoxide group isoreactivity functional group on polyolefine, (2009), 48 (4): 823-833.),, improve the toughness of polylactic acid blend to the poly(lactic acid) increase-volume.
Select for use the PLLA-PE segmented copolymer as expanding material, add linear low density polyethylene (LLDPE) to in the PLLA melt blending system, reach to the toughness reinforcing purpose of PLLA (Journal of Applied PolymerScience, (2003), 89:3757-3768.).Poly(lactic acid) and Research on Toughening (Polymer, (2009), 50 (3): 747-751.) of gathering (ethylene-methyl methacrylate glycidyl ester) multipolymer (EGMA).(2008,24 (4): 53～57.) reported the toughening modifying of E-MA-GMA triblock copolymer to poly(lactic acid), the impact property of PLLA is significantly improved for polymer material science and engineering.Polymer journal (1999,6:761～764.) has been introduced dendritic multibranched polymer and can be used as crystallization rate and the crystallizability that nucleator improves PLA, can improve tensile strength and the extension at break of PLA greatly.Poly-(the 3-hydroxy alkane acid ester) of length side chain (PHA) or can improve the impelling strength of PLA through the PHA (having epoxy group(ing) side chain ePHA) of chemical modification and PLA blend in having, reduce its tensile strength, can improve the consistency and the physical properties of blend better.(Journal ofApplied Polymer Science, (2004), 93:2363～2369.) have been reported 70/30 poly(lactic acid) and have been had 16 times of the poly-purer PLA Charpy of (3-hydroxy alkane acid ester) the blend shock strength raisings of epoxy group(ing) side chain.Such plasticizing polylactic acid method effect is better, and epoxide groups such as GMA have played reactive behavior preferably, have promoted the consistency of poly(lactic acid) and non-polar polymer.
5, poly(lactic acid) and rubber-like or the blend of esters of acrylic acid toughner.Contrasted poly(lactic acid) and ethylene-propylene copolymer, ethylene-acrylic rubber, acrylonitrile-butadiene rubber or polyisoprene rubber blend (Journal of AppliedPolymer Science, (2009), 113 (1): 558-566.), only acrylonitrile-butadiene rubber slightly improves the resistance to impact shock of poly(lactic acid), about polyisoprene rubber doubles the elongation at break of poly(lactic acid).
More than research is main around improving elongation at break, and the raising of impact intensity is very limited.Elongation at break and shock strength are all improved, and are to enlarge poly(lactic acid) to use the practical problems that must solve.
Summary of the invention
The purpose of this invention is to provide a kind of high-toughness polylactic acid resin and preparation method thereof.
A kind of high-toughness polylactic acid resin, the composition of its prescription and mass fraction proportioning are: 100 parts of poly(lactic acid), toughner 5-35 part, softening agent 2-19 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 MBS; The methyl methacrylate mass percentage content is in the described multipolymer: 13～27%, and the divinyl degree is: 68～76%, the vinylbenzene degree is: 5～15%;
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 high-toughness polylactic acid resin is as follows:
By said ratio, to carry out mechanical blending through exsiccant poly(lactic acid), toughner and softening agent, oxidation inhibitor, 3-10 minute blend time, preferred 5 minutes, then mixed material is joined extruding pelletization in the twin screw extruder, obtain high-toughness polylactic acid resin; The condition of described 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 high-toughness polylactic acid resin provided by the invention and preparation method thereof, with the toughner of MBS as poly(lactic acid), and adopt citric acid ester type as softening agent, effectively improved the resistance to impact shock and the tension fracture elongation rate of poly(lactic acid), shock strength is up to 104.2KJ/m
2, solved the brittle major defect of poly(lactic acid).Used softening agent can obviously improve the rheological behaviour of material, improves the processing characteristics of poly(lactic acid), can be used for preparing film, sheet material, sheet material, foaming and injection-molded plastic spare.Softening agent is nonpoisonous and tasteless, and compliance with environmental protection requirements is fit to multiple process requirements.This method equipment is simple, technical maturity.The high-toughness polylactic acid resin Application Areas is extensive, and alternative PE and PVC etc. make various environmental protection plastic products.The industrialization of poly(lactic acid) helps the needs of China's energy and material resources long term growth, break the Green Trade Barrier of developed country for China, promote deep processing of farm products, minimizing is to the dependence of oil, solve white pollution, promote the development of novel environment friendly material industry, have great economy and social effect.
Embodiment
Embodiment 1: a kind of high-toughness polylactic acid resin, and the composition of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
20 parts of toughner MBSs; The methyl methacrylate mass percentage content is in the described multipolymer: 17%, and the divinyl degree is: 68%, the vinylbenzene degree is: 15%;
8 parts of softening agent ATBC;
0.5 part in oxidation inhibitor;
Described oxidation inhibitor is that the quality proportioning is four (β-(3, the 5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters of 1:2 and the mixture of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
The method for making of high-toughness polylactic acid resin is as follows, by above-mentioned proportioning, will carry out mechanical blending through exsiccant poly(lactic acid), toughner and softening agent, oxidation inhibitor, the blend time is 5 minutes, then mixed material is joined extruding pelletization in the twin screw extruder, obtain high-toughness polylactic acid 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 of resulting high-toughness polylactic acid resin is as follows: tensile strength is 33.7MPa, elongation at break 241%, and notched Izod impact strength is 51.1KJ/m
2
Embodiment 2: take by weighing each component by following prescription and weight:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
The toughner MBS, methyl methacrylate content is in the composition: 17%, butadiene content is: 68%, vinylbenzene is: 15%; 35 parts;
2 parts of softening agent ATBC;
0.3 part in oxidation inhibitor;
Described oxidation inhibitor is 1: 2 four (β-(3, the 5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and the mixture of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning;
The step of the method for making of high-toughness polylactic acid resin and condition are with embodiment 1.The mechanical property of resulting high-toughness polylactic acid resin is as follows: tensile strength is 34.6MPa, elongation at break 324%, and notched Izod impact strength is 104.2KJ/m
2
Embodiment 3: take by weighing each component by following prescription and weight:
200,000 100 parts of poly(lactic acid) number-average molecular weights;
The toughner MBS, methyl methacrylate content is in the composition: 13%, butadiene content is: 72%, vinylbenzene is: 15%; 20 parts;
7 parts of softening agent ATBC;
0.3 part in oxidation inhibitor;
Described for the quality proportioning be 1: 2 four (β-(3, the 5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and the mixture of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester;
The step of the method for making of high-toughness polylactic acid resin and condition are with embodiment 1.The mechanical property of resulting high-toughness polylactic acid resin is as follows: tensile strength is 41.3MPa, elongation at break 216%, and notched Izod impact strength is 49.8KJ/m
2
Embodiment 4: take by weighing each component by following prescription and weight:
200,000 100 parts of poly(lactic acid) number-average molecular weights
The toughner MBS, methyl methacrylate content is in the composition: 15%, butadiene content is: 72%, vinylbenzene is: 13%; 20 parts
12 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
The step of the method for making of high-toughness polylactic acid resin and condition are with embodiment 1.The mechanical property of resulting high-toughness polylactic acid resin is as follows: tensile strength is 26.7MPa, elongation at break 311%, and notched Izod impact strength is 74.4KJ/m
2
Embodiment 5: take by weighing each component by following prescription and weight:
50,000 100 parts of poly(lactic acid) number-average molecular weights
The toughner MBS, methyl methacrylate content is in the composition: 17%, butadiene content is: 76%, vinylbenzene is: 7%; 10 parts
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
The step of the method for making of high-toughness polylactic acid resin and condition are with embodiment 1.The mechanical property of resulting high-toughness polylactic acid resin is as follows: tensile strength is 40.0MPa, elongation at break 288%, and notched Izod impact strength is 25.2KJ/m
2
Embodiment 6: take by weighing each component by following prescription and weight:
50,000 100 parts of poly(lactic acid) number-average molecular weights
The toughner MBS, methyl methacrylate content is in the composition: 27%, butadiene content is: 68%, vinylbenzene is: 5%; 10 parts
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
The step of the method for making of high-toughness polylactic acid resin and condition are with embodiment 1.The mechanical property of resulting high-toughness polylactic acid resin is as follows: tensile strength is 52.3MPa, elongation at break 182%, and notched Izod impact strength is 29.6KJ/m
2
Embodiment 7: take by weighing each component by following prescription and weight:
80,000 100 parts of poly(lactic acid) number-average molecular weights
The toughner MBS, methyl methacrylate content is in the composition: 17%, butadiene content is: 73%, vinylbenzene is: 10%; 11 parts
17 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
The method for making of high-toughness polylactic acid resin is as follows, by above-mentioned proportioning, will carry out mechanical blending through exsiccant poly(lactic acid), toughner and softening agent, oxidation inhibitor, the blend time is 3 minutes, then mixed material is joined extruding pelletization in the twin screw extruder, obtain high-toughness polylactic acid resin; The condition of extruding pelletization is with embodiment 1.The mechanical property of resulting high-toughness polylactic acid resin is as follows: tensile strength is 31.5MPa, elongation at break 321%, and notched Izod impact strength is 59.8KJ/m
2
Embodiment 8: take by weighing each component by following prescription and weight:
80,000 100 parts of poly(lactic acid) number-average molecular weights
The toughner MBS, methyl methacrylate content is in the composition: 17%, butadiene content is: 68%, vinylbenzene is: 15%; 18 parts
19 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
The method for making of high-toughness polylactic acid resin is as follows, by above-mentioned proportioning, will carry out mechanical blending through exsiccant poly(lactic acid), toughner and softening agent, oxidation inhibitor, the blend time is 10 minutes, then mixed material is joined extruding pelletization in the twin screw extruder, obtain high-toughness polylactic acid resin; The condition of extruding pelletization is with embodiment 1.The mechanical property of resulting high-toughness polylactic acid resin is as follows: tensile strength is 24.9MPa, elongation at break 286%, and notched Izod impact strength is 85.7KJ/m
2
Claims (11)
1. a high-toughness polylactic acid resin is characterized in that, the composition of its prescription and mass fraction proportioning are: 100 parts of poly(lactic acid), toughner 5-35 part, softening agent 2-19 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 MBS; The methyl methacrylate mass percentage content is in the described multipolymer: 13～27%, and the divinyl degree is: 68～76%, the vinylbenzene degree is: 5～15%;
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 high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
35 parts of toughner;
The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 17%, divinyl per-cent mass content is: 68%, vinylbenzene per-cent mass content is: 15%;
2 parts of softening agent ATBC;
0.3 part in oxidation inhibitor;
Described oxidation inhibitor is 1: 2 four (β-(3, the 5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and the mixture of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
3. a kind of high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
35 parts of toughner;
The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 17%, divinyl per-cent mass content is: 68%, vinylbenzene per-cent mass content is: 15%;
2 parts of softening agent ATBC;
0.3 part in oxidation inhibitor;
Described oxidation inhibitor is 1: 2 four (β-(3, the 5-di-t-butyl-4-hydroxyl) propionic acid) pentaerythritol esters and the mixture of tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester for the quality proportioning.
4. a kind of high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
200,000 100 parts of poly(lactic acid) number-average molecular weights;
20 parts of toughner;
The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 13%, divinyl per-cent mass content is: 72%, vinylbenzene per-cent mass content is: 15%;
7 parts of softening agent ATBC;
0.3 part in oxidation inhibitor.
5. a kind of high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
200,000 100 parts of poly(lactic acid) number-average molecular weights;
20 parts of toughner; The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 15%, divinyl per-cent mass content is: 72%, vinylbenzene per-cent mass content is: 13%;
12 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 high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
50,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 17%, divinyl per-cent mass content is: 76%, vinylbenzene per-cent mass content is: 7%;
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 high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
50,000 100 parts of poly(lactic acid) number-average molecular weights;
10 parts of toughner;
The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 27%, divinyl per-cent mass content is: 68%, vinylbenzene per-cent mass content is: 5%;
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 high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
11 parts of toughner;
The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 17%, divinyl per-cent mass content is: 73%, vinylbenzene per-cent mass content is-10%;
17 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 high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, the composition of its prescription and mass fraction proportioning are:
80,000 100 parts of poly(lactic acid) number-average molecular weights;
18 parts of toughner;
The toughner MBS, methyl methacrylate per-cent mass content is in the multipolymer: 17%, divinyl per-cent mass content is: 68%, vinylbenzene per-cent mass content is: 15%;
19 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 high-toughness polylactic acid resin as claimed in claim 1 is characterized in that, step and condition are as follows:
By described proportioning, will carry out mechanical blending through exsiccant poly(lactic acid), toughner and softening agent, oxidation inhibitor, 3-10 minute blend time, then mixed material is joined extruding pelletization in the twin screw extruder, obtain high-toughness polylactic acid resin; The condition of described 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.
11. the method for making of a kind of high-toughness polylactic acid resin as claimed in claim 10 is characterized in that, step and condition are as follows: it is 5 minutes that described poly(lactic acid), toughner and softening agent, oxidation inhibitor carry out the mechanical blending time.
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| CN102690704A (en) * | 2012-04-23 | 2012-09-26 | 上海应用技术学院 | Heat stabilizer composition of high-pressure hydrogenated cycloalkyl lubricating oil, preparation method thereof, and application thereof |
| CN103459498A (en) * | 2011-04-11 | 2013-12-18 | 斯洛伐克科学院聚合物研究所 | Biologically degradable polymeric composition with high deformability |
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| US8859690B2 (en) | 2011-06-23 | 2014-10-14 | China Petroleum & Chemical Corporation | Biodegradable composite, the preparation process thereof, and a disposable article made therefrom |
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| CN102690704A (en) * | 2012-04-23 | 2012-09-26 | 上海应用技术学院 | Heat stabilizer composition of high-pressure hydrogenated cycloalkyl lubricating oil, preparation method thereof, and application thereof |
| CN102690704B (en) * | 2012-04-23 | 2013-12-04 | 上海应用技术学院 | Heat stabilizer composition of high-pressure hydrogenated cycloalkyl lubricating oil, preparation method thereof, and application thereof |
| CN109694559A (en) * | 2018-11-30 | 2019-04-30 | 中粮集团有限公司 | Polylactic acid modifier, the method and polydactyl acid for preparing polydactyl acid |
| CN109694559B (en) * | 2018-11-30 | 2022-02-08 | 中粮集团有限公司 | Polylactic acid modifier, method for preparing modified polylactic acid and modified polylactic acid |
| CN112500672A (en) * | 2020-11-17 | 2021-03-16 | 杨勇 | Degradable polylactic resin preservative film and preparation method thereof |
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