WO2022146162A1 - Composition et procédé de production de bio-nanocomposites remplis de minéraux argileux - Google Patents

Composition et procédé de production de bio-nanocomposites remplis de minéraux argileux Download PDF

Info

Publication number
WO2022146162A1
WO2022146162A1 PCT/RU2020/000781 RU2020000781W WO2022146162A1 WO 2022146162 A1 WO2022146162 A1 WO 2022146162A1 RU 2020000781 W RU2020000781 W RU 2020000781W WO 2022146162 A1 WO2022146162 A1 WO 2022146162A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
bio
nanocomposite
palygorskite
vinyltrimethoxysilane
Prior art date
Application number
PCT/RU2020/000781
Other languages
English (en)
Russian (ru)
Inventor
Георгий Иванович ЛАЗОРЕНКО
Антон Сергеевич КАСПРЖИЦКИЙ
Original Assignee
Общество С Ограниченной Ответственностью "Научно-Производственное Объединение "Минералика"
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 Общество С Ограниченной Ответственностью "Научно-Производственное Объединение "Минералика" filed Critical Общество С Ограниченной Ответственностью "Научно-Производственное Объединение "Минералика"
Priority to PCT/RU2020/000781 priority Critical patent/WO2022146162A1/fr
Publication of WO2022146162A1 publication Critical patent/WO2022146162A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • 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

Definitions

  • the invention relates to the field of polymer nanocomposites and methods for their production, namely the field of creating biodegradable organic-inorganic polymer nanocomposite materials, and can be used for the production of a polymer bio-nanocomposite in the form of extruded threads and nanocomposite chips for the manufacture of packaging, covering material and products, production of textiles and non-woven materials for the food industry and the agro-industrial sector; production of materials and products for the pharmaceutical, medical and perfumery-cosmetic industries.
  • Poly(lactic acid) or polylactide (PLA) is a linear aliphatic thermoplastic polyester and is one of the most promising biodegradable polymers.
  • PLA is synthesized from renewable resources such as corn, rice, potatoes or sugar cane and has great potential as a candidate for replacing traditional non-degradable polymers - petrochemical products that have caused significant environmental pollution to date and require the development of special methods for their disposal [ fourteen].
  • the competitiveness of PLA is due to its best processability among other biopolymers during heat treatment, high melting point and plasticity, which allows its processing on existing production extrusion lines [5,6], the possibility of recycling the polymer mass [7,8], biocompatibility and good speed. biological degradation [9-11], as well as relatively low cost [12].
  • the production of PLA requires 40% less energy than the production of polymers from petroleum products, and further cost reduction ( ⁇ 10%) is possible [13]. This opens up prospects for the introduction of PLA in a wide range of areas of production, primarily in the food and agricultural sectors of the economy, as a packaging material, as well as in the pharmaceutical and medical industries.
  • Clay minerals are a class of natural minerals with a layered crystal structure and a controlled adsorption surface [24]. Such features make these inorganic materials interesting for industrial applications, since they can impart improved mechanical and barrier properties to composite materials, achieving these effects at a low content in the polymer matrix [25]. Such improvements are associated with the emerging interfacial structure of the composite, caused by layered silicate delamination during the intercalation of polymer chains into its interlayer space, and are determined by two main factors: the degree of affinity in the “polymer matrix-layered silicate” system and the method for obtaining a specific polymer composition [2,25- 27].
  • the identified aspects of improving the affinity of silicates with the polymer matrix and the morphology of clay particles are fully related to minerals of the sepiolite-palygorskite group, which feature an extended ribbon (chain) structure [28].
  • the increased adsorption area of these minerals, due to the extended structure of silicate layers, can provide the formation of a greater number of interfacial interactions and, as a result, leads to an increase in their affinity for polymer chains with appropriate surface modification.
  • polymer chains can diffuse into the interlayer space of layered silicates, forming from an intercalated to exfoliated structure (depending on the degree of penetration of polymer chains into the interlayer space of layered silicate) [25];
  • a known method of compounding poly(lactic acid) (PLA) with a layered clay mineral comprising the following steps: (1) mixing layered clay mineral with methanol; (2) drying the resulting material to a solid; and (3) melt blending the dry processed layered clay mineral in an amount of 5-40 wt % with PLA in an extruder.
  • the use of talc is preferred.
  • the authors point to an increase in the compatibility of the layered clay mineral with PLA, and an increase in the thermal stability of the composition (JP2003313307A [30]).
  • the presented solution has a number of significant limitations associated with the fact that the use of fillers such as clay minerals, which are hydrophilic in nature, in a hydrophobic polymer matrix leads to microcomposites.
  • composition based on PLA obtained by mixing layered silicate, previously dispersed in water or an aqueous solvent, with PLA at a composition temperature of 0 °C or higher without exceeding the melting point of PLA.
  • Mixing according to the method described is preferably carried out with a twin screw extruder.
  • the mixing method aims to improve the dispersibility of the layered silicate in the polymer matrix and impart improved properties to the polymer composition (JP2004027136A [31]).
  • the proposed method has limitations: for example, despite the fact that the proposed approach to the dispersion of layered silicate is not new and is used in extrusion lines, the mixing of layered silicate dissolved in water with PLA at a temperature not exceeding its melting point cannot be used in existing extrusion lines.
  • an inorganic additive a metal hydroxide, metal hydrate, and/or layered silicate is used. It is preferable to use aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium aluminate hydrate, tin oxide hydrate, zinc nitrate hexahydrate and nickel nitrate hexahydrate.
  • the inorganic powder contains talc, smectite, kaolin, mica and/or montmorillonite.
  • the content of the plasticizer and nucleating agent JP5608540B, CN 103260840B [32,33] is provided.
  • the proposed solution has a limitation: when using metal oxides, zinc nitrate hexahydrate and nickel nitrate hexahydrate as an inorganic additive, the improvement of mechanical properties occurs in a limited range, due to the lack of a compatibilizer. In addition, the morphology of such particles does not significantly affect the mechanical properties of the composition.
  • the use of layered silicates in this method does not lead to their delamination and provides the formation of only a microcomposite, which does not lead to a significant increase in mechanical and barrier properties.
  • a method for producing a nanocomposite based on polylactide and clay minerals including obtaining modified clays by introducing a lactide copolymer or obtaining a modified clay by introducing a copolymer of lactide and caprolactone into a clay having hydroxyl groups on the surface by ring-opening polymerization; and melt mixing of modified clay, aliphatic polyester plasticizer and high molecular weight polylactide to obtain a new polylactide/clay nanocomposite (patent KR100683941 B1 [34]).
  • the limitation of this method of obtaining a composite is the mechanism of interfacial bonding, which requires the presence of hydroxyl groups on the surfaces of clay minerals. This significantly limits the range of application of clay minerals for this case.
  • not all surfaces of clay minerals contain similar molecular groups, which makes this binding mechanism selective and leads to differentiation of properties on different mineral surfaces, reducing the isotropy of the final composite.
  • the technical task and technical result of the invention is to develop a composition of a polymer bio-nanocomposite based on polylactide and a method for its production, providing high mechanical and barrier properties of the polymer composition, with the possibility of its compounding on standard industrial equipment.
  • bio-nanocomposite material containing a polymer matrix and a nanofiller, characterized in that the polymer matrix is a polylactide, and as a nanofiller, the bio-nanocomposite material contains palygorskite (attapulgite) silanized and surface-modified with vinyltrimethoxysilane ), with the following ratio of components, wt.%: palygorskite silanized and surface-modified with vinyltrimethoxysilane - 0.1-11.0; polylactide - the rest.
  • palygorskite attapulgite silanized and surface-modified with vinyltrimethoxysilane
  • the bio-nanocomposite material is in the form of extruded filaments or polymer chips.
  • the mixture of palygorskite and vinyltrimethoxysilane is preliminarily, prior to the introduction of an organic solvent, homogenized using ultrasonic treatment with a power of 100-2500 W.
  • step (a) mixing is carried out by constant mixing with a rotation speed of 500-2000 rpm. at a temperature of 45-75 °C and pH 4-6.
  • the monohydric alcohol is ethanol.
  • the obtained bio-nanocomposite material is drawn in a twin screw extruder to obtain extruded filaments.
  • the obtained extruded threads are crushed into particles of equal size to obtain polymer chips.
  • the morphology of the selected clay mineral palygorskite (attapulgite) with a ribbon (chain) structure (having a fibrous morphology) provides an increased reinforcing effect, and the modifying agent used (vinyltrimethoxysilane), due to the presence of functional vinyl groups that react with polyesters and hydroxyl groups, forms a bond with mineral surfaces and provides an increase in affinity in the system "polylactide - clay mineral with a ribbon (chain) structure", playing the role of a crosslinking agent.
  • the uniform distribution of the clay mineral in the polymer matrix is accompanied by an additional "cross-linking", reinforcing effect between the components of the polymer compound, which is achieved by surface modification of the clay mineral with vinyltrimethoxysilane.
  • Such a uniform distribution of the nanofiller also provides a decrease in the permeability coefficient, hindering the diffusion of gases, and thereby providing improved barrier properties of the bionanocomposite.
  • a synergistic effect is achieved, which consists not only in improving the mechanical properties of the resulting polymeric bio-nanocomposite, but also in an increase in barrier properties, which significantly increases the diffusion path for gases and molecular agents of the resulting polymer composition.
  • the polymeric bio-nanocomposite according to the invention can be obtained on existing industrial extrusion lines and used for the manufacture of packaging, covering material and products, the production of textiles and non-woven materials for the food industry and the agro-industrial sector, as well as for the manufacture of materials and products for the pharmaceutical, medical and perfumery-cosmetic industries.
  • Fig. 1 Chemical-technological scheme for the implementation of the method for obtaining a bionanocomposite filled with clay minerals. The stages of implementation of this procedure are presented.
  • Fig. 3 - IR spectra of polylactide (PLA) and bio-nanocomposite according to the invention - polylactide filled with palygorskite modified with vinyltrimethoxysilane (PLA/PAL/VTMS).
  • Fig. 4 Results of mechanical tensile and bending tests of samples of polylactide (PLA) and bio-nanocomposite according to the invention - polylactide filled with palygorskite modified with vinyl trimethoxysilane (PLA / PAL / VTMS).
  • “Nanocomposite” a multicomponent composite material consisting of 2 or more separated phases, in which at least one of the phases has an average size of individual elements (particles, crystallites, fibers, plates, etc.) less than 100 nm at least in one dimension.
  • Organicsilicon compound - silane derivatives containing silicon-carbon (nitrogen) bonds and providing the functionalization of the mineral surface by attaching a silane group to it through a covalent bond, which allows the formation of cross-linking bonds at the interface between the mineral and organic components of the system.
  • Polylactide is an aliphatic polyester whose monomer is lactic acid. Both lactic acid and lactide exhibit optical activity, that is, they exist as two L- and D- stereoisomers, which are mirror images of each other. Within the scope of the present invention, the stereoisomer of the polylactide, as well as the relative content of these forms in the polylactide, may be arbitrary.
  • the method for producing the polymeric bionanocomposite material according to the invention is shown in FIG. 1 and includes the following operations:
  • PAL palygorskite
  • crosslinking agent an organosilicon compound from the group of silane derivatives - vinyltrimethoxysilane. Grafting is carried out by mixing PAL with an organosilicon compound in an organic solvent, which is a monohydric alcohol (eg, methanol, ethanol). The ratio of PAL and monohydric alcohol is chosen in the range from 1/20 to 1/60. Vinyltrimethoxysilane is added to the resulting mixture in a ratio of 25 wt.% to 50 wt.% of the original PAL.
  • a monohydric alcohol eg, methanol, ethanol
  • the mixture is pre-homogenized (for example, using ultrasonic treatment with a power of 100-2500 W or a magnetic stirrer at a speed of 1500-2500 rpm for 4 to 12 hours) and then its uniformity is maintained (in the preferred embodiment, mixing can be used with a rotation speed of 500-2000 rpm with a constant temperature in the range of 45-75 ° C) with a specified pH range (4-6);
  • extruder parameters for example, can be: D> 28 mm, L / D> 48: 1 (hereinafter D is the screw diameter, L is the length of the barrel), the screw speed is at least 80 rpm) based on pre-dried polylactide (preferably at a temperature in the range of 30-90°C), with direct controlled introduction of the prepared nanofiller (in the amount of 01.-11.0 wt.%) at a temperature exceeding the melting point of polylactide (i.e. not less than 170-180°C; in private cases, choose a temperature of 180-210°C), which allows you to get homogenized polymer mixture in the melt.
  • the polymer composition thus obtained is produced in the form of an extruded thread; after cooling, if necessary, the production of polymer chips (granulate) on its basis is carried out.
  • the polymeric bio-nanocomposite material obtained according to the proposed invention contains:
  • nanofiller based on palygorskite, which is surface-modified with an organosilicon compound from the group of silane derivatives, vinyltrimethoxysilane.
  • the nanofiller is used in an amount of 0.1-11% of the total mass of the nanocomposite material;
  • thermoplastic complex polyester polylactide
  • Example 1 Obtaining a nanofiller
  • palygorskite (30 grams) and ethyl alcohol (600 grams) were mixed in a ratio of 1:20.
  • the resulting mixture was sequentially treated with 500 W ultrasound for 30 minutes and 30 minutes on a magnetic stirrer at a speed of 1500 rpm at room temperature to homogenize the suspension.
  • vinyltrimethoxysilane (7.5 grams, which corresponds to 25 wt.% with respect to the original palygorskite) was added to the resulting mixture.
  • the resulting mixture was then adjusted to pH 4.5-5.5 by adding a solution of acetic acid (1.25 ml) in deionized water (30 ml).
  • the pre-dried components of the polymer composition (palygorskite (7 wt%) silanized and surface-modified with vinyltrimethoxysilane and polylactide (93 wt%)) were mechanically mixed for 10–12 hours at a temperature of 80°C in an oven and fed into the extruder loading zone.
  • the twin-neck extruder after melting the polymer matrix, makes it possible to homogenize the components in the melt, where, due to the action of strong shear forces, the ingredients are distributed in the melt (Fig. 1).
  • FIG. 3 shows the IR spectrum of polylactide (PLA) and bio-nanocomposite according to the invention - polylactide filled with palygorskite modified with vinyltrimethoxysilane (PLA/PAL/VTMS).
  • PLA polylactide
  • PLA/PAL/VTMS palygorskite modified with vinyltrimethoxysilane
  • a polymeric bio-nanocomposite material was used, obtained according to examples 1 and 2, containing: nanofiller (silanized and surface-
  • Example 4 Comparative analysis of a bio-nanocomposite material according to the invention with a material based on palygorskite silanized with 3-aminopropyltriethoxysilane
  • JP2004027136 A Polylactic acid-based resin composition, process for producing the same and processed product using polylactic acid-based resin composition as stock material. Published: 29.01.2004

Landscapes

  • 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)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matériaux polymères nanocomposites et des procédés de production de ces derniers. L'invention concerne un bio-nanocomposite (BNC) qui se présente sous forme de fils extrudés et de morceaux nanocomposites, et qui peut être utilisé afin de produire un matériau d'emballage ou de couverture ainsi que des articles, d'élaborer des articles textiles et des matériaux non tissés pour l'industrie alimentaire et le secteur agro-alimentaire, ainsi que pour produire des matériaux et des articles pour le domaine pharmaceutique, médical et de la parfumerie et de la cosmétique. Ce BNC comprend une matrice polymère (acide polylactique et matière de charge), de la palygorskite (attapulgite) à modification de surface selon le rapport suivant des composants en % en poids: matière de charge 0,1-11,0, le reste se composant de la matrice polymère. On utilise en qualité de modificateur du vinyltriméthoxsilane. L'invention permet de produire un BNC ayant de meilleures propriétés mécaniques et de barrière sur des chaînes d'extrusion industrielles existantes.
PCT/RU2020/000781 2020-12-30 2020-12-30 Composition et procédé de production de bio-nanocomposites remplis de minéraux argileux WO2022146162A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/RU2020/000781 WO2022146162A1 (fr) 2020-12-30 2020-12-30 Composition et procédé de production de bio-nanocomposites remplis de minéraux argileux

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/RU2020/000781 WO2022146162A1 (fr) 2020-12-30 2020-12-30 Composition et procédé de production de bio-nanocomposites remplis de minéraux argileux

Publications (1)

Publication Number Publication Date
WO2022146162A1 true WO2022146162A1 (fr) 2022-07-07

Family

ID=82260939

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2020/000781 WO2022146162A1 (fr) 2020-12-30 2020-12-30 Composition et procédé de production de bio-nanocomposites remplis de minéraux argileux

Country Status (1)

Country Link
WO (1) WO2022146162A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9447283B2 (en) * 2011-02-01 2016-09-20 Tolsa, S.A. Method for producing a compound based on pseudolaminar silicates and the use thereof as a filler for polymeric materials
WO2019219546A1 (fr) * 2018-05-16 2019-11-21 Byk-Chemie Gmbh Composition d'acide polylactique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9447283B2 (en) * 2011-02-01 2016-09-20 Tolsa, S.A. Method for producing a compound based on pseudolaminar silicates and the use thereof as a filler for polymeric materials
WO2019219546A1 (fr) * 2018-05-16 2019-11-21 Byk-Chemie Gmbh Composition d'acide polylactique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUPRAKAS SINHA RAY, MASAMI OKAMOTO: "Polymer/layered silicate nanocomposites: a review from preparation to processing", PROGRESS IN POLYMER SCIENCE, PERGAMON, vol. 28, no. 11, 1 November 2003 (2003-11-01), pages 1539 - 1641, XP055018743, ISSN: 00796700, DOI: 10.1016/j.progpolymsci.2003.08.002 *

Similar Documents

Publication Publication Date Title
Yee et al. Preparation and characterization of poly (lactic acid)-based composite reinforced with oil palm empty fruit bunch fiber and nanosilica
Pracella et al. Morphology and properties tuning of PLA/cellulose nanocrystals bio-nanocomposites by means of reactive functionalization and blending with PVAc
Luo et al. Effect of TiO2 nanoparticles on the long-term hydrolytic degradation behavior of PLA
Hoidy et al. Preparation and characterization of polylactic acid/polycaprolactone clay nanocomposites
Shah et al. Nylon 6 nanocomposites prepared by a melt mixing masterbatch process
Kumar et al. Effect of glycidyl methacrylate (GMA) on the thermal, mechanical and morphological property of biodegradable PLA/PBAT blend and its nanocomposites
Ren et al. Preparation, characterization and properties of poly (vinyl chloride)/compatibilizer/organophilic-montmorillonite nanocomposites by melt intercalation
As’habi et al. Tuning the processability, morphology and biodegradability of clay incorporated PLA/LLDPE blends via selective localization of nanoclay induced by melt mixing sequence
Sabet et al. Interfacially compatibilized poly (lactic acid) and poly (lactic acid)/polycaprolactone/organoclay nanocomposites with improved biodegradability and barrier properties: effects of the compatibilizer structural parameters and feeding route
Shayan et al. Effect of modified starch and nanoclay particles on biodegradability and mechanical properties of cross-linked poly lactic acid
Kumar et al. Studies of poly (lactic acid) based calcium carbonate nanocomposites
US20110263776A1 (en) Resin Compositions Comprising Polyolefins, Poly(hydroxy Carboxylic Acid) and Nanoclays
Paci et al. Nanostructure development in nylon 6-Cloisite® 30B composites. Effects of the preparation conditions
Wang et al. Effects of organoclay platelets on morphology and mechanical properties in PTT/EPDM-g-MA/organoclay ternary nanocomposites
Wu et al. Linear rheological behaviour and thermal stability of poly (butylene terephthalate)/epoxy/clay ternary nanocomposites
Motamedi et al. Modification of nanostructure and improvement of mechanical properties of polypropylene/polyamide 6/layered silicate ternary nanocomposites through variation of processing route
Cailloux et al. Reactive extrusion: A useful process to manufacture structurally modified PLA/o-MMT composites
Keshavarzi et al. ZnO nanoparticles as chain elasticity reducer and structural elasticity enhancer: Correlating the degradating role and localization of ZnO with the morphological and mechanical properties of PLA/PP/ZnO nanocomposite
EP2861658B1 (fr) Compositions biodegradables
Jena et al. New strategies for the construction of eggshell powder reinforced starch based fire hazard suppression biomaterials with tailorable thermal, mechanical and oxygen barrier properties
Palma-Ramírez et al. An assembly strategy of polylactic acid (PLA)-SiO2 nanocomposites embedded in polypropylene (PP) matrix
Daitx et al. Kaolinite-based Janus nanoparticles as a compatibilizing agent in polymer blends
Girdthep et al. Formulation and characterization of compatibilized poly (lactic acid)‐based blends and their nanocomposites with silver‐loaded kaolinite
JPH10182892A (ja) 粘土複合材料及びその製造方法
Xu et al. Synthesis, characterization and its compatibilization on polymer blends of arched Janus nanosheets

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20968104

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20968104

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 07/12/2023)