CN103571165A - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN103571165A CN103571165A CN201310547355.8A CN201310547355A CN103571165A CN 103571165 A CN103571165 A CN 103571165A CN 201310547355 A CN201310547355 A CN 201310547355A CN 103571165 A CN103571165 A CN 103571165A
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- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004626 polylactic acid Substances 0.000 title abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 130
- 239000004310 lactic acid Substances 0.000 claims description 65
- 235000014655 lactic acid Nutrition 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 42
- -1 poly(lactic acid) Polymers 0.000 claims description 38
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 36
- 239000012764 mineral filler Substances 0.000 claims description 23
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 229940006015 4-hydroxybutyric acid Drugs 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- OPZZWWFHZYZBRU-UHFFFAOYSA-N butanedioic acid;butane-1,1-diol Chemical compound CCCC(O)O.OC(=O)CCC(O)=O OPZZWWFHZYZBRU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical group CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- 238000005502 peroxidation Methods 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- VXHFNALHLRWIIU-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)C VXHFNALHLRWIIU-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 36
- 238000002474 experimental method Methods 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 7
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 238000005065 mining Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical class 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polylactic acid composite material and a preparation method thereof. The polylactic acid composite material comprises the following active ingredients respectively in parts by weight: 80-120 parts of polylactic acid, 100-200 parts of inorganic fillers, 15-35 parts of ester copolymer, 0.5-10 parts of polyfunctional group coupling agent, and 0.02-2 parts of radical initiator. According to the preparation method provided by the invention, the filling capacity and dispersity of the inorganic fillers, as well as the interface binding force between the inorganic fillers and the polymer, in the polylactic acid composite material can be remarkably improved. The composite material has the advantages of being excellent in properties, low in cost, biodegradable and the like, and the preparation method is simple, and easy for realization of industrial production.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of lactic acid composite material and preparation method thereof.
Background technology
Using in a large number and discarding of tradition macromolecular material not only causes the day by day in short supply of petroleum resources, but also ecotope is done great damage.Greatly develop bio-based and biodegradable material, progressively substituting the traditional macromolecular material generally using is the effective way addressing the above problem.Poly(lactic acid) (PLA) is considered to one of material of the most promising in biological plastics family and competitive power, and it derives from biomass, under composting conditions, can degradablely be CO
2and H
2o, can be to environment.
Poly(lactic acid), comprises PLLA (PLLA), poly-dextrolactic acid (PDLA) and D-lactic acid-dextrolactic acid multipolymer (PDLLA), is considered to one of material of the most promising in biological plastics family and competitive power.Lactic acid poly-(PLA) derives from biomass, under composting conditions, can degradablely be CO
2and H
2o, can be to environment.In addition, PLA has biocompatibility, excellent light transmission and good hot workability.Yet the cost of PLA high (1.5-2 that price is PE doubly), heat-drawn wire is low, fragility is large etc., and defect has restricted its application and development in fields such as disposable product, packing film bag, container, automobile, household electrical appliances.
Along with the progress of macromolecule modified technology, the performance deficiency of PLA has larger improvement, yet high price but becomes the bottleneck that it substitutes traditional macromolecular material.In order to reduce its cost, prior art generally adopts the fillers such as cheap starch, silicate, carbonate to fill PLA.Yet, poly(lactic acid) and above-mentioned packing material consistency are poor, when loading level is higher, filler is easily reunited, cause its blend performance degradation (Yuan Hua etc. of material afterwards, < < plastics > >, 2011,40 (4), 40-43).A small amount of filler can improve crystallinity and the intensity of PLA, but the cost of gained matrix material is limited, and elongation at break is lower.
(the Gong Faming etc. such as Gong Faming, plastics industry, 2012,40 (3), 58-60) adopt silane coupling agent to carry out finishing to calcium carbonate, improved the mechanical property of PLA/ calcium carbonate composite material, when calcium carbonate-filled amount < 40%, the notched Izod impact strength of matrix material is about 5kJ/m
2, elongation at break is about 4%.
Publication number is that the Chinese invention patent of CN102250454A discloses the composition that a kind of PLA of take, calcium carbonate, softening agent and functional additive are main ingredient, improves the flexibility of material.Publication number is that the Chinese invention patent of CN102241877A discloses the composition that a kind of PLA, polyurethane elastomer, softening agent and filler are main ingredient, improved the toughness of PLA, but the loading level of filler is lower than 20%.Publication number is that the Chinese invention patent of CN101638509A discloses a kind of esters polymer and calcium carbonate physical blending used, carry out with poly(lactic acid) the technology that toughened calcium carbonate filling polylactic acid is prepared in blend again, yet the simple blend between esters polymer and calcium carbonate is difficult to produce stronger interfacial adhesion power, and the loading level of calcium carbonate is lower.
Visible, the loading level that improves mineral filler is one of current polylactic acid modified problem urgently to be resolved hurrily to reduce poly-lactic acid material cost, to improve its toughness simultaneously.
Summary of the invention
In view of this, the object of the invention is to propose a kind of lactic acid composite material and preparation method thereof, to improve loading level and the dispersiveness of mineral filler in PLA simultaneously, improve its performance and reduce the cost of PLA matrix material.
Based on above-mentioned purpose, lactic acid composite material provided by the invention, by following raw material, according to weight part proportioning separately, formed: 80～120 parts of poly(lactic acid), 100～200 parts of mineral fillers, 15～35 parts of lipin polymers, 0.5～10 part of polyfunctional group coupling agent, 0.02～2 part of radical initiator.
Alternatively, described mineral filler is at least one in calcium carbonate and talcum powder.
Alternatively, described lipin polymer is at least one in tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester multipolymer, 3 butyric ester-4 hydroxybutyric acid ester copolymers, 3 butyric ester-3 hydroxycaproic acid ester copolymers, 3 butyric ester-3 hydroxyl pentanoate copolymers, succinic acid-butanediol ester-tetramethylene adipate multipolymer and ethylene-vinyl acetate copolymer.
Preferably, in described ethylene-vinyl acetate copolymer, the quality percentage composition of vinyl acetate is 41%～90%, is preferably 50%～70%.
Alternatively, described polyfunctional group coupling agent is at least one in vinylformic acid, methacrylic acid, butenoic acid and methylene-succinic acid.
Alternatively, described radical initiator is at least one in organic peroxide initiator and azo-initiator.
Preferably, described radical initiator is selected from bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexin, 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane, at least one in di-t-butyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, dilauroyl peroxide, dibenzoyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate and 2,2'-Azobis(2,4-dimethylvaleronitrile).
The present invention also provides a kind of method of preparing described lactic acid composite material, comprise the following steps: first lipin polymer, mineral filler, polyfunctional group coupling agent and radical initiator are obtained to finely dispersed blend by rotor Banbury mixer or two roller mill or twin screw extruder reactively blending according to proportioning at the first temperature, then poly(lactic acid) and described blend are obtained to described lactic acid composite material by Banbury mixer or twin screw extruder reactively blending at the second temperature.
Alternatively, described the first temperature is 40～140 ℃, and the second temperature is 150～200 ℃.
Alternatively, described closed-smelting machine rotor and two roller mill mixer roller rotating speed are 20～100 revs/min, preferably 30～60 revs/min.
Alternatively, the screw speed of described twin screw extruder is 50～500 revs/min, preferably 100～300 revs/min.
As can be seen from above, the lactic acid composite material obtaining according to preparation method provided by the invention can significantly improve the bounding force between loading level, dispersiveness, filler and the polymkeric substance of mineral filler.This matrix material has mechanical property excellence, cost is low and the advantage such as biodegradable, and its preparation method simply, is easily realized industrialization.This lactic acid composite material can be directly used in extrusion moulding, hot-forming, injection moulding or plastics sucking moulding etc., to prepare various plastics.In addition, micro-or a small amount of functional aid, such as oxidation inhibitor, softening agent, tinting material, thermo-stabilizer etc. can not affect the fundamental property of this lactic acid composite material.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in more detail.
It should be noted that, umber used in embodiment is weight part, and poly(lactic acid) used in embodiment, lipin polymer, mineral filler be all vacuum-drying 12 hours at 60 ℃ before using.The tensile strength of lactic acid composite material sheet material and elongation adopt Shenzhen WDT-10 of Kai Qiangli Machinery Co., Ltd. tensile testing machine to record according to GB/T1040-2006 standard, and rate of extension is 10mm/min; Notched Izod impact strength adopts the MZ-2056 shock-testing machine of Jiangdu jewel test machines to record according to ASTM D256.Described lactic acid composite material sheet material is made by following condition, be about to lactic acid composite material and put into mould and (175 ℃ of the hot pressing temperatures of hot pressing on vulcanizing press, hot pressing time 3min, hot pressing pressure 10MPa) colding pressing, (time 10min colds pressing again, pressure 10MPa colds pressing), make the sheet material that thickness is 1mm and 4mm, be respectively used to stretch and impact experiment.
Embodiment 1
By tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester multipolymer (PBAT, Hangzhou Xin Fu medicine company limited-liability company product) 30 parts and calcium carbonate (2500 orders, Ningbo of Zhejiang Jiu Feng mining industry company limited product) 110 parts of blend 2min in rotor Banbury mixer, then add respectively 0.6 part of 3.0 parts of methacrylic acids and dicumyl peroxide, continue to mix 5min and obtain blend, rotor speed is that 40rpm, temperature are 120 ℃.
120 parts of PLA (4032D, Natureworks LLC company product) are obtained to lactic acid composite material with said mixture melt blending 5min in rotor Banbury mixer, and rotor speed is that 40rpm, temperature are 170 ℃.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 25MPa, and elongation at break is 60%, and notched Izod impact strength is 4.5kJ/m
2.
Embodiment 2
By 3 butyric ester-4 hydroxybutyric acid ester copolymers, (4 butyric ester molar content are 10%, Shenzhen Yi Keman Science and Technology Ltd. product) 28 parts, talcum powder (1250 orders, Jiangxi special meticulous breeze difficult to understand company limited product) 0.5 part of 100 parts, 2.5 parts, vinylformic acid and dicumyl peroxide blend 6min in rotor Banbury mixer obtains blend, and rotor speed is that 50rpm, temperature are 135 ℃.
100 parts of PLA (4032D, Natureworks LLC company product) are obtained to lactic acid composite material with said mixture melt blending 5min in rotor Banbury mixer, and rotor speed is that 40rpm, temperature are 170 ℃.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 28MPa, and elongation at break is 55%, and notched Izod impact strength is 4.8kJ/m
2.
Embodiment 3
By ethylene-vinyl acetate copolymer, (vinyl acetate quality percentage composition is 50%, Germany Lanxess Corporation product) 30 parts and calcium carbonate (60-80 nanometer, day raw white stone company product) 165 parts of blend 2min in rotor Banbury mixer, then add respectively 1.0 parts of 5.2 parts of methacrylic acids and dicumyl peroxides, continue to mix 5min and obtain blend, rotor speed is that 40rpm, temperature are 100 ℃.
100 parts of PLA (4032D, Natureworks LLC company product) are obtained to lactic acid composite material with said mixture melt blending 5min in rotor Banbury mixer, and rotor speed is that 40rpm, temperature are 170 ℃.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 32MPa, and elongation at break is 65%, and notched Izod impact strength is 7.3kJ/m
2.
Embodiment 4
By ethylene-vinyl acetate copolymer, (vinyl acetate quality percentage composition is 60%, Germany Lanxess Corporation product) 28 parts and calcium carbonate (5000 orders, Ningbo of Zhejiang Jiu Feng mining industry company limited product) 120 parts of blend 2min in rotor Banbury mixer, then add respectively 1.0 parts of 4.8 parts of methacrylic acids and dicumyl peroxides, continue to mix 5min and obtain blend, rotor speed is that 40rpm, temperature are 100 ℃.
100 parts of PLA (4032D, Natureworks LLC company product) are obtained to lactic acid composite material with said mixture melt blending 5min in rotor Banbury mixer, and rotor speed is that 40rpm, temperature are 170 ℃.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 26MPa, and elongation at break is 70%, and notched Izod impact strength is 5.5kJ/m
2.
Embodiment 5
By ethylene-vinyl acetate copolymer, (vinyl acetate quality percentage composition is 60%, Germany Lanxess Corporation product) in two roller mills, plasticate 2 minutes for 28 parts, then tune up roll spacing, bag roller, slowly add talcum powder (1500 orders, Jiangxi special meticulous breeze difficult to understand company limited product) 110 parts and vinylformic acid are 3.6 parts, after calcium carbonate is sneaked into completely, add 0.8 part of dibenzoyl peroxide, then play triangle bag, clot each 7 times, slice, makes mixture, and drum rotational speed 50rpm, temperature are 40 ℃.
100 parts of PLA (2002D, Natureworks LLC company product) are obtained to lactic acid composite material with said mixture melt blending 5min in rotor Banbury mixer, and rotor speed is that 40rpm, temperature are 170 ℃.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 28MPa, and elongation at break is 65%, and notched Izod impact strength is 5.6kJ/m
2.
Embodiment 6
By succinic acid-butanediol ester-tetramethylene adipate multipolymer (PBSA, Korea S Li Lai KCC product) 25 parts, calcium carbonate (5000 orders, Ningbo of Zhejiang Jiu Feng mining industry company limited product) 100 parts, 4.0 parts of methylene-succinic acids and 2, 5-dimethyl-2, 0.6 part of 5-bis(t-butylperoxy) hexin mixes and within 5 minutes, obtains pre-composition in high-speed mixer (2500rpm), this pre-composition is obtained to granulation blend by the granulation of twin screw extruder blending extrusion, forcing machine is respectively 40 ℃ from feeding section to a mouthful temperature for mould section, 105 ℃, 115 ℃, 125 ℃ and 135 ℃, screw speed is 100rpm.
By PLA (2002D, Natureworks LLC company product) extrude and obtain lactic acid composite material with above-mentioned granulation blend employing twin screw extruder reactively blending for 100 parts, forcing machine is respectively 40 ℃, 155 ℃, 165 ℃, 175 ℃ and 185 ℃ from feeding section to a mouthful temperature for mould section, and screw speed is 150rpm.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 30MPa, and elongation at break is 60%, and notched Izod impact strength is 5.6kJ/m
2.
Embodiment 7
By ethylene-vinyl acetate copolymer, (vinyl acetate quality percentage composition is 70%, Germany Lanxess Corporation product) 25 parts, calcium carbonate (5000 orders, Ningbo of Zhejiang Jiu Feng mining industry company limited product) 0.6 part of 100 parts, 3.0 parts of butenoic acids and dilauroyl peroxide mix and within 5 minutes, obtain pre-composition in high-speed mixer (2500rpm), this pre-composition is obtained to granulation blend by the granulation of twin screw extruder blending extrusion, forcing machine is respectively 40 ℃, 60 ℃, 80 ℃, 90 ℃ and 100 ℃ from feeding section to a mouthful temperature for mould section, and screw speed is 100rpm.
By PLA (2002D, Natureworks LLC company product) extrude and obtain lactic acid composite material with above-mentioned granulation blend employing twin screw extruder reactively blending for 100 parts, forcing machine is respectively 40 ℃, 150 ℃, 160 ℃, 170 ℃ and 180 ℃ from feeding section to a mouthful temperature for mould section, and screw speed is 150rpm.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 27MPa, and elongation at break is 65%, and notched Izod impact strength is 5.5kJ/m
2.
Comparative example 1
By PLA (4032D, Natureworks LLC company) 100 parts and calcium carbonate (5000 orders, Ningbo of Zhejiang Jiu Feng mining industry company limited product) 120 parts in rotor Banbury mixer melt blending 5min obtain lactic acid composite material, rotor speed is that 40rpm, temperature are 170 ℃.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 43MPa, and elongation at break is 3%, and notched Izod impact strength is 2.0kJ/m
2.
Comparative example 2
By PLA (4032D, Natureworks LLC company) 100 parts, (vinyl acetate quality percentage composition is 60% to ethylene-vinyl acetate copolymer, Germany Lanxess Corporation product) 25 parts and calcium carbonate (5000 orders, Ningbo of Zhejiang Jiu Feng mining industry company limited product) 85 parts in rotor Banbury mixer melt blending 5min obtain lactic acid composite material, rotor speed is that 40rpm, temperature are 170 ℃.Adopting vulcanizing press to be pressed into thickness this lactic acid composite material is that the sheet material of 1mm and 4mm is not for stretching and impact experiment.The tensile strength that records this lactic acid composite material sheet material is 25MPa, and elongation at break is 10%, and notched Izod impact strength is 2.3kJ/m
2.
The lactic acid composite material obtaining in embodiment 1-7 has higher intensity, elongation and impelling strength.Compare with the lactic acid composite material obtaining in the comparative example 1 of poly(lactic acid) and mineral filler two component simple blend, elongation at break and the notched Izod impact strength of the lactic acid composite material obtaining in embodiment 1-7 are all significantly increased, and mineral filler is uniformly dispersed.Compare with the lactic acid composite material obtaining in the comparative example 2 of poly(lactic acid), mineral filler, lipin polymer single stage method simple blend, elongation at break and the notched Izod impact strength of the lactic acid composite material obtaining in embodiment 1-7 are also significantly increased.Visible, according to preparation method provided by the invention, can significantly improve the toughness of lactic acid composite material, can keep higher intensity simultaneously.
In esters polymer, mineral filler, polyfunctional group coupling agent, radical initiator Blending Processes, at the first temperature, there is ionic bonding in the hydroxy-acid group of polyfunctional group coupling agent and inorganic filler surface metal ion, make polyfunctional group coupling agent evenly be coated on inorganic filler particle surface, promoted the dispersion of mineral filler in lipin polymer.Because the first temperature is lower, radical initiator not yet occurs to decompose or only have a small amount of decomposition, can not cause esters polymer crosslinked and affect its properties for follow.Because mineral filler, polyfunctional group coupling agent, radical initiator are scattered in lipin polymer in advance, in above-mentioned blend and polylactic acid blend process, the carbon carbon unsaturated double-bond of esters polymer and polyfunctional group coupling agent is caused in-situ chemical bonding is occurred by radical initiator at the second temperature, thereby improved the interfacial adhesion power between mineral filler and esters polymer, lipin polymer is dispersed in poly(lactic acid) matrix simultaneously.In addition, at the second temperature, esters polymer, because slight being cross-linked can occur in the effect of initiator, improves its elasticity, thereby poly(lactic acid) is shown to better modified effect.
As can be seen here, lactic acid composite material provided by the invention and preparation method thereof has following characteristics:
(1) in described lactic acid composite material, the loading level of mineral filler is high.
(2) in lactic acid composite material provided by the present invention, mineral filler is mainly scattered in esters polymer, and the interfacial adhesion power of esters polymer and mineral filler is strong, described lactic acid composite material but has excellent mechanical property under mineral filler high filler loading capacity.
(3) poly(lactic acid) that the present invention adopts comes from biomass, and the mineral filler adopting comes from natural materials, and the lactic acid composite material of therefore preparing by the present invention is conducive to alleviate many problems that energy scarcity and white pollution bring.
(4) this patent mineral filler wide material sources used, cheap, its loading level in lactic acid composite material is large, and therefore lactic acid composite material cost provided by the invention is lower, can be used for producing disposable product, container, automobile and household electrical appliances with material etc.
(5) preparation method's technique of lactic acid composite material provided by the invention simple, with short production cycle, can on existing processing of high molecular material equipment, implement, be easy to realize industrialization and produce.
Those of ordinary skill in the field are to be understood that: the foregoing is only specific embodiments of the invention and oneself; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a lactic acid composite material, it is characterized in that, by following raw material, according to weight part proportioning separately, formed: 80～120 parts of poly(lactic acid), 100～200 parts of mineral fillers, 15～35 parts of lipin polymers, 0.5～10 part of polyfunctional group coupling agent, 0.02～2 part of radical initiator.
2. lactic acid composite material according to claim 1, is characterized in that, described mineral filler is at least one in calcium carbonate and talcum powder.
3. lactic acid composite material according to claim 1, it is characterized in that, described lipin polymer is tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester multipolymer, 3 butyric ester-4 hydroxybutyric acid ester copolymers, 3 butyric ester-3 hydroxycaproic acid ester copolymers, 3 butyric ester-3 hydroxyl pentanoate copolymers, at least one in succinic acid-butanediol ester-tetramethylene adipate multipolymer and ethylene-vinyl acetate copolymer, in therein ethylene-vinyl acetate copolymer, the quality percentage composition of vinyl acetate is 41%～90%, be preferably 50%～70%.
4. lactic acid composite material according to claim 1, is characterized in that, described polyfunctional group coupling agent is at least one in vinylformic acid, methacrylic acid, butenoic acid and methylene-succinic acid.
5. lactic acid composite material according to claim 1, is characterized in that, described radical initiator is at least one in organic peroxide initiator and azo-initiator.
6. according to the lactic acid composite material described in claim 1 and 5, it is characterized in that, described radical initiator is selected from bis(t-butylperoxy)diisopropylbenzene, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexin, 1, 1-di-t-butyl peroxy--3, 3, 5-trimethyl-cyclohexane, di-t-butyl peroxide, dicumyl peroxide, peroxidized t-butyl perbenzoate, dilauroyl peroxide, dibenzoyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, at least one in di-cyclohexylperoxy dicarbonate and 2,2'-Azobis(2,4-dimethylvaleronitrile).
7. prepare according to a method for the lactic acid composite material described in any one in claim 1～6, it is characterized in that, said method comprising the steps of:
First lipin polymer, mineral filler, polyfunctional group coupling agent and radical initiator are obtained to blend by rotor Banbury mixer or two roller mill or twin screw extruder reactively blending according to proportioning at the first temperature, then poly(lactic acid) and described blend are obtained to described lactic acid composite material by Banbury mixer or twin screw extruder reactively blending at the second temperature.
8. the preparation method of lactic acid composite material according to claim 7, is characterized in that, described closed-smelting machine rotor and two roller mill mixer roller rotating speed are 20～100 revs/min, preferably 30～60 revs/min.
9. the preparation method of lactic acid composite material according to claim 7, is characterized in that, the screw speed of described twin screw extruder is 50～500 revs/min, preferably 100～300 revs/min.
10. the preparation method of lactic acid composite material according to claim 7, is characterized in that, described the first temperature is 40～140 ℃, and the second temperature is 150～200 ℃.
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