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WO2013010290A1 - Composite biodégradable par enfouissement dans le sol et produit à base de celui-ci - Google Patents

Composite biodégradable par enfouissement dans le sol et produit à base de celui-ci Download PDF

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Publication number
WO2013010290A1
WO2013010290A1 PCT/CN2011/001178 CN2011001178W WO2013010290A1 WO 2013010290 A1 WO2013010290 A1 WO 2013010290A1 CN 2011001178 W CN2011001178 W CN 2011001178W WO 2013010290 A1 WO2013010290 A1 WO 2013010290A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
acid
poly
polyhydroxyalkanoate
hydroxybutyrate
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.)
Ceased
Application number
PCT/CN2011/001178
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English (en)
Chinese (zh)
Inventor
吕渭川
张谦
胡文艳
程曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Greenbio Material Co Ltd
Original Assignee
Tianjin Greenbio Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin Greenbio Material Co Ltd filed Critical Tianjin Greenbio Material Co Ltd
Priority to PCT/CN2011/001178 priority Critical patent/WO2013010290A1/fr
Publication of WO2013010290A1 publication Critical patent/WO2013010290A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to a composition which is biodegradable and belongs to the field of polymer technology, and more particularly to a composition which can be decomposed in a common soil environment; the present invention also relates to an article of the composition.
  • Polylactic acid is a polymer obtained by artificial chemical synthesis of lactic acid produced by biological fermentation, which maintains good biocompatibility and biodegradability.
  • Polylactic acid has similar impermeability to polyester, has similar gloss, clarity and processability to polystyrene, and provides lower temperature heat sealability than polyolefin. It can be processed by melt processing technology.
  • Various packaging plastics such as plastic profiles for plastics and construction, films, and non-woven fabrics and polyester fibers for chemical and textile industries.
  • the production energy of polylactic acid is only 20%_50% of that of traditional petrochemical products, and only 50% of the carbon dioxide gas is produced.
  • Polylactic acid materials can be completely decomposed under composting conditions, but it takes a long time, which is far from meeting people's increasingly demanding environmental protection, not to mention decomposition in general soil. What is more serious is that compost decomposition needs to establish specific Composting facilities also need to provide compostable organic matter, which greatly increases the cost of waste disposal. In real life, it is very difficult for plastics to be completely recycled. There is still a large amount of plastic waste left in the environment, which seriously pollutes the living environment of residents. How to improve the degradation rate of waste polylactic acid products and reduce the cost of waste disposal is one of the problems to be solved in environmental protection work today.
  • the present invention provides a composition formed by blending polylactic acid and a polyhydroxyalkanoate, which can be treated by a soil burying method, and the composition is very It completely decomposes in the soil quickly, which not only increases the decomposition rate of the polylactic acid material, but also reduces the processing cost of the polylactic acid product.
  • the present invention also provides an article of the composition comprising a heat-shrinkable film of a food package, a plastic sheet, a foamed material, a woven product, which can be quickly decomposed in a natural environment after being discarded.
  • Polyhydroxyalkanoate is a class of biodegradable materials that can be completely decomposed into carbon dioxide and water in the natural environment. Decomposition is first of all under certain conditions, a variety of microorganisms attached to the surface of the polymer to release a specific decomposing enzyme, under the catalysis of the enzyme, the polymer is broken down into small segments, when the molecular weight drops to a certain extent, it will be very It is easily absorbed by microorganisms and digested. Many factors have an impact on the decomposition process of the material. In a sense, the structure of the material determines the strength of biodegradability.
  • a composition which can be biodegraded by soil burying method comprising polylactic acid and polyhydroxyalkanoate, the polyhydroxyalkanoate accounting for 20%-90 of the mass fraction of the composition. %.
  • the polyhydroxyalkanoate comprises from 25% to 75% of the mass fraction of the composition.
  • the polyhydroxyalkanoate is selected from the group consisting of poly(3-hydroxybutyric acid-CO-3-hydroxyvaleric acid), poly(3-hydroxybutyric acid-CO-3-hydroxyhexanoic acid), poly(3) - hydroxyvaleric acid -CO-3-hydroxyhexanoic acid), one of poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester.
  • the polyhydroxyalkanoate is poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester, wherein a component of the monomer unit 4-hydroxybutyric acid accounts for the poly(3-hydroxyl group) 5% to 20% by mass ratio of butyric acid-CO-4-hydroxybutyrate), and the poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester has a weight average molecular weight of 300,000 to 400,000 The crystallinity is between 43% and 53%.
  • the polylactic acid is L-polylactic acid having a molecular weight of between 180,000 and 250,000.
  • the polyhydroxyalkanoate of the present invention is selected from the group consisting of poly(3-hydroxybutyric acid-CO-3-hydroxyvaleric acid) and poly(3-hydroxybutyric acid-CO-3-hydroxyl group).
  • One of hexanoic acid), poly(3-hydroxyvaleric acid-CO-3-hydroxyhexanoic acid), and poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester is preferred, which can be produced in various microorganisms and can be decomposed by various microorganisms, and has good Biodegradability and biocompatibility.
  • the copolymerization unit 4-hydroxybutyric acid has a great influence on the properties of P(3HB-4HB).
  • the difference in the composition of 4HB determines whether the copolymer is crystalline or elastomer, and its mechanical properties are greatly changed. It is important that the 4HB content has a large effect on the rate of decomposition of the copolymer.
  • the molecular arrangement of the PLA material is relatively regular and the crystallinity is high, so the biodegradation rate is relatively slow.
  • PHA PHA
  • the microorganism first erodes the surface of the PHA.
  • the enzyme secreted by the microorganism then acts on the ester bond in the PHA to cause decomposition.
  • the small molecular intermediates and microbial secretions produced during the decomposition of PHA can be used as a nutrient or growth promoter for degrading PLA microorganisms, promoting their rapid growth and reproduction, forming the advantage of degrading PLA micro-ecological regions, thus destroying the entire crystal.
  • titanate coupling agent may be added, and the titanate coupling agent is titanium monoalkoxy fatty acid or titanium monoalkoxy phosphate. It can bend and entangle the long, soft aliphatic carbon chain and organic binder, enhance the bonding force with the binder, improve their compatibility, cause the surface energy of the filler to change, resulting in a significant decrease in viscosity, and improve the filler. And the melt flow and processing of the binder system.
  • a free radical initiator such as benzoyl peroxide may be added, and the radical initiator is selected from one of benzoyl peroxide, peroxydicarbonate, and azobisisobutyronitrile.
  • PLA-PHA graft or block copolymer Under heating conditions, it promotes radical polymerization of the free radical chain formed by homopolymerization of the covalent bond of the polymer to form a PLA-PHA graft or block copolymer. Since PHA is easily decomposed by microorganisms, when PHA is degraded in the block copolymer, more polar end groups are left in the copolymer matrix, which accelerates the decomposition of PLA.
  • FIGS. 1 to 10 are views showing states of different burying times when a first embodiment of the present invention is buried at 20 cm.
  • 11 to 20 are views showing states of different burying times when the first embodiment of the present invention is buried at 40 cm.
  • 21 to 30 are views showing states of different burying times when the second embodiment of the present invention is buried at 20 cm.
  • 31 to 40 are views showing states of different burying times when the second embodiment of the present invention is buried at 40 cm.
  • 41 to 50 are views showing states of different burying times when the third embodiment of the present invention is buried at 20 cm.
  • 51 to 60 are views showing states of different burying times when the third embodiment of the present invention is buried at 40 cm.
  • 61 to 70 are views showing states of different burying times when the fourth embodiment of the present invention is buried at 20 cm.
  • 71 to 80 are views showing states of different burying times when the fourth embodiment of the present invention is buried at 40 cm.
  • 81 to 84 show detection views of SEMs of different buried times of the first embodiment of the present invention.
  • 85 to 87 show detection views of SEMs of different buried times of the second embodiment of the present invention.
  • 88 to 90 are diagrams showing the detection of SEM of different buried times in the third embodiment of the present invention.
  • Poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester can be produced according to a conventional production method in which a monomer unit of 4-hydroxybutyric acid accounts for the poly(3-hydroxyl group).
  • the poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester used in this example is derived from Tianjin Guoyun Biomaterial Co., Ltd.
  • Test unit test conditions Test standard mg/cm 1. 2 A method GB/T 1033-2008 Glass transition temperature "C 1 DSC method melting temperature” C 142 GB/T 19466-2004 Melt index g/10min 3. 6 170°C, 2. 16kg GB/T 3682-2000 Tensile strength MPa 33
  • Type 1A specimen lOOmm/min GB/T 1040. 2-2006 Elongation at break % 10 Notched impact strength kj/m 2 9. 2 Cantilever beam: A-notch GB/T 1843-2008 Bending strength MPa 42 Speed: 2 mm/min
  • Polylactic acid is a commercially available L-polylactic acid.
  • Parameter item means the test condition test standard white to pale yellow, regular, columnar particles; no odor density g/cm 1.
  • 25 A Method GB/T 1033-2008 Melt index g/10min 3 170°C, 2. 16kg GB/T 3682-2000 Melting point °C 210 Molecular weight million 22 Vicat softening point °C 90 A 50 method GB/T 1633-2000 Pull Stretching portrait 41
  • the film selected in the examples of the present invention can be produced by a conventional method in which poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) ester and L-polylactic acid are melted, mixed, and then extruded.
  • the test area size is: 4m X 6m long plot.
  • the test period is from May 2010 to December 2010.
  • the test area is planted with grass seeds and watered regularly.
  • the prepared film strips were filled in the soil landfill experimental zone according to the ratio of different poly(3-hydroxybutyric acid-CO-4-hydroxybutyric acid) esters, and the filling depth was 20 cm and 40 cm.
  • the film samples were taken for photographing and performance testing.
  • Test items include: photo taking, dimensional measurement, infrared, and electron microscopy.
  • the numbers shown in the figure are, for example, 50-21-20, where 50 is PHA 50%, 21 is the number of days of excavation, and 20 is 20 cm from the ground.
  • a colorant is added to make the composition white.
  • the sample fill depth is 20 cm, and the results are shown in Fig. 61-70.
  • the samples were selected and examined by SEM scanning electron microscopy.
  • Scanning electron microscopy SEM was used as a material observation method to observe the surface morphology and crystal structure of the material.
  • SEM scanning electron microscopy
  • the SEM photo shows that as the decomposition time increases, significant voids and cracks appear on the surface of the material, indicating that the material has decomposed. As shown in Figure 81-90.
  • the film Compared with the film with different landfill time, the film showed a gradual decomposition as the landfill time increased.
  • the decomposition process is the occurrence of decomposed spots, which are gradually broken and broken into smaller pieces.
  • the decomposability of the film gradually increases.
  • the decomposition performance increases with the PHA/PLA ratio, the decomposition of the film becomes more pronounced, and the time required is shorter.
  • the film with a PHA ratio of 25% showed obvious breakage at 105 days. From the results of electron scanning electron microscopy, the intermolecular force had begun to change at 42 days, and it was broken at 126 days. Smaller pieces.
  • the film with a PHA ratio of 50% has been ruptured significantly at 42 days. From the results of its scanning electron microscopy, the surface has become quite rough, indicating that the decomposition effect of the microorganism on the film is already very obvious. A film with a PHA ratio of 75% has been substantially decomposed at 63 days.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition biodégradable par enfouissement dans le sol, comprenant de l'acide polylactique et un polyhydroxyalcanoate, lequel polyhydroxyalcanoate représente de 20 à 90 % en poids de la composition. Ledit polyhydroxyalcanoate est du poly(3-hydroxybutyrate-co-4-hydroxybutyrate) dans lequel le composant correspondant au motif monomère de 4-hydroxybutyrate représente de 5 à 20 % en poids du poly(3-hydroxybutyrate-co-4-hydroxybutyrate), la masse moléculaire moyenne en poids du poly(3-hydroxybutyrate-co-4-hydroxybutyrate) se situe dans un intervalle de 300 000 à 400 000 et le degré de cristallisation peut varier de 43 à 53 %. Lorsque la composition de la présente invention se dégrade après son enfouissement dans le sol, les microorganismes s'attaquent d'abord à la surface du PHA, puis les enzymes sécrétées par les microorganismes agissent sur une liaison ester du polyhydroxyalcanoate et la rompent, ce qui entraîne la destruction de la régularité de la structure de l'intégralité du cristal et une réduction de la force intermoléculaire. En conséquence, les microorganismes peuvent aisément attaquer ou briser la chaîne moléculaire, ce qui améliore significativement la vitesse de dégradation de la composition. Plus important encore, il n'est pas nécessaire de composter la composition et elle peut subir une dégradation complète et rapide suite à son enfouissement dans le sol.
PCT/CN2011/001178 2011-07-18 2011-07-18 Composite biodégradable par enfouissement dans le sol et produit à base de celui-ci Ceased WO2013010290A1 (fr)

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PCT/CN2011/001178 WO2013010290A1 (fr) 2011-07-18 2011-07-18 Composite biodégradable par enfouissement dans le sol et produit à base de celui-ci

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1923890A (zh) * 2006-08-29 2007-03-07 天津国韵生物科技有限公司 用于发泡材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
CN101210101A (zh) * 2006-12-29 2008-07-02 天津国韵生物科技有限公司 用于片材、薄膜、管材、纤维材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
CN101387046A (zh) * 2008-09-23 2009-03-18 中国民航大学 可生物完全降解的无纺织物及其专用熔喷装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1923890A (zh) * 2006-08-29 2007-03-07 天津国韵生物科技有限公司 用于发泡材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
CN101210101A (zh) * 2006-12-29 2008-07-02 天津国韵生物科技有限公司 用于片材、薄膜、管材、纤维材料的含聚羟基丁酸酯共聚物和聚乳酸的组合物
CN101387046A (zh) * 2008-09-23 2009-03-18 中国民航大学 可生物完全降解的无纺织物及其专用熔喷装置

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