CN101671485A - 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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- CN101671485A CN101671485A CN200910140236A CN200910140236A CN101671485A CN 101671485 A CN101671485 A CN 101671485A CN 200910140236 A CN200910140236 A CN 200910140236A CN 200910140236 A CN200910140236 A CN 200910140236A CN 101671485 A CN101671485 A CN 101671485A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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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 biopolymerand 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 goodmechanical 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 matrix material and production method thereof, be used for substituting traditional plastics, the environmental problem that causes to avoid using the plastics of petrochemical industry origin on a large scale based on thermoplastic material and protein material.More specifically, the present invention uses protein material, castorseed cake for example, as the described filler of producing by the mixture of the polymer manufacture that extensively can get, purpose is to increase the biodegradable ability of described material and does not damage its mechanical properties, because these polymkeric substance are widely used in having the production of the product in short work-ing life, for example sanitary cup, plastics bag, jar and packing.
Background of invention
Conventional plastic substitutes for example extensive consumption of timber, glass and iron and steel of other material, caused the huge concern of part government and the general public to the final processing of these materials, because they are not biodegradable, and the recovery of these products is impossible always.This concern impels at the quantitative aspects of the waste products of the reasonable final result of seeking Plastic wastes and/or reduction generation seeks alternative solution, for example develops biodegradable polymkeric substance, blend polymer or mixture.The optional method of the environmental problem of using the alternative traditional plastics of biodegradable polymkeric substance or mixture can be considered to avoid using the plastics of petrochemical industry origin on a large scale and causing.
Worry for environmental problem has caused generation and the accumulation of not only paying close attention to Plastic wastes, and comprises the refuse of all any kinds.Castorseed cake is the byproduct that is produced by the seed production biofuel of castor-oil plants, described in patent application PI0105888-6.Environment sustainability and economical efficiency by castor seeds production method of bio-diesel oil require to improve and this bottom product of upgrading.The work that forms the present patent application basis uses castorseed cake as by the polymer production that extensively can get high-impact polystyrene (HIPS), linear low density polyethylene (LLDPE), polypropylene (PP) and the biodegradable biological polymer filler of polyhydroxyalkanoatefrom (PHAs) production mixture for example for example.
For the influence that this castor seeds residue is produced minimizes, we have studied and have added the filler of these residues (natural with solid state fermentation after) as the mixture that obtains from thermoplastic resin.For high-impact polystyrene (HIPS), linear low density polyethylene (LLDPE) and polypropylene (PP), the purpose of using the 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 having the production of the product in short work-ing life, for example sanitary cup, plastics bag, jar and packing.For described polyhydroxyalkanoatefrom (PHAs), the castor seeds residue that adds fermentation can impel the production cost that reduces described material as filler, keeps or improve its character simultaneously.
Importance of the present invention relates to economy and environment aspect, because use the byproduct that produces from seed production biofuel to increase the environment sustainability and the economical efficiency of producing by this waste products of upgrading.
Prior art
Polymkeric substance derived from oil has constituted the raw material that is used to produce multiple plastic ware, and is present widely used material.Yet, because its not biodegradable characteristics see that from the environment viewpoint they become a very big problem, decompose average needs 100 years fully as them.
Use biodegradable polymkeric substance, blend or mixture to substitute traditional polymkeric substance, be considered to avoid the optional method of many environmental problems that the consumption of the thermoplastics in these petrochemical industry sources of being increased by every year causes at present.Therefore, described biological polymer, it is defined as being derived from the polymeric material of renewable source, no matter whether it represents biodegradable, see from ecological view and to have shown bigger magnetism, even because they can not provide the high speed biodegradable, 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 estimating separately, J., Cantwell, W.J.Composite Materials, Chapter in KirkOthmer Encyclopedia of Chemical Technology, the 4th edition, the 7th volume, John Wiley﹠amp; Sons, NY, page 1,1994).Occurring in nature has many this synergistic examples, for example timber, leaf, tooth and bone.Matrix material is represented one of fastest-rising commodity in world market.The traditional market of these materials is based on civil engineering work, industry, transportation and aviation field, though for the latter, scale is still very little.
In recent years, people have sought optional method, make it can obtain biodegradable mixture, are mainly used in disposable products.
Disposable products have produced very big problem from the environment viewpoint, because the overwhelming majority of employed plastics is not biodegradable in the manufacturing of these products.An optional method that increases the biodegradable of these mixtures is to introduce biological polymer or biodegradable material in it is formed.Thought in blend or mixture different amounts natural polymer, biological polymer and biodegradable materials have a degraded that helps described synthetic component.
Prior art shows, studied the mixture with the renewable raw materials that obtains to use the thermoplastic polymer that is derived from oil and multiple source.
Patent application PI0106351-0 has described the mixture that comprises thermoplastic material and lignocellulosic plants fiber.
Patent application PI0402485-0 relates to the matrix material that contains vegetable fibre, industrial waste and mineral filler and thermoplastic resin.
Yet we do not find any work of protein material as the filler of these mixtures of using that relates to.
The biological polymer of microorganisms comprises polyhydroxyalkanoatefrom (PHAs), has represented by carbohydrate, by some vegetables oil and the family of polyester widely that obtained by the direct biosynthesizing of glycerine.These biological polyester have and the similar character of present widely used polymkeric substance (for example polypropylene and linear high-density polyethylene).
The method that two kinds of different production PHAs are arranged: submerged fermentation and solid state fermentation (SSF).
First method is that tradition is used for the method that PHAs produces, but production cost is very high.In order to reduce the technology cost, proposed 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, the 26th volume, 1851-1855 page or leaf, 2004).Except using cheaply starting material (agricultural and industrial waste), SSF also allows directly to use the solid of the fermentation that contains biomaterial, and the needs that separate with purification step have been eliminated, for the method for producing biological polymer by submerged fermentation, separation and purification step account for about 40% of total cost of production.
One of step of this work comprises the castorseed cake that uses fermentation, it contains the microbial biomass that inside has biological polymer, removed the recovery stage of described polymkeric substance fully, and directly used the solid of described fermentation to prepare mixture with multiple commercial polymer.
Solid state fermentation (SSF) method has outstanding feature, and uses the insoluble substrate of the water have low ratio in their composition, the nutrition of described insoluble substrate during not only as physiological carrier but also as no free-water.Use several kinds of carbon source (main substrate) preparation fermentation media: wheat-flour, rice meal, barley meal, bagasse, coconut cake, soya-bean cake, palm oil cake, castorseed cake etc., some promote the carbon source (oil, lipid acid, sanitising agent) that lipase produces to add optional adding.In some cases, use extra nitrogenous source: corn steep liquor, yeast extract, urea, ammonium salt etc.Can add metal-salt and trace element needs with the supply microorganism.
In recent years, the researchist is used for the production of enzyme and is used to obtain solid-state fermentation technology having given bigger concern to the valuable material of foodstuffs industry, because it has shown that it can provide than higher productive rate of submerged fermentation or the product with better character.And, might use low value-added substrate, reduce production costs thus.
Since 1986, mainly due to the increase of the generation of Brazil area agricultural and industrial waste, carried out a series of investigation in Brazil, purpose is to increase the value of described tropical agriculture product and byproduct.The utilization of the waste products of Brazilian agriculture industry not only provides the fermentation substrate of plurality of optional, and helps to reduce pollution problem.
The selectivity of solid-state substrate is handled and is depended on multiple factor, comprises cost and feasibility, therefore relates to the investigation of various agricultural and industrial waste.Usually they are to be rich in nutraceutically, and therefore they not only provide the cultivation nutrition in solid ferment process, and serve as the carrier of microorganism cells.
Castorseed cake is traditional and the most important byproduct in the product chain of castor-oil plants, and it is from the Extraction oil of seed of this oil plant (Ricinus) and obtain.In the whole world, its main application is as the high-quality organic fertilizer, because it is high nitrogen mixed fertilizer, provides depleted soil that efficient recovery is arranged.
Brazil is third place in the world big castor seeds producing country, and 2004/2005 harvest season was produced about 210,000 tons.The geographic northeastward Bahia of concentration of production state accounts for about 90% of total amount.Castor seeds shells and the process of extract 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 is created in the Rural areas, be usually dumped at next door, castor seeds farm, and described cake is created in the described oily factory that extracts, 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 only is returned when cultivating or utilizes in farm itself.
Summary of the invention
The present invention relates to the production of mixture, this mixture is based on traditional polymkeric substance and biological polymer, for example high-impact polystyrene (HIPS), linear low density polyethylene (LLDPE), polypropylene (PP) and polyhydroxyalkanoatefrom (PHA), and natural and protein material (for example castorseed cake) fermentation.For the great difficulty that use ran into of the polyester of extensive poly butyric ester (PHB) type is that their production is accompanied by expensive.When comparing with the plastics that obtain by the petrochemical industry route, described biological polymer has about 4 times of high total costs of production.Therefore the importantly cost effective method of these biological polymers of Development and Production, for example solid state fermentation.
Three kinds of polymkeric substance for the front, the target of using the castor seeds residue to prepare mixture is the biodegradable that increases described material, and do not damage its mechanical properties, because these polymkeric substance are widely used in having the production of the product in short work-ing life, for example sanitary cup, plastics bag, jar and packing.For polyhydroxyalkanoatefrom (PHA), the castor seeds residue that adds described fermentation can promote the reduction of described material produce cost as filler, keeps or improve its character simultaneously.
The accompanying drawing summary
In order to understand the present invention better, enclosed synoptic diagram, it should combine with specification sheets of the present invention and check.
Fig. 1 has shown the castor seeds residue (CSR of poly butyric ester (PHB) and fermentation
F) the mechanical properties of mixture.
Fig. 2 A and 2B have shown high-impact polystyrene (HIPS) and unfermentable castor seeds residue (CSR
U) the mechanical properties (2A) and the thermal properties (2B) of mixture.
Fig. 3 has shown polypropylene (PP) and unfermentable castor seeds residue (CSR
U) the mechanical properties of mixture.
Fig. 4 A and 4B have shown linear low density polyethylene (LLDPE) and unfermentable castor seeds residue (CSR
U) the mechanical properties (4A) and the thermal properties (4B) of mixture.
Detailed Description Of The Invention
The present invention relates to by the thermoplastic material matrix material that obtains of traditional polymer and biodegradable biological polymer and protein material for example.Use castorseed cake,, change the time that granularity, filler content and this mixture of preparation are consumed by polyhydroxyalkanoatefrom (PHAs), high-impact polystyrene (HIPS), polypropylene (PP) and linear low density polyethylene (LLDPE) preparation mixture.Preparation castor seeds residue and described mixture of polymers in Haake Rheocord 9000 mixing sections.
Use the castor seeds residue behind the natural and solid state fermentation fully pulverize and to sieve, with described four kinds of different polymkeric substance (PHB, HIPS, PP and LLDPE) preparation mixture.The weight percent of described protein material is 5-60%; The granularity of described castor seeds residue is 45-256 μ m, and described mixing time is 5-10min.Under the temperature between 20 ℃ and 200 ℃, make mixture homogenization, then moulding.
Solid state fermentation allows directly to use the fermentation solid that contains biomaterial, has eliminated the needs that carry out described polymkeric substance separation and purification step.In one of step of this work, we adopt the castorseed cake of fermentation, and it contains the microbial biomass that inside has biological polymer, has eliminated the recycling step of described polymkeric substance fully, and directly use the solid of described fermentation in the preparation of mixture.In this way, obtained by the castor seeds residue (CSR that ferments
F) with the mixture of poly butyric ester (PHB) preparation, because confirm, described raw material castor seeds residue is rich in and uses bacterium really to support the polyhydroxyalkanoatefrom (PHAs) that thunder Salmonella (Cupriavidus necator) and other bacterial strain produce by the solid state fermentation cultivation.Carry out the fermentation of this residue then, and after drying used as the preparation described mixture filler.
Mechanical properties is analyzed (Fig. 1) and is shown, for the granularity of being tested (256 μ m), with respect to pure PHB, the filler that adds as many as 15% (w/w) in described mixture does not influence the mechanical properties of described material.
High-impact polystyrene (HIPS) is well-known frangible polymkeric substance.Usually in mechanical test (Fig. 2 A), found to compare, in this polymkeric substance, added castor seeds residue (CSR) and obviously changed mechanical properties, reduced Young's modulus, breaking tenacity and elongation at break as filler with straight polymer.
Fig. 2 B has shown the hot analytical results of the differential scanning calorimetric (DSC) of HIPS-RM mixture.Because HIPS is an amorphous polymer, the data of acquisition are second-order transition temperature (Tg).With the data of the HIPS of pure processing relatively, we have seen the little but still influence that exist of processing to the Tg of described material, obviously reduce Tg because add described castor seeds filler, in containing the mixture of 40% castor seeds residue, reached about 50% the range of decrease.These data show, the vinylbenzene that described filler has entered described polymkeric substance mutually in, and reduced its Tg.The behavior may be relevant with the absorption of oil residues in the castor seeds residue, produces the plasticization effect of described vinylbenzene phase.
Fig. 3 has shown the mechanical properties by the mixture of the mixture acquisition of polypropylene and castor seeds residue (PP-CSR).As can be seen, though for high-caliber filler content (40%) significant reduction is arranged on elongation at break and Young's modulus mainly, the matrix material of gained still demonstrates the part that very induces one: the variation with littler Young's modulus.
Fig. 4 A has shown the mechanical properties by the mixture of the mixture acquisition of linear low density polyethylene and castor seeds residue (LLDPE-CSR).As can be seen, though tangible reduction is arranged on elongation at break, especially for high-caliber filler content (40%) and high-caliber granularity (256 μ m), yet the matrix material of gained still demonstrates the part that very induces one: have 123% elongation before the fracture.
Fig. 4 B has shown the DSC data of the mixture (LLDPE-CSR) of [linearity] low [density] polyethylene and castor seeds residue.Because LLDPE is a semi-crystalline polymer, we measure fusing point (in heat-processed and in process of cooling) and Tc.Find to add the castor seeds residue and do not influence described thermal properties.
In this way the mixture of Huo Deing has favorable mechanical character and thermal properties.Prepared a series of mixtures use the industry of timber and have found purposes in the field of civil engineering industry a large amount of, and have also found purposes in disposable products.
Claims (10)
1. the matrix material that contains thermoplastic material and protein material is characterized in that it is by traditional polymkeric substance, biodegradable biological polymer and protein material preparation.
2. according to the matrix material that contains thermoplastic material and protein material of claim 1, it is characterized in that it is by for example high-impact polystyrene (HIPS), linear low density polyethylene (LLDPE) and polypropylene (PP) preparation of traditional polymkeric substance.
3. according to the matrix material that contains thermoplastic material and protein material of claim 1, it is characterized in that it is by for example polyhydroxyalkanoatefrom (PHAs) preparation of biodegradable biological polymer.
4. according to the matrix material that contains thermoplastic material and protein material of claim 1, it is characterized in that it is by adding protein material preparation natural and fermentation.
5. according to the matrix material that contains thermoplastic material and protein material of claim 3, it is characterized in that for example protein material preparation of the solid state fermentation of polyhydroxyalkanoatefrom (PHAs) of its use biopolymer-containing.
6. according to the matrix material that contains thermoplastic material and protein material of claim 3, it is characterized in that in the process of solid state fermentation, using described polyhydroxyalkanoatefrom (PHAs), for example poly butyric ester (PHB).
7. according to the matrix material that contains thermoplastic material and protein material of claim 1 and 3, it is characterized in that described protein material is a castorseed cake.
8. according to the matrix material that contains thermoplastic material and protein material of claim 1 and 3, the concentration that it is characterized in that described protein material 5% and 60%w/w between.
9. the production method that contains the matrix material of thermoplastic material and protein material is characterized in that it may further comprise the steps: pulverize the granularity of described protein material to regulation; The described natural protein material with fermentation is mixed with thermoplastic resin; Make described mixture homogenizing under the temperature between 20 ℃ and 200 ℃, and make described mixture forming.
10. according to the production method of the matrix material that contains thermoplastic material and protein material of claim 9, it is characterized in that using and contain for example solid state fermentation of polyhydroxyalkanoatefrom (PHAs) of biodegradable biological polymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| BRPI08041016 | 2008-09-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101671485A true CN101671485A (en) | 2010-03-17 |
| CN101671485B 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 |
|---|---|---|---|---|
| JPH03174449A (en) * | 1989-10-05 | 1991-07-29 | Biodata Oy | Biodegradable film and its manufacture |
| 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 |
Family Cites Families (1)
| 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 |
-
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 |
|---|---|---|---|---|
| JPH03174449A (en) * | 1989-10-05 | 1991-07-29 | Biodata Oy | Biodegradable film and its manufacture |
| 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 |
|---|---|
| CN101671485B (en) | 2015-04-29 |
| BRPI0804101A2 (en) | 2010-07-06 |
| AR072627A1 (en) | 2010-09-08 |
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