EP1664184A1 - Matiere thermoplastique biodegradable - Google Patents
Matiere thermoplastique biodegradableInfo
- Publication number
- EP1664184A1 EP1664184A1 EP04765232A EP04765232A EP1664184A1 EP 1664184 A1 EP1664184 A1 EP 1664184A1 EP 04765232 A EP04765232 A EP 04765232A EP 04765232 A EP04765232 A EP 04765232A EP 1664184 A1 EP1664184 A1 EP 1664184A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- starch
- material according
- fraction
- ponderal
- pcl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
Definitions
- the present invention concerns a biodegradable thermoplastic material, according to the characteristics outlined in the preamble of the main claim.
- the present invention falls within the field of so-called compostable materials, i.e. those materials that can be biodegraded into compost when subjected to certain temperature and relative humidity conditions for a certain period of time.
- the biodegrading into compost of a material is a controlled oxidisation process, carried out by microorganisms, which leads to the formation of carbon dioxide, water, minerals and a stabilised organic substance (actual compost) .
- a first class of materials comprising a polymeric matrix in combination with polymers of vegetable origin is made up of materials in which a thermoplastic polymer is chemically bonded with starch, through a suitable reaction in a chemical reactor.
- This class includes, for example, materials comprising a polymeric matrix based upon biodegradable thermoplastic polymers and water-soluble products, by themselves or in mixture, such as poly (epsilon- caprolactone) (hereafter, for the sake of brevity, PCL) , or poly vinyl alcohols (PVA) , in which organic chains deriving from corn starch, wheat starch and potato starch are integrated, with covalent bindings.
- PCL poly (epsilon- caprolactone)
- PVA poly vinyl alcohols
- this class of materials is negatively characterised in that they are not very thermally stable, which substantially limits recycling (also of production discards and waste) with a consequent worsening of the overall costs. Indeed, recycled material has totally insufficient resistance to traction and resistance to collisions for its actual practical application.
- a second class of materials is formed from compounds substantially consisting of a physical mixture of olefin-based, or else styrene-based, polymers, and starch (possibly pre-treated) , together with other substances the function of which is that of making the (non-polar) polyolefin polymer and the (polar) starch compatible .
- Examples of this second class of materials are described in US patent application no. 2003/0100635, as well as in US patents nos. 4337181 and 5292782. These materials, however, have proven unsuitable for requirements of mechanical resistance and low production costs.
- the problem forming the basis of the present invention is that of making a biodegradable thermoplastic material structurally and functionally conceived to overcome the limitations outlined above with reference to the quoted prior art .
- a primary purpose of the finding is that of making a thermoplastic material that responds to the requirements laid down by current standards for being classified as compostable. This problem is solved and this purpose is achieved by the present finding through a biodegradable thermoplastic material made in accordance with the following claims.
- the material object of the finding comprises a physical mixture of an olefin and/or styrene-based polymeric matrix, a starch of vegetable origin, in turn consisting of a suitable mixture of rice starch and corn starch, and an effective fraction of poly (epsilon- caprolactone) (PCL) .
- the polymeric matrix preferably consists of linear polyethylene (LLDPE) , or else low-density polyethylene (LDPE) , high-density polyethylene (HDPE) , polypropylene homopolymer, block or statistical polyethylene- polypropylene copolymer, high-impact polystyrene (HIPS) or polystyrene crystal (PS) .
- the primary function of the polymeric matrix is that of giving the material the required mechanical properties. Moreover, the selection of the compounds indicated above is also determined by their low price on the market .
- the starch used is a suitably dosed mixture of rice starch and corn starch.
- the starch in the same way as the other materials of this technical field, is the component that by decomposing causes the degradation process of the thermoplastic material. Indeed, in certain temperature and humidity conditions, it hydrolyses forming dextrin and glucose which are in turn converted, following the oxidising action of thermophiles (fermentation process) , into ethanol and carbon dioxide .
- the degradation of the starch inevitably leads to the decay of the entire material (and therefore to its degradation) since the starch is intimately connected with the polymer constituting the base matrix.
- the PCL used preferably has a medium or medium-high viscosity index.
- the PCL in the mixture is the one that decomposes most quickly and at the lowest temperatures, in this way promoting the start of the hydrolysis reaction of the starch.
- the rice starch and the corn starch are in a ponderal ratio of between 1:1 and 1:4, synergically exploiting the different characteristics of the two types of starch.
- Rice starch indeed, possesses greater mechanical resistance at low temperatures and tends to ferment at lower temperatures with respect to corn starch. This means, first of all, greater mechanical resistance of the entire thermoplastic material at low temperatures (measured at -20°C, according to a known standard) .
- Such a positive characteristic of rice starch indeed, proves particularly important for those materials whose polymeric matrix is styrene-based, which would have, per se, a rather high glass transition temperature, with a consequent tendency of the material to become fragile.
- the presence of rice starch promotes faster biodegradation of the entire material at the end of its life, since, fermenting at lower temperatures, substantially acts as initiator of the fermentation of the corn starch.
- the material can comprise a hydrophilic agent, preferably siloxane-based, the purpose of which is that of promoting the hydrolysis reaction of the starch.
- the material has a range of compositions in which the ponderal fraction of the polymeric matrix is between 40% and 50%, the PCL between 3% and 10%, the rice starch between 10% and 20% and the corn starch between 20% and 40%.
- a preferred composition within this range has also been identified, shown in greater detail in the examples described hereafter, thanks to which the different properties of the material have been optimised.
- the material according to the finding can also comprise mineral or organic loads, preferably selected from calcium carbonate, talc and pumice, or else fossil flour and wood flour.
- the addition of pumice gives the material a high mechanical resistance to traction and compression, whereas the addition of wood flour improves the material in terms of dimensional stability.
- the material object of the present invention has particular application in the production of containers such as pots, boxes and in the field of packaging in general.
- figure 1 is a graph representing the progression through time of the degradation of a first example of thermoplastic material made according to the present invention
- figures 2 and 3 are graphs analogous to that of figure 1, in which the progression through time of the degradation of a second and third thermoplastic material made according to the present invention.
- four different samples have been prepared, made according to the following formulations.
- the material having the composition shown above was prepared in the following way.
- the polypropylene copolymer (in this example ethylene and propylene have been block copolymerised) was mixed with PCL in a vertical screw mixer for 15 minutes, whereas the rice starch, the corn starch and the hydrophilic agent were mixed apart for 15 minutes in a rotating mixer (sifting machine) .
- the polypropylene copolymer and the PCL are loaded at the mouth of a co-rotating twin-screw extruder equipped with 2 degassers and dispensers, preferably of the gravimetric type, whereas the starch and the hydrophilic agent were entered into the extruder after the first degasser through forced lateral feeding.
- the mixture (compound) was extruded at a temperature of 215-220°C, cooled in a water tank at 15°C and then cut into the shape of cylindrical granules.
- the possible organic load flour and/or wood flour
- mineral load talc, calcium carbonate and/or pumice
- Examples 2-4 can be inserted into the extruder through a second forced lateral dispenser, before the second degasser. Examples 2-4
- the preparation of the samples took place according to the same methods as the previous example, apart from the extrusion temperature that was, respectively, 185- 200 °C for the formulation with low-density polyethylene 200-205° for the formulation with linear polyethylene and 210-220°C in the formulation with polystyrene.
- the granules formed from the samples obtained according to examples 1 to 4 were subsequently dried for 6 hours at 105°C in a ther ostatted stove with forced air circulation and then injection moulded into the shape of multi purpose test specimens (MPTS) , according to standard ISO R527.
- MPTS multi purpose test specimens
- the samples were tested according to standard ISO/CD 14852, so as to verify the possibility of classifying the material in question as compostable.
- This test foresees the arrangement of the samples for 56 days at a temperature of 58°C (+/-2°C) in an area with a relative humidity of more than 65%.
- the material is classified as compostable if at the end of the test period it has disintegration equal to or greater than 90%.
- the present invention thus solves the aforementioned problem with reference to the quoted prior art, at the same time offering numerous other advantages, including the possibility of recycling the material and of washing it even after its first production.
- This material indeed, can be thermally treated without causing particular drawbacks, since the triggering of the degrading process requires, as well as temperature, the presence of water.
- the material according to the invention has good mechanical characteristics and a low production cost (estimated to be about 50%less with respect to the cost of the most common materials currently on the market .
- the material according to the invention can normally be worked in normal transformation plants used in the field, such as plants for the production of blown film, with a flat head, or injection moulding plants or thermoforming plants, without any need to make mechanical changes.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
L'invention concerne une matière thermoplastique biodégradable comprenant un mélange physique d'une matrice polymère, à base d'oléfines et/ou à base de styrènes, et d'un amidon, cet amidon consistant en un mélange d'amidon de riz et d'amidon de maïs et comprenant une fraction efficace de poly(epsilon-caprolactone) (PCL).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITPD20030213 ITPD20030213A1 (it) | 2003-09-17 | 2003-09-17 | Materiale termoplastico biodegradabile. |
PCT/EP2004/010320 WO2005026254A1 (fr) | 2003-09-17 | 2004-09-14 | Matiere thermoplastique biodegradable |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1664184A1 true EP1664184A1 (fr) | 2006-06-07 |
Family
ID=34308137
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04765232A Withdrawn EP1664184A1 (fr) | 2003-09-17 | 2004-09-14 | Matiere thermoplastique biodegradable |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1664184A1 (fr) |
IT (1) | ITPD20030213A1 (fr) |
WO (1) | WO2005026254A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9045630B2 (en) * | 2011-06-29 | 2015-06-02 | Fina Technology, Inc. | Epoxy functional polystyrene for enhanced PLA miscibility |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5412005A (en) * | 1991-05-03 | 1995-05-02 | Novamont S.P.A. | Biodegradable polymeric compositions based on starch and thermoplastic polymers |
US5254607A (en) * | 1991-06-26 | 1993-10-19 | Tredegar Industries, Inc. | Biodegradable, liquid impervious films |
US5861461A (en) * | 1995-12-06 | 1999-01-19 | Yukong Limited | Biodegradable plastic composition, method for preparing thereof and product prepared therefrom |
WO2003006545A1 (fr) * | 2001-07-13 | 2003-01-23 | Biorepla Corporation | Composition plastique biodegradable |
-
2003
- 2003-09-17 IT ITPD20030213 patent/ITPD20030213A1/it unknown
-
2004
- 2004-09-14 EP EP04765232A patent/EP1664184A1/fr not_active Withdrawn
- 2004-09-14 WO PCT/EP2004/010320 patent/WO2005026254A1/fr active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2005026254A1 * |
Also Published As
Publication number | Publication date |
---|---|
ITPD20030213A1 (it) | 2005-03-18 |
WO2005026254A1 (fr) | 2005-03-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101484521B (zh) | 用于制备生物可降解塑料的新型生物可降解聚合物组合物以及所述组合物的制备方法 | |
US8389614B2 (en) | Biodegradable nanopolymer compositions and biodegradable articles made thereof | |
KR101376642B1 (ko) | 생분해성 수지 발포 시트, 생분해성 수지 발포체 및 생분해성 수지 성형 용기 | |
US11674018B2 (en) | Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics | |
EP1725614B1 (fr) | Compositions biodegradables comportant des polymeres polylactiques, des copolymeres d'adipate et du silicate magnesien | |
US5225490A (en) | Biodisintegrable thermoplastic resin moldings and a process for producing same | |
US20090149606A1 (en) | Degradable plastic composition and methods | |
IL94495A (en) | Polymeric preparations for the production of biodegradable products and methods for their preparation | |
Khare et al. | Studies toward producing eco-friendly plastics | |
CN101580642A (zh) | 一种全生物降解天然高分子合金及其制备方法 | |
CN101717537B (zh) | 一种聚烯烃薄膜及其制造方法 | |
CN112430382A (zh) | 一种可堆肥化全降解一次性餐具及其制备方法 | |
EP3162841B1 (fr) | Plastique biodigestible, biocompostable, biodégradable | |
US20050176856A1 (en) | Disasemble resin and the manufacturing method for thereof | |
US9925707B2 (en) | Process for preparation of biodegradable biocompostable biodigestible polyolefins | |
KR101627616B1 (ko) | 트레이용 수지조성물 및 이를 이용하여 제조된 트레이 | |
CA3025716A1 (fr) | Procede d'obtention de polyesteretheramide biodegradable | |
KR20220035142A (ko) | 증가된 강도 및 기타 특성을 위해 소립자의 전분 및 전분계 물질을 합성 폴리머와 혼합 | |
EP1664184A1 (fr) | Matiere thermoplastique biodegradable | |
TWI598389B (zh) | 新型低碳排可降解片材及其製品 | |
KR102579310B1 (ko) | 폴리비닐알코올을 포함하는 생분해성 수지 조성물 및 그 제조방법 | |
CA2910848C (fr) | Un procede de preparation de polymere de peplene biodigestible, biocompostable et biodegradable | |
KR0128994B1 (ko) | 생분해성 수지 조성물 | |
AU2015249059B2 (en) | A process for preparation of biodegradable biocompostable biodigestible peplene polymer | |
JP2023141764A (ja) | 生分解性複合体組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20060320 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20090519 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20091201 |