CN105440700A - Preparation method for polylactic acid-based alloy material with high strength and toughness - Google Patents
Preparation method for polylactic acid-based alloy material with high strength and toughness Download PDFInfo
- Publication number
- CN105440700A CN105440700A CN201510009868.2A CN201510009868A CN105440700A CN 105440700 A CN105440700 A CN 105440700A CN 201510009868 A CN201510009868 A CN 201510009868A CN 105440700 A CN105440700 A CN 105440700A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- alloy material
- preparation
- hydroxyl
- based alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a preparation method for a polylactic acid-based alloy material with high strength and toughness. The material is prepared from main materials and auxiliary materials by compounding. The main materials comprise hydroxyl-terminated polylactic acid, hydroxyl-terminated hyperbranched polyester and ethylene-acrylic acid copolymer. The auxiliary materials comprise a condensation catalyst, a nucleating agent, an antioxidant, a plasticizer and an anti-UV agent. In the main materials, the mass ratio of the hydroxyl-terminated polylactic acid is between 35% and 55%, the mass ratio of the hydroxyl-terminated hyperbranched polyester is between 25% and 35%, and the mass ratio of ethylene-acrylic acid copolymer is between 10% and 40%. In the auxiliary materials, the using amount of the condensation catalyst accounts for 1%-3% of the mass of the main materials, the using amount of nucleating agent accounts for 1.5%-2.5% of the mass of the main materials, and the mass percentages of the antioxidant, the plasticizer, and the anti-UV agent all account for 1%-2% of the mass of the main materials. The material is prepared through co-melted extrusion, the alloy material has excellent strength and toughness, and the material can be applied to structural materials.
Description
Technical field
The present invention relates to a kind of preparation method of polylactic acid based alloy material, particularly relate to a kind of preparation method with high tough polylactic acid based alloy material.
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 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 toughening modifying research of poly(lactic acid), poly(lactic acid) and multiple material compound are to reach toughening effect, as starch, polycaprolactone, polyethylene etc., above method for toughening is widely studied, but because the intensity of intermingling material itself is lower, and there is larger difference with poly(lactic acid) consistency, therefore toughening effect is limited, and have a strong impact on the intensity of lactic acid composite material.In addition, multiple method is also had to carry out toughening modifying to poly(lactic acid).Multiple patent all describes the preparation method of poly(lactic acid) composite toughening material, as a kind of toughened polylactic resin that CN101333333 announces and preparation method thereof, this resin is dry in 60 DEG C of baking ovens by poly(lactic acid) base resin, toughner polystyrene-butyl acrylate-acrylic acid, oxidation inhibitor B215, then on Banbury mixer with 180 DEG C, rotating speed 40 revs/min, 5 minutes time carries out the blended gained of banburying; CN101935390A discloses and a kind ofly obtains described polylactic acid toughening modifier by after the terminal hydroxy group of poly butylene succinate is caused rac-Lactide ring-opening polymerization through purifying, after add the preparation method of the matrix material carrying out toughening modifying in poly(lactic acid).By poly butylene succinate directly to be introduced in poly(lactic acid) macromolecular chain thus to improve the toughness of material.CN103194052A discloses a kind of preparation method of plasticizing polylactic acid, this plasticizing polylactic acid adopts polyether polyester to carry out toughening modifying by the method for melt blending to poly(lactic acid), polyether polyester take polyoxyethylene glycol as Material synthesis, owing to containing polyether segment in polyether polyester, polyether segment can improve the toughness of poly(lactic acid).CN102906193A also discloses the composition of the blend polymer of a kind of poly(lactic acid) (PLA) and PHA, because PHA has complete amorphous feature, therefore is conducive to the raising of composite material toughness.
But all in all, due to the existence of many materials, the consistency of lactic acid composite material still has problems, and causes the reduction of toughening effect, the intensity reduction caused after especially toughness reinforcing also creates certain impact to application.The present invention adopts in situ Polycondensation method, is introduced in poly(lactic acid) by toughness segment, controls crystallization to a certain degree simultaneously, thus realizes the effect not reducing the strength of materials while significantly improving toughness.
Summary of the invention
The object of the invention is to overcome poly-lactic acid material fragility large, the defect of resiliency difference, provides a kind of polylactic acid alloy material with 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 tough polylactic acid based alloy material, this material is formed by major ingredient and auxiliary material Compound Machining, major ingredient comprises hydroxyl-terminated polylactic acid, superbrnaching end-hydroxy polyester, ethylene-acrylic acid copolymer, auxiliary material comprises polycondensation catalyst, nucleator and oxidation inhibitor, fluidizer, anti UV agent, in major ingredient, the mass ratio of hydroxyl poly(lactic acid) is between 35%-55%, the mass ratio of superbrnaching end-hydroxy polyester is between 25%-35%, the mass ratio of ethylene-acrylic acid copolymer is between 10%-40%, in auxiliary material, the consumption of polycondensation catalyst is between the 1-3% of major ingredient quality, the consumption of nucleator is between the 1.5%-2.5% of major ingredient quality, oxidation inhibitor, softening agent, the quality of anti UV agent is all 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 superbrnaching end-hydroxy polyester be 3-5 for branched product, its molecular weight is between 8000-30000g/mol.Its preparation method and raw material can be used more.As can be linear B2 type and AB2 type as synthon, carry out esterification in a solvent.As with neopentyl glycol, dimethylol propionic acid and catalyzer p-methyl benzenesulfonic acid for raw material, take acid dimethyl as backflow reagent, in 140 degree oil baths heating, react underpressure distillation desolvation and water after 4 hours and obtain paying out of 3-4 and hold hydroxyl polyester product.Also CN1405200 invention disclosed patent superbrnaching end-hydroxy polyester and preparation method thereof method or CN1384127 invention disclosed patent water soluble superbrnaching end-hydroxy polyester and preparation method can be adopted to be prepared.Typical preparation 4 generation superbrnaching end-hydroxy polyester molecular formula as follows:
Further, described polycondensation catalyst is the arbitrary proportion of one or more combination in stannous octoate, tetra-n-butyl titanate, tindichloride.
The above catalyzer all can catalytic fusion polycondensation.Under polycondensation catalyst catalysis, the condensation reaction in the hydroxyl-terminated polylactic acid in system, ethylene-acrylic acid copolymer, superbrnaching end-hydroxy polyester between terminal hydroxy group.
Further, described nucleator can be inorganic nucleator and comprises nano imvite, nano hydrotalcite, nano-calcium carbonate etc., also can comprise organic nucleating agent and comprise phosphorus compound metal-salt, multiamide compounds etc.
Further, described ethylene-acrylic acid copolymer (EAA) at high temperature occurs except polycondensation except because of the existence of acrylic acid groups and poly(lactic acid) end group, and meanwhile, EAA polarity is comparatively large, and relative consistency is improved and the improvement of processing fluidity serves preferably effect.When selecting, to be chosen as EAA be Tao Shi 3003(melting index is 190 DEG C of 7.8g/10min in suggestion).
Further, described oxidation inhibitor is antioxidant 264, BHT, 168, and the combination of one or more in 1010.
Further, described softening agent is first esters of gallic acid or Phthalates fluidizer.
Further, described anti UV agent is the one or more combination thing in UV531, UV-2908, UV477.
Further, described novel its working method of high ductility polylactic acid base alloy material is: by after abundant for all raw materials drying at 60 DEG C in high speed blender kind high speed after blended 5-10 minute, melt blending in twin screw extruder, processing temperature scope is 190 DEG C-210 DEG C, screw speed is 300-600 rev/min, and the residence time is 2-3 minute, and extrusion vacuumizes, pressure, lower than 0.01Mpa, obtains particulate state alloy material after drying, cooling, pelletizing.
Beneficial effect of the present invention is: take superbrnaching end-hydroxy polyester as core, by polycondensation random introducing poly(lactic acid) macromolecular chain and ethylene-acrylic acid copolymer macromolecular chain.First, owing to being introduced as polycondensation, and all there is polyester group properties, therefore there is very excellent homogeneity, there will not be phase-splitting.Secondly, due to the introducing of EAA, improve the toughness of material, but because random polymerization significantly reduces the crystallinity of poly(lactic acid), and adding of nucleator has to poly(lactic acid) the effect promoting crystallization, be conducive to poly(lactic acid) macromole local-crystalized in system, ensure that with polyester acting in conjunction the intensity that alloy material is excellent.
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.
Specific embodiment 1
A kind of preparation method of high tough polylactic acid based alloy material, formed by major ingredient and auxiliary material Compound Machining, major ingredient comprises 123.3g hydroxyl-terminated polylactic acid, 73.8g superbrnaching end-hydroxy polyester, 49.3g ethylene-acrylic acid copolymer, 3.7g polycondensation catalyst, 4.9g nucleator, 3.5g oxidation inhibitor, 3.2g fluidizer DOP and 2.9g anti UV agent UV531.
By after abundant for all raw materials drying at 60 DEG C in high speed blender kind high speed after blended 5-10 minute, melt blending in twin screw extruder, processing temperature scope is 190 DEG C-210 DEG C, screw speed is 400 revs/min, the residence time is 2-3 minute, extrusion vacuumizes, pressure lower than 0.01MPa.Particulate state alloy material is obtained after drying, cooling, pelletizing.
The molecular weight of described hydroxyl-terminated polylactic acid is between 100000-300000g/mol, and in end group, hydroxyl ratio accounts for 85% of total end group ratio.
Described superbrnaching end-hydroxy polyester be 4-5 for branched product, its molecular weight is between 15000-30000g/mol.Its preparation method is using linear neopentyl glycol type and dimethylol propionic acid as synthon, carries out esterification in a solvent and prepares.
Described polycondensation catalyst is that stannous octoate and tetra-n-butyl titanate are with 1:1 mass mixing.
Described nucleator is inorganic nucleator nano imvite.
Specific embodiment 2
A kind of preparation method of high tough polylactic acid based alloy material, formed by major ingredient and auxiliary material Compound Machining, major ingredient comprises 103.2g hydroxyl-terminated polylactic acid, 75.1g superbrnaching end-hydroxy polyester, 79.7g ethylene-acrylic acid copolymer, 4.2g polycondensation catalyst, 5.1g nucleator, 3.91g oxidation inhibitor, 3.52g fluidizer DOP and 3.28g anti UV agent UV531.
By after abundant for all raw materials drying at 60 DEG C in high speed blender kind high speed after blended 5-10 minute, melt blending in twin screw extruder, processing temperature scope is 190 DEG C-210 DEG C, screw speed is 400 revs/min, the residence time is 2-3 minute, extrusion vacuumizes, pressure lower than 0.01MPa.Particulate state alloy material is obtained after drying, cooling, pelletizing.
The molecular weight of described hydroxyl-terminated polylactic acid is between 150000-300000g/mol, and in end group, hydroxyl ratio accounts for 87% of total end group ratio.
Described superbrnaching end-hydroxy polyester be 3-5 for branched product, its molecular weight is between 10000-30000g/mol.Its preparation method is using linear hexylene glycol type and dimethylol propionic acid as synthon, carries out esterification in a solvent and prepares.
Described polycondensation catalyst is stannous octoate.
Described nucleator is inorganic nucleator nano hydrotalcite.
Carry out Evaluating Mechanical Properties with following methods to the sample in embodiment 1-2, its result provides in the following table 1.
Tensile property: measure based on ASTMD638 and D639.
Heat-drawn wire: measure based on ASTMD648.
Nicked shock strength (IZOD): measure based on ASTMD256.
Table 1
| Index | Unit | Embodiment 1 | Embodiment 2 |
| Tensile strength | Kgf/cm 2 | 512.5 | 523.4 |
| Heat-drawn wire | ℃ | 67.4 | 69.5 |
| Shock strength (IZOD) | Kgf.cm/cm | 27.3 | 26.9 |
Claims (5)
1. the preparation method of one kind high tough polylactic acid based alloy material, it is characterized in that, this alloy material is formed by major ingredient and auxiliary material Compound Machining, major ingredient comprises hydroxyl-terminated polylactic acid, superbrnaching end-hydroxy polyester, ethylene-acrylic acid copolymer, auxiliary material comprises polycondensation catalyst, nucleator and oxidation inhibitor, fluidizer, anti UV agent, in major ingredient, the mass ratio of hydroxyl poly(lactic acid) is between 35%-55%, the mass ratio of superbrnaching end-hydroxy polyester is between 25%-35%, the mass ratio of ethylene-acrylic acid copolymer is between 10%-40%, in auxiliary material, the consumption of polycondensation catalyst is between the 1-3% of major ingredient quality, the consumption of nucleator is between the 1.5%-2.5% of major ingredient quality, oxidation inhibitor, softening agent, the consumption of anti UV agent is all between the 1-2% of major ingredient quality,
Its working method is:
By after abundant for all raw materials drying at 60 DEG C in high speed blender kind high speed after blended 5-10 minute, melt blending in twin screw extruder, processing temperature scope is 190 DEG C-210 DEG C, screw speed is 300-600 rev/min, the residence time is 2-3 minute, extrusion vacuumizes, and pressure, lower than 0.01MPa, obtains particulate state alloy material after drying, cooling, pelletizing.
2. the preparation method of a kind of high tough polylactic acid based alloy material as claimed in claim 1, is characterized in that, the molecular weight of 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%.
3. the preparation method of a kind of high tough polylactic acid based alloy material as claimed in claim 1, is characterized in that, described superbrnaching end-hydroxy polyester be 3-5 for branched product, its molecular weight is between 8000-30000g/mol.
4. the preparation method of a kind of high tough polylactic acid based alloy material as claimed in claim 1, is characterized in that, described polycondensation catalyst is the arbitrary proportion of one or more combination in stannous octoate, tetra-n-butyl titanate, tindichloride.
5. the preparation method of a kind of high tough polylactic acid based alloy material as claimed in claim 1, it is characterized in that, described nucleator is inorganic nucleator or organic nucleating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510009868.2A CN105440700A (en) | 2015-01-09 | 2015-01-09 | Preparation method for polylactic acid-based alloy material with high strength and toughness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510009868.2A CN105440700A (en) | 2015-01-09 | 2015-01-09 | Preparation method for polylactic acid-based alloy material with high strength and toughness |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105440700A true CN105440700A (en) | 2016-03-30 |
Family
ID=55551365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510009868.2A Pending CN105440700A (en) | 2015-01-09 | 2015-01-09 | Preparation method for polylactic acid-based alloy material with high strength and toughness |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105440700A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108530853A (en) * | 2018-05-17 | 2018-09-14 | 北京工商大学 | A kind of derivative blended objects of PLA/HBP and preparation method thereof |
| CN108707323A (en) * | 2018-05-17 | 2018-10-26 | 北京工商大学 | A kind of derivative blended objects of PLA/PPC/HBP and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060247387A1 (en) * | 2005-04-29 | 2006-11-02 | Board Of Trustees Of Michigan State University | Hyperbranched polymer modified biopolymers, their biobased materials and process for the preparation thereof |
| CN1962714A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | Method for modifying polylactic acid using superbranched polymer |
| CN101319088A (en) * | 2008-07-02 | 2008-12-10 | 东华大学 | Shape memory material based on polylactic acid, manufacturing and using process thereof |
| CN102504271A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing hyperbranched polyester modified organic silicon resin |
-
2015
- 2015-01-09 CN CN201510009868.2A patent/CN105440700A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060247387A1 (en) * | 2005-04-29 | 2006-11-02 | Board Of Trustees Of Michigan State University | Hyperbranched polymer modified biopolymers, their biobased materials and process for the preparation thereof |
| CN1962714A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | Method for modifying polylactic acid using superbranched polymer |
| CN101319088A (en) * | 2008-07-02 | 2008-12-10 | 东华大学 | Shape memory material based on polylactic acid, manufacturing and using process thereof |
| CN102504271A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing hyperbranched polyester modified organic silicon resin |
Non-Patent Citations (2)
| Title |
|---|
| 肖伟娜，等: ""聚乳酸增韧改性研究进展"", 《化工进展》 * |
| 邓如生: "《共混改性工程塑料》", 31 July 2003 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108530853A (en) * | 2018-05-17 | 2018-09-14 | 北京工商大学 | A kind of derivative blended objects of PLA/HBP and preparation method thereof |
| CN108707323A (en) * | 2018-05-17 | 2018-10-26 | 北京工商大学 | A kind of derivative blended objects of PLA/PPC/HBP and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3404067B1 (en) | Plasticised biodegradable polyester film and preparation method therefor | |
| AU2009295910B2 (en) | Aliphatic polyester | |
| CN102070880B (en) | Biodegradable resin composition and product thereof | |
| CN108822514B (en) | Completely biodegradable polylactic acid based blown film and preparation method thereof | |
| CN108047658B (en) | Biodegradable polyester agricultural mulching film | |
| US8691913B2 (en) | Polylactic acid compositions, polylactic acid materials and methods of preparing the same | |
| EP3660097B1 (en) | Polylactic acid composite material and application thereof | |
| JP2014518297A (en) | Thermoplastic starch and biodegradable polyester / starch composites and their preparation | |
| KR20090054434A (en) | Mastermatch and polymer composition | |
| CN107868416A (en) | A kind of lactic acid composite material and its application | |
| CN111205602A (en) | Modified polyhydroxyalkanoate material and film for biodegradable mulching film, and preparation method and application thereof | |
| CN105062024A (en) | High-transparency high-temperature-resistance polylactic acid composite material and preparation method thereof | |
| CN105440609A (en) | High-toughness polylactic acid based material and preparation process therefor | |
| CN113956630A (en) | Completely biodegradable film and preparation method thereof | |
| CN105440700A (en) | Preparation method for polylactic acid-based alloy material with high strength and toughness | |
| CN110358273B (en) | Biomass antibacterial film with high puncture resistance | |
| JP4503215B2 (en) | Lactic acid-based resin composition, peroxide-modified lactic acid-based resin composition, and molded articles thereof | |
| CN115558256A (en) | High-transparency toughened fully-biodegradable PLA film and preparation method thereof | |
| US20110178211A1 (en) | Biodegradable polyester resin composition and molded body composed of the same | |
| CN108641318B (en) | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method thereof | |
| CN103865245A (en) | Preparation method of hydrolysis-resistant polylactic resin | |
| KR101768319B1 (en) | Biodegradable resin composition and preparing method of the same | |
| CN113402868A (en) | Preparation method of hyperbranched polyester modified polylactic acid/polypropylene carbonate composite material | |
| WO2010038860A1 (en) | Polylactic acid composition and method for producing same | |
| CN108559238B (en) | Biodegradable polyhydroxycarboxylic acid alloy material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160330 |
|
| WD01 | Invention patent application deemed withdrawn after publication |