CN105462194A - Preparation method of high-strength and high-buffering POSS hybrid polylactic acid foamed material - Google Patents
Preparation method of high-strength and high-buffering POSS hybrid polylactic acid foamed material Download PDFInfo
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Abstract
The invention relates to a preparation method of a high-strength and high-buffering POSS hybrid polylactic acid foamed material. The foamed material is prepared through compounding a main material and an auxiliary material, the main material comprises hydroxyl terminated polylactic acid, a thermoplastic elastomer, polyurethane and polylactic acid, and the auxiliary material comprises a compatilizer octyl maleamic polyhedral oligomeric silsesquioxane, a polycondensation catalyst tetrabutyl titanate, an antioxidant, a plasticizer and an ultraviolet resisting agent; in the main material, the mass proportion of hydroxyl terminated polylactic acid is 45-65%, the mass proportion of the thermoplastic polyurethane elastomer is 10-25%, and the mass proportion of polylactic acid is 20-30%; and in the auxiliary material, the use amount of octyl maleamic polyhedral oligomeric silsesquioxane is 3.5-6% of the mass of hydroxyl terminated polylactic acid in the main material, the use amount of the polycondensation catalyst tetrabutyl titanate is 0.5-1.5% of the mass of hydroxyl terminated polylactic acid in the main material, and the mass fractions of the antioxidant, the plasticizer and the ultraviolet resisting agent are 1-2% of the mass of the main material. The foamed material is prepared through water vapor extrusion foaming formation, and the method is simple. The material has good strength and buffering property, and can be used in packaging and industry fields with high strength and high buffering requirements.
Description
Technical field
The present invention relates to a kind of preparation method of foam material, particularly relate to one and can have high strength, high resiliency, and there is the preparation method of the polylactic acid foam material of good degradability.
Background technology
Although plastic material has more excellent performance and suitability widely; but it derives from petroleum products and cannot degrade; in crisis of resource and environmental pollution serious all the more today, find excellent property and reproducible equivalent material then becomes the most important thing of current Material Field research.In buffering package field, polystyrol foam material (EPS) is because of its excellent forming ability, and foam expansion and shock-absorbing capacity occupy most of share of amortizing packaging material.And polyethylene foam-material (EPE) is although its resiliency is general, with low cost, be also widely used in the packaging field low to resiliency requirement.But along with the enhancing of people's environmental consciousness, " white pollution " that brought by the nondegradation of plastics has become increasingly serious problem, because of expanded plastic decomposition as not perishable in polystyrene, obnoxious flavour can be distributed during burning, cause environmental pollution and Chlorofluorocarbons (CFCs) (CFC8) for foamed polystyrene agent can destroy atmospheric ozone layer, harm is biological, in Europe and Some Areas of USA, prohibite and used EPS.Find a kind of preparation technology simple, excellent property, the method for eco-friendly expanded plastic equivalent material and foaming capable of being industrialized thereof then becomes a large problem of material science.At home and abroad, some investigators have carried out exploratory development in this field, but still there is larger defect at the aspect of performance of technique realization and material, as adopted part degradation material to prepare expanded plastic only, still there is broken plastic grain after degraded; Degradable foam material expansion ratio is not enough, and in high foamability aftershaping ability, resiliency is poor, and difficult forming etc.And general degradable foam materials is due to the use of much starch, also cause easy water suction, namely easily causing goes mouldy also easily causes declining to a great extent of mechanical property.As one can be found to have excellent mechanical performances, and there is the environmental-protecting foam material of excellent barrier and water-repellancy, will huge market potential be had undoubtedly.
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 poly(lactic acid) changes this present situation.Poly(lactic acid) (PLA) is aliphatic polyester, with lactic acid (2 hydroxy propanoic acid) for basic structural unit.PLA obtains by natural matters 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 modulus in flexure and tensile strength are better, but thermostability and shock resistance poor, in the thermoforming course of processing, 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 application of PLA, usually employing different substances as toughness reinforcing in starch, polycaprolactone, EVA etc. after with alternative common plastics.And poly(lactic acid) is due to its characteristic, also has prospect as can be used as foam material.In this type of research, CN1544525 discloses a kind of biodegradable polylactic acid foam plastic preparation method, namely in foaming process, peroxide crosslinking poly(lactic acid) is added, CN103642185A discloses a kind of Polylactic acid foam material and preparation method thereof, this patent adopts water to be whipping agent, add a small amount of nucleator, realized the feature of environmental protection of material by Water blown.CN103242632A also discloses to adopt and adds linking agent, nucleator to realize the technology of expanded polylactic acid.CN1600814 discloses a kind of poly(lactic acid), the multipolymer of aliphatic-aromatic polyester, nucleator, interior lubrication prescription and the mixed foaming technique of outer lubrication prescription.But in general, for polylactic acid foam material, the how intensity of overall equilbrium material and toughness, and ensure the even of foaming process, remain the problem needing to solve.
Summary of the invention
The fragility that the object of the invention is to overcome polylactic acid foam material is large, and resiliency is poor, not the defect of easy-formation, provides a kind of preparation method with the polylactic acid foam material of excellent in strength and damping characteristics.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of high strength high buffering POSS hydridization polylactic acid foam material, this foam material is formed by major ingredient and auxiliary material Compound Machining, major ingredient comprises hydroxyl-terminated polylactic acid, thermoplastic polyurethanes, poly(lactic acid), auxiliary material comprises compatilizer eight arm maleinamide acidic group caged silsesquioxane, polycondensation catalyst tetrabutyl titanate and oxidation inhibitor, fluidizer, anti UV agent; In major ingredient, the mass ratio of hydroxyl-terminated polylactic acid is between 45-65%, the mass ratio of Polyurethane Thermoplastic Elastomer is between 10-25%, the mass ratio of poly(lactic acid) is between 20-30%, in auxiliary material, the consumption of eight arm maleinamide acidic group caged silsesquioxanes is the 3.5-6% of hydroxyl-terminated polylactic acid quality in major ingredient, the consumption of polycondensation catalyst tetrabutyl titanate is the 0.5-1.5% of hydroxyl-terminated polylactic acid quality in major ingredient, and the massfraction of oxidation inhibitor, softening agent, anti UV agent is between the 1-2% of major ingredient quality.
Further, described hydroxyl-terminated polylactic acid is end group is-OH(hydroxyl) copolymer of poly lactic acid, carry out copolymerization end-blocking to obtain by introducing the monomer with hydroxyl in poly(lactic acid) building-up process.As poly-(lactic acid/Isosorbide-5-Nitrae butyleneglycol) multipolymer, poly-(lactic acid/diethanolamine) multipolymer, poly-(lactic acid/6-caprolactone) multipolymer.Its preparation can be prepared by temperature gradient method with two carboxylic monomer such as Isosorbide-5-Nitrae butyleneglycol, diethanolamine, 6-caprolactone by lactic acid.Also existing commercial product can be bought.
Further, the molecular weight of described hydroxyl-terminated polylactic acid is between 50000-300000g/mol, and in end group, hydroxyl ratio accounts between the 70-90% of total end group ratio.
Further, described Polyurethane Thermoplastic Elastomer is Polyether-type thermoplastic polyurethane elastomer.This type of Polyurethane Thermoplastic Elastomer has lower second-order transition temperature and better stability to hydrolysis.
Further, described tetrabutyl titanate is polycondensation catalyst, can polycondensation effectively between catalysis hydroxyl.In body series, catalyzer can polycondensation effectively between catalysis hydroxyl-terminated polylactic acid and in hydroxyl-terminated polylactic acid and eight arm maleinamide acidic group caged silsesquioxanes between terminal hydroxy group.Thus formation syndeton, make POSS and poly(lactic acid) stable bond, and thermoplastic shape polyurethane elastomer is wrapped up wherein uniformly.
Further, compatilizer eight arm maleinamide acidic group caged silsesquioxane involved in the present invention is the derivative of caged silsesquioxane (POSS).Caged silsesquioxane is a kind of silica structure with octahedra cage structure, and it exists the radicals R that 8 can be carried out modification on the corner of cage structure.When R is hydrophilic molecules chain, because the molecular structure of its nanoscale and hydrophilic-hydrophobic structure are employed for the compatible modification of both sexes blend.R in the POSS adopted in the present invention is maleinamide acidic group, and its molecular structure is as follows:
Wherein the caged silicon-oxide structure of POSS has hydrophobicity, can be combined by the oleophylic segment in poly(lactic acid) and Polyurethane Thermoplastic Elastomer, and the maleamic acid group of end group has good wetting ability, can be combined by the hydrophilic segment in poly(lactic acid) and thermoplastic polyurethane molecule.Be conducive to the raising of consistency.The more important thing is, wherein maleamic acid group end hydroxyl can with the end group generation polycondensation of hydroxyl-terminated polylactic acid, be connected closely with System forming, thus make POSS compatilizer better play the effect improving consistency.
Further, the abscess of described high strength high buffering POSS hydridization polylactic acid foam material is unicellular structure, and pore size is between 20-100um.
Further, described poly(lactic acid) is poly (l-lactic acid), and poly-D-ALPHA-Hydroxypropionic acid or poly-L, poly-D-ALPHA-Hydroxypropionic acid composition, the molecular weight of this poly(lactic acid) is 80000g/mol-600000g/mol.
Further, described oxidation inhibitor is antioxidant 264, BHT, 168, and one or more in 1010.
Further, described fluidizer is aliphatic dibasic acid ester or Phthalates fluidizer.
Further, described anti UV agent is the one or more combination in UV531, UV-2908, UV477.
Further, a kind of preparation method of high strength high buffering POSS hydridization polylactic acid foam material is as follows:
(1) drying of material: by hydroxyl-terminated polylactic acid, poly(lactic acid), Polyurethane Thermoplastic Elastomer, eight arm maleinamide acidic group caged silsesquioxanes, tetrabutyl titanate 60 degree of lower dry 6-8 hour in vacuum drying oven, pressure is lower than 0.01MPa, for subsequent use;
(2) extrusion foaming:
(I) by hydroxyl-terminated polylactic acid, thermoplastic shape elastomer polyurethane, eight arm maleinamide acidic group caged silsesquioxanes, tetrabutyl titanate in proportion in high speed blender 50 degree of blended 5-8 minute of lower high speed, vacuum extruding granulation in rear input forcing machine.Extrusion temperature is between 170-180 degree, and low vacuum, in 0.01MPa, finds time as 3-4 minute.Obtain masterbatch A;
(II) by masterbatch A, poly(lactic acid), other auxiliary agents in high speed blender 50 degree of blended 5-8 minute of lower high speed, in rear input forcing machine, extrusion temperature is between 170-190 degree, water vapor is passed in extrusion, steam temperature is between 120-140 degree, and pressure-controlling is between 1-1.5MPa, and extruding the residence time is 2-3 minute, decompression rate, between 20-50MPa/s, is extruded and is obtained foam material.
Further, preferably, decompression rate is between 40-50MPa/s.
Further, adopting two-step approach to extrude is that second step adds poly(lactic acid) and various auxiliary agent is then conducive to auxiliary agent dispersion wherein because the extrusion not adding poly(lactic acid) and auxiliary agent of the first step is conducive to reaction and elastomerics effective dispersion wherein of hydroxyl-terminated polylactic acid and POSS compatilizer.Second step is extruded adding of middle poly(lactic acid) and is conducive to processibility, and ensures the homogeneity of foaming.
Beneficial effect of the present invention is, by the polycondensation of poly(lactic acid) and POSS terminal hydroxy group by dispersed for POSS and be connected to system, evenly wraps up thermoplastic elastomer simultaneously.This key is connected with the dimensionally stable of material when being beneficial to foaming, meanwhile, has increased substantially the consistency between each component in system, makes elastomerics can be dispersed in poly(lactic acid), and in foam more effective raising toughness of material.In system, poly(lactic acid) provides intensity, Polyurethane Thermoplastic Elastomer provides toughness.The expressing technique of two-step approach, is conducive to ensureing the dispersion in system of the polycondensation of first step and various auxiliary agent and foaming, by pressure-controlling, can realizes effective control of cell size.
Embodiment
Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Take 80.4g hydroxyl-terminated polylactic acid, the moulding elastomer polyurethane of 31.4g, 34.9g poly(lactic acid), 3.6g eight arm maleinamide acidic group caged silsesquioxane, 0.88g tetrabutyl titanate, 2.15 antioxidant BHTs, 2g fluidizer DOP and 2.1g anti UV agent UV531.
By each raw material of above mass ratio in vacuum drying oven 60 degree lower dry 7 hours, pressure is lower than 0.01MPa, for subsequent use.
By hydroxyl-terminated polylactic acid, thermoplastic shape elastomer polyurethane, eight arm maleinamide acidic group caged silsesquioxanes, tetrabutyl titanate in proportion in blended 6 minutes of high speed blender 50 degree of lower high speeds, vacuum extruding granulation in rear input forcing machine.Extrusion temperature is between 170-180 degree, and wherein extrude 1 section of temperature and be set as 170 degree, 2 sections are set to 175 degree, and 3 sections are set to 175 degree, and four sections are set to 180 degree, and 5 sections are set to 175 degree, and low vacuum, in 0.01MPa, finds time as 3-4 minute.Obtain masterbatch A.
By masterbatch A, poly(lactic acid), other auxiliary agents in high speed blender 50 degree of blended 5-8 minute of lower high speed, in rear input forcing machine, extrusion temperature is between 170-190 degree, wherein extrude 1 section of temperature and be set as 170 degree, 2 sections are set to 175 degree, 3 sections are set to 180 degree, four sections are set to 190 degree, 5 sections are set to 185 degree, and pass into water vapor extruding in 2 sections, steam temperature is between 130 degree, pressure-controlling is between 1-1.5MPa, extruding the residence time is 2-3 minute, and decompression rate is between 45MPa/s, extrudes and obtains foam material.
Described poly(lactic acid) is poly (l-lactic acid), and the molecular weight of this poly(lactic acid) is 200000g/mol-600000g/mol.
The molecular weight of described hydroxyl-terminated polylactic acid is between 100000-200000g/mol, and in end group, hydroxyl ratio accounts for 85% of total end group ratio.
Specific performance is as table 1:
Embodiment 2
Take 100.2g hydroxyl-terminated polylactic acid, the moulding elastomer polyurethane of 36.2g, 64.1g poly(lactic acid), 4.5g eight arm maleinamide acidic group caged silsesquioxane, 1.2g tetrabutyl titanate, 3.2 antioxidant BHTs, 3g fluidizer DOP and 2.8g anti UV agent UV531.
By each raw material of above mass ratio in vacuum drying oven 60 degree lower dry 7 hours, pressure is lower than 0.01MPa, for subsequent use.
By hydroxyl-terminated polylactic acid, thermoplastic shape elastomer polyurethane, eight arm maleinamide acidic group caged silsesquioxanes, tetrabutyl titanate in proportion in blended 6 minutes of high speed blender 50 degree of lower high speeds, vacuum extruding granulation in rear input forcing machine.Extrusion temperature is between 170-180 degree, and wherein extrude 1 section of temperature and be set as 170 degree, 2 sections are set to 175 degree, and 3 sections are set to 175 degree, and four sections are set to 180 degree, and 5 sections are set to 175 degree, and low vacuum, in 0.01MPa, finds time as 3-4 minute.Obtain masterbatch A.
By masterbatch A, poly(lactic acid), other auxiliary agents in high speed blender 50 degree of blended 5-8 minute of lower high speed, in rear input forcing machine, extrusion temperature is between 170-190 degree, wherein extrude 1 section of temperature and be set as 170 degree, 2 sections are set to 175 degree, 3 sections are set to 180 degree, four sections are set to 190 degree, 5 sections are set to 185 degree, and pass into water vapor extruding in 2 sections, steam temperature is 130 degree, pressure-controlling is between 1-1.5MPa, extruding the residence time is 2-3 minute, and decompression rate is between 40MPa/s, extrudes and obtains foam material.
Described poly(lactic acid) is poly (l-lactic acid), and the molecular weight of this poly(lactic acid) is 200000g/mol-600000g/mol.
The molecular weight of described hydroxyl-terminated polylactic acid is between 100000-200000g/mol, and in end group, hydroxyl ratio accounts for 85% of total end group ratio.
Specific performance is as table 1:
Table 1: embodiment 1 and embodiment 2 prepare the performance of foam material
| Performance perameter | Reference standard | Embodiment 1 | Embodiment 2 |
| Cell diameter | GB/T6343-1995 | 40-100um | 40-100um |
| Compressive strength | GB/T6669-2001 | 4800KPa | 4500KPa |
| Compression set | GB/T6669-2001 | After when 30 minutes/24 3.3%/0.5% | After 30 minutes/24 hours 4%/0.3% |
| Tensile strength | GB/T6344-1996 | 74.5MPa | 78MPa |
| Elongation at break | GB/T6344-1996 | ≥280% | ≥260% |
| Oxygen index | GB/T2406-1993 | 2.43 | 2.51 |
Claims (4)
1. the preparation method of a high strength high buffering POSS hydridization polylactic acid foam material, it is characterized in that: this foam material is formed by major ingredient and auxiliary material Compound Machining, major ingredient comprises hydroxyl-terminated polylactic acid, thermoplastic polyurethanes, poly(lactic acid), auxiliary material comprises compatilizer eight arm maleinamide acidic group caged silsesquioxane, polycondensation catalyst tetrabutyl titanate and oxidation inhibitor, fluidizer, anti UV agent; In major ingredient, the mass ratio of hydroxyl-terminated polylactic acid is between 45-65%, the mass ratio of Polyurethane Thermoplastic Elastomer is between 10-25%, the mass ratio of poly(lactic acid) is between 20-30%, in auxiliary material, the consumption of eight or eight arm maleinamide acidic group caged silsesquioxanes is the 3.5-6% of hydroxyl-terminated polylactic acid quality in major ingredient, the consumption of polycondensation catalyst tetrabutyl titanate is the 0.5-1.5% of hydroxyl-terminated polylactic acid quality in major ingredient, and the massfraction of oxidation inhibitor, softening agent, anti UV agent is between the 1-2% of major ingredient quality;
Its working method is:
(1) drying of material: by hydroxyl-terminated polylactic acid, poly(lactic acid), Polyurethane Thermoplastic Elastomer, eight arm maleinamide acidic group caged silsesquioxanes, tetrabutyl titanate 60 degree of lower dry 6-8 hour in vacuum drying oven, pressure is lower than 0.01MPa, for subsequent use;
(2)extrusion foaming:
(I) by hydroxyl-terminated polylactic acid, thermoplastic shape elastomer polyurethane, eight arm maleinamide acidic group caged silsesquioxanes, tetrabutyl titanate in proportion in high speed blender 50 degree of blended 5-8 minute of lower high speed, extruding pelletization is vacuumized in rear input forcing machine, extrusion temperature is between 170-180 degree, low vacuum is in 0.01MPa, find time as 3-4 minute, obtain masterbatch A;
(II) by masterbatch A, poly(lactic acid), other auxiliary agents in high speed blender 50 degree of blended 5-8 minute of lower high speed, in rear input forcing machine, extrusion temperature is between 170-190 degree, water vapor is passed in extrusion, steam temperature is between 120-140 degree, and pressure-controlling is between 1-1.5MPa, and extruding the residence time is 2-3 minute, decompression rate, between 20-50MPa/s, is extruded and is obtained foam material.
2. a kind of high strength high buffering POSS hydridization polylactic acid foam material as claimed in claim 1, it is characterized in that, described poly(lactic acid) is poly (l-lactic acid), and poly-D-ALPHA-Hydroxypropionic acid or poly-L, poly-D-ALPHA-Hydroxypropionic acid composition, the molecular weight of this poly(lactic acid) is 80000g/mol-600000g/mol.
3. a kind of high strength high buffering POSS hydridization polylactic acid foam material as claimed in claim 1, it is characterized in that, the molecular weight of described hydroxyl-terminated polylactic acid is between 50000-300000g/mol, and in end group, hydroxyl ratio accounts for total end group mol ratio between 70-90%.
4. a kind of high strength high buffering POSS hydridization polylactic acid foam material according to claims 1, it is characterized in that, described Polyurethane Thermoplastic Elastomer is polyester type Polyurethane Thermoplastic Elastomer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778446A (en) * | 2014-12-26 | 2016-07-20 | 湖南工业大学 | Preparation method of high strength and high buffer POSS hybrid polylactic acid foaming material |
| CN106005748A (en) * | 2016-06-29 | 2016-10-12 | 苏州市盛百威包装设备有限公司 | Packaging box of precision part |
| CN106009628A (en) * | 2016-06-29 | 2016-10-12 | 苏州市盛百威包装设备有限公司 | Box body for transporting precise auto parts |
| CN106433055A (en) * | 2016-10-05 | 2017-02-22 | 湖南工业大学 | Preparation method of high-strength biomass board with good fire resistance |
-
2015
- 2015-01-09 CN CN201510009860.6A patent/CN105462194A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778446A (en) * | 2014-12-26 | 2016-07-20 | 湖南工业大学 | Preparation method of high strength and high buffer POSS hybrid polylactic acid foaming material |
| CN106005748A (en) * | 2016-06-29 | 2016-10-12 | 苏州市盛百威包装设备有限公司 | Packaging box of precision part |
| CN106009628A (en) * | 2016-06-29 | 2016-10-12 | 苏州市盛百威包装设备有限公司 | Box body for transporting precise auto parts |
| CN106433055A (en) * | 2016-10-05 | 2017-02-22 | 湖南工业大学 | Preparation method of high-strength biomass board with good fire resistance |
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