EP3997171A1 - Articles polymères comprenant des mélanges de pbat, de pea et d'un matériau polymère à base d'hydrate de carbone - Google Patents
Articles polymères comprenant des mélanges de pbat, de pea et d'un matériau polymère à base d'hydrate de carboneInfo
- Publication number
- EP3997171A1 EP3997171A1 EP20837209.4A EP20837209A EP3997171A1 EP 3997171 A1 EP3997171 A1 EP 3997171A1 EP 20837209 A EP20837209 A EP 20837209A EP 3997171 A1 EP3997171 A1 EP 3997171A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- blend
- pla
- materials
- carbohydrate
- pbat
- 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.)
- Pending
Links
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/26—Carbonates; Bicarbonates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/06—Biodegradable
-
- 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
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Definitions
- Petrochemical-based plastics materials such as large quantities of polyethylene and polypropylene, as well as numerous other plastics (polyethylene terephalate, polystyrene, ABS, polyvinyl chloride, polycarbonate, nylon, and the like) are typically not readily biodegradable in typical land disposal environments (e.g., in a landfill), or even more so, when discarded in a marine environment. Such is typically the case even for so called“green” plastics of such materials, where a fraction of the plastic may be sourced from renewable or sustainable sources, rather than petro-chemical feedstocks.
- PBAT Film materials including PBAT would be desirable for use in applications such as carry-out bags, where unfortunately, considerable littering still occurs, even in the U.S. and other developed nations.
- the rationale for using PBAT in such articles would be that PBAT exhibits biodegradability characteristics, e.g., even under relatively low temperature home composting conditions.
- the vast majority of such carry-out bags (and other film articles) are formed from polyethylene, which exhibits negligible biodegradability under essentially any standardized testing or real world disposal conditions.
- the PLA may be present in an amount of at least 10%, or greater than 10% by weight of the blend.
- an inorganic filler may also be included, such as calcium carbonate, ,talc, or the like. Inclusion of such a filler material may further reduce the amount of polymeric components needed in manufacture of a particular bag, other film, or other article, and may also aid in reducing any tendency of a bag formed from such a film to exhibit“blocking” or cohesion, where the sides of such a bag tend to adhere to one another, making it somewhat difficult to actually open the bag.
- any such inorganic filler may be included in an amount from 0% to 30% by weight of the article, for example.
- Any of various other additives may also be included, where desired, e.g., including but not limited to slip and/or processing aids.
- Figure 10A shows results of a disintegration test from the start to 26 weeks based on ISO 20200 standards, meant to simulate ambient temperature (28°C) compost conditions, for sample BC27240 made according to the present disclosure, as described in Example 2.
- Figure 10F shows a photograph of the content of the composting reactor with test sample BC27251 after 8 weeks, as described in Example 3.
- Figure 10H shows a photographic comparison of test sample BC27251 at the start and after 12 weeks of testing, as described in Example 3.
- Bing refers to a container made of a relatively thin, flexible film that can be used for containing and/or transporting goods.
- Bottom refers to a container that can be made from the presently disclosed plastics, typically of a thickness greater than a film, and which typically includes a relatively narrow neck adjacent an opening. Such bottles may be used to hold a wide variety of products (e.g., beverages, personal care products such as shampoo, conditioner, lotion, soap, cleaners, and the like).
- products e.g., beverages, personal care products such as shampoo, conditioner, lotion, soap, cleaners, and the like.
- NuPlastiQ starch-based polymers described herein are an example of starch-based material that can provide the benefits described herein, it will be appreciated that the scope of the present invention extends broadly, to other starches or starch-based materials that might exhibit similar small particle size characteristics (e.g., developed at some future time), or even to a material that may be synthesized from starting materials other than starch, which may achieve similar results due to the presence of the same or similar chemical structures or functional groups. For example, if a material having a chemical structure similar or identical to NuPlastiQ were synthesized (e.g., in a reactor) starting from non-starch materials, such is also within the scope of the present invention.
- Elevated temperature and moisture may cause degradation but will not cause biodegradation of such articles unless the necessary microorganisms are also present.
- the combination of such conditions causes the articles formed from such a blend of materials to begin to biodegrade.
- Third party testing as described herein confirms that not only is the carbohydrate- based polymeric material and the PBAT biodegrading under home compost conditions, but that the PLA also biodegrades under such moderate conditions, which PLA otherwise resists biodegradation under lower temperature (i.e., 28°C) home composting conditions.
- Examples of suitable carbohydrate-based or starch-based polymeric materials that have been shown to lend or increase biodegradability to polyester plastic materials exhibiting limited or no biodegradability are available from BiologiQ, under the tradename NuPlastiQ. Specific examples include but are not limited to NuPlastiQ GP and NuPlastiQ CG. Specific characteristics of such NuPlastiQ materials will be described in further detail herein.
- Other carbohydrate-based or starch-based polymeric materials may also be suitable for use so long as they are capable of, and specifically selected for the purpose of increasing biodegradability of the PLA material included in the blend. In order to select such a material for this purpose, its ability to lend or increase biodegradability of PLA must be recognized.
- NuPlastiQ Applicant is not currently aware of any such materials recognized to perform as such.
- Applicant also provides masterbatch blends of NuPlastiQ and conventional polymeric materials under the tradename BioBlend, e.g., including, but not limited to, BioBlend XP, BioBlend XD, BioBlend MB, BioBlend BC, and BioBlend CB.
- Such masterbatches may contain higher proportions of the modified polysaccharide (NuPlastiQ) which may be down- blended with the other polymeric material(s) prior to forming the final product.
- Such blends may be formed in manufacture into a desired article through any conceivable process.
- An example of such would be an extrusion process.
- the polyester plastic materials e.g., PBAT and PLA
- the carbohydrate-based polymeric material can be fed into an extruder (e.g., into one or more hoppers thereof).
- the different materials can be fed into the extruder into the same chamber, into different chambers, at approximately the same time (e.g., through the same hopper), or at different times (e.g., through different hoppers, one being introduced into the extruder earlier on along the screw than the other), etc. It will be apparent that many numerous configurations are possible.
- the two polyester materials may be sourced from petrochemical sources, or from so-called“green” or sustainable sources (e.g., com used to produce lactic acid, used for forming PLA, or the like).
- petrochemical sources e.g., PBAT and PLA
- so-called“green” or sustainable sources e.g., com used to produce lactic acid, used for forming PLA, or the like.
- renewable or sustainable source materials refer to e.g., plant sources that are renewable within less than 100 years, rather than petro-chemical feedstocks.
- there are various tests for confirming sustainable or renewable content in plastics or other materials e.g., as the ratio of C 14 to C 12 is elevated in renewable materials containing carbon, as compared to fossil fuel sourced materials.
- the finished carbohydrate-based polymeric material may include no greater than 5%, no greater than 4%, no greater than 3%, no greater than 2%, no greater than 1.5%, no greater than 1.4%, no greater than 1.3%, no greater than 1.2%, no greater than 1.1%, or no greater than 1% by weight water.
- the NuPlastiQ materials available from BiologiQ are examples of such finished carbohydrate-based polymeric materials, although it will be appreciated that other materials available elsewhere (e.g., at some future time) may also be suitable for use.
- Figure 7 illustrates comparative DSC melting temperature data on a conventional starch material, which shows a melting temperature of 287.7°C, which is far higher than the melting temperature of about 170°C for NuPlastiQ.
- the present blends exhibit at least (or better than) 90% biodegradation within 365 days, which is sufficient to meet the biodegradability portion of applicable “home compostability” standards, such as NF T51-800 (2015); AS 5810 (2010); and the OK Compost Home Certification scheme of Tl)V Austria Belgium.
- the 90% or higher biodegradation may be achieved more rapidly than the permitted 365 days, e.g., such as within 350 days, within 325 days, within 300 days, within 275 days, within 250 days, within 200 days, or within 180 days.
- the mixture of materials can pass through a number of chambers, such as the first chamber 206, a second chamber 208, a third chamber 210, a fourth chamber 212, a fifth chamber 214, and an optional sixth chamber 216.
- the mixture of materials can be heated in the chambers 206, 208, 210, 212, 214, 216.
- a temperature of one of the chambers can be different from a temperature of another one of the chambers.
- the first chamber 206 is heated to a temperature from 120°C to 140°C; the second chamber 208 is heated to a temperature from 130°C to 160°C; the third chamber 210 is heated to a temperature from 135°C to 165°C; the fourth chamber 212 is heated to a temperature from 140°C to 170°C; the fifth chamber 214 is heated to a temperature from 145°C to 180°C; and the optional sixth chamber 216 is heated to a temperature from 145°C to 180°C.
- the film 224 can be comprised of a single layer. In other cases, the film 224 can be comprised of multiple layers. Where multiple layers are present, at least one of the layers may include the carbohydrate-based polymeric material. In some embodiments, the carbohydrate-based polymeric material may be present in one or more outer layers, in an inner layer, or in all layers.
- the biodegradation may be determined as is customary in respirometry-based tests, according to a mass balance on the carbon, whereby carbon atoms beginning in the material of the blend (e.g., in the carbohydrate-based polymeric material and/or in the polyesters) are accounted for in off-gassed products, as CEE and/or CO2, as a result of biodegradation.
- CEE and/or CO2 off-gassed products
- at least 90% of carbon atoms of any of the polyesters or the blend as a whole may become at least one of CO2, or CEE within 365 days (or 300 days, or 200 days, or 180 days, etc.) in such simulated home composting conditions.
- the biodegradation percentage for the cellulose control that is over 100% can be explained by a synergistic effect, referred to as priming.
- the absolute biodegradation for test samples BC27130 and BC27241 was measured at 79.2% and 86%, respectively.
- the notation on Figure 9 refers to a re-inoculation with 20% fresh vegetable, garden, and fruit waste (VGF) at day 46 in the test.
- VVF fresh vegetable, garden, and fruit waste
- Figure 10A shows progression of the disintegration of sample BC27240/1 (similar to sample BC27241 of Example 1, above) over the 26 week (182 days) test.
- Test sample BC27240/1 was put into slide frames and mixed with compost inoculum. The obtained mixture was incubated in the dark at ambient temperatures (28 ⁇ 2°C). The test was performed in 2 replicates.
- Figure 10A shows photographs giving the visual presentation of the progression of the disintegration of test material BC27240/1 during the 26 weeks of composting at ambient temperature. After 20 weeks, only a small border of test materials remained present in the major part of the slide frames. Moreover, it was noticed that loosened pieces of the film could easily be retrieved from the composting reactor. A re- inoculation of all reactors with 5% fresh VGF waste was performed after an incubation period of 18 weeks in order to renew the microbial population and supply fresh nutrients. After 26 weeks, an average disintegration percentage of at least 90% was reached based on any remaining surface of test material still in the slide frames. No loosened pieces of test material were found in the compost inoculum after 26 weeks.
- Each test item was mixed with a 80/20 mixture of ⁇ 10 mm mature compost and fresh milled Vegetable, Garden and Fruit waste (VGF) and incubated at 28°C in the dark. Regularly the moisture content is verified and adjusted when needed. The content of the reactors was regularly manually stirred, and the test item was visually monitored. The maximum test duration during which disintegration should be demonstrated was 26 weeks.
- VCF Vegetable, Garden and Fruit waste
- the compost from each reactor was sieved by means of a vibrating sieve over 2 mm in order to recover any not disintegrated residues of the test material in the > 2 mm fraction. Disintegration was evaluated very precisely by manual selection. If possible, a mass balance is calculated. The compost obtained at the end of the composting process can be used for further measurements such as chemical and physical analyses.
- the test procedure is based on ISO 20200 Plastics - Determination of the degree of disintegration of plastic materials under simulated composting conditions in a laboratory- scale test (2015), with the following deviations when compared to ISO 20200 (2015):
- test is considered valid if (when performed with a thermophilic and mesophilic incubation period):
- PBAT, PBS, and PCL typically exhibit far higher elongation at break values (e.g., from about 500 to about 800%), but relatively low elastic modulus (e.g., less than 1 GPa, and often less than 0.5 GPa).
- the present invention thus contemplates blending one of the low stiffness (i.e., low elastic modulus) materials (e.g., PBAT, PCL, PBS or the like) exhibiting high elongation at break with one of the polyester materials exhibiting high stiffness (high elastic modulus) and low elongation at break, in combination with the carbohydrate-based polymeric material, so that the blend as a whole is able to meet home compostability conditions.
- inventive features disclosed herein are illustrative of the principles of the inventive features. Other modifications that may be employed are within the scope of the inventive features. Thus, by way of example, but not of limitation, alternative configurations of the inventive features may be utilized in accordance with the teachings herein, e.g., at least as described in the above paragraph.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
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US201962872589P | 2019-07-10 | 2019-07-10 | |
US201962875872P | 2019-07-18 | 2019-07-18 | |
PCT/US2020/041643 WO2021007534A1 (fr) | 2019-07-10 | 2020-07-10 | Articles polymères comprenant des mélanges de pbat, de pea et d'un matériau polymère à base d'hydrate de carbone |
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EP3997171A1 true EP3997171A1 (fr) | 2022-05-18 |
EP3997171A4 EP3997171A4 (fr) | 2023-07-26 |
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JP (1) | JP2022539869A (fr) |
KR (1) | KR20220035141A (fr) |
CN (1) | CN114430759A (fr) |
WO (1) | WO2021007534A1 (fr) |
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WO2024096478A1 (fr) * | 2022-10-31 | 2024-05-10 | 주식회사 엘지화학 | Composition de résine et produit moulé en résine biodégradable la comprenant |
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ITTO20010060A1 (it) * | 2001-01-25 | 2002-07-25 | Novamont Spa | Miscele ternartie di poliesteri alifatici biodegradabili e prodotti da queste ottenuti. |
US8067485B2 (en) * | 2006-07-28 | 2011-11-29 | Biograde (Hong Kong) Pty Ltd | Masterbatch and polymer composition |
US8188185B2 (en) * | 2008-06-30 | 2012-05-29 | Kimberly-Clark Worldwide, Inc. | Biodegradable packaging film |
IT1396597B1 (it) * | 2009-11-05 | 2012-12-14 | Novamont Spa | Miscele di poliesteri biodegradabili |
IT1399031B1 (it) * | 2009-11-05 | 2013-04-05 | Novamont Spa | Copoliestere alifatico-aromatico biodegradabile |
WO2012151693A1 (fr) * | 2011-05-06 | 2012-11-15 | Cerestech, Inc. | Mélanges de polymères comprenant de l'amidon thermoplastique encapsulé dans une phase et leur procédé de fabrication |
CN105524430A (zh) * | 2014-10-22 | 2016-04-27 | 六安载丰新材料有限公司 | 一种可降解薄膜及其制备方法 |
US11111363B2 (en) * | 2015-06-30 | 2021-09-07 | BiologiQ, Inc. | Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability |
JP7250678B2 (ja) * | 2016-12-29 | 2023-04-03 | バイオロジック インコーポレイテッド | 炭水化物系ポリマー材料 |
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- 2020-07-10 JP JP2022500925A patent/JP2022539869A/ja active Pending
- 2020-07-10 EP EP20837209.4A patent/EP3997171A4/fr active Pending
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CN114430759A (zh) | 2022-05-03 |
KR20220035141A (ko) | 2022-03-21 |
WO2021007534A1 (fr) | 2021-01-14 |
EP3997171A4 (fr) | 2023-07-26 |
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