CN101671485B - Composite material containing thermoplastic material and protein material and preparation method thereof - Google Patents
Composite material containing thermoplastic material and protein material and preparation method thereof Download PDFInfo
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- CN101671485B CN101671485B CN200910140236.4A CN200910140236A CN101671485B CN 101671485 B CN101671485 B CN 101671485B CN 200910140236 A CN200910140236 A CN 200910140236A CN 101671485 B CN101671485 B CN 101671485B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The present invention relates to a composite material, and a preparation method of the composite material which contains a traditional thermoplastic material, a biodegradable thermoplastic biopolymer and a protein material. In the invention, castorseed cake is used as a filler for producing the composite material which is prepared by the widely available polymer, such as high impact polystyrene (HIPS), linear low density polyethylene (LLDPE), polypropylene (PP) and a biodegradable biopolymer such as polyhydroxyalkanoates. The composite material obtained from the mode of the invention has good mechanical property and heat property. A series of prepared composite material can be used for the industries which require using the wood for large amount and the industries in the fields of civil engineering, and can be used in the disposable product.
Description
Invention field
The present invention relates to the matrix material based on thermoplastic material and protein material and production method thereof, for substituting traditional plastics, to avoid the plastics using petrochemical industry to originate from a large scale and the environmental problem caused.More specifically, the present invention uses protein material, such as castorseed cake, as the filler that the described mixture prepared by extensive available polymkeric substance is produced, object is to increase the biodegradable ability of described material and does not damage its mechanical properties, because these polymkeric substance are widely used in the production of the product with short work-ing life, such as sanitary cup, plastics bag, jar and packaging.
Background of invention
Conventional plastic substitutes the extensive consumption of other material such as timber, glass and iron and steel, part government and the general public are caused to the huge concern of the final process of these materials, because they are not biodegradable, and the recovery of these products is impossible always.This concern impels the quantitative aspects of the waste products produced in the reasonable final result and/or reduction of finding Plastic wastes to seek alternative solution, such as, develop biodegradable polymkeric substance, blend polymer or mixture.Use biodegradable polymkeric substance or mixture to substitute plastics that traditional plastics can be considered to avoid using petrochemical industry to originate from a large scale and the optional method of the environmental problem caused.
Worry for environmental problem has caused the generation and accumulation of not only paying close attention to Plastic wastes, and comprises the refuse of all any types.Castorseed cake is the byproduct produced by the seed produces biofuel of castor-oil plants, as described in patent application PI0105888-6.Required to improve and this bottom product of upgrading by the Environmental Sustainability of the method for castor seeds production biofuel and economical efficiency.The work forming present patent application basis uses castorseed cake to produce the filler of mixture as by extensive available polymer production such as high-impact polystyrene (HIPS), linear low density polyethylene (LLDPE), polypropylene (PP) and biodegradable biological polymer such as polyhydroxyalkanoatefrom (PHAs).
In order to the impact making this castor seeds residue produce minimizes, we have studied and add the filler of these residues (natural with solid state fermentation after) as the mixture obtained from thermoplastic resin.For high-impact polystyrene (HIPS), linear low density polyethylene (LLDPE) and polypropylene (PP), the object using castor seeds residue to prepare mixture is to increase the biodegradable of described material, and do not damage its mechanical properties, because these polymkeric substance are widely used in the production of the product with short work-ing life, such as sanitary cup, plastics bag, jar and packaging.For described polyhydroxyalkanoatefrom (PHAs), the castor seeds residue adding fermentation can impel the production cost reducing described material as filler, maintain simultaneously or improve its character.
Importance of the present invention relates to economy and environment aspect, because use the byproduct produced from seed produces biofuel to be added Environmental Sustainability and the economical efficiency of production by this waste products of upgrading.
Prior art
Polymkeric substance derived from oil constitutes the raw material for the production of multiple plastic ware, and is present widely used material.But due to its not biodegradable feature, viewed from environment viewpoint, they become a very large problem, as they decompose average needs 100 years completely.
Use biodegradable polymkeric substance, blend or mixture to substitute traditional polymkeric substance, be considered to the optional method avoiding the many environmental problems caused by the consumption of the thermoplastics of these petrochemical origin increased every year at present.Therefore, described biological polymer, it is defined as the polymeric material being derived from renewable source, no matter whether it represents biodegradable, larger magnetism is shown viewed from ecological view, even if because they can not provide biodegradable at a high speed, but they come from reproducible starting material.
Matrix material is defined as the macroscopic view combination as follows of two or more materials: the different in kind that described mixture obtains is in the character (Morton of each moiety when evaluating separately, J., Cantwell, W.J.Composite Materials, Chapter in KirkOthmer Encyclopedia of Chemical Technology, 4th edition, 7th volume, John Wiley & Sons, NY, page 1,1994).Occurring in nature has many this synergistic examples, such as timber, leaf, tooth and bone.Matrix material represents one of fastest-rising commodity in world market.The traditional market of these materials is based on civil engineering work, industry, transport and aviation field, although for the latter, scale is still very little.
In recent years, people have found optional method, can obtain biodegradable mixture, be mainly used in disposable products.
Disposable products create very large problem from environment viewpoint, because the overwhelming majority of the plastics used in the manufacture of these products is not biodegradable.The optional method increasing the biodegradable of these mixtures introduces biological polymer or biodegradable material in its composition.That to have thought in blend or mixture the natural polymer of different amount, biological polymer and biodegradable material has the degraded helping described synthesis component.
Prior art shows, and has carried out studying to obtain the mixture using and be derived from the thermoplastic polymer of oil and the renewable raw materials in multiple source.
Patent application PI0106351-0 describes the mixture comprising thermoplastic material and lignocellulosic plants fiber.
Patent application PI0402485-0 relates to the matrix material containing vegetable fibre, industrial waste and mineral filler and thermoplastic resin.
But we do not find that any relating to uses protein material as the work of the filler of these mixtures.
The biological polymer that microorganism produces comprises polyhydroxyalkanoatefrom (PHAs), represents by carbohydrate, by some vegetables oil and the race of polyester widely that obtained by the direct biosynthesizing of glycerine.These Biopolvester have the character similar to now widely used polymkeric substance (such as polypropylene and linear high-density polyethylene).
There is the method for two kinds of different production PHAs: submerged fermentation and solid state fermentation (SSF).
First method is the method being conventionally used to PHAs production, but production cost is very high.In order to reduce process costs, propose to use solid fermentation (SSF) (Oliveira, F.C., Freire, D.M.G., Castilho, L.R.Production of poly (3-hydroxybutyrate) by solid-state fermentation with Ralstonia eutropha.Biotechnology Letters, 26th volume, 1851-1855 page, 2004).Except the starting material (agricultural and industrial waste) using low cost, SSF also allows the solid directly using the fermentation containing biomaterial, and eliminate the needs carrying out isolation andpurification step, for the method for being produced biological polymer by submerged fermentation, isolation andpurification step accounts for about 40% of total cost of production.
One of step of this work comprises the castorseed cake using fermentation, it contains the microbial biomass that inside has biological polymer, eliminate the recovery stage of described polymkeric substance completely, and directly use the preparation of the solid of described fermentation to have the mixture of multiple commercial polymer.
Solid state fermentation (SSF) method has outstanding feature, and is used in the insoluble substrate of the water in their composition with low ratio, and described insoluble substrate is not only as physiological carrier but also as without nutrition during free-water.Use several kinds of carbon source (main substrate) to prepare fermentation media: wheat-flour, rice meal, barley meal, bagasse, coconut cake, soya-bean cake, palm oil cake, castorseed cake etc., add the optional carbon source (oil, lipid acid, sanitising agent) adding some promotion lipase generations.In some cases, extra nitrogenous source is used: corn steep liquor, yeast extract, urea, ammonium salt etc.Metal-salt can be added with trace element to supply the needs of microorganism.
In recent years, researchist is used for the production of enzyme to solid-state fermentation technology and gives larger concern for obtaining to the valuable material of foodstuffs industry, because it has shown the product that it can provide the productive rate higher than submerged fermentation or have better character.And, likely use low value-added substrate, reduce production cost thus.
Since 1986, mainly due to the increase of generation of Brazil's area agricultural and industrial waste, carried out a series of investigation in Brazil, object is the value increasing described tropical agriculture product and byproduct.The utilization of the waste products of Brazilian agriculture industry provide not only the fermentation substrate of plurality of optional, and contributes to decreasing pollution problem.
Many factors is depended in the selectivity process of Solid-state substrates, comprises cost and feasibility, therefore relates to the investigation of various agricultural and industrial waste.Usually they are rich in nutraceutical, and therefore in solid ferment process, they not only provide cultivation nutrition, and serve as the carrier of microorganism cells.
Castorseed cake is byproduct traditional and the most important in the product chain of castor-oil plants, and it obtains from the Extraction oil of seed of this oil plant (Ricinus).In the whole world, its main application is as high-quality organic fertilizer, because it is high nitrogen mixed fertilizer, provides depleted soil to have efficient recovery.
Brazil is the large castor seeds producing country in third place in the world, and 2004/2005 harvest season produced about 210,000 tons.The Bahia state that the concentration of production is regional northeastward, accounts for about 90% of total amount.Castor seeds shells and the process of extracting oil produces two kinds of important waste products: the shell of fruit and cake.The suitable utilization of these products may increase the income of described product chain, therefore increases its profitability.Described castor seeds shell produces in Rural areas, is usually dumped at side, castor seeds farm, and described cake produces in described oil extraction factory, and this factory is positioned at farm distance quite far away usually.Traditionally, these two kinds of products are used as organic fertilizer, and cake is sold because of its high nitrogen-containing, and shell is only returned when cultivating or utilizes in itself on farm.
Summary of the invention
The present invention relates to the production of mixture, this mixture is based on traditional polymkeric substance and biological polymer, such as high-impact polystyrene (HIPS), linear low density polyethylene (LLDPE), polypropylene (PP) and polyhydroxyalkanoatefrom (PHA), and protein material (such as castorseed cake) that is natural and fermentation.The great difficulty run into for the use of the polyester of extensive poly butyric ester (PHB) type is that their production is along with high cost.When compared with the plastics obtained by petrochemical industry route, described biological polymer has about 4 times of high total costs of production.Therefore the cost effective method of importantly these biological polymers of Development and Production, such as solid state fermentation.
For kind of the polymkeric substance of three above, the target using castor seeds residue to prepare mixture is the biodegradable increasing described material, and do not damage its mechanical properties, because these polymkeric substance are widely used in the production of the product with short work-ing life, such as sanitary cup, plastics bag, jar and packaging.For polyhydroxyalkanoatefrom (PHA), the castor seeds residue adding described fermentation can promote as filler maintain the reduction of described material produce cost simultaneously or improve its character.
Accompanying drawing is sketched
In order to understand the present invention better, append schematic diagram, it should be combined with specification sheets of the present invention and check.
Fig. 1 shows the castor seeds residue (CSR of poly butyric ester (PHB) and fermentation
f) the mechanical properties of mixture.
Fig. 2 A and 2B shows high-impact polystyrene (HIPS) and unfermentable castor seeds residue (CSR
u) the mechanical properties (2A) of mixture and thermal properties (2B).
Fig. 3 shows polypropylene (PP) and unfermentable castor seeds residue (CSR
u) the mechanical properties of mixture.
Fig. 4 A and 4B shows linear low density polyethylene (LLDPE) and unfermentable castor seeds residue (CSR
u) the mechanical properties (4A) of mixture and thermal properties (4B).
Detailed Description Of The Invention
The present invention relates to the matrix material obtained by thermoplastic material such as traditional polymer and biodegradable biological polymer and protein material.Use castorseed cake, prepare mixture by polyhydroxyalkanoatefrom (PHAs), high-impact polystyrene (HIPS), polypropylene (PP) and linear low density polyethylene (LLDPE), change the time that granularity, filler content and this mixture of preparation consume.The mixture of castor seeds residue and described polymkeric substance is prepared in Haake Rheocord 9000 mixing section.
Use the castor seeds residue after the natural and solid state fermentation fully pulverized and sieve, prepare mixture from described four kinds of different polymkeric substance (PHB, HIPS, PP and LLDPE).The weight percent of described protein material is 5-60%; The granularity of described castor seeds residue is 45-256 μm, and described mixing time is 5-10min.Mixture homogenization is made at temperature between 20 DEG C and 200 DEG C, then shaping.
Solid state fermentation allows the fermentation solid directly used containing biomaterial, eliminates the needs carrying out described polymkeric substance isolation andpurification step.In one of the step of this work, we adopt the castorseed cake of fermentation, and it contains the microbial biomass that inside has biological polymer, completely eliminates the recycling step of described polymkeric substance, and directly use the solid of described fermentation in the preparation of mixture.In this way, obtain by the castor seeds residue (CSR fermented
f) mixture prepared with poly butyric ester (PHB), because confirm, described raw material castor seeds residue is rich in the polyhydroxyalkanoatefrom (PHAs) using bacterium Ralstonia eutropha (Cupriavidus necator) and other bacterial strain to be cultivated by solid state fermentation and produce.Then the fermentation of this residue is carried out, and after the drying used as the filler of the described mixture of preparation.
Mechanical properties analyzes (Fig. 1) display, and for tested granularity (256 μm), relative to pure PHB, the filler adding as many as 15% (w/w) in described mixture does not affect the mechanical properties of described material.
High-impact polystyrene (HIPS) is well-known frangible polymkeric substance.Usually in mechanical test (Fig. 2 A), found compared with straight polymer, in this polymkeric substance, added castor seeds residue (CSR) obviously change mechanical properties as filler, reduce Young's modulus, breaking tenacity and elongation at break.
Fig. 2 B shows the thermal analyses result of the means of differential scanning calorimetry (DSC) of HIPS-RM mixture.Because HIPS is amorphous polymer, the data of acquisition are second-order transition temperature (Tg).Compare with the data of the HIPS of pure processing, we see processing to the little of the Tg of described material but still the impact that exists, because add described castor seeds filler to significantly reduce Tg, containing 40% castor seeds residue mixture in reach about 50% the range of decrease.These data show, the vinylbenzene that described filler enters described polymkeric substance mutually in, and reduce its Tg.The behavior may be relevant with the absorption of the oil residues in castor seeds residue, produces the plasticization effect of described vinylbenzene phase.
Fig. 3 shows the mechanical properties of the mixture obtained by the mixture of polypropylene and castor seeds residue (PP-CSR).Can find out, although mainly have significant reduction on elongation at break and Young's modulus for high-caliber filler content (40%), but the matrix material of gained still demonstrates the part that extremely induces one: the change with less Young's modulus.
Fig. 4 A shows the mechanical properties of the mixture obtained by the mixture of linear low density polyethylene and castor seeds residue (LLDPE-CSR).Can find out, although there is obvious reduction on elongation at break, especially for high-caliber filler content (40%) and high-caliber granularity (256 μm), but the matrix material of gained still demonstrates the part that extremely induces one: have the elongation of 123% before fracture.
Fig. 4 B shows the DSC data of the mixture (LLDPE-CSR) of [linearly] low [-density] polyethylene and castor seeds residue.Because LLDPE is semi-crystalline polymer, we measure fusing point (in heat-processed and in process of cooling) and Tc.Discovery adds castor seeds residue does not affect described thermal properties.
The mixture in this way obtained has good mechanical properties and thermal properties.Prepared a series of mixtures use the industry of timber a large amount of and have found purposes in field of civil engineering industry, and also in disposable products, have found purposes.
Claims (4)
1. contain the matrix material of thermoplastic material and protein material, it is characterized in that it is prepared by traditional polymkeric substance, biodegradable biological polymer and protein material; Wherein said traditional polymkeric substance is selected from high-impact polystyrene, linear low density polyethylene and polypropylene; Described biodegradable biological polymer is polyhydroxyalkanoatefrom; Described protein material is castorseed cake that is natural and fermentation, and the concentration of described protein material is between 5% and 60%w/w, and the granularity of castor seeds residue is 45-256 μm.
2. the matrix material containing thermoplastic material and protein material according to claim 1, is characterized in that its uses the protein material preparation containing the solid state fermentation of polyhydroxyalkanoatefrom.
3. the matrix material containing thermoplastic material and protein material according to claim 2, is characterized in that using described polyhydroxyalkanoatefrom in the process of solid state fermentation.
4. containing the production method of the matrix material of thermoplastic material and protein material, it is characterized in that it comprises the following steps: pulverize described protein material to the granularity of 45-256 μm, wherein said protein material is natural in the castorseed cake fermented; By described natural mixing with the thermoplastic resin be selected from high-impact polystyrene, linear low density polyethylene and polypropylene and polyhydroxyalkanoatefrom with the castorseed cake of fermentation; Make homogenizing at the temperature of mixture between 20 DEG C and 200 DEG C, and make described mixture forming, the concentration of described protein material is between 5% and 60%w/w.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI08041016 | 2008-09-09 | ||
| BRPI0804101-6 | 2008-09-09 | ||
| BRPI0804101-6A BRPI0804101A2 (en) | 2008-09-09 | 2008-09-09 | composite material containing thermoplastic material and protein material and process for obtaining |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101671485A CN101671485A (en) | 2010-03-17 |
| CN101671485B true CN101671485B (en) | 2015-04-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910140236.4A Expired - Fee Related CN101671485B (en) | 2008-09-09 | 2009-07-09 | Composite material containing thermoplastic material and protein material and preparation method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN101671485B (en) |
| AR (1) | AR072627A1 (en) |
| BR (1) | BRPI0804101A2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159462A (en) * | 1996-03-09 | 1997-09-17 | 拜奥帕克技术有限公司 | Legradable thermoplastics from lactides |
| JP3174449B2 (en) * | 1993-12-22 | 2001-06-11 | 東京電力株式会社 | Method of melting coal ash |
| CN1583884A (en) * | 2004-05-24 | 2005-02-23 | 武汉大学 | Soya protein plastic with water polyurethane modification and preparing method thereof |
| CN100999602A (en) * | 2006-12-18 | 2007-07-18 | 中山大学 | Degradable carbon dioxide plastic base composite material and preparation process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI894735A (en) * | 1989-10-05 | 1991-04-06 | Biodata Oy | BIOLOGISKT NEDBRYTBAR KOMBINATIONSFILM OCH FOERFARANDE FOER ATT FRAMSTAELLA EN SAODAN. |
-
2008
- 2008-09-09 BR BRPI0804101-6A patent/BRPI0804101A2/en not_active Application Discontinuation
-
2009
- 2009-07-09 CN CN200910140236.4A patent/CN101671485B/en not_active Expired - Fee Related
- 2009-07-29 AR ARP090102894 patent/AR072627A1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3174449B2 (en) * | 1993-12-22 | 2001-06-11 | 東京電力株式会社 | Method of melting coal ash |
| CN1159462A (en) * | 1996-03-09 | 1997-09-17 | 拜奥帕克技术有限公司 | Legradable thermoplastics from lactides |
| CN1583884A (en) * | 2004-05-24 | 2005-02-23 | 武汉大学 | Soya protein plastic with water polyurethane modification and preparing method thereof |
| CN100999602A (en) * | 2006-12-18 | 2007-07-18 | 中山大学 | Degradable carbon dioxide plastic base composite material and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101671485A (en) | 2010-03-17 |
| BRPI0804101A2 (en) | 2010-07-06 |
| AR072627A1 (en) | 2010-09-08 |
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Granted publication date: 20150429 Termination date: 20210709 |