CN104804387B - A kind of full bio-based degradable poly lactic acid composite and preparation method thereof - Google Patents
A kind of full bio-based degradable poly lactic acid composite and preparation method thereof Download PDFInfo
- Publication number
- CN104804387B CN104804387B CN201510129952.8A CN201510129952A CN104804387B CN 104804387 B CN104804387 B CN 104804387B CN 201510129952 A CN201510129952 A CN 201510129952A CN 104804387 B CN104804387 B CN 104804387B
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- composite material
- starch
- base composite
- based degradable
- 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.)
- Active
Links
Abstract
The invention discloses a kind of full bio-based degradable polylactic acid-base composite material, percentage by weight be the polylactic acid of 55～79%；The starch of 20～40% and/or bamboo fibre；The epoxy furane resins composition of 1～5%, this composite is maintaining on the basis of polylactic acid high strength and modulus advantage, has recyclability and completely biodegradable energy, complies fully with the sustainable expanding economy demand of green low-carbon.The preparation method that the invention also discloses this full bio-based degradable polylactic acid-base composite material: polylactic acid, starch and/or bamboo fibre are after drying, mix homogeneously with epoxy furane resins, through melt extruding, cooling down, after pelletize, obtain this full bio-based degradable polylactic acid-base composite material.This preparation method is simple, it is easy to controls and implements, workable, low production cost, and the composite prepared is highly suitable to be applied for the field such as disposable tableware and hotel's easily-consumed products.
Description
Technical field
The present invention relates to lactic acid composite material and preparation field thereof, be specifically related to a kind of full bio-based degradable polylactic acid-base composite material and preparation method thereof.
Background technology
Along with global economy is fast-developing, plastics have become the material that every field is indispensable.But, existing overwhelming majority plastics derive from oil and non-degradable, thus causing white pollution.It addition, the process means of petroleum-based plastics are mainly burning, this can aggravate greenhouse effect and haze weather significantly.Along with petroleum resources shortage, white pollution, greenhouse effect and haze weather are severe gradually, bio-based degradable high polymer material progressively receives the concern of people.In recent years, China, European Union member countries and the U.S. have promulgated that restriction uses disposable non-degradable plastic product measure all.Therefore, the environment-friendly and bio based high molecular material meeting green low-carbon economy development requirement has wide development space at disposable tableware and packaging field, will certainly will progressively substitute non-degradable petroleum base macromolecular material.
Polylactic acid (PLA) is thought the environment-friendly polymers of most industrialization prospect by business circles.This derives from the living resources such as Semen Maydis mainly due to polylactic acid thus possessing recyclability, and has the biodegradability of excellence and the mechanical mechanics property of similar polystyrene.But, price height is a key factor of the restriction extensive commercial application of polylactic acid.
Starch and bamboo fibre derive from biomass resource, have wide material sources, recyclability, biodegradable and cheap advantage.Therefore, starch and/or the filling-modified lactic acid composite material of bamboo fibre is utilized to have wide application space.But, the thermodynamic compatibility of starch and bamboo fibre and polylactic acid is poor, causes that this composite comprehensive mechanical property is poor.Adding diisocyanate acid esters coupling agent, silane coupler and maleic anhydride graft polylactic acid etc., lactic acid composite material carries out capacity increasing modifying is the most commonly used method.But, the bulking agent such as diisocyanate acid esters coupling agent, silane coupler and maleic anhydride graft polylactic acid exists that the little molecule of petroleum base is poisonous or the shortcoming such as expendable material toughness.
In recent years, utilize epoxidized vegetable oil that polylactic acid-base composite material capacity increasing modifying is subject to the concern of people gradually.The Chinese patent literature that publication number is CN103275472A discloses a kind of full bio-based hard lactic acid composite material and preparation method thereof, this full bio-based hard lactic acid composite material making by following weight percentage 60～80% polylactic acid, 10～31% maleic anhydride modified celluloses and 5～15% epoxidized vegetable oils.
And for example publication number is that CN103627154A discloses a kind of polylactic acid/starch Biobased degradable composite material and preparation method thereof, this polylactic acid/starch Biobased degradable composite material, by the polylactic acid of percentage by weight 30～94%, 0.1～10% phenols epoxide, 5～60% native starch, 0～1% antioxidant, the lubricant of 0～5%, the catalyst of 0～1% and 0～1% hydrolysis-resisting agent make.
Above-mentioned patent utilizes epoxidized vegetable oil increasing reaction polylactic acid-base composite material, is prepared for the full bio-based composite material of excellent combination property.But, the addition of epoxidized vegetable oil is higher, and is flexible little molecule, significantly sacrifices high intensity and the high-modulus of polylactic acid.
Summary of the invention
The invention provides and a kind of prepare simple, renewable, biodegradable and that there is high strength and modulus polylactic acid-base composite material.
A kind of full bio-based degradable polylactic acid-base composite material, is made up of the raw material of following percentage by weight:
Polylactic acid 55～79%；
Starch and/or bamboo fibre 20～40%；
Epoxy furane resins 1～5%.
Described polylactic acid can adopt the commercially available general trade mark, as preferably, described polylactic acid is transparent extrusion grade or injection grade, fusing point is 145～170 DEG C, melt index is 2～30g/10min, such as 4032D and the 3251D of U.S. Natureworks, positive biological REVODE110 and the REVODE210 etc. in sea, Zhejiang.The more preferably 4032D of U.S. Natureworks, relative to the polylactic acid of other trades mark, it is more excellent that the 4032D type polylactic acid of Natureworks enables to composite materials property.
What adopt in the present invention is native starch, at least one in corn starch, wheat and barley starch, sweet potato starch, potato starch, tapioca；Being preferably corn starch, relative to the native starch of other kind, corn starch source is more extensive, relative low price.
As preferably, described bamboo fibre is the natural bamboo fibres extracted from natural bamboo；Consider universality and the relative low price of Phyllostachys pubescens Mazei ex H.de Lebaie fiber, more preferably Phyllostachys pubescens Mazei ex H.de Lebaie fiber.
Epoxy furane resins are a kind of bio-based epoxide with stiffening ring structure, in described polylactic acid-base composite material, have the effect of compatilizer, plasticiser and lubricant concurrently.As preferably, the viscosity of described epoxy furane resins is 50～5000mPa.s, and density is 1.05～1.12g/cm3；The more preferably epoxy furane resins of Hebei Liang Kang International Trading Company Ltd, the compatibilization effect in the course of processing of the epoxy furane resins under above-mentioned performance parameter becomes apparent from, and has lubricity and the plasticity of excellence simultaneously.
It is preferred that, it is made up of the raw material of following percentage by weight:
Polylactic acid 65～70%；
Starch and/or bamboo fibre 25～30%；
Epoxy furane resins 2～3%.
Further preferably, it is made up of the raw material of following percentage by weight:
Polylactic acid 65～70%；
Starch and bamboo fibre 25～30%；
Epoxy furane resins 2～3%；
The mass ratio of described starch and bamboo fibre is 1:2～2:1.
Most preferably, it is made up of the raw material of following percentage by weight:
Described polylactic acid is the 4032D of U.S. Natureworks；
Described starch is corn starch；
Described bamboo fibre is Phyllostachys pubescens Mazei ex H.de Lebaie fiber；
Described epoxy furane resins are the epoxy furane resins of Hebei Liang Kang International Trading Company Ltd.
The preparation method that the invention also discloses described full bio-based degradable polylactic acid-base composite material, step is as follows:
Polylactic acid, starch and/or bamboo fibre after drying, are mixed homogeneously with epoxy furane resins, through melt extruding, cooling down, after pelletize, obtain described full bio-based degradable polylactic acid-base composite material.
As preferably, each raw material is extruded through double screw extruder, and the draw ratio of screw rod is 35:1～45:1, and extrusion temperature is 170～180 DEG C.
As preferably, the baking temperature of polylactic acid, starch and/or bamboo fibre is 105 DEG C, and drying time is 30min.
Compared with prior art, present invention have the advantage that
The present invention utilizes the epoxy furane resins containing stiffening ring structure to polylactic acid-base composite material reacting property increase-volume, promotes this polylactic acid-base composite material to have the mechanical mechanics property of high intensity, high-modulus, high tenacity and high impact properties.It addition, except increasing reaction effect, epoxy furane resins also have the effect of lubricant and plasticiser concurrently, thus improve the processing characteristics of this composite.
Polylactic acid-base composite material of the present invention has renewable and complete biodegradable environmental friendliness characteristic: each component derives from living resources, has recyclability；It addition, under microbial action, each component is all capable of being fast degraded, also there is the biodegradability of excellence.
Detailed description of the invention
Further describe the present invention by the following examples with comparative example, but the present invention is not limited to these embodiments.
Embodiment 1
Weigh the raw material of following weight:
Polylactic acid (4032D of U.S. Natureworks) 79Kg, corn starch (Xingmao Corn Development Co., Ltd., Zhucheng) 20Kg, epoxy furan (Hebei Liang Kang International Trading Company Ltd) 1Kg.
The preparation method of PLA/Starch Blends:
First, the polylactic acid of 79Kg and 20Kg corn starch are added high-speed mixer, at 105 DEG C of dry 30min, is subsequently adding 1kG epoxy furan, obtains mixed material；Then mixed material is added to melt blending in double screw extruder (extruder temperature is 170 DEG C-180 DEG C) tie rod afterwards, air-cooled, pelletizing, obtain granular composite material resin.The screw slenderness ratio of the double screw extruder selected is 40:1.
Embodiment 2
Weigh the raw material of following weight:
Polylactic acid (4032D of U.S. Natureworks) 67Kg, corn starch (Xingmao Corn Development Co., Ltd., Zhucheng) 30Kg, epoxy furan (Hebei Liang Kang International Trading Company Ltd) 3Kg.
Preparation method is as described in Example 1.
Embodiment 3
Weigh the raw material of following weight:
Polylactic acid (4032D of U.S. Natureworks) 55Kg, corn starch (Xingmao Corn Development Co., Ltd., Zhucheng) 40Kg, epoxy furan (Hebei Liang Kang International Trading Company Ltd) 5Kg.
Preparation method is as described in Example 1.
Embodiment 4
Weigh the raw material of following weight:
Polylactic acid (4032D of U.S. Natureworks) 67Kg, corn starch (Xingmao Corn Development Co., Ltd., Zhucheng) 20Kg, bamboo fibre (Hebei Jigao Fiber Co., Ltd) 10Kg, epoxy furan (Hebei Liang Kang International Trading Company Ltd) 3Kg.
Preparation method is as described in Example 1.
Comparative example 1
Weigh the raw material of following weight:
Polylactic acid (4032D of U.S. Natureworks) 70Kg, corn starch (Xingmao Corn Development Co., Ltd., Zhucheng) 30Kg.
Preparation method is as described in Example 1.
Comparative example 2
Weigh the raw material of following weight:
Polylactic acid (4032D of U.S. Natureworks) 67Kg, corn starch (Xingmao Corn Development Co., Ltd., Zhucheng) 30Kg, epoxy soybean oil (Aladdin reagent (China) company limited) 3Kg.
Preparation method is as described in Example 1.
Being standard tensile batten and impact batten by the biodegradable composite material injection mo(u)lding that embodiment 1～4 and comparative example 1～2 obtain, wherein, injection temperature is 175～185 DEG C, and injection pressure is 70～90MPa, and dwell pressure is 45MPa.Carrying out tensile property, bending property and notch impact strength test according to GB/T1040.2-2006, GB/T9341-2008 and GB/T1843-2008, its test result is as shown in table 1.
Table 1
As shown in Table 1, by embodiment 1～4 compared with comparative example 1～2, utilize the polylactic acid-base composite material of epoxy furane resins capacity increasing modifying to have the mechanical property of excellence, particularly maintain the high intensity of polylactic acid and the advantage of high-modulus.It addition, each component of this composite derives from living resources, there is recyclability and biodegradability, have great importance with solving white pollution to alleviating petroleum resources shortage.Therefore, this composite complies fully with green low-carbon expanding economy demand, has wide application space.
Claims (7)
1. a full bio-based degradable polylactic acid-base composite material, it is characterised in that be made up of the raw material of following percentage by weight:
Polylactic acid 55～79%；
Starch and/or bamboo fibre 20～40%；
Epoxy furane resins 1～5%.
2. full bio-based degradable polylactic acid-base composite material according to claim 1, it is characterised in that described polylactic acid is transparent extrusion grade or injection grade, and fusing point is 145～170 DEG C, and melt index is 2～30g/10min.
3. full bio-based degradable polylactic acid-base composite material according to claim 1, it is characterised in that described starch is at least one in corn starch, wheat and barley starch, sweet potato starch, potato starch, tapioca.
4. full bio-based degradable polylactic acid-base composite material according to claim 1, it is characterised in that described bamboo fibre is natural bamboo fibres.
5. full bio-based degradable polylactic acid-base composite material according to claim 1, it is characterised in that the viscosity of described epoxy furane resins is 50～5000mPa.s, and density is 1.05～1.12g/cm3。
6. the preparation method of a full bio-based degradable polylactic acid-base composite material according to claim 1, it is characterised in that step is as follows:
Polylactic acid, starch and/or bamboo fibre after drying, are mixed homogeneously with epoxy furane resins, through melt extruding, cooling down, after pelletize, obtain described full bio-based degradable polylactic acid-base composite material.
7. the preparation method of full bio-based degradable polylactic acid-base composite material according to claim 6, it is characterised in that each raw material is extruded through double screw extruder, and the draw ratio of screw rod is 35:1～45:1, and extrusion temperature is 170～180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510129952.8A CN104804387B (en) | 2015-03-24 | 2015-03-24 | A kind of full bio-based degradable poly lactic acid composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510129952.8A CN104804387B (en) | 2015-03-24 | 2015-03-24 | A kind of full bio-based degradable poly lactic acid composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104804387A CN104804387A (en) | 2015-07-29 |
| CN104804387B true CN104804387B (en) | 2016-07-06 |
Family
ID=53689602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510129952.8A Active CN104804387B (en) | 2015-03-24 | 2015-03-24 | A kind of full bio-based degradable poly lactic acid composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104804387B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161214A (en) * | 2018-08-15 | 2019-01-08 | 深圳市永尚环保包装材料有限责任公司 | A kind of composition and preparation method thereof and the application in degradable dinner set field |
| CN110016217A (en) * | 2019-04-30 | 2019-07-16 | 封金财 | A kind of preparation method of degradable agricultural composite plastic mulch |
| CN112961474B (en) * | 2021-02-04 | 2022-07-22 | 衡阳市力达康医疗器械有限公司 | Preparation method of polylactic acid/epoxy vegetable oil all-bio-based composite material |
| CN113278272A (en) * | 2021-06-04 | 2021-08-20 | 四川宽窄纸品有限责任公司 | Plant cellulose-based full-biodegradable material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348560A (en) * | 2008-08-29 | 2009-01-21 | 中山大学 | Epoxide resin containing furan group and preparation thereof |
| CN102952253A (en) * | 2012-11-01 | 2013-03-06 | 中国科学院宁波材料技术与工程研究所 | Epoxy resin based on 2,5-furandicarboxylic acid, preparation method and application thereof |
| CN104387733A (en) * | 2014-11-18 | 2015-03-04 | 四川大学 | Biodegradable toughened heat-resistant polylactic acid modified resin and preparation method thereof |
-
2015
- 2015-03-24 CN CN201510129952.8A patent/CN104804387B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348560A (en) * | 2008-08-29 | 2009-01-21 | 中山大学 | Epoxide resin containing furan group and preparation thereof |
| CN102952253A (en) * | 2012-11-01 | 2013-03-06 | 中国科学院宁波材料技术与工程研究所 | Epoxy resin based on 2,5-furandicarboxylic acid, preparation method and application thereof |
| CN104387733A (en) * | 2014-11-18 | 2015-03-04 | 四川大学 | Biodegradable toughened heat-resistant polylactic acid modified resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104804387A (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103146160B (en) | Complete biodegradable composition and method of making the same | |
| EP2586821B1 (en) | Degradable starch-based plastic masterbatch and preparation method thereof | |
| CN103131150B (en) | Polypropylene/polylactic acid/starch composite material and preparation method thereof | |
| US9650475B2 (en) | Thermoplastic starch composition derivatives from agricultural byproducts | |
| CN104804387B (en) | A kind of full bio-based degradable poly lactic acid composite and preparation method thereof | |
| CN104072957B (en) | A kind of food grade biodegradable polylactic acid based composites and application thereof | |
| CN103113727B (en) | A kind of completely biological degradation polylactic acid matrix material and its preparation method and application | |
| CN101525487B (en) | Composite material degraded by environment and preparation method thereof | |
| CN103627154B (en) | A kind of polylactic acid/starch Biobased degradable composite material and preparation method thereof | |
| Castaño et al. | Physical, chemical and mechanical properties of pehuen cellulosic husk and its pehuen-starch based composites | |
| CN112029154A (en) | Biodegradable material and preparation method thereof | |
| CN105273377A (en) | Biodegradable material and preparation method and use thereof | |
| CN105219044A (en) | A kind of complete biodegradable heat-proof polylactic acid foam material and preparation method thereof | |
| CN104788920A (en) | Full-biodegradable composite material having high strength and high modulus as well as formula and preparation method of full-biodegradable composite material | |
| CN102321354A (en) | A kind of plasticizing polylactic acid/composite polyethylene material and preparation method thereof | |
| CN105295111A (en) | Total biomass composite injection moulding material and preparation method thereof | |
| CN105585759A (en) | Full-biomass composite plastic and preparing method thereof | |
| CN102250389B (en) | Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof | |
| CN107312295B (en) | A kind of lactic acid composite material and preparation method thereof of high transparency low cost | |
| CN105254976A (en) | Biomass lamination material for lamination paper and preparation method thereof | |
| CN105061971A (en) | Method for preparing completely-degradable composite material through acid anhydride and microcrystalline cellulose synergetic modification on poly(propylene carbonate) | |
| CN102702655B (en) | Polyvinyl alcohol/high amylose biodegradable material and melting preparation method thereof | |
| CN104151774B (en) | A kind of organosilicon-polyvinyl alcohol double degradation plastic film formula and preparation method thereof | |
| CN103102657B (en) | Biodegradable blend and preparation method and application thereof | |
| CN107177074A (en) | A kind of high-strength wood plastic composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |