CN103319865A - Polylactic acid alloy membrane and application thereof - Google Patents
Polylactic acid alloy membrane and application thereof Download PDFInfo
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- CN103319865A CN103319865A CN2013102287891A CN201310228789A CN103319865A CN 103319865 A CN103319865 A CN 103319865A CN 2013102287891 A CN2013102287891 A CN 2013102287891A CN 201310228789 A CN201310228789 A CN 201310228789A CN 103319865 A CN103319865 A CN 103319865A
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- polylactic acid
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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
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
Abstract
The present invention discloses a polylactic acid alloy membrane, which comprises polylactic resin, polyvinyl alcohol resin and a bulking agent, wherein the three are in parts by weight of 1to 99 parts, 1 to 99 parts and 0.05to 5 parts respectively, with the total account of polylactic resin and polyvinyl alcohol resin in parts by weight of 100 parts. By the invention, the oxygen barrier property of the polylactic acid alloy membrane is effectively improved under the premise of keeping the membrane completely biodegradable and providing the membrane high mechanical strength. The technology method provided by the invention is easy with low cost, and is able to effectively promote widespread use of the environmentally friendly polylactic acid products.
Description
Technical field
The present invention relates to a kind of polylactic acid film, relate in particular to a kind of biodegradable, polylactic acid alloy film with barrier properties for gases.
Background technology
The petroleum-based plastics goods, especially the widespread use of Plastic Packaging Materials brings a large amount of facilities to the human lives, but the raw material of the materials such as common plastics such as polyethylene, polypropylene, polyethylene terephthalate is mainly derived from oil, along with the day by day scarcity of petroleum resources, the raw material sources of alkylene macromolecular material commonly used will face huge challenge.In addition, the processing after the petroleum base macromolecular material is used also is a very large difficult problem, especially a Plastic Packaging Materials, because its application cycle is shorter, and large usage quantity is more serious to the pollution that environment brings.Plastic refuse is mainly by burning or burying and process in the prior art, burn to discharge a large amount of poisonous by products, and plastics bury after since the stable chemical-biological character of plastics decompose and a large amount of residual land wastage that causes hardly.Therefore, the full-biodegradable material of exploitation non-petroleum base is very important.
Wherein, poly(lactic acid) is with its good physical strength and biodegradability and receive much attention.The raw material of poly(lactic acid) can derive from the farm crop such as corn, and the methods such as utilization fermentation obtain monomer lactic acid, obtain poly(lactic acid) by monomer polymerization again.This material is discarded into nature after application just can be degraded to nontoxic small molecules very soon, what is more important, and this class material has been broken away from traditional Polymeric Industry to the high dependency of petrochemical complex, and very good application prospect is arranged.
On the other hand, because poly(lactic acid) is nontoxic, can also be manufactured into film product or be used for food flexible packing.Although the oxygen barrier property of poly(lactic acid) is higher than the polyolefine materials such as traditional polyethylene, polypropylene, still not enough, oxygen is easier to enter in the packing bag by polylactic acid film, causes Food Oxidation, corruption, rotten.Usually, can adopt the laminated film technology to improve the oxygen-barrier property of polylactic acid film, such as three layers of laminated film polylactic acid film being made " sandwich " structure with barrier film.Wherein, barrier film generally is ethylene-vinyl alcohol copolymer film, polyvinylidene chloride film, aluminium foil, glassine paper, polyamide layer etc.Chinese invention patent CN1198715C discloses a kind of composite material for package of food that is made of polylactic acid layers and polyvinyl alcohol layer, and its used polyvinyl alcohol layer is exactly in order to play the effect of waterproof, trapping and heat-sealing.
Especially, the oxygen barrier property of PVA (PVOH) FILM is outstanding, in general the preparation method of PVA (PVOH) FILM comprises wet processes and two kinds of working methods of dry process: a. wet processes is that polyvinyl alcohol is mixed with (only) moisture softening agent, under lesser temps (general below 100 ℃), pass through thermo forming again.Since moisture through the polyvinyl alcohol product of wet processes, so generally need to dewater through subsequent handling, such as drying, can cause like this production cost of product higher.B. dry process is that polyvinyl alcohol is mixed with water-free softening agent, under comparatively high temps (general more than 150 ℃), passes through thermo forming again.Because polyvinyl alcohol to thermo-responsive, when dry process, easily makes its oxidation flavescence, cause its viscosity increase, mechanical property variation.
In addition, by polylactic acid film and PVA (PVOH) FILM is compound, although can improve the oxygen barrier property of laminated film, complex method often needs to use solvent, the use meeting of solvent affects to environment, and facility investment is higher, production efficiency is lower.
Chinese patent CN100406498C uses vulcabond as chainextender (end-capping reagent), the preparation vinol/polylactic acid graft copolymer.Because vulcabond is toxic, be unfavorable for environment protection, and the carboxyl that contains in polyvinyl alcohol and the polylactic resin and moisture also can affect the chain extension effect of vulcabond.
In sum, those skilled in the art need further research, develop a kind of novel poly(lactic acid)-PVA (PVOH) FILM, with when possessing biological degradability, improve its oxygen-barrier property, also can be to environment.
Summary of the invention
The objective of the invention is the problem that exists in order to solve above-mentioned prior art, and a kind of biodegradable, polylactic acid alloy film with superior in gas barrier property is provided.
Polylactic acid alloy film of the present invention, its component comprises (A) polylactic resin, (B) polyvinyl alcohol resin and (C) expanding material, wherein, take (A) polylactic resin and (B) total amount of polyvinyl alcohol resin as 100 weight parts, (A) weight content of polylactic resin is 1～99 part, (B) weight content of polyvinyl alcohol resin is 1～99 part, and (C) weight content of expanding material is 0.05-5 part.
Further, described polylactic resin is Pfansteihl homopolymer, D-ALPHA-Hydroxypropionic acid homopolymer or L, one or more in the D-ALPHA-Hydroxypropionic acid multipolymer.Preferably, the weight-average molecular weight of described polylactic resin is 10,000～1,000,000, and more preferably, its weight-average molecular weight is 50,000～500,000.
Further, described polyvinyl alcohol resin is the polymerization degree 1,000～10,000, the polyvinyl alcohol of alcoholysis degree 50%～100%.
Further, described expanding material is to have at least two a kind of and two or more micromolecular compounds or polymkeric substance that are selected from acid anhydrides, the epoxy-functional.Particularly, expanding material can be, the alkene esters of gallic acid expanding material of the olefines expanding material of maleic anhydride graft, maleic anhydride graft, with the alkene esters of gallic acid expanding material of epoxy base side chain, with olefines expanding material of epoxy base side chain etc.Be preferably maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene-vinyl alcohol copolymer, glycidyl methacrylate graft polyethylene wax, glycidyl methacrylate graft polymethylmethacrylate, glycidyl methacrylate/methacrylic ester/styrol copolymer, ethene/acrylic ester/glycidyl methacrylate copolymer.
Although not necessarily, but in order to improve better the color of film, to be adapted to different occasions and demand, polylactic acid alloy film of the present invention, take (A) polylactic resin and (B) total amount of polyvinyl alcohol resin also comprise (D) oxidation inhibitor 0.01-3 weight part as 100 weight parts.Preferably, its weight content is 0.05-1.5 part.
Further, described oxidation inhibitor comprises but is not limited in phenols, amine, phosphorous acid esters, aliphatic ester, pentaerythritol esters, esters of acrylic acid, triazines, the agent of cyanurate class one or more.Be preferably, tri-butyl-phenol, 4,4 '-sulfo--two (3-methyl-6-tert butyl phenol), 2,2 '-sulfo--two (3-methyl-6-tert butyl phenol), two (3,5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine, phosphoric acid [3,5 (1, the 1-dimethyl ethyl)-and the 4-hydroxy phenyl] methyl list ethyl ester calcium salt, triphenyl phosphite, triisodecyl phosphite ester, Wytox 312,3,5-di-tert-butyl-4-hydroxyl benzyl phosphoric acid fat, four [B-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, pentaerythritol tetrastearate, 12-oxystearic acid glyceryl ester, the trimethylolpropane tris stearate, stearic acid 13 esters, Tyox B, thio-2 acid 2 stearyl ester, 2-(4-hydroxyl-3,5-di-tert-butyl amido)-4, two (the n-octyl sulfo-s)-1 of 6-, in 3, the 5-triazine one or more.
Although not necessarily, but for processing characteristics and the snappiness of better improving polylactic acid alloy film, polylactic acid alloy film of the present invention, take (A) polylactic resin and (B) total amount of polyvinyl alcohol resin also comprise (E) softening agent 1-40 weight part as 100 weight parts.Preferably, its weight content is the 3-25 weight part.
Further, described softening agent includes but not limited to one or more in glycerine, ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, acrylamide, glyceryl ester, citrate, sebate, suberate, phthalic acid ester, lactic acid, rac-Lactide, PLA-PEG copolymer, poly(lactic acid)-polypropylene glycol multipolymer, the polyethylene glycol-propylene glycol copolymers.Be preferably one or more in the PLURONIC F-127 of the polyoxyethylene glycol of glycerine, ethylene glycol, vanay, triethyl citrate, tributyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, number-average molecular weight 200-10000, the polypropylene glycol of number-average molecular weight 200-6000, number-average molecular weight 500-10000, the PLA-PEG-PLA triblock copolymer of number-average molecular weight 1000-20000.
Although not necessarily, but for processing characteristics and the snappiness of better improving film, polylactic acid alloy film of the present invention, take (A) polylactic resin and (B) total amount of polyvinyl alcohol resin also comprise (F) toughner 1-100 weight part as 100 weight parts.
Further, described toughner is selected from one or more in aliphatic polyester, aliphatic-aromatic copolyester, aliphatic polycarbonate, elastomerics, the rubber.Wherein, described aliphatic polyester is one or more in polycaprolactone, poly butylene succinate, poly-succinic tetramethylene adipate, polyhydroxybutyrate-hydroxypentanoic acid copolyesters, poly-Hydroxyoctanoic acid-oxyacetic acid copolyesters, poly-sebacic acid glyceryl ester, the poly-hexanodioic acid glyceryl ester.Described aliphatic-aromatic copolyester is one or more in poly terephthalic acid tetramethylene adipate, the poly terephthalic acid succinic acid-butanediol ester.Described elastomerics is one or more among PLA dcS511, the S515 of Biomax Strong, the Rohm and Haas Chemicals PARALOID BPM-500 of company, Sukano company of ethylene-vinyl acetate copolymer, MBS, ethylene-acrylic acid copolymer, E.I.Du Pont Company.Described rubber is one or more in natural rubber, styrene-butadiene rubber(SBR), the ethylene-propylene rubber(EPR).
Although not necessarily, but for processing characteristics, snappiness, barrier and the reduction cost that better improves polylactic acid alloy film, polylactic acid alloy film of the present invention, take (A) polylactic resin and (B) total amount of polyvinyl alcohol resin also comprise (G) weighting agent 1-80 weight part as 100 weight parts.Preferably, its weight content is the 3-50 weight part.
Further, described weighting agent includes but not limited to calcium carbonate, calcium sulfate, barium sulfate, barium titanate, mica powder, talcum powder, carbon black, silicon-dioxide, titanium dioxide, polynite, zeolite, wilkinite, vermiculite, aluminum oxide, phosphatic rock, glass fibre, hollow glass ball, is preferably in calcium carbonate, calcium sulfate, talcum powder, titanium dioxide, polynite, the vermiculite one or more.
Described calcium carbonate can be selected the micron order calcium carbonate of mean diameter (D50) 1-10 micron or the nanometer grade calcium carbonate of mean diameter (D50) 5 nanometers-900 nanometer.In order to obtain preferably mechanical property, especially in order to improve toughness, the nanometer grade calcium carbonate of preferred average diameter (D50) 10 nanometers-100 nanometer.
Described calcium carbonate can further carry out surface modification with surface-modifying agent.Described surface-modifying agent is one or more in phosphoric acid ester, stearic acid, silane coupling agent, titanate coupling agent or above-mentioned (E) softening agent.
Described calcium carbonate is carried out surface modification can adopt this area routine techniques, such as calcium carbonate and surface-modifying agent are put in the reactor, be heated to 60-95 ℃, after continue stirring, discharging namely obtains the calcium carbonate of surface modification.Preferably, described weighting agent is one or more in the nanometer grade calcium carbonate of nanometer grade calcium carbonate, glycerine and titanate coupling agent modified of nanometer grade calcium carbonate, glycerine and silane coupling agent surface modification of glycerine surface modification.
Further, but in order better to improve the various performances of alloy firm, can also comprise the various common agents such as an amount of end-capping reagent, nucleator, fire retardant, UV stabilizer, pigment, whitening agent, lubricant.
Wherein, above-mentioned selectable components (D) oxidation inhibitor 0.01-3 weight part, (E) softening agent 1-40 weight part, (F) toughner 1-100 weight part and (G) weighting agent 1-80 weight part can add any one or more component wherein according to actual needs.
The preparation method of polylactic acid alloy film of the present invention can be with reference to existing thin film preparation process technology.A kind of preparation method provided by the invention comprises: each component is mixed; Join twin screw extruder, extrude in 150 ℃～220 ℃ melt blendings; Under 180-210 ℃, be blow molded into film after the granulation.
Another kind of preparation method provided by the invention comprises: each component is mixed; Join twin screw extruder, extrude in 150 ℃～220 ℃ melt blendings; Become film 180-210 ℃ of lower curtain coating.
The preparation method of polylactic acid alloy film of the present invention also comprises: carry out unidirectional or two-way stretching, to give its more mechanical property.
The preparation method of polylactic acid alloy film of the present invention also comprises: apply heat setting type under 60-180 ℃, more be conducive to improve mechanical property.
Polylactic acid alloy film of the present invention can be used for preparing wrapping material, agricultural film or plastics bag, needing to be particularly suitable for the packaging material for food of oxygen-barrier property.
Wherein, in " one or more " of the present invention " more than " all comprise given figure " two kinds ".
Polylactic acid alloy film of the present invention, keep thin-film material can be by the prerequisite of complete biodegradable and high strength under, effectively improved the oxygen barrier property of polylactic acid alloy film.Processing method of the present invention is simple, and is with low cost, can effectively promote the widespread use of environment-friendly type polylactic acid article.
Embodiment
Mode below by embodiment further specifies the present invention, does not therefore limit the present invention among the described scope of embodiments.
Embodiment 1～9
Table 1 has provided prescription and the performance evaluation of polylactic acid alloy film embodiment 1～9.After pressing the preliminary mixing of the component shown in the table 1, use twin-screw extrusion, 190 ℃ of extrusion temperatures, water-cooled, pelletizing; Particle after drying, under 180 ℃ with single screw extrusion machine extrude, blowing, the preparation thickness be the film of 20 μ m.
Wherein, the content of each prescription is parts by weight, and various components are as follows:
(A) polylactic resin
A1: U.S. Natureworks company, 4032D
A2: U.S. Natureworks company, 4060D
(B) polyvinyl alcohol resin
B1: oil of SPC, the polymerization degree 1700, alcoholysis degree 99%
B2: oil of SPC, the polymerization degree 1700, alcoholysis degree 88%
(C) expanding material
C1:BASF company, Joncyrl ADR4368, the polymkeric substance of many epoxy-functionals
C2: traditional Chinese medicines group, maleic anhydride grafted polyethylene
(D) oxidation inhibitor
D1: traditional Chinese medicines group, triphenyl phosphite
D2: traditional Chinese medicines group, Tyox B
D3: traditional Chinese medicines group, 2-(4-hydroxyl-3,5-di-tert-butyl amido)-4, two (n-octyl the sulfo-)-1,3,5-triazines of 6-
Wherein, the performance evaluation in the table 1 comprises:
Can processing characteristics be observed each prescription and be passed through the thermo forming film;
Tensile property is pressed tensile strength and the elongation at break of GB1040.3-2006 specimen;
The oxygen transit dose is pressed the oxygen transit dose of GB/T1038-2000 specimen under 23 ℃, 60%RH, the cm of unit
3/ m
2Dayatm.
Comparative Examples 1
Table 1 gives prescription and the performance evaluation of Comparative Examples 1.After pressing the preliminary mixing of the component shown in the table 1, use twin-screw extrusion, 190 ℃ of extrusion temperatures, water-cooled, pelletizing; Particle after drying, under 180 ℃ with single screw extrusion machine extrude, blowing, the preparation thickness be the film of 20 μ m.
Comparative Examples 2～4
Table 1 gives prescription and the performance evaluation of Comparative Examples 2～4.After pressing that the component shown in the table 1 is preliminary and mixing, use twin-screw extrusion, 190 ℃ of extrusion temperatures are extruded unstablely, and polyvinyl alcohol can't plastify, and color is sallow, can't further prepare film.
Embodiment 10～17
Table 2 has provided that A1/A2/B2/C2/D2/D3 is respectively on the basis of 35/35/30/5/0.2/0.2 weight part in table 1, further adds prescription and the performance evaluation of pressing the embodiment 10～17 after the component shown in the table 2.Tentatively mix by the component shown in the table 2, use twin-screw extrusion, 190 ℃ of extrusion temperatures, curtain coating, preparation thickness is the film of 20 μ m.
Wherein, the content of each prescription is parts by weight, and various components are as follows:
(E) softening agent
E1: traditional Chinese medicines group, the positive butyl ester of acetyl tributyl citrate
E2: traditional Chinese medicines group, glycerine
E3: traditional Chinese medicines group, polyoxyethylene glycol, number-average molecular weight 1000
(F) toughner
F1:BASF company, Ecoflex7011, poly terephthalic acid tetramethylene adipate
F2: Japanese clear and polymer company, Bionolle3001, poly-succinic tetramethylene adipate
F3: E.I.Du Pont Company, Biomax Strong100, ethylene-acrylic acid copolymer elastomerics
Wherein, the performance evaluation in the table 2 comprises:
Can processing characteristics be observed each prescription and be passed through the thermo forming film;
Tensile property is pressed tensile strength and the elongation at break of GB1040.3-2006 specimen;
The oxygen transit dose is pressed the oxygen transit dose of GB/T1038-2000 specimen under 23 ℃, 60%RH, the cm of unit
3/ m
2Dayatm.
Embodiment 18～22
Table 3 has provided that A1/A2/B2/C2/D2/D3 is respectively on the basis of 35/35/30/5/0.2/0.2/ weight part in table 1, after being respectively the E3/F1 of 20/10 weight part in the adding table 2 again, prescription and the performance evaluation of the embodiment 18～22 after the component shown in the table 3 is pressed in further adding.Tentatively mix by the component shown in the table 3, use twin-screw extrusion, 190 ℃ of extrusion temperatures, curtain coating, preparation thickness is the film of 20 μ m.
Wherein, the content of each prescription is parts by weight, and various components are as follows:
(G) weighting agent
G1: the bright rising sun industry and trade in Zibo company limited, micron order calcium carbonate, D50=2～2 micron.
G2: Xintai City, Ruicheng nano material company limited, nanometer grade calcium carbonate, D50=15-25 nanometer.
G3: the nanometer grade calcium carbonate of glycerine surface modification, self-control joins 1kg G2 and 100g glycerine in the reactor, is heated to 80 ℃, after continuing to stir, discharging.
G4: the nanometer grade calcium carbonate of glycerine and silane coupling agent KH560 surface modification, self-control joins 1kg G2,100g glycerine and 30g KH560 in the reactor, is heated to 80 ℃, after continuing to stir, discharging.
G5: the bright rising sun industry and trade in Zibo company limited, talcum powder, D50=2～2 micron.
Wherein, the performance evaluation in the table 3 comprises:
Can processing characteristics be observed each prescription and be passed through the thermo forming film;
Tensile property is pressed tensile strength and the elongation at break of GB1040.3-2006 specimen;
The oxygen transit dose is pressed the oxygen transit dose of GB/T1038-2000 specimen under 23 ℃, 60%RH, the cm of unit
3/ m
2Dayatm.
Table 3
Claims (16)
1. polylactic acid alloy film, it is characterized in that: its component comprises (A) polylactic resin, (B) polyvinyl alcohol resin and (C) expanding material, wherein, take (A) polylactic resin and (B) total amount of polyvinyl alcohol resin as 100 weight parts, (A) weight content of polylactic resin is 1～99 part, (B) weight content of polyvinyl alcohol resin is 1～99 part, and (C) weight content of expanding material is 0.05-5 part.
2. polylactic acid alloy film according to claim 1, it is characterized in that: described polylactic resin is Pfansteihl homopolymer, D-ALPHA-Hydroxypropionic acid homopolymer or L, one or more in the D-ALPHA-Hydroxypropionic acid multipolymer, and the weight-average molecular weight of described polylactic resin is 10,000～1,000,000.
3. polylactic acid alloy film according to claim 1, it is characterized in that: described polyvinyl alcohol resin is the polymerization degree 1,000～10,000, the polyvinyl alcohol of alcoholysis degree 50%～100%.
4. polylactic acid alloy film according to claim 1, it is characterized in that: described expanding material is to have at least two a kind of and two or more micromolecular compounds or polymkeric substance that are selected from acid anhydrides, the epoxy-functional.
5. polylactic acid alloy film according to claim 4 is characterized in that: described expanding material is the alkene esters of gallic acid expanding material of olefines expanding material, the maleic anhydride graft of maleic anhydride graft, with the alkene esters of gallic acid expanding material of epoxy base side chain or with the olefines expanding material of epoxy base side chain.
6. polylactic acid alloy film according to claim 5, it is characterized in that: described expanding material is maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, maleic anhydride grafted polyethylene-vinyl alcohol copolymer, glycidyl methacrylate graft polyethylene wax, glycidyl methacrylate graft polymethylmethacrylate, glycidyl methacrylate/methacrylic ester/styrol copolymer or ethene/acrylic ester/glycidyl methacrylate copolymer.
7. according to claim 1 to 6 each described polylactic acid alloy films, it is characterized in that: described polylactic acid alloy film take (A) polylactic resin and (B) total amount of polyvinyl alcohol resin also comprise in the following component one or more: (D) oxidation inhibitor 0.01-3 weight part as 100 weight parts; (E) softening agent 1-40 weight part; (F) toughner 1-100 weight part; And (G) weighting agent 1-80 weight part.
8. polylactic acid alloy film according to claim 7, it is characterized in that: described oxidation inhibitor is selected from one or more in phenols, amine, phosphorous acid esters, aliphatic ester, pentaerythritol esters, esters of acrylic acid, triazines, the agent of cyanurate class.
9. polylactic acid alloy film according to claim 8, it is characterized in that: described oxidation inhibitor is selected from tri-butyl-phenol, 4,4 '-sulfo--two (3-methyl-6-tert butyl phenol), 2,2 '-sulfo--two (3-methyl-6-tert butyl phenol), two (3,5-di-tert-butyl-hydroxy phenyl propionic acid propionyl) hydrazine, phosphoric acid [3,5 (1, the 1-dimethyl ethyl)-and the 4-hydroxy phenyl] methyl list ethyl ester calcium salt, triphenyl phosphite, triisodecyl phosphite ester, Wytox 312,3,5-di-tert-butyl-4-hydroxyl benzyl phosphoric acid fat, four [B-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, pentaerythritol tetrastearate, 12-oxystearic acid glyceryl ester, the trimethylolpropane tris stearate, stearic acid 13 esters, Tyox B, thio-2 acid 2 stearyl ester, 2-(4-hydroxyl-3,5-di-tert-butyl amido)-4, two (the n-octyl sulfo-s)-1 of 6-, in 3, the 5-triazine one or more.
10. polylactic acid alloy film according to claim 7, it is characterized in that: described softening agent is selected from one or more in glycerine, ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, acrylamide, glyceryl ester, citrate, sebate, suberate, phthalic acid ester, lactic acid, rac-Lactide, PLA-PEG copolymer, poly(lactic acid)-polypropylene glycol multipolymer, the polyethylene glycol-propylene glycol copolymers.
11. polylactic acid alloy film according to claim 10 is characterized in that: described softening agent is selected from one or more in the PLA-PEG-PLA triblock copolymer of PLURONIC F-127, number-average molecular weight 1000-20000 of polypropylene glycol, the number-average molecular weight 500-10000 of polyoxyethylene glycol, the number-average molecular weight 200-6000 of glycerine, ethylene glycol, vanay, triethyl citrate, tributyl citrate, acetyl triethyl citrate, tributyl acetylcitrate, number-average molecular weight 200-10000.
12. polylactic acid alloy film according to claim 7 is characterized in that: described toughner is selected from one or more in aliphatic polyester, aliphatic-aromatic copolyester, aliphatic polycarbonate, elastomerics, the rubber.
13. polylactic acid alloy film according to claim 12 is characterized in that: described aliphatic polyester is one or more in polycaprolactone, poly butylene succinate, poly-succinic tetramethylene adipate, polyhydroxybutyrate-hydroxypentanoic acid copolyesters, poly-Hydroxyoctanoic acid-oxyacetic acid copolyesters, poly-sebacic acid glyceryl ester, the poly-hexanodioic acid glyceryl ester; Described aliphatic-aromatic copolyester is one or more in poly terephthalic acid tetramethylene adipate, the poly terephthalic acid succinic acid-butanediol ester; Described elastomerics is one or more in ethylene-vinyl acetate copolymer, MBS, the ethylene-acrylic acid copolymer; Described rubber is one or more in natural rubber, styrene-butadiene rubber(SBR), the ethylene-propylene rubber(EPR).
14. polylactic acid alloy film according to claim 7, it is characterized in that: described weighting agent is selected from calcium carbonate, calcium sulfate, barium sulfate, barium titanate, mica powder, talcum powder, carbon black, silicon-dioxide, titanium dioxide, polynite, zeolite, wilkinite, vermiculite, aluminum oxide, phosphatic rock, glass fibre, hollow glass ball, is preferably in calcium carbonate, calcium sulfate, talcum powder, titanium dioxide, polynite, the vermiculite one or more.
15. polylactic acid alloy film according to claim 14 is characterized in that: described weighting agent is selected from one or more in the nanometer grade calcium carbonate of nanometer grade calcium carbonate, glycerine and titanate coupling agent modified of nanometer grade calcium carbonate, glycerine and silane coupling agent surface modification of glycerine surface modification.
16. polylactic acid alloy film claimed in claim 1 is as the application of wrapping material, agricultural film or plastics bag.
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| CN104194289A (en) * | 2014-08-25 | 2014-12-10 | 浙江渤海卫生用品有限公司 | Bio-based biodegradable plastic bag material |
| JP2015063672A (en) * | 2013-08-29 | 2015-04-09 | 三菱化学株式会社 | Aliphatic polyester resin composition |
| CN104629281A (en) * | 2015-02-11 | 2015-05-20 | 北京工商大学 | Biodegradable polylactic acid thermal conductive composite material and prepration method thereof |
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| JP2015063672A (en) * | 2013-08-29 | 2015-04-09 | 三菱化学株式会社 | Aliphatic polyester resin composition |
| CN104559092B (en) * | 2013-10-10 | 2017-08-25 | 黑龙江鑫达企业集团有限公司 | A kind of shock resistance, the preparation method of the modified polylactic acid material of resistance to deformation |
| CN104194289B (en) * | 2014-08-25 | 2016-03-30 | 浙江渤海卫生用品有限公司 | Bio-based biological decomposition plastics bag material |
| CN104194289A (en) * | 2014-08-25 | 2014-12-10 | 浙江渤海卫生用品有限公司 | Bio-based biodegradable plastic bag material |
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| CN106189013B (en) * | 2016-07-15 | 2017-09-22 | 怀化学院 | Thermoplastic polyvinyl alcohol material and preparation method thereof |
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| CN109337312A (en) * | 2018-09-10 | 2019-02-15 | 武汉金发科技有限公司 | A kind of lactic acid composite material and preparation method thereof |
| CN109337312B (en) * | 2018-09-10 | 2021-08-06 | 武汉金发科技有限公司 | Polylactic acid composite material and preparation method thereof |
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| CN109880325A (en) * | 2019-03-06 | 2019-06-14 | 南京工程学院 | A kind of degradable new polyester composite material and preparation method |
| CN113817303A (en) * | 2019-07-09 | 2021-12-21 | 中山市金群瑞科技有限公司 | Degradable food packaging material with high mechanical strength |
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| CN113817303B (en) * | 2019-07-09 | 2023-12-12 | 重庆和创简一科技有限公司 | Degradable food packaging material with high mechanical strength |
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Inventor after: Chun Shengli Inventor after: Shu Guisong Inventor after: Liu Xiangwen Inventor after: Zhang Junchao Inventor after: Bai Chengpo Inventor before: Chun Shengli Inventor before: Shu Guisong Inventor before: Liu Xiangwen |
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Effective date of registration: 20170510 Address after: 213000 workshop No. 9, No. 1, Taihu Road, Taihu science and Technology Industrial Park, Changzhou, Jiangsu Patentee after: Changzhou Bo Xinjiang new Mstar Technology Ltd Address before: 201505 Shanghai city Pudong New Area Jinshan District ting Lin Zhen Lin Po No. 39 building 6 A20 Patentee before: Shanghai Bojiang New Material Technology Co., Ltd. |