CN103113730A - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polylactic acid composite material and a preparation method thereof. The polylactic acid composite material is prepared from polylactic acid, polycaprolactone, nano-silica, an antioxidant and a compatilizer, wherein the toughness of the polylactic acid composite material is improved by adding the biodegradable polycaprolactone, and the nano-silica with high strength, toughness and high stability is dispersed in the material and is bonded with macromolecule chains to form a three-dimensional reticulate structure, so that the basic performances such as impact strength and elasticity of the polylactic acid composite material are improved, and biological environmentally-friendly requirements are also satisfied.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to lactic acid composite material of a kind of high-intensity high-tenacity and preparation method thereof.
Background technology
Poly(lactic acid) can derive from renewable resources fully, thoroughly broken away from the dependence to petroleum resources, its machinery and physicals are relatively good comparatively speaking in polyester, have also that the glossiness transparency is high, rebound resilience and curling persistence is good, oil-proofness and dyeing behavior is good, flammable low, to advantages such as human body toxicological harmlesss.
Poly(lactic acid) also is not widely used at present, is that main manifestations is that degree of crystallinity is low, causes intensity low because be subject to the restriction of some shortcomings of material existence; Easily degraded in the melt process, molecular weight and molecular weight distribution are restive; Matter is crisp hard, and poor toughness lacks flexibility and elasticity, and anti-shock strength is little etc.Although taked certain methods to improve for the shortcoming of poly(lactic acid) at present, as with poly(lactic acid) and other material such as acrylonitrile-butadiene-styrene (ABS) copolymerization, poly(lactic acid) is carried out chain extension and branching, is carried out reactive blending etc. with other material and poly(lactic acid), wherein the most simple with poly(lactic acid) and other material blend with the method for improving the poly(lactic acid) performance, but usually the poly(lactic acid) after modification still well on satisfying the market to the requirement of engineering part.The application section biodegradable material polycaprolactone of the present invention innovation comes polydactyl acid, makes the mechanical property of the matrix material of preparation improve, and because nano silicon is uniformly dispersed in matrix material, thereby makes the excellent material performance of preparation stable.
Summary of the invention
The object of the present invention is to provide a kind of matrix material and preparation method thereof of poly(lactic acid) of high-intensity high-tenacity, the composite manufacture method of this biodegradable polyesters plasticizing polylactic acid is simple, and makes the matrix material that makes have good mechanical property and biodegradable performance.
Purpose of the present invention can be achieved through the following technical solutions, and a kind of lactic acid composite material is prepared from by weight by following component:
Poly(lactic acid) 60-85 part
Polycaprolactone 10-33 part
Nano silicon 3-8 part
Oxidation inhibitor 0.1-5 part
Compatilizer 0.1-5 part.
Described poly(lactic acid) is the composition of L-type lactic acid and D type lactic acid, and wherein the L-type lactic acid content is 70%-96%, and weight-average molecular weight is 10000-200000g/mol.
Described polycaprolactone is linear polycaprolactone, and weight-average molecular weight is 10000-100000g/mol.
Described nano silicon is the parental type nano silicon of producing by chemical Vapor deposition process.
Described oxidation inhibitor is three (2, the 4-di-t-butyl) phenyl-phosphite (being called for short Irganox168), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (being called for short Irganox1010) and 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxybenzene methyl) at least a in benzene (being called for short Irganox1330).
Described compatilizer is N, N, N ', N '-four glycidyl group-4, at least a in 4 ' diaminodiphenyl-methane (Ag80), bisphenol A-type liquid-state epoxy resin (E44), isocyanuric acid three-glycidyl ester (TGIC).
A kind of method for preparing above-mentioned lactic acid composite material comprises the following steps:
(1) first poly(lactic acid) and polycaprolactone are carried out drying treatment, poly(lactic acid) was in 80 ℃ of dry oven dry 8 hours, and polycaprolactone was in 60 ℃ of dry oven dry 6 hours;
(2) poly(lactic acid), polycaprolactone and oxidation inhibitor, the compatilizer after with drying treatment stirred 10～12 minutes by high-speed mixer by proportioning, the formation mixture;
(3) mixture in (2) is put in the hopper of twin screw extruder, through frit reaction, in the 3rd district, the 4th district or place, the 5th district add nano silicon by the reinforced mode in side position, then extruded, granulation gets lactic acid composite material.
The temperature of respectively distinguishing of described twin screw extruder is 70～100 ℃ of district's temperature, two 190～210 ℃ of district's temperature, three 190～210 ℃ of district's temperature, four 180～200 ℃ of district's temperature, five 180～200 ℃ of district's temperature, six 180～200 ℃ of district's temperature, 170～190 ℃ of head temperatures; The rotating speed of extruder screw is 150～200r/min.
The present invention has following beneficial effect:
1, the present invention by adding the biodegradable polycaprolactone to improve the toughness of poly(lactic acid), improves the resistance to impact shock of poly(lactic acid).
2, because nano silicon at high temperature still has high strength, toughness and stable high, it is dispersed in to be combined with macromolecular chain in material form tridimensional network, thus the fundamental propertys such as the intensity of raising matrix material, elasticity.
3, the auxiliary agent such as compatilizer adds the adhesivity that has improved between poly(lactic acid) and biodegradable polycaprolactone component, further improved the performance of poly(lactic acid), lactic acid composite material shock strength under the condition that keeps its higher tensile strength of preparation is improved.
4, adopt the biodegradable polycaprolactone to come polydactyl acid, guaranteed that the biodegradable performance of poly(lactic acid) is not destroyed, satisfy again the needs of biological environmental production when making the existing high strength of matrix material, the high tenacity of preparation.
Embodiment
Below in conjunction with specific embodiment, the present invention is done a detailed elaboration.
The matrix material of the poly(lactic acid) of a kind of high-intensity high-tenacity of the present invention comprises following component according to weight percent: poly(lactic acid) 60-90 part; Polycaprolactone 10-40 part; Nano silicon 3-8 part; Oxidation inhibitor 0.1-5 part; Compatilizer 0.1-5 part.
In following each Comparative Examples and embodiment, poly(lactic acid) (PLA) is the composition of L type lactic acid and D type lactic acid, and wherein the L-type lactic acid content is 70%-96%, and weight-average molecular weight is 10000-200000g/mol.
Polycaprolactone (PCL) is linear polycaprolactone, and weight-average molecular weight is 10000-100000g/mol.
Nano silicon is a kind of by chemical Vapor deposition process, claims again the silicon-dioxide that pyrolysis method, dry method or combustion method are produced.
Oxidation inhibitor is three (2 of BASF AG, the 4-di-t-butyl) phenyl-phosphite (being called for short Irganox168), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (being called for short Irganox1010) and 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxybenzene methyl) at least a in benzene (being called for short Irganox1330).
Compatilizer is N, N, N ', N '-four glycidyl group-4,4 ' diaminodiphenyl-methane (Ag80), bisphenol A-type liquid-state epoxy resin 6101(E44), at least a in isocyanuric acid three-glycidyl ester (TGIC).
Embodiment 1
First with poly(lactic acid) dry oven dry 8 hours under 80 ℃, polycaprolactone is dry the oven dry 6 hours under 60 ℃; Get 85 parts of poly(lactic acid), 10 parts of polycaprolactones, Irganox168 are 0.3 part again, and Irganox1010 is 0.4 part, and Ag80 is 0.3 part and stirred 11 minutes by high-speed mixer together, forms mixture; At last mixture is put in the hopper of twin screw extruder, through frit reaction, added 5 parts of nano silicons in the 3rd district by the reinforced mode in side position, then extrude, granulation gets lactic acid composite material.Wherein twin screw extruder respectively distinguish temperature and screw speed is respectively: 80 ℃ of district's temperature, two 200 ℃ of district's temperature, three 200 ℃ of district's temperature, four 195 ℃ of district's temperature, five 190 ℃ of district's temperature, six 190 ℃ of district's temperature, 180 ℃ of head temperatures; Screw speed 170r/min.
Embodiment 2
First with poly(lactic acid) dry oven dry 8 hours under 80 ℃, polycaprolactone is dry the oven dry 6 hours under 60 ℃; Get 60 parts of poly(lactic acid), 33 parts of polycaprolactones, Irganox1330 are 3.2 parts again, and Irganox1010 is 1.8 parts, and Ag80 is 0.2 part, and E44 is 0.3 part and stirred 10 minutes by high-speed mixer together, forms mixture; At last mixture is put in the hopper of twin screw extruder, through frit reaction, added 7 parts of nano silicons in the 4th district by the reinforced mode in side position, then extrude, granulation gets lactic acid composite material.Wherein twin screw extruder respectively distinguish temperature and screw speed is respectively: district's temperature 70 C, two 190 ℃ of district's temperature, three 190 ℃ of district's temperature, four 180 ℃ of district's temperature, five 180 ℃ of district's temperature, six 180 ℃ of district's temperature, 170 ℃ of head temperatures; Screw speed 150r/min.
Embodiment 3
First with poly(lactic acid) dry oven dry 8 hours under 80 ℃, polycaprolactone is dry the oven dry 6 hours under 60 ℃; Get 80 parts of poly(lactic acid), 10 parts of polycaprolactones, Irganox168 are 0.3 part again, and Irganox1330 is 0.3 part, and E44 is 2.5 parts, and TGIC is 2.5 parts and stirred 11 minutes by high-speed mixer together, forms mixture; The poly(lactic acid), polycaprolactone and the auxiliary agent that mix are put in the hopper of twin screw extruder, through frit reaction, added 5 parts of nano silicons in the 3rd district by the reinforced mode in side position, then extrude, granulation gets lactic acid composite material.Wherein Zhong Ge district's temperature and the screw speed of twin screw extruder are respectively: 80 ℃ of district's temperature, two 200 ℃ of district's temperature, three 200 ℃ of district's temperature, four 195 ℃ of district's temperature, five 190 ℃ of district's temperature, six 190 ℃ of district's temperature, 180 ℃ of head temperatures; Screw speed 170r/min.
Embodiment 4
First with poly(lactic acid) dry oven dry 8 hours under 80 ℃, polycaprolactone is dry the oven dry 6 hours under 60 ℃; Get 77 parts of poly(lactic acid), 25 parts of polycaprolactones, Irganox1010 are 0.5 part again, and Ag80 is 0.4 part and stirred 12 minutes by high-speed mixer together, forms mixture; The poly(lactic acid), polycaprolactone and the auxiliary agent that mix are put in the hopper of twin screw extruder, through frit reaction, added 8 parts of nano silicons in the 5th district by the reinforced mode in side position, then extrude, granulation gets lactic acid composite material.Wherein twin screw extruder respectively distinguish temperature and screw speed is respectively: 100 ℃ of district's temperature, two 210 ℃ of district's temperature, three 210 ℃ of district's temperature, four 200 ℃ of district's temperature, five 200 ℃ of district's temperature, six 200 ℃ of district's temperature, 190 ℃ of head temperatures; Screw speed 200r/min.
Embodiment 5
First with poly(lactic acid) dry oven dry 8 hours under 80 ℃, polycaprolactone is dry the oven dry 6 hours under 60 ℃; Get 67 parts of poly(lactic acid), 30 parts of polycaprolactones, Irganox1330 are 0.3 part again, and Irganox168 is 0.3 part, and Ag80 is 0.1 part and stirred 11 minutes by high-speed mixer together, forms mixture; The poly(lactic acid), polycaprolactone and the auxiliary agent that mix are put in the hopper of twin screw extruder, through frit reaction, added 3 parts of nano silicons in the 3rd district by the reinforced mode in side position, then extrude, granulation gets lactic acid composite material.Wherein twin screw extruder respectively distinguish temperature and screw speed is respectively: 80 ℃ of district's temperature, two 200 ℃ of district's temperature, three 200 ℃ of district's temperature, four 195 ℃ of district's temperature, five 190 ℃ of district's temperature, six 190 ℃ of district's temperature, 180 ℃ of head temperatures; Screw speed 170r/min.
In order to embody better the high-performance of lactic acid composite material of the present invention, existing lactic acid composite material to be made batten by identical method carry out performance comparison with material of the present invention as a comparison case, its result data sees Table 1.
Comparative Examples 1
First with 75 parts of poly(lactic acid), 20 parts of acrylonitrile-butadiene-styrene (ABS)s, Irganox1010 are 0.6 part, and Irganox168 is 0.3 part, and TGIC is 0.2 part and stirred 11 minutes by high-speed mixer together, forms mixture; The poly(lactic acid), acrylonitrile-butadiene-styrene (ABS) and the auxiliary agent that mix are put in the hopper of twin screw extruder, through frit reaction, then extruded, granulation gets lactic acid composite material.Wherein Zhong Ge district's temperature and the screw speed of twin screw extruder are respectively: 80 ℃ of district's temperature, two 200 ℃ of district's temperature, three 200 ℃ of district's temperature, four 195 ℃ of district's temperature, five 190 ℃ of district's temperature, six 190 ℃ of district's temperature, 180 ℃ of head temperatures; Screw speed 170r/min.
Performance test:
The polylactic acid composition material of above-mentioned enforcement 1-5 and Comparative Examples 1 preparation is made the batten test with injection moulding machine.
Tensile strength is pressed ASTM D 638 standard testings, elongation at break is pressed ASTM D 638 standard testings, flexural strength and modulus in flexure are pressed ASTM D790 standard testing, and notched Izod impact strength is pressed ASTM D256 standard testing, and heat-drawn wire is pressed ASTM D648 standard testing.Test data such as following table 1:
Each embodiment product performance test of table 1
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative Examples 1 |
| Tensile strength | MPa | 50 | 52 | 53 | 50 | 55 | 39 |
| Elongation at break | % | 200 | 205 | 215 | 210 | 220 | 250 |
| Flexural strength | MPa | 50 | 51 | 55 | 57 | 60 | 39 |
| Modulus in flexure | MPa | 1750 | 1700 | 1690 | 1790 | 1800 | 1450 |
| The socle girder notched Izod impact strength | KJ/m 2 | 50 | 60 | 70 | 65 | 55 | 35 |
As can be seen from Table 1, compare with Comparative Examples 1, the lactic acid composite material that uses the present invention to make has also possessed good tensile strength when shock strength is improved, and its modulus in flexure also is improved to some extent, improve the mechanical property of material, so just expanded the Application Areas of material.Present method method of processing by reaction in the poly(lactic acid) course of processing is quoted biodegradable polycaprolactone it is carried out modification in addition, make the existing high strength of matrix material of preparation, the needs that high tenacity satisfies again biological environmental production simultaneously, improve the application limitations of poly(lactic acid), guaranteed the widespread use of material at medical field.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and in the General Principle of this explanation is applied to other embodiment and needn't pass through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (8)
1. lactic acid composite material is characterized in that: be prepared from by weight by following component:
Poly(lactic acid) 60-85 part
Polycaprolactone 10-33 part
Nano silicon 3-8 part
Oxidation inhibitor 0.1-5 part
Compatilizer 0.1-5 part.
2. a kind of lactic acid composite material according to claim 1, it is characterized in that: described poly(lactic acid) is the composition of L-type lactic acid and D type lactic acid, and wherein the L-type lactic acid content is 70%-96%, and weight-average molecular weight is 10000-200000g/mol.
3. a kind of lactic acid composite material according to claim 1, it is characterized in that: described polycaprolactone is linear polycaprolactone, weight-average molecular weight is 10000-100000g/mol.
4. a kind of lactic acid composite material according to claim 1, it is characterized in that: described nano silicon is the parental type nano silicon of producing by chemical Vapor deposition process.
5. a kind of lactic acid composite material according to claim 1, it is characterized in that: described oxidation inhibitor is three (2, the 4-di-t-butyl) phenyl-phosphite, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1,3,5-trimethylammonium-2,4,6-(3,5-di-t-butyl-4-hydroxybenzene methyl) at least a in benzene.
6. a kind of lactic acid composite material according to claim 1, it is characterized in that: described compatilizer is N, N, N ', N '-four glycidyl group-4, at least a in 4 ' diaminodiphenyl-methane, bisphenol A-type liquid-state epoxy resin, isocyanuric acid three-glycidyl ester.
7. method for preparing lactic acid composite material as claimed in claim 1 is characterized in that: comprise the following steps:
(1) first poly(lactic acid) and polycaprolactone are carried out drying treatment, poly(lactic acid) was in 80 ℃ of dry oven dry 8 hours, and polycaprolactone was in 60 ℃ of dry oven dry 6 hours;
(2) by proportioning, poly(lactic acid), polycaprolactone and oxidation inhibitor, the compatilizer of drying stirred 10～12 minutes the formation mixture by high-speed mixer;
(3) mixture in (2) is put in the hopper of twin screw extruder, through frit reaction, in the 3rd district, the 4th district or place, the 5th district add nano silicon by the reinforced mode in side position, then extruded, granulation gets lactic acid composite material.
8. preparation method according to claim 7, it is characterized in that: the temperature of respectively distinguishing of described twin screw extruder is 70～100 ℃ of district's temperature, two 190～210 ℃ of district's temperature, three 190～210 ℃ of district's temperature, four 180～200 ℃ of district's temperature, five 180～200 ℃ of district's temperature, six 180～200 ℃ of district's temperature, 170～190 ℃ of head temperatures; The rotating speed of extruder screw is 150～200r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292782A (en) * | 2014-05-13 | 2015-01-21 | 浙江大学 | Complete bio-based biodegradable polylactic acid composition and preparation method thereof |
| CN104962052A (en) * | 2015-07-13 | 2015-10-07 | 中国石油大学(北京) | Degradable resin nano-composite material for oil and gas field operation and preparation method thereof |
| CN104987682A (en) * | 2015-07-13 | 2015-10-21 | 中国石油大学(北京) | Biodegradable resin material applied to oil and gas fields and preparation method for biodegradable resin material |
| CN105295321A (en) * | 2015-07-13 | 2016-02-03 | 中国石油大学(北京) | Degradable material for oil and gas field operation and preparation method thereof |
| CN105442187A (en) * | 2015-12-16 | 2016-03-30 | 浙江理工大学 | Preparation method of polylactic acid/ polycaprolactone melt-blown nonwoven materials |
| CN106221161A (en) * | 2016-08-23 | 2016-12-14 | 唐山师范学院 | A kind of polylactic acid and caprolactone/sesbania gum composite and preparation method thereof |
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| WO2024032073A1 (en) * | 2022-08-10 | 2024-02-15 | 浙江旺林生物科技有限公司 | Polylactic acid/polycaprolactone/plant carbon black composite material and preparation method therefor |
| CN118003608A (en) * | 2024-03-04 | 2024-05-10 | 保定市富新包装有限公司 | Preparation method for improving compression resistance of environment-friendly packaging material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821303A (en) * | 2006-03-30 | 2006-08-23 | 上海大学 | Biological degradable thin film material for transfusion bag and its preparing method |
| CN101735583A (en) * | 2009-12-15 | 2010-06-16 | 中国科学院长春应用化学研究所 | Completely biodegraded polylactic acid nanometer composite material and preparation method thereof |
-
2013
- 2013-02-20 CN CN201310054430.7A patent/CN103113730B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821303A (en) * | 2006-03-30 | 2006-08-23 | 上海大学 | Biological degradable thin film material for transfusion bag and its preparing method |
| CN101735583A (en) * | 2009-12-15 | 2010-06-16 | 中国科学院长春应用化学研究所 | Completely biodegraded polylactic acid nanometer composite material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| A. DORIGATO ET AL: ""Effect of Silica Nanoparticles on the Mechanical Performances of Poly(Lactic Acid)"", 《JOURNAL OF POLYMERS AND THE ENVIRONMENT》 * |
| D.R.保罗等: "《聚合物共混物：组成与性能（上卷）》", 31 May 2004 * |
| 杨斌: "《绿色塑料聚乳酸》", 30 September 2007 * |
| 黄进等: "《生物质化工与生物质材料》", 31 August 2009 * |
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| WO2024032073A1 (en) * | 2022-08-10 | 2024-02-15 | 浙江旺林生物科技有限公司 | Polylactic acid/polycaprolactone/plant carbon black composite material and preparation method therefor |
| GB2625615A (en) * | 2022-08-10 | 2024-06-26 | Zhejiang Wanglin Bio Tech Co Ltd | Polylactic acid/polycaprolactone/plant carbon black composite material and preparation method therefor |
| CN118003608A (en) * | 2024-03-04 | 2024-05-10 | 保定市富新包装有限公司 | Preparation method for improving compression resistance of environment-friendly packaging material |
| CN118003608B (en) * | 2024-03-04 | 2024-09-17 | 保定市富新包装有限公司 | Preparation method for improving compression resistance of environment-friendly packaging material |
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