CN103265798B - Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof - Google Patents
Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof Download PDFInfo
- Publication number
- CN103265798B CN103265798B CN201310214998.0A CN201310214998A CN103265798B CN 103265798 B CN103265798 B CN 103265798B CN 201310214998 A CN201310214998 A CN 201310214998A CN 103265798 B CN103265798 B CN 103265798B
- Authority
- CN
- China
- Prior art keywords
- ethylene
- eva
- vinyl acetate
- pla
- acetate copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and the moulded products thereof of the improvement of a kind of toughness, said composition comprises: poly(lactic acid) (PLA), ethylene-vinyl acetate copolymer (EVA) and modified additive, wherein, modified additive at least comprises two or more in oxidation inhibitor, linking agent, toughner, softening agent and transesterification catalyst.Modified additive is utilized to make ethylene-vinyl acetate copolymer (EVA) be dispersed in poly(lactic acid) (PLA), ethylene-vinyl acetate copolymer (EVA) is made to form elementary cross-linked structure when melt blending, the loss to elongation at break is reduced while improving tensile strength of material, simultaneously in conjunction with the polar group on ethylene-vinyl acetate copolymer (EVA), the consistency of EVA and PLA is improved by the method for transesterify, thus obtain mechanical property and processing characteristics all more excellent, can be applicable to molding, the blend composition of extrusion moulding product.
Description
Technical field
The present invention relates to polymeric material field, particularly relate to a kind of poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof.
Background technology
Poly(lactic acid) (PLA) is a kind of thermoplastic aliphatic's polyester of bio-based, and has biodegradable characteristic concurrently.Poly(lactic acid) derives from the reproducible plant resources such as corn, potato, through hydrolysis, fermentation, purifying, is polymerized, and generate lactic acid through microbial process degraded in vivo or in soil, final meta-bolites is water and carbonic acid gas.The development and application of poly(lactic acid) (PLA) material, not only can solve problem of environmental pollution, and prior meaning is as the plastics industry based on petroleum resources opens inexhaustible raw material resources.
The forming process such as the thermoplasticity of poly(lactic acid) (PLA) equally can carry out extruding as these polymers of PP, PS and PET on general processing units, injection moulding.The modulus of poly(lactic acid) (PLA) and intensity are also relatively high, glossiness and excellent transparency, and these advantages make it also be used widely at key areas such as biomedicine, packaging industries.But poly(lactic acid) (PLA) also exists some shortcomings, as crisp in PLA, extension at break is little, poor toughness, poor heat stability, high in cost of production series of problems, especially the defect of large, the poor toughness of its fragility, greatly limit its application.
In order to improve the toughness of poly(lactic acid) (PLA), people have carried out many research work, poly(lactic acid) (PLA) and the good material of other toughness carry out blended by bibliographical information, as polycaprolactone (PCL), poly-hexanodioic acid-butylene terephthalate (PBAT), urethane (PU), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate-glyceryl methacrylate (E-MA-GMA), the toughness of poly(lactic acid) (PLA) can be improved by polymer blending.But existing poly(lactic acid) (PLA) intermingling material also exists a common problem, be exactly that interface compatibility between poly(lactic acid) matrix and another kind of intermingling material is poor, this can cause the over-all properties of poly(lactic acid) (PLA) intermingling material to decline.
As mentioned above, although ethylene-vinyl acetate copolymer (EVA) has splendid toughness and cheap, can be used to plasticizing polylactic acid (PLA), but due to both poor compatibility, after the massfraction of EVA is more than 25%, its dispersing uniformity in PLA is poor, and the agglutinating value(of coal) of two-phase is poor, causes toughening effect to decline.(blending technology of poly(lactic acid)/ethene-vinyl acetate copolymer and the mechanical property such as Sun Qiangying, Donghua University's journal natural science edition, 2009, 135 (4), 376-380) adopt ethylene-methyl acrylate glycidyl methacrylate (E-MA-GMA) and maleic anhydride grafted ethene-vinyl acetate (EVA-MAH) as the compatilizer of PLA and EVA, prepare toughness reinforcing poly(lactic acid), but after adding merely ethylene-methyl acrylate glycidyl methacrylate (E-MA-GMA), mechanical property such as intensity and the toughness of intermingling material do not have the obvious improvement obtained, larger gap is had from materials application, and the price of product is higher, (the performance study of EVA plasticizing polylactic acid such as Fu Xuejun, plastics science and technology, 2007,35 (7), dioctyl phthalate (DOP) (DOP) 50-54) is adopted to improve the consistency of PLA and EVA, viewed from result, the compatibilization effect of DOP to PLA/EVA blend is unsatisfactory, and due to DOP toxic to the person, therefore promote the use of existing problems.In addition, a kind of method utilizing amides modification PLA is described in Chinese patent CN101759971A, utilize the synergy of amides and ethylene-vinyl acetate copolymer (EVA) partly can solve the problem of the impact property difference of PLA, but the tensile strength of PLA and elongation at break to be improved and not obvious.
As can be seen here, for improving the mechanical property of poly(lactic acid) (PLA), add ethylene-vinyl acetate copolymer (EVA) when carrying out blending and modifying, there is the shortcoming of poor compatibility between poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) intermingling material.
Summary of the invention
The object of the present invention is to provide a kind of poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof, solve the serious problem of phase separation of poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA), by adding modified additive, the toughness of regulation and control PLA/EVA intermingling material and processing characteristics.
According to an aspect of the present invention, a kind of poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition are provided, comprise:
(1) poly(lactic acid) (PLA) of 75-95wt%;
(2) ethylene-vinyl acetate copolymer (EVA) of 4-25wt%;
(3) modified additive of 1-10wt%;
Wherein, described modified additive at least comprise in oxidation inhibitor, linking agent, toughner, softening agent and transesterification catalyst two or more.
Described poly(lactic acid) (PLA) can be the blended of lactic acid homopolymer, lactic acid copolymer, lactic acid homopolymer and lactic acid copolymer, but in order to ensure the fusing point of poly(lactic acid) (PLA), thus ensure the thermotolerance of blend composition, the addition of initial option poly(lactic acid) (PLA) is 60-95wt%, is preferably 75-90wt%.
Described ethylene-vinyl acetate copolymer (EVA) is prepared by the method for high-pressure free radical copolymerization by ethene and vinyl acetate.
Preferably, in order to ensure the processing characteristics of intermingling material and ensure the consistency of PLA and EVA, the range of choice of described ethylene-vinyl acetate copolymer (EVA) melting index is 1.5-150g/10min, wherein, the mensuration temperature of described melting index is 190 DEG C, the counterweight weight that measures is 2.16kg.
Because ethylene-vinyl acetate copolymer (EVA) is non-biodegradable material, therefore addition is unsuitable too high, to keep the biodegradability of goods, thus ensures that material can not increase the carrying capacity of environment of discarding when reclaiming.But the addition of ethylene-vinyl acetate copolymer (EVA) words very little can affect the impelling strength of material, therefore, the addition of initial option ethylene-vinyl acetate copolymer (EVA) is 4-30wt%, is preferably 10-25wt%.
Preferably, in described ethylene-vinyl acetate copolymer (EVA), acetate unit content is preferably between 60-90wt%, the remarkable decline causing poly(lactic acid) thermotolerance because of the interpolation of ethylene-vinyl acetate copolymer can not be caused like this, the impact property of poly(lactic acid) can be improved simultaneously.
Easily there is DeR in ethylene-vinyl acetate copolymer (EVA) and poly(lactic acid) (PLA), what make goods occur xanthochromia and performance sharply descends degradation phenomenon under light or heat effect.Therefore, described modified additive can comprise one or more oxidation inhibitor, described oxidation inhibitor can be selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, β-(3,5-di-tert-butyl-hydroxy phenyl) one or more of the positive octadecanol ester of propionic acid or Triethylene glycol two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], described oxidation inhibitor accounts at most the 50wt% of modified additive gross weight, preferred 10-40wt%.
Described modified additive can comprise one or more linking agents, and described linking agent can be selected from dicumyl peroxide, benzoyl peroxide, one or more in di-t-butyl peroxide, and wherein, described linking agent accounts at most the 20wt% of modified additive gross weight.
Described modified additive can comprise one or more toughner, described toughner can be selected from ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA), ethylene-maleic acid-glycidyl methacrylate terpolymer (E-MAH-GMA), one or more in ethylene-methyl acrylate-methacrylic glycidyl ester terpolymer (E-MA-GMA), wherein, described toughner accounts at most the 50wt% of modified additive gross weight.
Preferably, described ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA) is prepared by Raolical polymerizable for ethene and glycidyl methacrylate, its preparation method can be still reaction or twin-screw extrusion reacting processing, wherein, in described ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA), select the repeating unit content of monomer ethylene between 70-95wt%, to ensure that ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA) is containing enough polar groups and non-polar group, thus play good toughening effect.
Preferably, described ethylene-maleic acid-glycidyl methacrylate terpolymer (E-MAH-GMA) is ethene, maleic anhydride and glycidyl methacrylate are prepared by high-pressure free radical polyreaction, wherein, in described ethylene-maleic acid-glycidyl methacrylate terpolymer (E-MAH-GMA), the repeating unit content of monomer ethylene is between 70-95wt%.
Preferably, ethylene-methyl acrylate-methacrylic glycidyl ester terpolymer (E-MA-GMA) is ethene, methyl acrylate and methacrylic glycidyl ester are prepared by high-pressure free radical polyreaction, wherein, in described ethylene-methyl acrylate-methacrylic glycidyl ester terpolymer (E-MA-GMA), the repeating unit content of monomer ethylene is between 60-95wt%.
Described modified additive can comprise one or more softening agent, described softening agent can be selected from oleic acid, triolein, one or more in glycidyl methacrylate (GMA), wherein, described softening agent accounts at most the 70wt% of modified additive gross weight.
Described modified additive can comprise one or more transesterification catalysts, described transesterification catalyst can be selected from tetrabutyl titanate, titanium isopropylate, zinc acetate, one or more in zinc sulfate, wherein transesterification catalyst accounts at most the 5wt% of properties-correcting agent gross weight.
Preferably, the preparation method of described poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition, melt blending can be adopted, poly(lactic acid) (PLA), ethylene-vinyl acetate copolymer (EVA) and modified additive mix by the mode of mechanical blending or the two combination, thus obtain described blend composition.Specifically can adopt the blend composition described in the preparation of high-speed mixer, Banbury mixer, twin screw extruder and/or vulcanizing press.
According to a further aspect in the invention, there is provided a kind of described poly(lactic acid) (PLA) and moulded products of ethylene-vinyl acetate copolymer (EVA) blend composition of comprising, described moulded products can by technique realizations such as hot-forming, extrusion moulding or blowfilm shapings.
According to poly(lactic acid) provided by the invention (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof, utilize the crosslinkable feature of molecular structure of ethylene-vinyl acetate copolymer (EVA), add two or more modified additive, ethylene-vinyl acetate copolymer (EVA) is made to form elementary cross-linked structure when melt blending, the loss to elongation at break is reduced while improving tensile strength of material, simultaneously in conjunction with the polar group on EVA, the consistency of EVA and PLA is improved by the method for transesterify.As can be seen here, by adding two or more modified additive, cost-saving basis can significantly improve the consistency of poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA), improve the toughness of poly(lactic acid) to a great extent, meanwhile take into account mechanical property and the processing characteristics of intermingling material, thus obtain the blend composition that can be applicable to molding, extrusion moulding product.
Accompanying drawing explanation
By the description to embodiment carried out below in conjunction with accompanying drawing, above-mentioned and/or other object of the present invention and advantage will become apparent, wherein:
Fig. 1 illustrates the SEM photo of the PLA/EVA blend composition section not adding modified additive;
Fig. 2 illustrates the SEM photo of the PLA/EVA blend composition section adding two or more modified additive.
Embodiment
Below by way of specific embodiment, technical scheme of the present invention is further described.Following examples further illustrate of the present invention, instead of limit the scope of the invention.
The poly(lactic acid) adopted in following examples is the 3051D of Natureworks injection grade, and second-order transition temperature is 55-58 DEG C, and melt temperature is 145 ~ 155 DEG C, and melting index is 10 ~ 30g/10min.Ethylene-vinyl acetate copolymer is respectively Exxon Mobil and produces Escorene
tMu1traEVAUL02528CC, UL00218CC, UL15028EM1, UL00728CC, UL04533EH2, UL05540EH2.Toughner: in ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA), GMA content is 5wt%, in ethylene-maleic acid-glycidyl methacrylate terpolymer (E-MAH-GMA), MAH content is 1wt%, GMA content is 4wt%, in ethylene-methyl acrylate-methacrylic glycidyl ester terpolymer (E-MA-GMA), MA content is 24wt%, GMA content is 8wt%.
The Banbury mixer used in following examples for Haake Rheomix Banbury mixer, hot-press forming device be 50T vulcanizing press.
Embodiment 1
To add in Banbury mixer at 180 DEG C after poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, glycidyl methacrylate and tetrabutyl titanate are mixed according to part by weight 100: 15: 2.5: 0.5,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 27MPa, elongation at break is 225%, and Izod notched impact is continuous.
Embodiment 2
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL00218CC, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide, to add in Banbury mixer at 180 DEG C after oleic acid and tetrabutyl titanate mix according to part by weight 100: 15: 0.05: 0.01: 2.5: 0.01, 80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 48MPa, elongation at break is 15%, Izod notched impact strength is 65J/m.
Embodiment 3
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL15028EM1, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide, to add in Banbury mixer at 180 DEG C after oleic acid and tetrabutyl titanate mix according to part by weight 100: 15: 0.05:0.01: 2.5: 0.01, 80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 42MPa, elongation at break is 88%, Izod notched impact strength is 70J/m.
Embodiment 4
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL00728CC, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, oleic acid and tetrabutyl titanate to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.01: 2.5: 0.01,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 49MPa, elongation at break is 75%, and Izod notched impact strength is 78J/m.
Embodiment 5
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL04533EH2, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide and oleic acid to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 20: 0.05: 0.01: 2.5,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 50MPa, elongation at break is 85%, and Izod notched impact strength is 70J/m.
Embodiment 6
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL05540EH2, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, oleic acid and tetrabutyl titanate to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 5: 0.01,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 27MPa, elongation at break is 160%, and Izod notched impact is continuous.
Embodiment 7
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide, triolein and tetrabutyl titanate to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 0.01: 3.0: 0.01,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 45MPa, and elongation at break is 30%.
Embodiment 8
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide, glycidyl methacrylate and tetrabutyl titanate to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 0.01: 3.0: 0.01,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 40MPa, and elongation at break is 60%.
Embodiment 9
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, di-t-butyl peroxide, oleic acid and zinc acetate to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 0.01: 2.5: 0.05,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 20MPa, and elongation at break is 67%.
Embodiment 10
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, benzoyl peroxide, to add in Banbury mixer at 180 DEG C after E-GMA and tetrabutyl titanate mix according to part by weight 100: 15: 0.05: 0.01: 2.5: 0.05, 80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 45MPa, elongation at break is 78%, Izod notched impact strength is 80J/m.
Embodiment 11
Poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, dicumyl peroxide, E-MAH-GMA and tetrabutyl titanate to be added in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 0.01: 5: 0.05,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 50MPa, elongation at break is 58%, and Izod notched impact strength is 95J/m.
Embodiment 12
To add in Banbury mixer at 180 DEG C after poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, Triethylene glycol two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], E-MA-GMA and tetrabutyl titanate are mixed according to part by weight 100: 15: 0.01: 3.5: 0.01,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 44MPa, elongation at break is 55%, and Izod notched impact strength is 138J/m.
Embodiment 13
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, four [β-(3,5--di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, E-MA-GMA and tetrabutyl titanate to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 7: 0.01,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 40MPa, elongation at break is 45%, and Izod notched impact is continuous.
Embodiment 14
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide and oleic acid to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 0.01: 3,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 41MPa, elongation at break is 55%, and Izod notched impact strength is 75J/m.
Embodiment 15
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide, oleic acid and tetrabutyl titanate to add in Banbury mixer at 180 DEG C after mixing according to part by weight 100: 15: 0.05: 0.01: 2.5: 0.01,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 39MPa, and elongation at break is 50%.
Embodiment 16
By poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, dicumyl peroxide, glycidyl methacrylate, to add in Banbury mixer at 180 DEG C after E-MA-GMA and tetrabutyl titanate mix according to part by weight 100: 15: 0.05: 0.01: 3: 0.1: 0.01, 80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 39MPa, elongation at break is 75%, Izod notched impact is continuous.
Comparative example 1
To add in Banbury mixer at 180 DEG C after poly(lactic acid) 3051D, ethylene-vinyl acetate copolymer UL02528CC are mixed according to part by weight 100: 15,80 revs/min, melt blending 10 minutes, obtain PLA/EVA intermingling material after being molded into block, being cut into ASTM standard batten, measuring its tensile strength is 45MPa, elongation at break is 25%, and Izod notched impact strength is the SEM photo that 70J/m, Fig. 1 show PLA/EVA blend composition section in comparative example 1.
By testing data and (blending technology of poly(lactic acid)/ethene-vinyl acetate copolymer and the mechanical property such as embodiment and Sun Qiangying of embodiment and comparative example, Donghua University's journal natural science edition, 2009,135 (4), testing data contrast 376-380) recorded can find, by adding two or more modified additive in poly(lactic acid) (PLA), impact property and the elongation at break of material significantly can be improved with optimal conditions.
Fig. 2 shows the SEM photo of the PLA/EVA blend composition section that with the addition of two or more modified additive, carry out contrasting from the SEM photo shown in Fig. 2 and Fig. 1 and also can find, after adding two or more modified additive, the consistency of poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) be improved significantly, illustrate in melt blending process, modified additive reduces the interfacial tension of PLA matrix and EVA disperse phase, make EVA particle under the effect of shearing force by refinement and dispersion, obtain the little and blend composition be evenly distributed of dispersed phase particles, enhance the interfacial adhesion between disperse phase and matrix.
Can machine-shaping goods according to poly(lactic acid) of the present invention (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition, described moulded products can by technique realizations such as hot-forming, extrusion moulding or blowfilm shapings.
According to poly(lactic acid) of the present invention (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof, improve the toughness of poly(lactic acid) to a great extent, cost-saving basis significantly improves the consistency of PLA/EVA blend, significantly can improve impact property and the elongation at break of material with optimal conditions, make product have excellent mechanical property simultaneously.
Each embodiment above of the present invention is only exemplary, and the present invention is not limited to this.Those skilled in the art should understand that: without departing from the principles and spirit of the present invention, can change these embodiments, wherein, scope of the present invention limits in claim and equivalent thereof.
Claims (15)
1. poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition, it is characterized in that, described blend composition comprises:
(1) poly(lactic acid) (PLA) of 75-95wt%;
(2) ethylene-vinyl acetate copolymer (EVA) of 4-25wt%;
(3) modified additive of 1-10wt%;
Wherein, described modified additive at least comprise in oxidation inhibitor, linking agent, toughner, softening agent and transesterification catalyst two or more.
2. blend composition as claimed in claim 1, is characterized in that: described poly(lactic acid) (PLA) content is 75-90wt%.
3. blend composition as claimed in claim 1, is characterized in that: described ethylene-vinyl acetate copolymer (EVA) content is 10-25wt%.
4. blend composition as claimed in claim 1, is characterized in that: in described ethylene-vinyl acetate copolymer (EVA), the content of ethylene unit is between 60-90wt%.
5. blend composition as claimed in claim 1, it is characterized in that: the melting index of described ethylene-vinyl acetate copolymer (EVA) is 1.5-150g/10min, wherein, the mensuration temperature of described melting index is 190 DEG C, the counterweight weight that measures is 2.16kg.
6. blend composition as claimed in claim 1, it is characterized in that: described oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester, β-(3,5-di-tert-butyl-hydroxy phenyl) one or more of the positive octadecanol ester of propionic acid or Triethylene glycol two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], wherein, described oxidation inhibitor accounts at most the 50wt% of modified additive gross weight.
7. blend composition as claimed in claim 6, is characterized in that: described oxidation inhibitor accounts for the 10-40wt% of modified additive gross weight.
8. blend composition as claimed in claim 1, it is characterized in that: described linking agent is selected from dicumyl peroxide, benzoyl peroxide, one or more in di-t-butyl peroxide, wherein, described linking agent accounts at most the 20wt% of modified additive gross weight.
9. blend composition as claimed in claim 1, it is characterized in that: described toughner is selected from ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA), ethylene-maleic acid-glycidyl methacrylate terpolymer (E-MAH-GMA), one or more in ethylene-methyl acrylate-methacrylic glycidyl ester terpolymer (E-MA-GMA), wherein, described toughner accounts at most the 50wt% of modified additive gross weight.
10. blend composition as claimed in claim 9, is characterized in that: in described ethylene-methyl methacrylate glycidyl ester copolymer (E-GMA), the repeating unit content of monomer ethylene is between 70-95wt%.
11. blend compositions as claimed in claim 9, is characterized in that: in described ethylene-maleic acid-glycidyl methacrylate terpolymer (E-MAH-GMA), the repeating unit content of monomer ethylene is between 70-95wt%.
12. blend compositions as claimed in claim 9, is characterized in that: in described ethylene-methyl acrylate-methacrylic glycidyl ester terpolymer (E-MA-GMA), the repeating unit content of monomer ethylene is between 60-95wt%.
13. blend compositions as claimed in claim 1, it is characterized in that: described softening agent is selected from oleic acid, triolein, one or more in glycidyl methacrylate (GMA), wherein, described softening agent accounts at most the 70wt% of modified additive gross weight.
14. blend compositions as claimed in claim 1, is characterized in that: described transesterification catalyst is selected from tetrabutyl titanate, titanium isopropylate, zinc acetate, one or more in zinc sulfate, wherein, transesterification catalyst accounts at most the 5wt% of modified additive gross weight.
15. 1 kinds of moulded products comprising poly(lactic acid) as claimed in claim 1 (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition, described moulded products is processed into by hot-forming, extrusion moulding or blowfilm shaping.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310214998.0A CN103265798B (en) | 2013-06-03 | 2013-06-03 | Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310214998.0A CN103265798B (en) | 2013-06-03 | 2013-06-03 | Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103265798A CN103265798A (en) | 2013-08-28 |
| CN103265798B true CN103265798B (en) | 2015-11-25 |
Family
ID=49009468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310214998.0A Active CN103265798B (en) | 2013-06-03 | 2013-06-03 | Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103265798B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483788B (en) * | 2013-09-09 | 2016-06-08 | 常州大学 | A kind of composite toughening method of modifying of the polylactic acid based on crystallization control |
| CN103756273B (en) * | 2013-12-27 | 2016-03-23 | 吴江市东泰电力特种开关有限公司 | A kind of environment-friendly degradable antirust film and preparation method thereof |
| CN103897260A (en) * | 2014-04-24 | 2014-07-02 | 山东昊达化学有限公司 | Blended composition of ethylene-ethylene vinyl-acetate copolymer (EVA) and polylactic acid (PLA) and molding product thereof |
| CN105733214A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Method for preparing shock-resistant and deformation-resistant modified polylactic-acid material |
| EP4389843A2 (en) | 2014-12-22 | 2024-06-26 | 3M Innovative Properties Company | Compositions and films comprising polylactic acid polymer, polyvinyl acetate polymer and plasticizer |
| CN105985615A (en) * | 2015-02-13 | 2016-10-05 | 汉达精密电子(昆山)有限公司 | Polylactic acid composite material and its product |
| CN106893279A (en) * | 2015-12-18 | 2017-06-27 | 四川鑫达企业集团有限公司 | A kind of biodegradable 3D printing toughening material and preparation method |
| CN105504726A (en) * | 2016-02-03 | 2016-04-20 | 黑龙江鑫达企业集团有限公司 | Composite material suitable for 3D printing and preparation method thereof |
| CN105585829A (en) * | 2016-02-18 | 2016-05-18 | 合肥市再德高分子材料有限公司 | Environment-friendly flame-retardant polylactic acid composite material |
| US11066551B2 (en) | 2016-05-20 | 2021-07-20 | 3M Innovative Properties Company | Oriented polylactic acid polymer based film |
| WO2017222824A1 (en) | 2016-06-21 | 2017-12-28 | 3M Innovative Properties Company | Graphic articles comprising semicrystalline polylactic acid based film |
| CN109135225B (en) * | 2018-08-08 | 2020-03-24 | 江南大学 | High-performance composite material and preparation method thereof |
| CN109651779A (en) * | 2018-11-27 | 2019-04-19 | 包惠芳 | A kind of PLA-POE composite material |
| CN111378261B (en) * | 2020-03-05 | 2022-06-28 | 温州三星环保包装有限公司 | Processing method of disposable lunch box |
| CN111534068B (en) * | 2020-06-02 | 2021-12-10 | 中国科学技术大学 | Polylactic acid material with ultrahigh impact strength and preparation method thereof |
| CN114685882A (en) * | 2022-04-03 | 2022-07-01 | 杭州师范大学 | Reactive micro-crosslinked elastomer and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5726220A (en) * | 1995-08-30 | 1998-03-10 | Shin-Etsu Chemical Co., Ltd. | Biodegradable polymer compositions and shrink films |
| CN100497477C (en) * | 2003-12-12 | 2009-06-10 | E.I.内穆尔杜邦公司 | Toughened poly(lactic acid) compositions |
-
2013
- 2013-06-03 CN CN201310214998.0A patent/CN103265798B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5726220A (en) * | 1995-08-30 | 1998-03-10 | Shin-Etsu Chemical Co., Ltd. | Biodegradable polymer compositions and shrink films |
| CN100497477C (en) * | 2003-12-12 | 2009-06-10 | E.I.内穆尔杜邦公司 | Toughened poly(lactic acid) compositions |
Non-Patent Citations (4)
| Title |
|---|
| "Poly(lactic acid) modifications";Rahul M.Rasal et al;《Progress in Polymer Science》;20100331;第35卷(第3期);第338-356页 * |
| "Relative melt viscosity, mechanical properties and morphology of polymer blend based on poly(lactic acid) and ethylene-vinylacetate copolymer modified by acrylic acid";THAI HOANG et al;《Journal of Science and Technology》;20091231;第47卷(第5A期);第411页倒数第1-6行 * |
| "Synthesis of EVA-g-PLA copolymers using transesterification reactions";I. Moura et al;《Materials Chemistry and Physics》;20120515;第134卷(第1期);摘要、第108页左半栏8-19行、右半栏第1-9行 * |
| "聚乳酸/乙烯-乙酸乙烯共聚物的共混工艺及力学性能";孙强英等;《东华大学学报（自然科学版）》;20090831;第35卷(第4期);第380页左半栏第1-5行、第378页右半栏第10-20行 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103265798A (en) | 2013-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103265798B (en) | Poly(lactic acid) (PLA) and ethylene-vinyl acetate copolymer (EVA) blend composition and moulded products thereof | |
| CN104119647B (en) | A kind of high-content of starch complete biodegradable composition and preparation method thereof | |
| CN102702705A (en) | Toughened polylactic acid/polyolefin elastomer composite material and preparation method thereof | |
| CN103992517B (en) | One can be continuously produced fully-degradable starch base plastic alloy and preparation method thereof | |
| CN1216101C (en) | Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition | |
| CN101205356A (en) | Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid | |
| CN101824211B (en) | Full-biodegradation high-tenacity heat-resistant type polylactic resin and preparation method thereof | |
| CN111286168A (en) | Biodegradable polyester/cellulose composite blown film material and preparation method thereof | |
| CN103013070A (en) | Polylactic acid composite material and preparation method thereof | |
| CN103897260A (en) | Blended composition of ethylene-ethylene vinyl-acetate copolymer (EVA) and polylactic acid (PLA) and molding product thereof | |
| CN106916424A (en) | A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof | |
| CN103589124A (en) | Fully-biodegradable PLA/PBAT composite film and making method thereof | |
| CN103589125B (en) | A kind of Polylactic acid/polypropylene blend and preparation method thereof | |
| CN106084697A (en) | A kind of lactic acid composite material having heat-resisting and mechanical property concurrently and preparation method thereof | |
| CN105440608B (en) | High-toughness high-strength polylactic acid composite material and preparation process therefor | |
| CN103965516A (en) | Fully biodegradable masterbatch and preparation method thereof | |
| CN104312121A (en) | High-toughness transparent polylactic acid film and preparing method thereof | |
| CN101570624B (en) | Method for preparing biomass base polylactic acid composite material | |
| CN106916421A (en) | One kind enhancing is poly-（Terephthalic acid (TPA) butanediol co adipic acid butanediols）Ester degradable material | |
| CN110317406A (en) | A kind of biodegradable polypropene composition and preparation method thereof | |
| CN114369347B (en) | Degradable flow modification auxiliary agent and preparation method and application thereof | |
| CN109535490A (en) | A kind of starch masterbatch and preparation method thereof for filling-modified degradable high polymer material | |
| CN103102657B (en) | Biodegradable blend and preparation method and application thereof | |
| CN103183939B (en) | A kind of method improved polylactic acid/polyether ester block copolymer and extrude and improve shock resistance | |
| CN114921069B (en) | Full-biodegradable film with high heat seal strength and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160321 Address after: Wujin District of Jiangsu city in Changzhou province 213000 Chang Wu Road No. 18, Changzhou Science City Science Hall South 3 building room 2312 Patentee after: LEVIMA (JIANGSU) NEW MATERIAL RESEARCH INSTITUTE CO., LTD. Address before: 277527 Shandong province Tengzhou City Stone Town resident (Stone Industrial Park) Patentee before: Shandong Haoda Chemical Co., Ltd. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160921 Address after: 277527 Shandong province Tengzhou City Stone Town resident (Stone Industrial Park) Patentee after: Union new materials Co., Ltd. Address before: Wujin District of Jiangsu city in Changzhou province 213000 Chang Wu Road No. 18, Changzhou Science City Science Hall South 3 building room 2312 Patentee before: LEVIMA (JIANGSU) NEW MATERIAL RESEARCH INSTITUTE CO., LTD. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 277527 Mushi Town, Tengzhou City, Zaozhuang City, Shandong Province (Mushi Industrial Park) Patentee after: Lianhong New Materials Technology Co., Ltd. Address before: 277527 Mushi Town, Tengzhou City, Shandong Province (Mushi Industrial Park) Patentee before: Union new materials Co., Ltd. |