CN105623212A - Preparation method of high-toughness biodegradable polylactic acid foamed plastic - Google Patents
Preparation method of high-toughness biodegradable polylactic acid foamed plastic Download PDFInfo
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- CN105623212A CN105623212A CN201410691587.5A CN201410691587A CN105623212A CN 105623212 A CN105623212 A CN 105623212A CN 201410691587 A CN201410691587 A CN 201410691587A CN 105623212 A CN105623212 A CN 105623212A
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- polylactic acid
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Abstract
The invention relates to a polylactic acid foamed plastic, and especially relates to a preparation method of a high-toughness biodegradable polylactic acid foamed plastic. The high-toughness biodegradable polylactic acid foamed plastic comprises the following raw materials by weight: 100 parts of polylactic acid resin, 5-10 parts of a flexibilizer, 0.5-2 parts of a cross-linking agent, 0.5-5 parts of a nucleating agent, 0.5-2.5 parts of a foaming agent, 0.5-3 parts of a plasticizer, and 0.5-1 part of an anti-oxidant. The method comprises the following steps: directly extruding the raw materials without addition of the foaming agent to obtain high-toughness polylactic acid master batch, adding the foaming agent in the master batch, extruding the materials, shaping the materials, cutting the product, spreading the product, coiling the product and packaging the product. The high-toughness biodegradable polylactic acid foamed plastic has the advantages of simple production process, good mechanical properties such as product toughness, biodegradable performance after usage, no environmental pollution, easy acquisition and low cost of the raw materials, and the product has high product cost performance, and can be widely used as various package materials.
Description
Technical field
The invention belongs to engineering plastics technical field, the preparation method being specifically related to a kind of biodegradable polylactic acid.
Background technology
Along with the development of 20th century petrochemical industry forties, it is widely used to daily life with the macromolecular material that petroleum chemicals derivant is raw material, entire society is created tremendous influence. Since emerging, macromolecular material has the advantage that much cannot replace, but at home and abroad macromolecular material industry is also faced with the environmental problem being difficult to ignore while developing rapidly, outstanding behaviours is in following two: one, the starting monomer of macromolecular material mostly is petroleum chemicals derivant, and oil is a kind of non-renewable resources; Its two, the final process of waste polymer material is still insurmountable problem so far. But, developing rapidly along with socioeconomic, people are to self health and the protective awareness of environment is also grown with each passing day. Therefore, develop a kind of environmentally friendly macromolecular material to be very important, in the middle of numerous macromolecular materials, wherein, poly-lactic acid material (Poly (lacticacid)/Polylactide, PLA) is considered as one of best succedaneum of conventional petroleum sill.
Polylactic acid (PLA) itself being absent from nature, it mainly by starch fermented after obtain lactic acid, and then occur polymerization to prepare poly-lactic acid material. It has good biodegradability, and decomposition afterproduct is CO-2And H2O, will not produce any harmful effect to environment. Owing to its mechanical property is better, it is with a wide range of applications, has been applied to the fields such as packaging for foodstuff, daily plastic and fiber textile. Meanwhile, polylactic acid has good biocompatibility and Bioabsorbable, has broad application prospects in medical field. But, it still suffers from some shortcomings, as poor in toughness, thermostability is not enough, and this limits its application in real life. Further, due to polylactic acid, to produce finished product of a relatively high, at present, domestic its research is started late, but along with the effort of more and more scientists, it will make the practical quickening process of polylactic acid.
Kameoka et al. utilize physical blowing agent and CBA directly extrude method successfully prepares expanded polylactic acid plastics. In the past few years, domestic also have a series of relevant report about expanded polylactic acid preparation method. But it is less to utilize directly extrusion to send out the relevant report preparing high-toughness polylactic acid foam applications. The present invention, according to the correlation properties about the prior art of toughener manufacture method and biodegradation material, draws the main thought of the present invention.
Summary of the invention
It is an object of the invention to provide certain feasible strategy for design synthesis high tenacity, biodegradable polylactic acid foam plastic.
The high tenacity biodegradable polylactic acid foam plastic that the present invention proposes, by the blended direct extrusion masterbatch of each component raw material, is subsequently adding foaming agent and directly extrudes and obtain, and by weight, formula is as follows for its raw material components:
Polylactic acid 100
Toughener 5-10
Cross-linking agent 0.5-2
Nucleator 0.5-5
Foaming agent 0.5-3
Plasticizer 0.5-3
Antioxidant 0.5-1
In the present invention, the optical activity of described polylactic acid resin is left-handed photosensitiveness or racemization photosensitiveness, and molecular weight is 17-21 ten thousand, its molecular weight distribution 1.7-2.2, and degree of crystallinity is 24-34%.
In the present invention, described high-toughness polylactic acid masterbatch is with hydroxyl valerate (HV) for toughener.
In the present invention, described cross-linking agent is one or more mixture in butanediol, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate.
In the present invention, described nucleator is Pulvis Talci or montmorillonite.
In the present invention, described foaming agent is AC foaming agent, and its decomposition temperature is between 140-190 DEG C.
In the present invention, described plasticizer is Polyethylene Glycol, mixture in the one or 2 in dioctyl phthalate.
In the present invention, described antioxidant is a kind or 2 kinds of mixture in hydroquinone and catechol.
The preparation method of the high tenacity biodegradable polylactic acid foam plastic that the present invention proposes, specifically comprises the following steps that
(1) by metering by polylactic acid, toughener, antioxidant, nucleator, Homogeneous phase mixing, masterbatch is made by extruder extrusion;
(2) by metering by masterbatch, foaming agent mix homogeneously, using extruder extrusion foaming, add plasticizer and cross-linking agent in the process in extruder, wherein, the temperature of extruder should be advisable at 140-240 DEG C;
(3) sizing, cutting, flatten, traction, batch, packaging.
The high tenacity biodegradable polylactic acid foam plastic of the present invention, is prepared by the direct extrusion foaming sizing of extruder, and has closed pore formula foaming structure. This material property is good, and discarded after biodegradable environment will not be had undesirable effect. Meanwhile, its raw material sources are extensive, cheap and easy to get, can be widely used and make various packaging material.
Detailed description of the invention
As no specific instructions, the various raw materials of the present invention all can pass through to be commercially available, or the conventional method according to this area prepares. Unless otherwise defined or described herein, the same meaning that all specialties used herein are familiar with scientific words and those skilled in the art. In addition any method similar or impartial to described content all can be applicable in the present invention.
Hereinafter will carry out the further details of explanation present invention by example. In an embodiment, mark and percentage ratio except as otherwise noted, all by weight, but it is not limited to these examples. The present invention can be done some unsubstantialities according to foregoing and improve and adjust by the person skilled in the art of this area.
Embodiment 1
The raw material mix homogeneously 100 parts of polylactic acid resins, 3 parts of hydroxyl valerates (HV), 2 parts of montmorillonites formed, joins extruder extrusion. Extruder parameter: extruder temperature is 160-210 DEG C, engine speed 800rpm, screw speed 35rpm. Prepare masterbatch cooling, pelletizing. Then, by gained masterbatch and 0.3 part of foaming agent mix homogeneously, adding extruder basic intumescent, extruder parameter is ibid. Extrusion is added 0.5 part of toluene di-isocyanate(TDI) and 0.5 part of o-phthalic acid dibutyl ester by dosing pump. The foam of extrusion, cools down, shapes, cuts, flattens, draws, batches. Product specification: thickness 3.2mm, width 1150mm, foam diameter 0.15mm, impact strength is 3.7KJ/m2, elongation at break 56%.
Embodiment 2
The raw material mix homogeneously 100 parts of polylactic acid resins, 6 parts of hydroxyl valerates (HV), 2 parts of montmorillonites formed, joins extruder extrusion. Extruder parameter: extruder temperature is 170-240 DEG C, engine speed 900rpm, screw speed 35rpm. Prepare masterbatch cooling, pelletizing. Then, by gained masterbatch and 0.5 part of foaming agent mix homogeneously, adding extruder basic intumescent, extruder parameter is ibid. Extrusion is added 0.5 part of toluene di-isocyanate(TDI) and 1.0 parts of o-phthalic acid dibutyl esters by dosing pump. The foam of extrusion, cools down, shapes, cuts, flattens, draws, batches. Product specification: thickness 3.0mm, width 1150mm, foam diameter 0.13mm, impact strength is 5.3KJ/m2, elongation at break 82%.
Embodiment 3
The raw material mix homogeneously 100 parts of polylactic acid resins, 9 parts of hydroxyl valerates (HV), 3 parts of montmorillonites formed, joins extruder extrusion. Extruder parameter: extruder temperature is 160-230 DEG C, engine speed 850rpm, screw speed 35rpm. Prepare masterbatch cooling, pelletizing. Then, by gained masterbatch and 1.0 parts of foaming agent mix homogeneously, adding extruder basic intumescent, extruder parameter is ibid. Extrusion is added 0.5 part of toluene di-isocyanate(TDI) and 1.0 parts of o-phthalic acid dibutyl esters by dosing pump. The foam of extrusion, cools down, shapes, cuts, flattens, draws, batches. Product specification: thickness is 3.1mm, width is 1150mm, and foam diameter is 0.125mm, and impact strength is 6.7KJ/m2, elongation at break 91%.
Embodiment 4
The raw material mix homogeneously 100 parts of polylactic acid resins, 9 parts of hydroxyl valerates (HV), 5 parts of Pulvis Talci, 1 part of hydroquinone formed, joins extruder extrusion. Extruder parameter: extruder temperature is 170-240 DEG C, engine speed 850rpm, screw speed 35rpm. Prepare masterbatch cooling, pelletizing. Then, by gained masterbatch and 1.6 parts of foaming agent mix homogeneously, adding extruder basic intumescent, extruder parameter is ibid. Extrusion is added 0.5 part of toluene di-isocyanate(TDI) and 1.0 parts of o-phthalic acid dibutyl esters by dosing pump. The foam of extrusion, cools down, shapes, cuts, flattens, draws, batches. Product specification: thickness is 2.9mm, width is 1150mm, and foam diameter is 0.105mm, and impact strength is 6.3KJ/m2, elongation at break 86%.
Embodiment 5
The raw material mix homogeneously 100 parts of polylactic acid resins, 9 parts of hydroxyl valerates (HV), 5 parts of montmorillonites, 0.5 part of hydroquinone, 0.5 part of catechol formed, joins extruder extrusion. Extruder parameter: extruder temperature is 140-210 DEG C, engine speed 850rpm, screw speed 35rpm. Prepare masterbatch cooling, pelletizing. Then, by gained masterbatch and 0.5 part of foaming agent mix homogeneously, adding extruder basic intumescent, extruder parameter is ibid. Extrusion is added 0.5 part of toluene di-isocyanate(TDI) and 0.5 part of o-phthalic acid dibutyl ester by dosing pump. The foam of extrusion, cools down, shapes, cuts, flattens, draws, batches. Product specification: thickness is 3.3mm, width is 1150mm, and foam diameter is 0.149mm, and impact strength is 5.8KJ/m2, elongation at break 76%.
Below it is only the concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation. The technical scheme that every employing equivalents or equivalence are replaced and formed, all falls within scope.
Claims (9)
1. a high tenacity biodegradable polylactic acid foam plastic, it is characterised in that have the blended direct extrusion of various raw material to prepare masterbatch, adds foaming agent and obtains final products by directly extrusion, and by weight, formula is as follows for its raw material components:
Polylactic acid 100
Toughener 5-10
Cross-linking agent 0.5-2
Nucleator 0.5-5
Foaming agent 0.5-2.5
Plasticizer 0.5-3
Antioxidant 0.5-1.
2. high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that the optical activity of described polylactic acid resin is left-handed photosensitiveness or racemization photosensitiveness, and molecular weight is 10-25 ten thousand, its molecular weight distribution 1.7-2.2, and degree of crystallinity is 24-34%.
3. high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that described high-toughness polylactic acid masterbatch is with hydroxyl valerate (HV) for toughener.
4. high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that described cross-linking agent is one or more mixture in butanediol, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate.
5. high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that described nucleator is Pulvis Talci or montmorillonite.
6. high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that described foaming agent is AC foaming agent, and its decomposition temperature is between 140-190 DEG C.
7. high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that described plasticizer is Polyethylene Glycol, mixture in the one or 2 in dioctyl phthalate.
8. high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that described antioxidant is a kind or 2 kinds of mixture in hydroquinone and catechol.
9. the preparation method of high tenacity biodegradable polylactic acid foam plastic according to claim 1, it is characterised in that concrete preparation process is as follows:
By metering by polylactic acid, toughener, antioxidant, nucleator, Homogeneous phase mixing, make masterbatch, cooling, pelletizing by extruder extrusion;
By metering by masterbatch, foaming agent mix homogeneously, using extruder extrusion foaming, add plasticizer and cross-linking agent in the process in extruder, wherein, the temperature of extruder should be advisable at 140-240 DEG C;
Sizing, cutting, flatten, traction, batch, packaging.
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| CN201410691587.5A CN105623212A (en) | 2014-11-27 | 2014-11-27 | Preparation method of high-toughness biodegradable polylactic acid foamed plastic |
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Cited By (5)
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|---|---|---|---|---|
| CN109233229A (en) * | 2018-08-13 | 2019-01-18 | 陕西理工大学 | A kind of 3D printing PLA silk material and preparation method thereof of shock resistance ultraviolet aging resistance |
| WO2019100713A1 (en) * | 2017-11-27 | 2019-05-31 | 金发科技股份有限公司 | Polylactic acid composite material and application thereof |
| CN110483963A (en) * | 2018-05-15 | 2019-11-22 | 湖北文理学院 | A kind of modified polylactic acid foam and preparation method thereof |
| CN112759906A (en) * | 2020-12-23 | 2021-05-07 | 青岛润兴塑料新材料有限公司 | Fully-biodegradable polylactic acid oil-absorbing foaming material for ocean |
| CN113563627A (en) * | 2021-05-06 | 2021-10-29 | 深圳光华伟业股份有限公司 | Controllable lightweight foam material for FDM printing and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019100713A1 (en) * | 2017-11-27 | 2019-05-31 | 金发科技股份有限公司 | Polylactic acid composite material and application thereof |
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| CN110483963A (en) * | 2018-05-15 | 2019-11-22 | 湖北文理学院 | A kind of modified polylactic acid foam and preparation method thereof |
| CN109233229A (en) * | 2018-08-13 | 2019-01-18 | 陕西理工大学 | A kind of 3D printing PLA silk material and preparation method thereof of shock resistance ultraviolet aging resistance |
| CN109233229B (en) * | 2018-08-13 | 2020-11-13 | 陕西理工大学 | Impact-resistant ultraviolet-aging-resistant PLA wire for 3D printing and preparation method thereof |
| CN112759906A (en) * | 2020-12-23 | 2021-05-07 | 青岛润兴塑料新材料有限公司 | Fully-biodegradable polylactic acid oil-absorbing foaming material for ocean |
| CN113563627A (en) * | 2021-05-06 | 2021-10-29 | 深圳光华伟业股份有限公司 | Controllable lightweight foam material for FDM printing and preparation method and application thereof |
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