CN105437636A - High-toughness multilayer polylactic acid composite plate - Google Patents
High-toughness multilayer polylactic acid composite plate Download PDFInfo
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- CN105437636A CN105437636A CN201510180162.2A CN201510180162A CN105437636A CN 105437636 A CN105437636 A CN 105437636A CN 201510180162 A CN201510180162 A CN 201510180162A CN 105437636 A CN105437636 A CN 105437636A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
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- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to a high-toughness multilayer polylactic acid composite plate. The high-toughness multilayer polylactic acid composite plate comprises from top to bottom a polylactic acid/polycarbonate composite plate, a polylactic acid/starch/plant fiber composite plate, and a polylactic acid/polylactic acid grafted glycidyl methacrylate ester composite plate. The high-toughness multilayer polylactic acid composite plate is characterized in that: the polylactic acid/polycarbonate composite plate is prepared through melt extrusion by using polylactic acid and polycarbonate as raw materials, the polylactic acid/starch/plant fiber composite plate is prepared through melt extrusion by using polylactic acid, plasticized starch, and plant fiber as raw materials, and the polylactic acid/polylactic acid grafted glycidyl methacrylate ester composite plate is prepared through melt extrusion by using polylactic acid and polylactic acid grafted glycidyl methacrylate ester as raw materials. The composite plate uses separate extrusion and lamination molding, and is simple in the process. The composite plate has excellent strength and toughness, and can be applied to the field of the packaging and industry with requirements of high strength and high toughness.
Description
Technical field
The present invention relates to a kind of preparation method of composite plate, particularly relate to a kind of all with the preparation method with the degradable composite plate of high-strength tenacity energy that PLA plate is composited.
Background technology
Although plastic material has more excellent performance and applicability widely; but it derives from oil product and cannot degrade; in crisis of resource and environmental pollution serious all the more today, find function admirable and reproducible alternative materials then becomes the most important thing of current Material Field research.
In current degradation material, starch is because of its cheap price and originate widely and furtherd investigate and prepared multiple life and industrial goods, as starch basement membrane, starch dishware etc. by modification and compound.But the defect that starch has it natural, its poor mechanical property, unstable properties, can only apply to the field low to mechanical property requirements.And the appearance of PLA changes this present situation.PLA (PLA) is aliphatic polyester, with lactic acid (2 hydroxy propanoic acid) for basic structural unit.PLA obtains by natural materials such as fermented maizes, and lactic acid polycondensation also can be adopted to obtain.PLA and end product thereof can become CO in natural decomposition under composting conditions
2and water, reducing solid waste discharge amount, is a kind of biogenic material of environmental protection.
PLA has the mechanical characteristic being similar to polystyrene, and bending modulus and hot strength are better, but heat endurance and shock resistance poor, in thermoforming process, there is the defect that melt viscosity is low, limit its application.After improving these shortcomings, PLA can be expected to can be employed for industry, civil area as the best substitute of plastic material.In the toughening modifying research of PLA, PLA and multiple material compound to reach toughening effect, as starch, polycaprolactone, polyethylene etc., after compound, although the toughness of material increases, the corresponding decline of its intensity, and notched-impact resistance is appointed poor.In general, single PLA sheet material is adopted still cannot to realize having excellent intensity, toughness and notched Izod impact.In sheet material preparation field, can the advantage of comprehensive each layer by the mode of MULTILAYER COMPOSITE, realize so collaborative that to do in order to obtain the sheet material with Good All-around Property.The present invention by compound between employing different performance PLA plate to provide a kind of composite degradable plate with excellent in strength, toughness, shock resistance.
Summary of the invention
The object of the invention is to overcome PLA timber intensity and toughness cannot be taken into account, the defect of notched-impact resistance difference, providing a kind of excellent mechanical performance that has, degradable polylactic acid based composite plate.
The object of the invention is to be achieved through the following technical solutions:
The high tough PLA composite plate of a kind of MULTILAYER COMPOSITE, comprises PLA/Merlon composite plate, polylactic acid/starch/plant fiber composite board, PLA/PLA graft glycidyl methacrylate composite plate from top to bottom.It is characterized in that: described PLA/Merlon composite plate is PLA, Merlon is that primary raw material melt extrudes obtained sheet material, polylactic acid/starch/plant fiber composite board is with PLA, plasticized starch, the string sheet material obtained for primary raw material melt extrudes, and PLA/PLA graft glycidyl methacrylate composite plate is with PLA, the PLA graft glycidyl methacrylate sheet material obtained for primary raw material melt extrudes.
Further, the thickness of described PLA/Merlon composite plate is between 1.5-3mm, described polylactic acid/starch/plant fiber composite board thickness is between 2-4mm, and described PLA/PLA graft glycidyl methacrylate composite plate thickness is between 2-4mm.
Further, described PLA/Merlon composite plate is for primary raw material with PLA, Merlon, add a small amount of acrylic compounds flexibilizer, ester exchange agent catalysts and antioxidant, lubricant etc. melt extrude shaping, and wherein the proportioning of PLA, Merlon, propylene class flexibilizer is between 100:50-80:30-60.Wherein said PP type flexibilizer can be ethylene acrylic acid co polymer (EAA) and ethylene-ethyl acrylate copolymer (EEA).
Further, described catalyst for ester exchange reaction is Dibutyltin oxide, also can be dioctyl tin oxide, or the combination of both arbitrary proportions.The consumption of ester exchange reaction agent is between PLA and the 1%-2% of Merlon quality.Both all can under this invention processing temperature can effectively catalysis PLA and between ester exchange reaction.
Further, described polylactic acid/starch/plant fiber composite board is that wherein the mass ratio of PLA, plasticized starch, string is between 100:30-60:5-15 with PLA, plasticized starch, the string sheet material obtained for primary raw material melt extrudes.
Further, described plasticized starch obtains for plastifying modification by glycerine to native starch, and native starch can be cornstarch, tapioca, preferred tapioca.
Further, described string is bamboo fibre, wood-fibred, rice-straw fibre, stalk fibre etc.Its length is between 50 microns-1 millimeter.Preferably, string is bamboo fibre, and length is between 100 microns-500 microns.
Further, described PLA/PLA graft glycidyl methacrylate be with PLA and PLA graft glycidyl methacrylate for primary raw material, add a small amount of antioxidant, processing aid, nano combined reinforce melt extrude obtained sheet material.The mass ratio of PLA and PLA graft glycidyl methacrylate is between 100:20-40.
Further, the percent grafting of described PLA graft glycidyl methacrylate is between 0.8%-2%, after access GMA segment, this material has good toughness and the compatibility with PLA excellence, effectively can improve the toughness of PLA, composite has excellent toughness and notched-impact resistance.The preparation of PLA graft glycidyl methacrylate can adopt PLA and GMA to be raw material, take dibenzoyl peroxide as the copolymerization of catalyst fusion-grafting.
Further, described nano combined reinforce can be nano silicon, nano imvite, nano hydrotalcite etc., and its yardstick is between 10-1000nm.
Further, described composite plate preparation process is: by PLA/Merlon composite plate, polylactic acid/starch/plant fiber composite board, after PLA/PLA graft glycidyl methacrylate composite plate is prepared respectively, hot-forming formation composite plate, its hot pressing temperature is between 190-210 DEG C, pressure is between 15-30Mpa, and the dwell time is 1.5-2.5 minute.
Further, the PLA described in the present invention is poly (l-lactic acid), and poly-D-ALPHA-Hydroxypropionic acid or poly-L, D-ALPHA-Hydroxypropionic acid composition, molecular weight the best of this PLA is 300000-500000, and being 150000-300000 again, is 80000-150000 again.
Further, in the present invention, described Merlon is bisphenol A polycarbonate, and molecular weight selects the best to be 20000-50000, and being 50000-80000 again, is 80000-100000 again.
Beneficial effect of the present invention is: arrange in pairs or groups to realize excellent composite performance by the PLA composite plate of three kinds of different mechanical properties features.Wherein PLA/Merlon composite plate has excellent intensity, but toughness is poor, and polylactic acid/starch/plant fiber composite board is as articulamentum, and quality is softer, and PLA/PLA graft glycidyl methacrylate composite plate then has good toughness.Wherein polylactic acid/starch/plant fiber composite board is due to the existence of starch, fusing point is lower, viscosity is larger, effectively can play connection and the mechanics transmission effect of PLA/Merlon composite plate and PLA/PLA graft glycidyl methacrylate composite plate.Meanwhile, this multilayer composite sheet all adopts degradation material to prepare, and the feature of environmental protection is excellent.
Below will describe illustrative embodiment of the present invention in detail.But these implementation methods are only exemplary object, and the present invention is not limited thereto.
Specific embodiment 1
The high tough PLA composite plate of a kind of MULTILAYER COMPOSITE, comprises PLA/Merlon composite plate, polylactic acid/starch/plant fiber composite board, PLA/PLA graft glycidyl methacrylate composite plate from top to bottom.
The thickness of described PLA/Merlon composite plate is 1.8mm, and described polylactic acid/starch/plant fiber composite board thickness is 3mm, and described PLA/PLA graft glycidyl methacrylate composite plate thickness is 2.7mm.
Described PLA/Merlon composite plate is for primary raw material with PLA, Merlon, add a small amount of EAA, ester exchange agent catalysts Dibutyltin oxide and antioxidant BHT, lubricant stearic acid calcium melt extrude shaping, and wherein the proportioning of PLA, Merlon, EAA is between 100:65:40.Wherein, the consumption of ester exchange agent catalysts Dibutyltin oxide is 1.5% of PLA and Merlon quality sum, antioxidant BHT, lubricant stearic acid calcium be PLA, Merlon, EAA quality sum 2%.
Described polylactic acid/starch/plant fiber composite board is that wherein the mass ratio of PLA, plasticized starch, string is between 100:45:10 with PLA, plasticized starch, the string sheet material obtained for primary raw material melt extrudes.
Described plasticized starch is by the tapioca of glycerin modification, and string is bamboo fibre, and length is between 100 microns-500 microns.
Described PLA/PLA graft glycidyl methacrylate be with PLA and PLA graft glycidyl methacrylate for primary raw material, add a small amount of antioxidant BHT, processing aid lubricant stearic acid calcium, nano silicon melt extrude obtained sheet material.The mass ratio of PLA and PLA graft glycidyl methacrylate is 100:25.The mass fraction of antioxidant BHT, processing aid lubricant stearic acid calcium, nano silicon is respectively 3.5%, 2.5% and 2% of PLA.
The percent grafting of described PLA graft glycidyl methacrylate is 1.4%.
Described composite plate preparation process is: by PLA/Merlon composite plate, polylactic acid/starch/plant fiber composite board, after PLA/PLA graft glycidyl methacrylate composite plate is prepared respectively, hot-forming formation composite plate, its hot pressing temperature is 210 DEG C, pressure is 25Mpa, and the dwell time is 2 minutes.
Described PLA is poly (l-lactic acid), and molecular weight is between 120000-160000.
Described Merlon is bisphenol A polycarbonate, and molecular weight is 42000.
Its performance is as following table 1
Specific embodiment 2
The high tough PLA composite plate of a kind of MULTILAYER COMPOSITE, comprises PLA/Merlon composite plate, polylactic acid/starch/plant fiber composite board, PLA/PLA graft glycidyl methacrylate composite plate from top to bottom.
The thickness of described PLA/Merlon composite plate is 2.1mm, and described polylactic acid/starch/plant fiber composite board thickness is 2.7mm, and described PLA/PLA graft glycidyl methacrylate composite plate thickness is 2.7mm.
Described PLA/Merlon composite plate is for primary raw material with PLA, Merlon, add a small amount of EAA, ester exchange agent catalysts Dibutyltin oxide and antioxidant BHT, lubricant stearic acid calcium melt extrude shaping, and wherein the proportioning of PLA, Merlon, EAA is between 100:58:41.Wherein, the consumption of ester exchange agent catalysts Dibutyltin oxide is 1.5% of PLA and Merlon quality sum, antioxidant BHT, lubricant stearic acid calcium be PLA, Merlon, EAA quality sum 1.5%.
Described polylactic acid/starch/plant fiber composite board is that wherein the mass ratio of PLA, plasticized starch, string is between 100:48:12 with PLA, plasticized starch, the string sheet material obtained for primary raw material melt extrudes.
Described plasticized starch is by the tapioca of glycerin modification.Described string is wood-fibred, and length is between 100 microns-500 microns.
Described PLA/PLA graft glycidyl methacrylate be with PLA and PLA graft glycidyl methacrylate for primary raw material, add a small amount of antioxidant BHT, processing aid lubricant stearic acid calcium, nano silicon melt extrude obtained sheet material.The mass ratio of PLA and PLA graft glycidyl methacrylate is 100:32.Wherein, the mass fraction of antioxidant BHT, processing aid lubricant stearic acid calcium, nano silicon is respectively 3.5%, 2.5% and 3% of PLA.
The percent grafting of described PLA graft glycidyl methacrylate is 1.5%.
Described composite plate preparation process is: by PLA/Merlon composite plate, polylactic acid/starch/plant fiber composite board, after PLA/PLA graft glycidyl methacrylate composite plate is prepared respectively, hot-forming formation composite plate, its hot pressing temperature is 200 DEG C, pressure is 20Mpa, and the dwell time is 1.8 minutes.
Described PLA is poly-D-ALPHA-Hydroxypropionic acid, and molecular weight is between 150000-200000.
Described Merlon is bisphenol A polycarbonate, and molecular weight is 60000.
Its performance is as following table 1.
The mechanical property contrast of table one embodiment 1,2
Claims (5)
1. the high tough PLA composite plate of MULTILAYER COMPOSITE, comprise PLA/Merlon composite plate from top to bottom, polylactic acid/starch/fiber composite plate, PLA/PLA graft glycidyl methacrylate composite plate, it is characterized in that: described PLA/Merlon composite plate is PLA, Merlon is that primary raw material melt extrudes obtained sheet material, polylactic acid/starch/plant fiber composite board is with PLA, plasticized starch, string is that primary raw material melt extrudes obtained sheet material, PLA/PLA graft glycidyl methacrylate composite plate is with PLA, PLA graft glycidyl methacrylate is that primary raw material melt extrudes obtained sheet material,
Its preparation process is: by PLA/Merlon composite plate, polylactic acid/starch/plant fiber composite board, after PLA/PLA graft glycidyl methacrylate composite plate is prepared respectively, hot-forming formation composite plate, its hot pressing temperature is between 190-210 DEG C, pressure is between 15-30Mpa, and the dwell time is 1.5-2.5 minute.
2. the high tough PLA composite plate of a kind of MULTILAYER COMPOSITE as claimed in claim 1, it is characterized in that: the thickness of described PLA/Merlon composite plate is between 1.5-3mm, described polylactic acid/starch/plant fiber composite board thickness is between 2-4mm, and described PLA/PLA graft glycidyl methacrylate composite plate thickness is between 2-4mm.
3. the high tough PLA composite plate of a kind of MULTILAYER COMPOSITE as claimed in claim 1, it is characterized in that: described PLA/Merlon composite plate is for primary raw material with PLA, Merlon, add tough dose of a small amount of acrylic compounds, ester exchange agent catalysts and antioxidant, lubricant etc. melt extrude shaping, and wherein the proportioning of PLA, Merlon, acrylic compounds flexibilizer is between 100:50-80:30-60.
4. the high tough PLA composite plate of a kind of MULTILAYER COMPOSITE as claimed in claim 1, it is characterized in that: described polylactic acid/starch/plant fiber composite board is that wherein the mass ratio of PLA, plasticized starch, string is between 100:30-60:5-15 with PLA, plasticized starch, the string sheet material obtained for primary raw material melt extrudes.
5. the high tough PLA composite plate of a kind of MULTILAYER COMPOSITE as claimed in claim 1, it is characterized in that: described PLA/PLA graft glycidyl methacrylate for PLA and PLA graft glycidyl methacrylate for primary raw material, add a small amount of antioxidant, processing aid, nano combined reinforce melt extrude obtained sheet material, the mass ratio of PLA and PLA graft glycidyl methacrylate is between 100:20-40.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510180162.2A CN105437636A (en) | 2015-04-16 | 2015-04-16 | High-toughness multilayer polylactic acid composite plate |
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| CN201510180162.2A CN105437636A (en) | 2015-04-16 | 2015-04-16 | High-toughness multilayer polylactic acid composite plate |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1361039A1 (en) * | 2002-05-10 | 2003-11-12 | Board of Trustees of Michigan State University | Environmentally friendly polylactide-based composite formulations |
| US20100028654A1 (en) * | 2004-10-04 | 2010-02-04 | Jsp Corporation | Multi-Layerd Polylactic Acid Resin Foamed Body And Multi-Layered Polylactic Acid Resin Foamed Molded Article |
| CN102603994A (en) * | 2012-03-09 | 2012-07-25 | 中国科学院宁波材料技术与工程研究所 | Glycidyl methacrylate grafted polylactic acid copolymer material, preparation method for same and application thereof |
| CN103205104A (en) * | 2013-05-06 | 2013-07-17 | 湖南工业大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy |
| CN104387733A (en) * | 2014-11-18 | 2015-03-04 | 四川大学 | Biodegradable toughened heat-resistant polylactic acid modified resin and preparation method thereof |
-
2015
- 2015-04-16 CN CN201510180162.2A patent/CN105437636A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1361039A1 (en) * | 2002-05-10 | 2003-11-12 | Board of Trustees of Michigan State University | Environmentally friendly polylactide-based composite formulations |
| US20100028654A1 (en) * | 2004-10-04 | 2010-02-04 | Jsp Corporation | Multi-Layerd Polylactic Acid Resin Foamed Body And Multi-Layered Polylactic Acid Resin Foamed Molded Article |
| CN102603994A (en) * | 2012-03-09 | 2012-07-25 | 中国科学院宁波材料技术与工程研究所 | Glycidyl methacrylate grafted polylactic acid copolymer material, preparation method for same and application thereof |
| CN103205104A (en) * | 2013-05-06 | 2013-07-17 | 湖南工业大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy |
| CN104387733A (en) * | 2014-11-18 | 2015-03-04 | 四川大学 | Biodegradable toughened heat-resistant polylactic acid modified resin and preparation method thereof |
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