CN103483788A - Composite toughening modification method for polylactic acid based on crystallization control - Google Patents
Composite toughening modification method for polylactic acid based on crystallization control Download PDFInfo
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- CN103483788A CN103483788A CN201310406705.9A CN201310406705A CN103483788A CN 103483788 A CN103483788 A CN 103483788A CN 201310406705 A CN201310406705 A CN 201310406705A CN 103483788 A CN103483788 A CN 103483788A
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- poly
- lactic acid
- vinyl acetate
- ethylene
- acetate copolymer
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 71
- 238000002425 crystallisation Methods 0.000 title claims abstract description 16
- 230000008025 crystallization Effects 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- 239000004626 polylactic acid Substances 0.000 title abstract description 9
- 238000002715 modification method Methods 0.000 title abstract description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 35
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 18
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000007731 hot pressing Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- -1 poly(lactic acid) Polymers 0.000 claims description 119
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a composite toughening modification method for polylactic acid based on crystallization control, and belongs to the technical field of high molecular materials. The method comprises the following steps: pre-putting polylactic acid and an ethylene-vinyl acetate copolymer in a vacuum oven at 60 DEG C and drying for 12 hours; sequentially adding polylactic acid, an ethylene-vinyl acetate copolymer and glycidyl methacrylate into the dried polylactic acid and ethylene-vinyl acetate copolymer at a blending temperature of 170-180 DEG C to obtain a blended material; cooling the product of the blending banburying and placing the product in a mould; preheating the product on a flat vulcanizing machine at 170-180 DEG C for 2-4 minutes; sequentially performing hot pressing of 2-3 minutes and cold pressing of 3-5 minutes to achieve the aims of crystallization control and toughening modification of polylactic acid. According to the method disclosed by the invention, the technological process for preparing polylactic acid with excellent toughness is simple, the processability is good, the cost is low, and large-scale industrial production can be realized.
Description
Technical field
The invention belongs to technical field of polymer materials, specifically a kind of composite toughening method of modifying of the poly(lactic acid) based on the crystallization regulation and control.
Background technology
Poly(lactic acid) is a kind ofly to take reproducible plant resources as raw material, the biodegradable polymer prepared through chemosynthesis, the forming process such as the thermoplasticity of poly(lactic acid) can equally be extruded as these polymers of PP, PS and PET on general processing units, injection moulding.In addition, poly(lactic acid) also has unique biocompatibility and biological degradability, and therefore, as a kind of biodegradable polymer, poly(lactic acid) has become the focus of the academic boundary of polymer and industrial community concern.
Intensity and the rigidity of poly(lactic acid) are high, but toughness and shock resistance are poor, under normal temperature, are a kind of hard and crisp materials.Therefore, to the toughness reinforcing plasticization and modification of poly(lactic acid), be its market-oriented important subject always.
Blending and modifying is a kind of comparatively economic and easy method of modifying.Blending and modifying be by poly(lactic acid), toughness preferably polymkeric substance jointly mix, thereby reach a kind of method of the toughness reinforcing purpose of poly(lactic acid).Blending modification method can improve the toughness of poly(lactic acid) effectively, also has but then between blend components that consistency is poor, a problem such as the system mechanical property is undesirable after blend.
Through the retrieval to prior art, find, in order to improve the toughness of poly(lactic acid), people have carried out many research work, as compound in adopted poly(lactic acid) and other aliphatic polyesters to carry out, but expensive, are difficult to be accepted by market.And ethylene-vinyl acetate copolymer is cheap and easy to get, and fabulous toughness is arranged, can be applied to the toughness reinforcing of poly(lactic acid).Japanese Patent JP-2007063435 proposes to prepare moulded products after poly(lactic acid), ethylene-vinyl acetate copolymer blend, although the shock strength of blend alloy is improved, the crystal property of poly(lactic acid) does not improve.(the plastics science and technology such as Fu Xuejun, 2007,35(7), 50) adopt ethylene-vinyl acetate copolymer to carry out toughness reinforcing to poly(lactic acid), and employing plasticizer phthalic acid dioctyl ester (DOP) improves the consistency of two-phase, but DOP has potential carinogenicity, and the application of its polylactic acid-based product also is restricted, and aforesaid method also makes poly(lactic acid) degree of crystallinity hang down difficult forming, and shaping cycle is long.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of composite toughening method of modifying of the poly(lactic acid) based on crystallization regulation and control is provided, simple in the implementation method step, further improved the toughness of matrix material when suitability is strong.
The present invention is achieved by the following technical solutions, and the present invention, by add glycidyl methacrylate and ethylene-vinyl acetate copolymer in poly(lactic acid), realizes crystallization regulation and control and toughening modifying to poly(lactic acid).
A kind of composite toughening method of modifying of the poly(lactic acid) based on the crystallization regulation and control, according to following step, carry out: (1) is placed in poly(lactic acid) and ethylene-vinyl acetate copolymer the dry 12h of vacuum drying oven of 60 ℃ in advance, (2) then by the poly(lactic acid) of drying and ethylene-vinyl acetate copolymer under the blending temperature of 170-180 ℃, add successively poly(lactic acid), ethylene-vinyl acetate copolymer and glycidyl methacrylate, and, with the mixing 8-10 minute of the speed of 60-80 rpm, obtain the PLA/EVA intermingling material; (3) be placed in mould the product of above-mentioned blend banburying is cooling, carry out successively hot pressing in 2-3 minute and cold pressing in 3-5 minute on vulcanizing press with after 170-180 ℃ of lower preheating 2-4 minute, pressure is 10-15MPa, can reach the crystallization regulation and control of poly(lactic acid) and the purpose of toughening modifying.
The parts by weight of wherein said poly(lactic acid), ethylene vinyl acetate copolymer and glycidyl methacrylate are respectively 80-85 part, 10-15 part, 2.5-10 part.
Described poly(lactic acid) melting index be (190 ℃, 2.16Kg) 10g/min, the poly(lactic acid) that the trade mark that for example Natureworks company produces is 3051D, density is 1.24g/cm
3.
The melting index of described ethylene-vinyl acetate copolymer be (190 ℃, 2.16Kg) 20g/min, wherein the content of vinyl acetate is 28wt%, the density that for example Hunan petro-chemical corporation produces is 0.95g/cm
3, the ethylene-vinyl acetate copolymer that the trade mark is VA800.
The present invention has adopted the method for ethylene-vinyl acetate copolymer and glycidyl methacrylate use, utilize the ethylene-vinyl acetate copolymer good elasticity to carry out toughness reinforcing to poly(lactic acid), utilize the crystallization behavior of glycidyl methacrylate regulation and control poly(lactic acid), to improve the elongation at break of material.Make material there are the characteristics of high tenacity.In poly(lactic acid), be 85, ethylene vinyl acetate copolymer is 15, and when glycidyl methacrylate is 10 mass parts, the elongation at break of intermingling material reaches 215%, and shock strength reaches 97.18J/m.The present invention prepares that the technical process of poly(lactic acid) of good-toughness is simple, and processing characteristics is good, and cost is low and can realize large-scale industrial production.The blend obtained can be used for preparing film, sheet material and injection-molded plastic product.
The accompanying drawing explanation
The DSC curve that Fig. 1 is lactic acid and blend thereof, wherein 1: poly(lactic acid); 2: poly(lactic acid)/ethylene-vinyl acetate copolymer; 3: poly(lactic acid)/ethylene-vinyl acetate copolymerization/10% glycidyl methacrylate.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Following examples material therefor is: poly(lactic acid): trade mark 3051D, melting index (190 ℃, 2.16kg) 10g/min, U.S. Natureworks product;
Ethylene-vinyl acetate copolymer, trade mark VA800, Korea S Hunan petro-chemical corporation produces.
Embodiment 1-4
The embodiment of the present invention comprises the following steps:
The first step, be placed in 60 ℃ of dry 12h of vacuum drying oven by poly(lactic acid), ethylene vinyl acetate copolymer;
Second step, be pre-mixed the poly(lactic acid) after dried, ethylene vinyl acetate copolymer and glycidyl methacrylate evenly in table one ratio, then melt blending in (Jiangsu Su Yan science and technology, SU-70c type) Banbury mixer.Blending temperature is 180 ℃, and rotating speed is 80 rpms, and the blend time is 10 minutes;
The 3rd step, be placed in mould by gained banburying product, in 180 ℃ of lower preheating 3min, and then hot pressing 2min under 10MPa, then the 3min moulding of colding pressing, pressure is 10MPa, presses the sample preparation of ASTM standard, and material is carried out to performance test.(concrete proportioning is in Table 1)
Comparative example 1
The first step, before blend, be placed in 60 ℃ of dry 12h of vacuum drying oven by poly(lactic acid), ethylene vinyl acetate copolymer;
Second step, by the melting in (Jiangsu Su Yan science and technology, SU-70c type) Banbury mixer of the poly(lactic acid) after dried.The banburying temperature is 180 ℃, and rotating speed is 80 rpms, and the blend time is 10 minutes;
The 3rd step, be placed in mould by gained banburying product, in 180 ℃ of lower preheating 3min, and then hot pressing 2min under 10MPa, then the 3min moulding of colding pressing, pressure is 10MPa, presses the sample preparation of ASTM standard, and material is carried out to performance test.
Comparative example 2
The first step, be placed in 60 ℃ of dry 12h of vacuum drying oven by poly(lactic acid), ethylene vinyl acetate copolymer;
Second step, be pre-mixed the poly(lactic acid) after dried, ethylene vinyl acetate copolymer evenly in table one ratio, then melt blending in (Jiangsu Su Yan science and technology, SU-70c type) Banbury mixer.Blending temperature is 180 ℃, and rotating speed is 80 rpms, and the blend time is 10 minutes;
The 3rd step, be placed in mould by gained banburying product, in 180 ℃ of lower preheating 3min, and then hot pressing 2min under 10MPa, then the 3min moulding of colding pressing, pressure is 10MPa, presses the sample preparation of ASTM standard, and material is carried out to performance test.
Table 1 embodiment and Comparative Examples formula (unit is weight part)
| ? | Embodiment 1 | |
|
Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| Poly(lactic acid) | 80 | 85 | 80 | 85 | 100 | 85 |
| Ethylene vinyl acetate copolymer | 15 | 10 | 10 | 15 | 0 | 15 |
| Glycidyl methacrylate | 2.5 | 5 | 7.5 | 10 | 0 | 0 |
Table 2 thickness of sample is 1.0mm, mechanical property result during rate of extension 50mm/min
| ? | Embodiment 1 | |
|
Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| Tensile strength (MPa) | 40.8 | 35 | 30.32 | 29.13 | 48.3 | 68.5 |
| Elongation at break (%) | 35 | 77 | 93 | 215 | 3 | 24 |
| Notched Izod impact strength (J/m) | 78 | 84 | 92 | 97 | 33 | 73 |
As can be seen from Table 2, adopt present method to add ethylene vinyl acetate copolymer to carry out toughness reinforcing to poly(lactic acid), when 15 parts of toughner add in 85 parts of poly(lactic acid), the notched Izod impact strength of poly(lactic acid) is approximately original 2 times, along with adding of softening agent glycidyl methacrylate and increasing of add-on, the elongation at break of material and notched Izod impact strength improve, and elongation at break has especially the highlyest improved 70 times of left and right.Ethylene-vinyl acetate copolymer and glycidyl methacrylate have been improved the toughness of poly(lactic acid) jointly.
The DSC data of table 3 poly(lactic acid) and blend thereof
As can be seen from Figure 1, the endotherm(ic)peak of pure poly(lactic acid) is very little, show that it still take amorphous state as main before second-heating, ethylene-vinyl acetate copolymer add the crystal property of failing to improve poly(lactic acid), from Fig. 1 and table 3, can find out, adding of the methyl methacrylate of 10% mass parts makes the second-order transition temperature of poly(lactic acid) in blend significantly descend, and the cold crystallization peak has appearred, it is large that the endotherm(ic)peak of poly(lactic acid) obviously becomes, the crystallization behavior of poly(lactic acid) that shown the methyl methacrylate Effective Regulation.
Claims (3)
1. the composite toughening method of modifying of the poly(lactic acid) based on crystallization regulation and control, it is characterized in that carrying out according to following step: (1) is placed in poly(lactic acid) and ethylene-vinyl acetate copolymer the dry 12h of vacuum drying oven of 60 ℃ in advance, (2) then by the poly(lactic acid) of drying and ethylene-vinyl acetate copolymer under the blending temperature of 170-180 ℃, add successively poly(lactic acid), ethylene-vinyl acetate copolymer and glycidyl methacrylate, and, with the mixing 8-10 minute of the speed of 60-80 rpm, obtain intermingling material; (3) be placed in mould the product of above-mentioned blend banburying is cooling, carry out successively hot pressing in 2-3 minute and cold pressing in 3-5 minute on vulcanizing press with after 170-180 ℃ of lower preheating 2-4 minute, pressure is 10-15MPa, can reach the crystallization regulation and control of poly(lactic acid) and the purpose of toughening modifying.
2. the composite toughening method of modifying of a kind of poly(lactic acid) based on crystallization regulation and control according to claim 1, the parts by weight that it is characterized in that wherein said poly(lactic acid), ethylene vinyl acetate copolymer and glycidyl methacrylate are respectively 80-85 part, 10-15 part, 2.5-10 part.
3. the composite toughening method of modifying of a kind of poly(lactic acid) based on crystallization regulation and control according to claim 1, it is characterized in that described ethylene-vinyl acetate copolymer adopts melting index to be (190 ℃, 2.16Kg) ethylene-vinyl acetate copolymer of 20g/min, wherein the content of vinyl acetate is 28wt%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265129A (en) * | 2020-11-26 | 2021-08-17 | 汕头市三马塑胶制品有限公司 | Foaming-grade polylactic acid with excellent processing fluidity and preparation method thereof |
| CN114907663A (en) * | 2022-05-30 | 2022-08-16 | 冯艳梅 | Blending modified packaging material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080026171A1 (en) * | 2006-07-28 | 2008-01-31 | Alcan Packaging Flexible France | Coextruded film with polylactic acid (PLA) and Ethylene Vinyl Acetate (EVA) |
| US7867422B2 (en) * | 2006-11-02 | 2011-01-11 | Diaserve, Inc. | Biological polymeric compositions and methods related thereto |
| CN103265798A (en) * | 2013-06-03 | 2013-08-28 | 山东昊达化学有限公司 | Polylactic acid (PLA) and ethylene-vinyl acetate (EVA) blended composition and formed product thereof |
-
2013
- 2013-09-09 CN CN201310406705.9A patent/CN103483788B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080026171A1 (en) * | 2006-07-28 | 2008-01-31 | Alcan Packaging Flexible France | Coextruded film with polylactic acid (PLA) and Ethylene Vinyl Acetate (EVA) |
| US7867422B2 (en) * | 2006-11-02 | 2011-01-11 | Diaserve, Inc. | Biological polymeric compositions and methods related thereto |
| CN103265798A (en) * | 2013-06-03 | 2013-08-28 | 山东昊达化学有限公司 | Polylactic acid (PLA) and ethylene-vinyl acetate (EVA) blended composition and formed product thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265129A (en) * | 2020-11-26 | 2021-08-17 | 汕头市三马塑胶制品有限公司 | Foaming-grade polylactic acid with excellent processing fluidity and preparation method thereof |
| CN114907663A (en) * | 2022-05-30 | 2022-08-16 | 冯艳梅 | Blending modified packaging material |
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| CN103483788B (en) | 2016-06-08 |
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