CN105038163A - Fully-biodegradable material as well as preparation method and application thereof - Google Patents
Fully-biodegradable material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fully-biodegradable material as well as a preparation method and application thereof. The fully-biodegradable material is prepared from the following raw materials in percentage by weight: 15%-70% of polylactic acid, 20%-50% of starch, 3%-65% of a copolymer of butanediol adipate and butanediol terephthalate, 1%-10% of polylactide polyol, 0.1%-5% of a titanate coupling agent and 0-5% of an aid. The fully-biodegradable material has excellent mechanical property, can be biologically degraded and is relatively low in cost. The preparation method can be easily implemented by virtue of existing high-speed mixing equipment and double-screw extruders. The fully-biodegradable material has excellent and stable performance, can be biologically degraded, is relatively low in cost and is applicable to the fields of plastic packaging materials, agricultural plastic mulching films, disposable tableware and the like.
Description
Technical field
The present invention relates to full-biodegradable material technical field, be specifically related to a kind of full-biodegradable material and its preparation method and application.
Background technology
Plastics industry develops rapidly, and plastics have been widely used in the every field of national economy, and purposes is very extensive.But, the consequent is the generation (the annual waste plastic produced of such as China is about 5,000,000 tons) of a large amount of waste plastic, wherein most of waste plastic is polypropylene (PP), polyethylene (PE) and polystyrene (PS) material, these materials can not natural decomposition, therefore, by PP material, PE material, the disposable plastic wrapping material that PS material is made, the product such as agricultural film and disposable tableware is after using, if its waste is arbitrarily abandoned, will be deposited on soil because of its nondegradation, thus cause serious white pollution, and this white pollution will aggravate along with the increase of usage quantity and the accumulation of time.
Along with improving constantly of people's environmental consciousness, biodegradable environment-friendly material receives increasing concern, in recent years people be devoted to research and develop can the degradation material of substituted for plastic, to solve white pollution problems, and slow down the consumption of oil.But, the degradation material of real meaning is as poly(lactic acid) (PLA), polyhydroxyalkanoate (PHA), poly butylene succinate (PBS) etc. at present, price is very expensive, and performance comparatively conventional plastic (as polypropylene PP and polythene PE) have certain gap, cause its traction in recent years not high.
Application publication number is that the Chinese invention patent application of CN103881211A (application number is 201410101063.6) discloses a kind of biodegradable plastic, comprises the component raw material of following weight part: polyethylene 100 parts, acrylic resin 60 ~ 80 parts, starch 30 ~ 55 parts, poly(lactic acid) 15 ~ 25 parts, titanate coupling agent 1 ~ 2.5 part, antiseptic-germicide 0.08 ~ 1.2 part, 1 ~ 3 part, softening agent, 0.2 ~ 15 part, oxidation inhibitor, stearic acid 0.5 ~ 1 part.This technical scheme, by adding starch, poly(lactic acid) and the auxiliary chemicals such as coupling agent, antiseptic-germicide in polyethylene, acrylic resin, makes plastics mechanical property of the present invention good, biodegradable, reduces bacteria breed, protection of the environment.But this plastic body material is still non-degradable material, still can cause white pollution to a certain extent.
Application publication number is that the Chinese invention patent application of CN103627154A (application number is 201310532786.7) discloses a kind of polylactic acid/starch Biobased degradable composite material, is made up: poly(lactic acid) 30% ~ 94%, phenols epoxy compounds 0.1% ~ 10%, native starch 5% ~ 60%, oxidation inhibitor 0% ~ 1%, lubricant 0% ~ 5%, catalyzer 0% ~ 1% and hydrolysis-resisting agent 0% ~ 1% of the raw material of following weight percent.This technical scheme adds phenols epoxy compounds in poly(lactic acid) base-material, the special molecular structure of poly(lactic acid), phenols epoxy compounds and native starch three can be impelled to combine, thus improve the mechanical property of this polylactic acid/starch Biobased degradable composite material, on the other hand, directly native starch is added in poly(lactic acid) base-material, can reduce the cost of material to a certain extent, but it is still containing certain non-degradable composition.
Summary of the invention
The invention provides a kind of full-biodegradable material and its preparation method and application, this full-biodegradable material excellent in mechanical performance, biodegradable, and price is lower.
The technical scheme adopted is as follows:
A kind of full-biodegradable material, be made up of the raw material of following weight percentage:
In the present invention, material based on the multipolymer (PBAT) of poly(lactic acid) (PLA), tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, add starch filler, polylactide polyol and titanate coupling agent is utilized to improve interface compatibility between PLA, PBAT and starch, thus increase substantially the mechanical property of this matrix material: on the one hand, under the initiation of titanate coupling agent, the hydroxyl of polylactide polyol and the hydroxyl generation chelate effect on starch surface; On the other hand, polylactide polyol and PLA and PBAT have good consistency, therefore, have good consistency in full-biodegradable material of the present invention between each component, thus ensure that the mechanical property of this material; In addition, polylactide polyol also has excellent nucleating effect for poly(lactic acid), can effective shortening forming time, and improves the resistance toheat of product.
In full-biodegradable material of the present invention, the content of each component can be selected according to practical situation, the words that poly(lactic acid) content is high, shock strength is better, the words that the multipolymer content of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester is high, elongation at break is better, can adjust according to suitable application area.
As preferably, described full-biodegradable material, be made up of the raw material of following weight percentage:
Further preferably, described full-biodegradable material, be made up of the raw material of following weight percentage:
Under this weight percentage, this material impact intensity is better, is more suitable for for the preparation of disposable tableware etc.
Further preferably, described full-biodegradable material, be made up of the raw material of following weight percentage:
Under this weight percentage, this Materials Fracture elongation is better, is more suitable for for the preparation of Plastic Packaging Materials, agricultural mulching etc.
Further preferred, described full-biodegradable material, be made up of the raw material of following weight percentage:
Under this weight percentage, this material impact intensity is best.
Described poly(lactic acid) can adopt commercially available general poly(lactic acid), and the model that the model of producing as Natureworks company is the product of 4032D, the model of Natureworks company production is the product of 3251D, Zhejiang Hai Zheng company produces is the product of REVODE101, the model of Zhejiang Hai Zheng company production is the product etc. of REVODE110.
Described native starch is one or more (comprising two kinds) in W-Gum, tapioca (flour), sweet potato starch, sweet potato starch, yam starch.
Described tetramethylene adipate and the multipolymer of mutual-phenenyl two acid bromide two alcohol ester, also i.e. poly-(tetramethylene adipate-mutual-phenenyl two acid bromide two alcohol ester), can adopt commercially available prod, as the PBAT that prosperous rich medicine company is produced.
Described polylactide polyol is L-type, D type or both blends, can adopt commercially available prod, and the model of producing as Shenzhen City Guanghua Weiye Industry Co., Ltd is the product of D-PLA220B.
Titanate coupling agent also can adopt commercially available prod, and the model as adopted Nanjing You Pu Chemical Co., Ltd. to produce is the product of UP-311W.
Described auxiliary agent is oxidation inhibitor, lubricant etc.
Full-biodegradable material of the present invention had both had excellent and stable performance, be applicable to the fields such as Plastic Packaging Materials, agricultural mulching and disposable tableware, with this full-biodegradable material for starting material, by existing processing technology, Plastic Packaging Materials, agricultural mulching and disposable tableware etc. can be produced.
Present invention also offers a kind of preparation method of full-biodegradable material, adopt existing high-speed mixing equipment and twin screw extruder to realize, easy to implement.
A preparation method for full-biodegradable material, comprises the following steps:
1) first by the multipolymer drying treatment (preferably drying treatment 20 ~ 40min at 100 DEG C ~ 110 DEG C) of poly(lactic acid), starch and tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, then add polylactide polyol and titanate coupling agent and mix, obtaining mixture;
2) mixture is joined melt blending in twin screw extruder, through air-cooled and granulation, obtain full-biodegradable material.
As preferably, the screw slenderness ratio of described twin screw extruder is 35 ~ 45:1, and the temperature of melt blending is 130 ~ 180 DEG C, and the screw slenderness ratio being preferably twin screw extruder is 40:1; The temperature of melt blending is 160 ~ 175 DEG C.
Compared with prior art, tool of the present invention has the following advantages:
One, full-biodegradable material of the present invention, polylactide polyol and titanate coupling agent is utilized to improve interface compatibility between PLA, PBAT and starch, thus increase substantially the mechanical property of this matrix material: on the one hand, under the initiation of titanate coupling agent, the hydroxyl of polylactide polyol and the hydroxyl generation chelate effect on starch surface; On the other hand, polylactide polyol and PLA and PBAT have good consistency, therefore, have good consistency in full-biodegradable material of the present invention between each component, thus ensure that the mechanical property of this material; In addition, polylactide polyol also has excellent nucleating effect for poly(lactic acid), can effective shortening forming time, and improves the resistance toheat of product.
Two, in full-biodegradable material of the present invention, main component starch, PLA, PBAT and polylactide polyol are all biodegradable, full-biodegradable material of the present invention is made to have good degradation property, its waste finally can by the microbial decomposition in soil and absorption, environmental pollution is little, has good environmental benefit and social value;
Three, in full-biodegradable material of the present invention, starch content is higher, because its price is comparatively cheap, particularly native starch more cheap, be easy to obtain, be conducive to reducing the cost of full-biodegradable material;
Four, full-biodegradable material preparation of the present invention is simple, easy to implement, is easy to operate and control, is easy to suitability for industrialized production, is conducive to the cost reducing full-biodegradable material.
In sum, full-biodegradable material of the present invention had both had excellent and stable performance, biodegradable again, and cost is low, well takes into account economic benefit and environmental benefit, has broad application prospects.Full-biodegradable material of the present invention is applicable to the fields such as Plastic Packaging Materials, agricultural mulching and disposable tableware, with this full-biodegradable material for starting material, by existing processing technology, can produce Plastic Packaging Materials, agricultural mulching and disposable tableware etc.
Embodiment
Embodiment 1
First, take the raw material of following weight part: poly(lactic acid) (Natureworks4032D) 60 weight part, W-Gum (National Starch) 30.5 weight part, multipolymer (prosperous rich medicine company) 6 weight parts of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, polylactide polyol (Shenzhen City Guanghua Weiye Industry Co., Ltd, D-PLA220B) 3 weight parts, titanate coupling agent (Nanjing You Pu Chemical Co., Ltd., UP-311W) 0.5 weight part.
Preparation process is as follows: utilize high-speed mixing equipment first by multipolymer drying treatment 30min at 105 DEG C of poly(lactic acid), starch and tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester; Then add polylactide polyol and titanate coupling agent and mix, obtaining mixture; Again mixture is joined melt blending in twin screw extruder; Finally by air-cooled and granulation, obtain full-biodegradable material.The screw slenderness ratio of twin screw extruder is 40:1; The temperature of melt blending is 160 ~ 175 DEG C.
Embodiment 2
First, take the raw material of following weight part: poly(lactic acid) (Natureworks4032D) 40 weight part, W-Gum (National Starch) 44.5 weight part, multipolymer (prosperous rich medicine company) 10 weight parts of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, polylactide polyol (Shenzhen City Guanghua Weiye Industry Co., Ltd, D-PLA220B) 5 weight parts, titanate coupling agent (Nanjing You Pu Chemical Co., Ltd., UP-311W) 0.5 weight part.
Preparation process is as embodiment 1.
Embodiment 3
First, take the raw material of following weight part: poly(lactic acid) (Natureworks4032D) 17 weight part, W-Gum (National Starch) 30 weight part, multipolymer (prosperous rich medicine company) 49.5 weight parts of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, polylactide polyol (Shenzhen City Guanghua Weiye Industry Co., Ltd, D-PLA220B) 3 weight parts, titanate coupling agent (Nanjing You Pu Chemical Co., Ltd., UP-311W) 0.5 weight part.
Preparation process is as embodiment 1.
Embodiment 4
First, take the raw material of following weight part: poly(lactic acid) (Natureworks4032D) 27 weight part, W-Gum (National Starch) 30 weight part, multipolymer (prosperous rich medicine company) 39.5 weight parts of tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, polylactide polyol (Shenzhen City Guanghua Weiye Industry Co., Ltd, D-PLA220B) 3 weight parts, titanate coupling agent (Nanjing You Pu Chemical Co., Ltd., UP-311W) 0.5 weight part.
Preparation process is as embodiment 1.
Comparative example 1
Adopt the polylactide polyol in compatilizer PLA-g-MAH (percentage of grafting 0.8%) alternative embodiment 1, other are with embodiment 1.
Comparative example 2
Adopt the polylactide polyol in compatilizer PLA-g-MAH (percentage of grafting 0.8%) alternative embodiment 3, other are with embodiment 3.
The biodegradable material that the full-biodegradable material obtain above-described embodiment 1 ~ 4 and comparative example 1 ~ 2 obtain is added to injection moulding in injection moulding machine (injection moulding district temperature 175 DEG C, template region temperature 25 DEG C) respectively, obtains each group of standard batten respectively.Carry out stretching experiment and impact property test (5 groups of experiments are averaged) according to GB/T1040.2-2006 and GB/T1043.1-2008 respectively to each group of sample, its test result is as shown in table 1.
Table 1
Visible, utilize polylactide polyol and titanate coupling agent to improve interface compatibility between PLA, PBAT and starch, thus increase substantially the mechanical property of this matrix material.
Above-mentioned standard batten at 100 DEG C of baking 5h, then carries out stretching experiment and impact property test (5 groups of experiments are averaged) according to GB/T1040.2-2006 and GB/T1043.1-2008 to each group of sample respectively, and its test result is as shown in table 2.
Table 2
Visible, polylactide polyol also has excellent nucleating effect for poly(lactic acid), can effective shortening forming time, and improves the resistance toheat of product.
Claims (10)
1. a full-biodegradable material, is characterized in that, is made up of the raw material of following weight percentage:
2. full-biodegradable material according to claim 1, is characterized in that, is made up of the raw material of following weight percentage:
3. full-biodegradable material according to claim 1, is characterized in that, is made up of the raw material of following weight percentage:
4. full-biodegradable material according to claim 3, is characterized in that, is made up of the raw material of following weight percentage:
5. full-biodegradable material according to claim 1, is characterized in that, is made up of the raw material of following weight percentage:
6. the full-biodegradable material according to any one of Claims 1 to 5, is characterized in that, described native starch is one or more in W-Gum, tapioca (flour), sweet potato starch, sweet potato starch, yam starch.
7. the preparation method of the full-biodegradable material according to any one of claim 1 ~ 6, is characterized in that, comprises the following steps:
1) first by drying treatment under the multipolymer of poly(lactic acid), starch and tetramethylene adipate and mutual-phenenyl two acid bromide two alcohol ester, then add polylactide polyol and titanate coupling agent and mix, obtaining mixture;
2) mixture is joined melt blending in twin screw extruder, through air-cooled and granulation, obtain full-biodegradable material.
8. the preparation method of full-biodegradable material according to claim 7, is characterized in that, step 1) in, drying treatment 20 ~ 40min at 100 DEG C ~ 110 DEG C.
9. the preparation method of full-biodegradable material according to claim 7, is characterized in that, step 2) in, the screw slenderness ratio of described twin screw extruder is 35 ~ 45:1, and the temperature of melt blending is 130 ~ 180 DEG C.
10. the full-biodegradable material according to any one of claim 1 ~ 6 is preparing the application in Plastic Packaging Materials, agricultural mulching and disposable tableware.
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| CN106995519A (en) * | 2016-01-25 | 2017-08-01 | 万华化学集团股份有限公司 | A kind of thermoplastic polyurethane and its production and use |
| CN108276745A (en) * | 2018-02-05 | 2018-07-13 | 东莞市鑫海环保材料有限公司 | Biodegradable packaging material and preparation method thereof |
| CN108276744A (en) * | 2018-02-05 | 2018-07-13 | 东莞市鑫海环保材料有限公司 | A kind of new bio degradable material film and preparation method thereof |
| CN108285622A (en) * | 2018-02-05 | 2018-07-17 | 东莞市鑫海环保材料有限公司 | Biodegradable material and preparation method thereof |
| CN110845830A (en) * | 2019-11-13 | 2020-02-28 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
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- 2015-08-19 CN CN201510510680.6A patent/CN105038163A/en active Pending
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| CN106995519B (en) * | 2016-01-25 | 2019-09-20 | 万华化学集团股份有限公司 | A kind of thermoplastic polyurethane and its preparation method and application |
| CN108276745A (en) * | 2018-02-05 | 2018-07-13 | 东莞市鑫海环保材料有限公司 | Biodegradable packaging material and preparation method thereof |
| CN108276744A (en) * | 2018-02-05 | 2018-07-13 | 东莞市鑫海环保材料有限公司 | A kind of new bio degradable material film and preparation method thereof |
| CN108285622A (en) * | 2018-02-05 | 2018-07-17 | 东莞市鑫海环保材料有限公司 | Biodegradable material and preparation method thereof |
| CN112409644A (en) * | 2019-08-23 | 2021-02-26 | 佛山市加翔环保新材料科技有限公司 | High-temperature-resistant PBAT/PLA full-biodegradable material |
| CN110845830A (en) * | 2019-11-13 | 2020-02-28 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
| CN110845830B (en) * | 2019-11-13 | 2022-04-26 | 青岛润兴塑料新材料有限公司 | Starch filled PLA/PBAT full-biodegradable composite material and preparation method thereof |
| CN111154244A (en) * | 2020-01-23 | 2020-05-15 | 海南明宸新材料有限公司 | Full-biodegradable balloon bottom support and preparation method thereof |
| CN111621239A (en) * | 2020-05-16 | 2020-09-04 | 中国科学院理化技术研究所 | Full-biodegradable adhesive tape and preparation method thereof |
| CN113563730A (en) * | 2021-07-28 | 2021-10-29 | 杭州靡特洛新材料科技有限公司 | Ultrafine filler and fully-degradable composite material for vinasse protein purification residues, and preparation method and application thereof |
| CN114479198A (en) * | 2021-12-13 | 2022-05-13 | 肖华蓉 | Starch-based degradable plastic film and preparation method thereof |
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