CN102585461A - Method for preparing heat-resisting polylactic acid nanocomposite through irradiation modification - Google Patents
Method for preparing heat-resisting polylactic acid nanocomposite through irradiation modification Download PDFInfo
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- CN102585461A CN102585461A CN2011100060530A CN201110006053A CN102585461A CN 102585461 A CN102585461 A CN 102585461A CN 2011100060530 A CN2011100060530 A CN 2011100060530A CN 201110006053 A CN201110006053 A CN 201110006053A CN 102585461 A CN102585461 A CN 102585461A
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Abstract
The invention belongs to a method for preparing a heat-resisting polylactic acid nanocomposite through irradiation modification. The heat-resisting polylactic acid nanocomposite comprises polylactic acid, modified montmorillonite, PE (Poly Ethylene) wax, antioxidant, and polyfunctional monomer. Extruding granulation is carried out through a double-screw, then forming is realized through mould pressing or other methods, and finally a formed workpiece is placed in nitrogen atmosphere and is irradiated by electron beams at room temperature. The obtained product has excellent heat resistance.
Description
Technical field
The invention belongs to polylactic acid modified method field, particularly a kind of through electron beam irradiation modified preparation poly lactic acid nano composite material.
Background technology
POLYACTIC ACID is to obtain lactic acid by renewable resources such as cereal or fermentation of plant straws, passes through the biodegradable polymkeric substance of chemosynthesis then.It has good biocompatibility, biodegradable absorption, intensity is high, plasticity-is good, be prone to machine-shaping, and environment is not caused any pollution, is considered to the most promising Biodegradable Polymers.But the second-order transition temperature of POLYACTIC ACID is about 60 ℃, and thermotolerance is relatively poor, and the dimensional stability of material product is very poor when being higher than its second-order transition temperature, and this has hindered the application of POLYACTIC ACID largely.Improve the stable on heating main method of POLYACTIC ACID and have three kinds: (1) and high glass-transition temperature or high heat-proof macromolecule blending and modifying; But this method requires selected high glass-transition temperature or high heat resistance macromolecular material and POLYACTIC ACID that consistency is preferably arranged, and has influenced the degradable performance of POLYACTIC ACID to a certain extent; (2) nanometer composite technology can not only improve the thermotolerance of material when forming intensive interface interaction power between POLYACTIC ACID matrix and the layered silicate, can also improve mechanical strength, and the effect of crystallization nucleating agent has also been played in the adding of nano material in addition.Disclosed a kind of preparation method of POLYACTIC ACID Nano composite material of montmorillonite like patent CN1760265A; This patent adopts one or more consistencies as compatilizer raising POLYACTIC ACID and modified montmorillonoid in pla-pcl, polyhydroxyalkanoate, polyoxyethylene glycol or the epoxy resin; Through the master batch method; Through the second melting blend, the thermotolerance of POLYACTIC ACID increases, and its Vicat softening point is brought up to 123 ℃ from 76 ℃ of maximums; But when its thermotolerance improved, its tensile strength was reduced to 42.4MPa from 52.4MPa.And the prescription that tensile strength is improved, its Vicat softening point has only improved 10 to 20 ℃; (3) crosslinking technological has slightly improved the degree of crosslinking of polylactic acid molecule through adding chemical initiator with methods such as adopting the energetic ray irradiation, thereby reduces the thermotolerance of the motor capacity raising macromolecular material of molecule.Electron beam irradiation is a kind of environmental protection safe material method of modifying.Polylactic acid molecule is very high to electron beam sensitive property, and originally electron beam irradiation only is used for biomedical polymer POLYACTIC ACID sterilization, have Australia scholar to it at Co
60-γDegraded product under ray and the electron beam irradiation condition is studied.On this basis, add the polyfunctionality monomer and carry out cross-linking radiation, can obtain the material modified of thermotolerance raising.Patent CN101225221A and CN101104706A have disclosed POLYACTIC ACID and multipolymer thereof respectively; The electron beam irradiation modified method of verivate; Mainly improved material modified mechanical property; And reduce cost, because crosslinking structure that electron beam irradiation forms is limited, and to improved heat resistance and not obvious.
Summary of the invention
The present invention combines nanometer composite technology with the electron beam to irradiate crosslinked technology; Through specific compound system and technological design; Make the strong interface effect of POLYACTIC ACID matrix and polynite formation and the tridimensional network that cross-linking radiation forms produce gain effect; Raising by a relatively large margin the resistance toheat of POLYACTIC ACID, increased the tensile property of POLYACTIC ACID simultaneously.The present invention adopts the mode of processing back irradiation earlier, also efficiently solves because cross-linking radiation causes the POLYACTIC ACID flowability to reduce the problem that processing characteristics descends.
The electron beam irradiation modified method for preparing the heat-proof polylactic acid nano composite material that the present invention proposes is earlier POLYACTIC ACID and other auxiliary agent to be passed through the twin screw granulation, is placed on nitrogen atmosphere through moulding and carries out electron beam irradiation, and irradiation dose is 5-30kGy.Actual conditions is:
With after POLYACTIC ACID and the modified montmorillonoid drying with PE wax, after inhibitor and multi-functional degree monomer mixed, through double-screw extruding pelletizing, extrusion temperature was 160-195 ℃, in ratio of quality and the number of copies:
POLYACTIC ACID: 100 parts
Modified montmorillonoid: 1-5 part
PE wax: 1-5 part
Inhibitor: 1-2 part
Multi-functional degree monomer: 1-5 part
The gained pellet is the material or the goods of desired shape through further machine-shaping.As to adopt compression molding, Heating temperature be 180-200 ℃, hot pressing time 10-15min, and time 10-15min colds pressing.Under nitrogen atmosphere, carry out electron beam irradiation then, irradiation dose is 5-30kGy.Said modified montmorillonoid is organically-modified by sodium base, calcium-base montmorillonite, through the Triple Pressed Stearic Acid surface treatment, need not add compatilizer, can reach dispersion effect preferably.
Among the present invention, polynite be calcium base, sodium base smectite clay through the dispersion of delaminating, the remodeling of purifying, super-fine classified, be composited, average wafer thickness is less than 25nm, smectite content is greater than 95%;
Among the present invention, the polyfunctionality monomer is usually used triallyl isocyanurate, pentaerythritol triacrylate, oxyethyl group trimethyl propane alcohol triacrylate, one or more in the TriMethylolPropane(TMP) alcohol TIB acid esters;
Among the present invention, the preferred PLLA of resin, its viscosity-average molecular weight is 30-40 ten thousand.Melt flow rate(MFR) is 5-10g/10min at 210 ℃/2.16kg, and this POLYACTIC ACID processing characteristics is excellent, is prone to form the strong interface effect with modified montmorillonoid;
Among the present invention, inhibitor preferred four [methyl-(3,5-di-t-butyl-4 – hydroxy phenyl) propionic acid] pentaerythritol ester.
Beneficial effect of the present invention:
(1) adopts the Vicat softening point of electron beam irradiation modified Nano-composite material of poly lactic acid/montmorillonite obviously to improve, can significantly bring up to more than 150 ℃ from 60.1 ℃ of pure POLYACTIC ACID.The prior art method of modifying is significantly improved relatively;
(2) adopt electron beam irradiation modified Nano-composite material of poly lactic acid/montmorillonite when its resistance toheat obviously improves, its tensile strength can improve 10%-30%;
(3) adopt electron beam irradiation modified Nano-composite material of poly lactic acid/montmorillonite controllability strong, through changing modified montmorillonoid, multi-functional degree monomer, irradiation dose can get the goods of required mechanical property, resistance toheat;
(4) to prepare the technology of Nano-composite material of poly lactic acid/montmorillonite simple in the present invention, easy for industrialized.
Embodiment:
Used polylactic acid raw material of the cited embodiment of the present invention and auxiliary agent are commercially available.In an embodiment through the granulation of ZSK-25WLE twin screw extruder, adopt QLB-D600 type and XQLB-500 vulcanizing press to carry out hot pressing respectively and cold pressing.The moulding sample is handled through the 10Mev linear electron accelerator, neatly is placed in the sheet material for preparing on the pallet of aluminum in advance during irradiation, lets the electron beam of 10Mev transport and passes, and is controlled the irradiation dose of its absorption by the residence time of irradiation thing through control.
Embodiment 1:
POLYACTIC ACID: 300g
Modified montmorillonoid: 9g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 9g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 15kGy.The products obtained therefrom tensile strength is 70MPa, and Vicat softening point is 156.9 ℃.
Embodiment 2:
POLYACTIC ACID: 300g
Modified montmorillonoid: 9g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 3g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 15kGy.The products obtained therefrom tensile strength is 63MPa, and Vicat softening point is 151.2 ℃.
Embodiment 3:
POLYACTIC ACID: 300g
Modified montmorillonoid: 9g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 6g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 15kGy.The products obtained therefrom tensile strength is 66MPa, and Vicat softening point is 153.4 ℃.
Embodiment 4:
POLYACTIC ACID: 300g
Modified montmorillonoid: 9g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 9g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 5kGy.The products obtained therefrom tensile strength is 64.6MPa, and Vicat softening point is 151.8 ℃.
Embodiment 5:
POLYACTIC ACID: 300g
Modified montmorillonoid: 9g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 9g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 10kGy.The products obtained therefrom tensile strength is 66.7MPa, and Vicat softening point is 152 ℃.
Embodiment 6:
POLYACTIC ACID: 300g
Modified montmorillonoid: 9g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 9g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 20kGy.The products obtained therefrom tensile strength is 68.6MPa, and Vicat softening point is 158 ℃.
Embodiment 7:
POLYACTIC ACID: 300g
Modified montmorillonoid: 3g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 9g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 15kGy.The products obtained therefrom tensile strength is 46.2MPa, and Vicat softening point is 98 ℃.
Embodiment 8:
POLYACTIC ACID: 300g
Modified montmorillonoid: 12g
PE wax: 3g
Inhibitor: 3g
Triallyl isocyanurate: 9g
Through the twin screw granulation, after moulding, resulting product is electron beam irradiation in nitrogen atmosphere, and irradiation dose is 15kGy.The products obtained therefrom tensile strength is 43.1MPa, and Vicat softening point is 146 ℃.
Claims (4)
1. an electron beam irradiation modified method for preparing the heat-proof polylactic acid nano composite material is characterized in that earlier POLYACTIC ACID and other auxiliary agent being passed through the twin screw granulation, is placed on through moulding and carries out electron beam irradiation in the nitrogen atmosphere; Irradiation dose is 5-30kGy; Its actual conditions is: with after POLYACTIC ACID and the modified montmorillonoid drying with PE wax, after inhibitor and multi-functional degree monomer mix, through double-screw extruding pelletizing; Extrusion temperature is 160-195 ℃, in ratio of quality and the number of copies:
POLYACTIC ACID: 100 parts
Modified montmorillonoid: 1-5 part
PE wax: 1-5 part
Inhibitor: 1-2 part
Multi-functional degree monomer: 1-5 part
The gained pellet is the material or the goods of desired shape through further machine-shaping, under nitrogen atmosphere, carries out electron beam irradiation then, and irradiation dose is 5-30kGy.
2. the electron beam irradiation modified method for preparing the heat-proof polylactic acid nano composite material according to claim 1; It is characterized in that modified montmorillonoid system is organically-modified by sodium base, calcium-base montmorillonite, through the Triple Pressed Stearic Acid surface treatment; Need not add compatilizer; Can reach dispersion effect preferably, its average wafer thickness is less than 25nm, and smectite content is greater than 95%.
3. radiation modification according to claim 1 prepares the method for heat-proof polylactic acid nano composite material; It is characterized in that; The polyfunctionality monomer is the isocyanuric acid triallyl ester; Pentaerythritol triacrylate, oxyethyl group trimethyl propane alcohol triacrylate, one or more in the TriMethylolPropane(TMP) alcohol TIB acid esters.
4. the electron beam irradiation modified method for preparing the heat-proof polylactic acid nano composite material according to claim 1; It is characterized in that; POLYACTIC ACID is preferably PLLA, and its viscosity-average molecular weight is 30-40 ten thousand, melt flow rate(MFR) be 5-10g/10min (210 ℃/2.16kg).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778799A (en) * | 2016-08-30 | 2018-03-09 | 汉达精密电子(昆山)有限公司 | Cross-linking modified lactic acid composite material and its products formed |
| CN108587096A (en) * | 2018-05-15 | 2018-09-28 | 战国昌 | A kind of environmentally protective soil matrix material and its preparation process |
| CN109251496A (en) * | 2018-10-22 | 2019-01-22 | 广州华大生物科技有限公司 | Modified polylactic acid material under low irradiation dose and preparation method thereof |
| CN114854186A (en) * | 2022-06-02 | 2022-08-05 | 苏州博大永旺新材股份有限公司 | Heat-resistant modified polylactic acid fully-degradable material for tableware |
| CN115012058A (en) * | 2022-07-14 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Preparation method and application of heat-resistant high-fluidity polylactic acid |
| CN116606536A (en) * | 2023-04-11 | 2023-08-18 | 富岭科技股份有限公司 | PHA modified full-biodegradable plastic for straw |
-
2011
- 2011-01-13 CN CN2011100060530A patent/CN102585461A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 沈斌: "聚乳酸/蒙脱土纳米复合材料", 《北京化工大学硕士研究生学位论文》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107778799A (en) * | 2016-08-30 | 2018-03-09 | 汉达精密电子(昆山)有限公司 | Cross-linking modified lactic acid composite material and its products formed |
| CN108587096A (en) * | 2018-05-15 | 2018-09-28 | 战国昌 | A kind of environmentally protective soil matrix material and its preparation process |
| CN109251496A (en) * | 2018-10-22 | 2019-01-22 | 广州华大生物科技有限公司 | Modified polylactic acid material under low irradiation dose and preparation method thereof |
| CN114854186A (en) * | 2022-06-02 | 2022-08-05 | 苏州博大永旺新材股份有限公司 | Heat-resistant modified polylactic acid fully-degradable material for tableware |
| CN114854186B (en) * | 2022-06-02 | 2022-12-30 | 苏州博大永旺新材股份有限公司 | Heat-resistant modified polylactic acid fully-degradable material for tableware |
| CN115012058A (en) * | 2022-07-14 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Preparation method and application of heat-resistant high-fluidity polylactic acid |
| CN115012058B (en) * | 2022-07-14 | 2023-12-08 | 中广核俊尔(浙江)新材料有限公司 | Preparation method and application of heat-resistant high-fluidity polylactic acid |
| CN116606536A (en) * | 2023-04-11 | 2023-08-18 | 富岭科技股份有限公司 | PHA modified full-biodegradable plastic for straw |
| CN116606536B (en) * | 2023-04-11 | 2024-03-26 | 富岭科技股份有限公司 | PHA modified full-biodegradable plastic for straw |
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Application publication date: 20120718 |