CN1422899A - Natural vegetable fiber reinforced fully-degradable polymer composite material and preparation method thereof - Google Patents
Natural vegetable fiber reinforced fully-degradable polymer composite material and preparation method thereof Download PDFInfo
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- CN1422899A CN1422899A CN 02149613 CN02149613A CN1422899A CN 1422899 A CN1422899 A CN 1422899A CN 02149613 CN02149613 CN 02149613 CN 02149613 A CN02149613 A CN 02149613A CN 1422899 A CN1422899 A CN 1422899A
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Abstract
The invention refers to a full-degradable polymer composite material strengthened by the natural plant fiber and the preparing method. It adopts India plant fiber-Hildegardia populifolia, sisal fiber, ramee, wood fibre and so on as the fiber raw material, tand the degradable plastic-the poly-methyl ethyl carbonic acid resin as the basic body, and smelts and commixes the filling and the basic body on the existent/nonexistent condition of the coupling agent to make the composite material. The weight percent content of the fiber is 5-80%, the better fiber 10-40%.
Description
Technical field
The present invention relates to polymer composites that the natural plant fibre enhanced can degrade fully and preparation method thereof.
Background technology
Synthon strengthen polymer matrix composites and are widely used in a lot of fields with good characteristics such as its distinctive light weight, intensity height.In recent years; minimizing day by day in the face of Nonrenewable resources such as oil; a series of problems such as energy dilemma and environment compatibility; adopt natural plant fibre to substitute synthon and more and more cause people's attention (A.K.Bledzki as the strongthener in the matrix material; J.Gassen; in:Handbook of Engineering Polymeric Materials; editedby N.P.Cheremisinoss; Marcel Dekker; New York; 1997; p.787-810); but owing to be difficult to natural degradation as the general resin of matrix, in fact therefore general vegetable fibre strengthens polymer matrix composites fails to reach the purpose that nature is degraded fully, still environment is threatened.
Summary of the invention
The purpose of this invention is to provide a kind of natural plant fibre matrix material and preparation method thereof, this matrix material can be realized complete natural degradation when improving performance, and technology is simple, and is applied widely.
The invention provides a kind of natural plant fibre enhanced, the polymer composites that can degrade fully, this matrix material is to be matrices of composite material with degradable lined polymethyl ethylene carbonate, with the strongthener of natural plant fibre as matrix material, the weight percentage of natural plant fibre is 5-80% in the matrix material, prepares matrix material through melt blending.Vegetable fibre as strongthener is a natural plant fibre, wherein fiber can be India vegetable fibre Hildegardiapopulifolia, sisal fibers, ramee, jute fibre, hemp fibre, flax fiber, abaca fibre, coir fibre, xylon and/or their mixture.
Specially suitable is India vegetable fibre Hildegardia populifolia, sisal fibers, ramee, wood powder etc.India vegetable fibre Hildegardia populifolia is the flexible fiber of phloem tissue of the branch of source a kind of trees of originating in India.Sisal fibers is the hard fiber that is become " sisal hemp hemp " of taking from the flexible fiber in the leaf that grows to 2m of sisal hemp Agave or being used to produce rope, brush etc.; Ramee can obtain from the ramie plant that is derived from China, Japan and South East Asia, and China is still maximum in the world sisal hemp and ramie production base so far.Timber scrap stock that xylon is inexpensive especially, amount is big and low-grade wood utilize direction again.
The aliphatic polycarbonate lined polymethyl ethylene carbonate is a kind of environment-friendly material, it is the complete alternating copolymer of carbonic acid gas and propylene oxide, carbonic acid gas structure weight percentage in its backbone structure is 43%, the preparation process of lined polymethyl ethylene carbonate is exactly one and consumes greenhouse gases, alleviates the process of topsoil.The ester bond structure of the main chain of lined polymethyl ethylene carbonate is given its degradable characteristic again.Strengthen the lined polymethyl ethylene carbonate resin with natural plant fibre, can improve the mechanical property of polymkeric substance, can not cause negatively influencing to the degradation property of described polymkeric substance and have.
According to the inventive method, the natural plant fibre that adds about 10-50% weight in the degradable polyalcohol group body is relatively good, certainly also can in polymkeric substance, add more natural plant fibre, yet this needs very high shearing force fiber could be joined in the polymkeric substance on the one hand, and high shear force will cause the polymer matrix material degraded on the other hand, and mechanical property worsens.
For the natural plant fibre strongthener, natural plant fibre can be directly used in this composite system, also can remove baregin and hemicellulose by known biochemical process and chemical method combination.The length of natural plant fibre is about 0.08-5mm.Usually with the mixed with polymers equipment that uses in the plastics technology, carry out melt blending as single screw rod, twin screw extruder or kneader.When adding to natural plant fibre in the degradable polymer matrix by proportioning, mixture temperature should guarantee that polymeric matrix do not degrade, and generally carries out melt blending at 130～200 ℃.Reasonable melt blending temperature is 150～180 ℃.
When the preparation strongthener, also can use coupling agent, lubricant, filler, pigment, forming agent, whipping agent etc.
It is strongthener that the present invention adopts aboundresources, cheap natural plant fibre, is matrices of composite material with the degradable polymer lined polymethyl ethylene carbonate, prepares matrix material through melt blending.Technology of the present invention is simple, use range is wide, the weight content of natural plant fibre can be controlled in 10-50% in the product, have higher intensity and modulus, and natural plant fibre and body material be degradable all, thereby the matrix material of gained finally can natural degradation, is a kind of matrix material of novel Sustainable development.It is a kind of degradable high polymer material with applications well prospect that this patent method utilizes efficient catalyst to prepare lined polymethyl ethylene carbonate, and cost and common plastics are approaching.Low-molecular-weight lined polymethyl ethylene carbonate appears in the newspapers as the research patent of processing aid, whipping agent, seal gum, but the preparation of lined polymethyl ethylene carbonate/vegetable fibre reinforced composite still belongs to blank, the degradation property of this type of matrix material is not because filler is additional separately, but the synergy of filler and matrix, make prepared matrix material material environmental protection, " no white pollution ".
Embodiment
Embodiment 1-2
The composition and the performance of matrix material are as shown in table 1.With untreated India vegetable fibre Hildegardia populifolia and lined polymethyl ethylene carbonate in melting mixing equipment, at 180 ℃, mixing revolution 35-180rrpm, mixing time 5min, carry out melt blending and prepare degradable composite material, the matrix material of gained carries out Mechanics Performance Testing with compression molding instrument compressing tablet by the standard sample preparation of ISO 527-2, and the intensity of staple fibre strongthener and modular ratio body material are greatly improved as can be seen from Table 1.
Embodiment 3-4
The composition and the performance of matrix material are as shown in table 1.Untreated India vegetable fibre Hildegardia populifolia and lined polymethyl ethylene carbonate are added the silane coupling agent of fiber consumption 0.1% weight again, in melting mixing equipment, at 180 ℃, mixing revolution 35-180rrpm, mixing time 5min, carry out melt blending and prepare degradable composite material, the matrix material of gained compression molding instrument compressing tablet, Mechanics Performance Testing is carried out in standard sample preparation by ISO 527-2, and the intensity of staple fibre strongthener and modular ratio body material are greatly improved as can be seen from Table 1.
Embodiment 5-9
With the India vegetable fibre Hildegardia populifolia of 2%NaOH solution-treated and lined polymethyl ethylene carbonate in melting mixing equipment, at 180 ℃, mixing revolution 35-180rrpm, mixing time 5min, carry out melt blending and prepare degradable composite material, the matrix material of gained carries out Mechanics Performance Testing with compression molding instrument compressing tablet by the standard sample preparation of ISO 527-2, and the composition and the performance of matrix material are as shown in table 2.The intensity of staple fibre strongthener and modular ratio body material are greatly improved as can be seen from Table 2.
Embodiment 10
The composition and the performance of matrix material are as shown in table 3.With sisal fibers and lined polymethyl ethylene carbonate in melting mixing equipment, at 170 ℃, mixing revolution 35-180rrpm, mixing time 10min, carry out melt blending and prepare degradable composite material, the matrix material of gained carries out Mechanics Performance Testing with compression molding instrument compressing tablet by the standard sample preparation of ISO 527-2, and the intensity of staple fibre strongthener and modular ratio body material are greatly improved as can be seen from Table 3.
Embodiment 11
The composition and the performance of matrix material are as shown in table 3.With ramee and lined polymethyl ethylene carbonate in melting mixing equipment, at 150 ℃, mixing revolution 35-180rrpm, mixing time 5min, carry out melt blending and prepare degradable composite material, the matrix material of gained carries out Mechanics Performance Testing with compression molding instrument compressing tablet by the standard sample preparation of ISO 527-2, and the intensity of staple fibre strongthener and modular ratio body material are greatly improved as can be seen from Table 3.
Embodiment 12
With wood powder and lined polymethyl ethylene carbonate in melting mixing equipment, at 160 ℃, mixing revolution 35-180rrpm, mixing time 10min, carry out melt blending and prepare degradable composite material, the matrix material of gained carries out Mechanics Performance Testing with compression molding instrument compressing tablet by the standard sample preparation of ISO 527-2, and the composition and the performance of matrix material are as shown in table 3.The intensity of staple fibre strongthener and modular ratio body material have the raising of certain amplitude as can be seen from Table 3.
Embodiment 1～12 just enumerates is used for example that the present invention is described in more detail, and also available other fiber such as jute fibre, hemp fibre, flax fiber, abaca fibre, coir fibre and/or their mixture substitutes India vegetable fibre Hildegardia populifolia, sisal fibers, ramee, xylon etc.Essence of the present invention is, self degradable polymer matrix can be owing to toughener loses its degradability, by sneaking into degradable natural plant fibre, as India vegetable fibre Hildegardia populifolia, sisal fibers, ramee, xylon etc., make polymer composites present significant enhancement, and do not lose degradability, the matrix material of being degraded fully.
Table 1 the be untreated composition and the performance of India vegetable fibre Hildegardia populifolia matrix material
| Embodiment | Fiber consumption, weight % | The coupling agent consumption, weight % | Yield strength, MPa | Young's modulus, MPa |
| Matrix | Do not have | Do not have | ????18.374 | ????840.493 |
| ????1 | ????20 | Do not have | ????32.372 | ????2270.814 |
| ????2 | ????40 | Do not have | ????34.455 | ????3037.920 |
| ????3 | ????20 | ????0.1 | ????34.890 | ????2290.493 |
| ????4 | ????40 | ????0.1 | ????36.980 | ????3050.290 |
The composition and the performance of table 2 alkaline purification India vegetable fibre Hildegardia populifolia matrix material
| Embodiment | Fiber consumption, weight % | Yield strength, MPa | Young's modulus, MPa |
| Matrix | Do not have | ????18.374 | ????840.493 |
| ????5 | ????10 | ????27.458 | ????1594.641 |
| ????6 | ????20 | ????30.402 | ????2250.374 |
| ????7 | ????30 | ????31.888 | ????2632.080 |
| ????8 | ????40 | ????35.240 | ????3034.173 |
| ????9 | ????50 | ????32.290 | ????3430.655 |
The composition and the performance of other natural plant fibre matrix materials of table 3
| Embodiment | Kinds of fibers | Fiber consumption, weight % | Yield strength, MPa | Young's modulus, MPa |
| Matrix | Do not have | Do not have | ????18.374 | ????840.493 |
| ????10 | Sisal hemp | ????20 | ????32.240 | ????2250.814 |
| ????11 | Ramie | ????20 | ????30.888 | ????2200.080 |
| ????12 | Wood powder | ????20 | ????29.118 | ????1640.974 |
Claims (5)
1, a kind of natural plant fibre matrix material, it is characterized in that with degradable lined polymethyl ethylene carbonate be matrices of composite material, with the strongthener of natural plant fibre as matrix material, the weight percentage of natural plant fibre is 5-80% in the matrix material.
2, according to the described natural plant fibre matrix material of claim 1, the content that it is characterized in that natural plant fibre in the matrix material is 10-50%.
3, according to claim 1 or 2 described natural plant fibre matrix materials, the length that it is characterized in that natural plant fibre in the matrix material is the staple fibre of 0.08-5mm.
4, a kind of method for preparing natural plant fibre matrix material as claimed in claim 1, it is characterized in that in the mixed with polymers equipment commonly used in plastics technology, with degradable aliphatic polycarbonate lined polymethyl ethylene carbonate and the natural plant fibre melting mixing of pressing proportioning weight, temperature is 130～200 ℃.
5, a kind of preparation method of natural mineral filler composite materials as claimed in claim 4, the temperature that it is characterized in that melting mixing is 150～180 ℃.
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| CNB021496137A CN1171951C (en) | 2002-12-12 | 2002-12-12 | Natural vegetable fiber reinforced fully-degradable polymer composite material and preparation method thereof |
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| CNB021496137A CN1171951C (en) | 2002-12-12 | 2002-12-12 | Natural vegetable fiber reinforced fully-degradable polymer composite material and preparation method thereof |
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| CN1422899A true CN1422899A (en) | 2003-06-11 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297606C (en) * | 2005-03-23 | 2007-01-31 | 中山大学 | Whole-degradable polymethyl ethylene carbonate foamed materials and process for preparing same |
| CN100383080C (en) * | 2006-08-25 | 2008-04-23 | 武汉科技学院 | Regenerated plastic base sisal hemp fiber reinforced construction mould plate and its processing method |
| CN101798465A (en) * | 2010-03-16 | 2010-08-11 | 龙海市奈特化工有限责任公司 | Composite material capable of releasing volatile substances persistently and preparation method thereof |
| CN101824227B (en) * | 2009-03-06 | 2011-09-14 | 西南科技大学 | Thermoplastic plant fiber/carbon dioxide-based plastic blending material and preparation method thereof |
| CN101302310B (en) * | 2008-06-26 | 2012-11-07 | 东华大学 | Preparation of fibrilia-reinforced cellulose ester-based composite material |
| CN102977460A (en) * | 2012-12-12 | 2013-03-20 | 奇瑞汽车股份有限公司 | Injecting molding grade natural fiber composite material and preparation method thereof |
| CN103946315A (en) * | 2011-11-15 | 2014-07-23 | 芬欧汇川集团 | A composite product, a method for manufacturing a composite product and its use, a material component and a final product |
| CN105647150A (en) * | 2016-04-12 | 2016-06-08 | 湖州新奥克化工有限公司 | Preparation method of polypropylene-carbonate-base composite material |
| CN106752007A (en) * | 2016-12-25 | 2017-05-31 | 符英 | Poly (propylene carbonate)/agricultural-forestry biomass composite, Preparation method and use |
| CN111171412A (en) * | 2018-11-13 | 2020-05-19 | 上海中化科技有限公司 | Fiber polymer composite material and preparation method thereof |
| CN111286174A (en) * | 2020-02-29 | 2020-06-16 | 华南理工大学 | Electromagnetic shielding plant fiber composite material and preparation method and application thereof |
| CN114213760A (en) * | 2022-01-12 | 2022-03-22 | 安徽工程大学 | Hemp-coconut shell hybrid polypropylene composite material and preparation method and application thereof |
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2002
- 2002-12-12 CN CNB021496137A patent/CN1171951C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297606C (en) * | 2005-03-23 | 2007-01-31 | 中山大学 | Whole-degradable polymethyl ethylene carbonate foamed materials and process for preparing same |
| CN100383080C (en) * | 2006-08-25 | 2008-04-23 | 武汉科技学院 | Regenerated plastic base sisal hemp fiber reinforced construction mould plate and its processing method |
| CN101302310B (en) * | 2008-06-26 | 2012-11-07 | 东华大学 | Preparation of fibrilia-reinforced cellulose ester-based composite material |
| CN101824227B (en) * | 2009-03-06 | 2011-09-14 | 西南科技大学 | Thermoplastic plant fiber/carbon dioxide-based plastic blending material and preparation method thereof |
| CN101798465A (en) * | 2010-03-16 | 2010-08-11 | 龙海市奈特化工有限责任公司 | Composite material capable of releasing volatile substances persistently and preparation method thereof |
| CN101798465B (en) * | 2010-03-16 | 2011-10-05 | 龙海市奈特化工有限责任公司 | Composite material capable of releasing volatile substances persistently and preparation method thereof |
| CN103946315B (en) * | 2011-11-15 | 2017-03-29 | 芬欧汇川集团 | Joint product, its manufacture method and its application, material component and final products |
| CN103946315A (en) * | 2011-11-15 | 2014-07-23 | 芬欧汇川集团 | A composite product, a method for manufacturing a composite product and its use, a material component and a final product |
| CN102977460A (en) * | 2012-12-12 | 2013-03-20 | 奇瑞汽车股份有限公司 | Injecting molding grade natural fiber composite material and preparation method thereof |
| CN105647150A (en) * | 2016-04-12 | 2016-06-08 | 湖州新奥克化工有限公司 | Preparation method of polypropylene-carbonate-base composite material |
| CN105647150B (en) * | 2016-04-12 | 2018-08-17 | 泰州市永欣金属有限公司 | A kind of preparation method of polytrimethylene carbonate composite material |
| CN106752007A (en) * | 2016-12-25 | 2017-05-31 | 符英 | Poly (propylene carbonate)/agricultural-forestry biomass composite, Preparation method and use |
| CN115678301A (en) * | 2016-12-25 | 2023-02-03 | 深圳市金凌软件有限公司 | PPC/agriculture and forestry biomass composite material, preparation method and application |
| CN111171412A (en) * | 2018-11-13 | 2020-05-19 | 上海中化科技有限公司 | Fiber polymer composite material and preparation method thereof |
| CN111171412B (en) * | 2018-11-13 | 2022-04-05 | 上海中化科技有限公司 | Fiber polymer composite material and preparation method thereof |
| CN111286174A (en) * | 2020-02-29 | 2020-06-16 | 华南理工大学 | Electromagnetic shielding plant fiber composite material and preparation method and application thereof |
| CN114213760A (en) * | 2022-01-12 | 2022-03-22 | 安徽工程大学 | Hemp-coconut shell hybrid polypropylene composite material and preparation method and application thereof |
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| CN1171951C (en) | 2004-10-20 |
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