EP4355938A1 - Procédé de préparation de systèmes composites autorenforçants structurés hiérarchiquement à base de biopolymères d'acide polylactique, et de tels systèmes composites - Google Patents

Procédé de préparation de systèmes composites autorenforçants structurés hiérarchiquement à base de biopolymères d'acide polylactique, et de tels systèmes composites

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Publication number
EP4355938A1
EP4355938A1 EP22760646.4A EP22760646A EP4355938A1 EP 4355938 A1 EP4355938 A1 EP 4355938A1 EP 22760646 A EP22760646 A EP 22760646A EP 4355938 A1 EP4355938 A1 EP 4355938A1
Authority
EP
European Patent Office
Prior art keywords
polylactic acid
poly
lactide
temperature
fabric
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
Application number
EP22760646.4A
Other languages
German (de)
English (en)
Inventor
Martin BORUVKA
Petr LENFELD
Ondrej BATKA
Josef SKRIVANEK
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.)
Technicka Univerzita v Liberci
Original Assignee
Technicka Univerzita v Liberci
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 Technicka Univerzita v Liberci filed Critical Technicka Univerzita v Liberci
Publication of EP4355938A1 publication Critical patent/EP4355938A1/fr
Pending legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/208—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
    • D03D15/225—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based artificial, e.g. viscose
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/30—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the fibres or filaments
    • D03D15/33—Ultrafine fibres, e.g. microfibres or nanofibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D10B2331/041—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/30—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensation products not covered by indexing codes D10B2331/02 - D10B2331/14
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/12—Physical properties biodegradable
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs

Definitions

  • the invention relates to a method of preparation of hierarchically structured self-reinforcing composite systems based on biopolymers of polylactic acid.
  • the invention relates to composite systems prepared by this method.
  • biodegradable polymers which are prepared from renewable raw material sources, have been the subject of ever-increasing interest.
  • the advantages of these materials primarily include their effect on reducing the carbon footprint, environmental benefits resulting from their ability to biodegrade and the potential to be sustainable material systems of the future.
  • biopolymers falling into this group are aliphatic polyesters, such as polyhydroxyalkanoates (PHA) and polylactic acid (PLA), which is also often called polylactide.
  • PLA With intensive research into the production of second and third generation high molecular weight PLA using lignocellulose-based raw material sources and direct conversion of greenhouse gases to lactic acid using microorganisms, PLA will gain in importance.
  • lactic acid contains a chiral carbon atom
  • L and D there are two optical isomeric forms of lactic acid monomer, referred to as L and D, i.e. , poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA).
  • L and D poly(L-lactide)
  • PLLA poly(L-lactide)
  • PDLA poly(D-lactide)
  • an amorphous or semicrystalline polymer can be prepared at a glass transition temperature (T g ) in the range of 50 °C to 60 °C and a melting temperature (Tm) in the range of 130 °C to 180 °C.
  • PLA is subject to biodegradation and, thanks to its good biocompatibility and bioresorbability, it belongs to the most widely studied polymers in clinical biomedical studies. In recent years, it has attracted interest not only as a replacement for traditional petroleum-based synthetic polymers, but also as a special polymer in various applications.
  • PLA also exhibits some properties that limit its use in technical applications. These properties mainly include low impact resistance and high brittleness, which are related to the glassy state of PLA at normal room temperature.
  • the low temperature resistance of PLA is mainly related to poor homonucleation of PLA and insufficient mobility of macromolecular chains during crystallization from melts. Since there is an ever-increasing interest in a long-term sustainable economy that is environmentally friendly, it is necessary to overcome the shortcomings mentioned above.
  • many strategies have been implemented in the last decades to improve the utility properties of PLA. The most commonly used strategies include heterogeneous nucleation, plasticization using plasticizers, copolymerization and mixing (blending) with other polymers.
  • PLA stereocomplexation Another option to improve the utility properties of PLA is stereocomplexation, which was described for the first time in 1987 by Ikada et al. [1 ],
  • the formation of a PLA stereocomplex (sc-PLA) between the optical isomers poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) leads not only to an increase in mechanical properties, but also to an increase in thermal and hydrolytic resistance.
  • sc-PLA melt samples by blending (mixing) PLLA/PDLA followed by an additional crystallisation step in the presence of steam or supercooled water at a temperature of 120 to 200 °C is disclosed in international application W02016172011A1 .
  • Application WO2014147132A1 describes the preparation of sc-PLA by mixing solutions or melts using specific nucleating agents.
  • the production of sc-PLA based samples by injection molding of PLLA/PDLA mixtures (blends) under specific temperature and pressure conditions is disclosed in international application W02008104757A1 .
  • Nanofibers are obtained by a complex process of spinning the PLLA/PDLA blend from a melt, which is followed by heat treatment, washing, selective extraction, drying and hot pressing.
  • the object of the invention is to provide a method of preparation of hierarchically structured self-reinforcing composite systems based on polylactic acid biopolymers and such composite systems. These systems will significantly improve the mechanical properties and temperature resistance of traditional PLA- based products, increasing their applicability in replacing fossil based polymers. Other advantages of such systems can be seen especially in the reduction of the carbon footprint and the fact that these materials can be completely based on renewable raw materials with targeted recyclability or biodegradability.
  • the object of the invention is achieved by a method of preparation of hierarchically structured self-reinforcing composite systems based on biopolymers of polylactic acid (PLA), which include nanofibers based on poly(L- lactide) (PLLA) or based on an asymmetric or symmetrical blend of poly(L-lactide) and poly(D-lactide) (PDLA).
  • PLA polylactic acid
  • these nanofibers are prepared by spinning a solution, preferably, for example, by the method according to WO2014094694A1 , using alternating current, where an electric field for spinning is alternately created between a spinning electrode to which alternating voltage is applied and air and/or gas ions created and/or brought into its vicinity.
  • a polymer dosing device known from W02019047990A1 and/or a spinning electrode in one of the embodiments known from W02017108012A1 can be used.
  • the nanofibers formed are carried in the direction of the gradient of the electric field away from the spinning electrode, forming a hollow plume (sleeve).
  • This is then deposited according to the method of WO2016192697A2 on a supporting fibrous core which rotates around its own axis and/or balloons, creating a nanofibrous sheath on its surface.
  • Another method of creating such a two-component linear structure is also known from WO2008149488A1 .
  • the formed two-component core yam 1. contains a fibrous core 2 on which a nanofibrous sheath 3 is deposited, the nanofibrous sheath 3 being formed by a nanofibrous plume wound in a helix.
  • the fibrous core 2 consists of a monofilament (see Figure 1 ) or multifilament (see Figure 2) textile yarn made from PLA biopolymer. This yam unwinds and simultaneously rotates around its own axis and/or balloons in the working space of the device in which the electrically neutral nanofibrous plume is created. Upon contact of the plume with the fibrous core 2, the plume is transformed into a flat stripe of oriented nanofibers and spirally wraps around the fibrous core 2.
  • the density of the nanofibrous sheath 3 thus formed can be controlled by the rate at which the solution is dispensed onto the surface of the spinning electrode and/or by the rate at which the continuous fibrous core 2 is unwound.
  • Both the fibrous core 2 and the nanofibrous sheath 3 are made from PLA biopolymer, wherein in the case of the fibrous core 2, the biopolymer usually has the same or lower melting temperature than in the case of the nanofibrous sheath 3, as will be explained below.
  • the fibrous core 2 Before entering the working space and the path of the nanofibrous plume, the fibrous core 2 is preferably preheated to a desired working temperature in the range of 25 to 55 ⁇ 1 °C.
  • the formed two-component core yarn 11 can, if necessary, be heat-fixed by passing through a die heated to a temperature of 55 to 100 ⁇ 1 °C and then dried in a tempering chamber located behind the working space of the device.
  • the two-component core yam 1. thus formed is subsequently processed by standard textile techniques into strands, planar (2D) and spatial (3D) textile structures which can serve independently or as self-reinforcing elements of hierarchically structured biodegradable composite systems based on PLA biopolymers, or PLA copolymers, mixtures with other biopolymers, their combination, or with the addition of additives (plasticizers, nucleating agents, flame retardants, lubricants, UV stabilizers, antioxidants, dyes, antistatic agents, blowing agents, impact modifiers, etc.), fillers and/or discontinuous fiber reinforcement. As a rule, these modifications must not compromise the biodegradability of the resulting material research.
  • the two-component core yarn 1. is processed into a flat (2D) textile, e.g., fabric - see Figs. 2 and 4, and deposited in a PLA- based matrix 4 - see Figs. 3 and 5. All components of this system have a melting temperature equal to or lower than the nanofibrous sheath 3 of the used two- component linear structure.
  • a knitted fabric made from the two- component core yarn 1. can also be used.
  • a PLA-based spinning solution is prepared by dissolving PLLA or a mixture of PLLA and PDLA in a suitable solvent system which contains dichloromethane (DCM), dimethyl sulfoxide (DMSO) and pyridine (PY).
  • DCM dichloromethane
  • DMSO dimethyl sulfoxide
  • PY pyridine
  • solutions of these polymers in DCM are preferably prepared separately, and after their mixing and homogenization, DMSO and PY are added to them.
  • the polymer solution thus prepared is homogenized and then spun using one of the methods of preparation of polymer nanofibers.
  • a particularly advantageous method is spinning using alternating current, during which an electrically neutral plume of nanofibers is created, which moves in the direction of the gradient of the electric field away from the spinning electrode, and at the same time is caught on a monofilament or multifilament PLA yam rotating or ballooning around its longitudinal axis, on which it creates a uniform and continuous nanofibrous sheath 3.
  • a two- component yarn 1_ is prepared.
  • a flat textile e.g., a fabric or knitted fabric of any type, is then prepared by a suitable textile technique and is subsequently incorporated into a PLA-based matrix 4.
  • a suitable textile technique e.g., a fabric or knitted fabric of any type, is then prepared by a suitable textile technique and is subsequently incorporated into a PLA-based matrix 4.
  • at least one layer of this fabric is inserted between two plates of PLA polymer or co-PLA and together with them is exposed to elevated temperature (150 to 200 °C) and pressure (150 to 250 kN).
  • this semiproduct is heated for 3 to 8 minutes to a temperature of 150 to 180 °C, at which the material of the plates melts and the flat fabric is saturated with this matrix 4, and then it is heated for 15 to 80 seconds to a temperature of 160 to 200 °C, at which the textile is saturated with the matrix 4 and the entire structure is fixed.
  • the core 2 and the sheath 3 of the two-component core yam 1_ do not melt, and consequently, the yam 1_ and its components retain their morphology and character.
  • the result of this process is a hierarchically structured self-reinforcing composite system based on PLA biopolymers with different melting temperatures, which contains at least one layer of fabric prepared from the two-component core yam 1_ based on PLA deposited in a PLA or co-PLA matrix 4.
  • the textile constitutes 5 to 35 wt. % of this composite.
  • these layers can be suitably oriented relative to each other, e.g., by rotating them by a suitable angle, e.g., 45 °, 90 °, or in any other way, or by combining textiles of different types.
  • Fig. 1 a shows a scheme of a two-component linear structure with a monofilament yam core
  • Fig. 1 b shows a scheme of a two- component linear structure with a multifilament yam core
  • Fig. 2 shows a scheme of a plain weave fabric made from a two-component linear structure with a monofilament yam core
  • Fig. 3 shows a scheme of a section through the hierarchically structured self-reinforcing composite system according to the invention with one fabric layer according to Fig. 2
  • Fig. 4 shows a scheme of a plain weave fabric made from a two-component linear structure with a multifilament yam core
  • Fig. 5 is a scheme of a section through the hierarchically structured self-reinforcing composite system according to the invention with one fabric layer according to Fig. 4.
  • Fig. 6 is an SEM image of one variant of PLLA nanofibers at a magnification of 25,000 times
  • Fig. 7 shows an SEM image of the two-component linear structure with the monofilament yam core and the sheath formed by the layer of PLLA nanofibers according to Fig. 6 at a magnification of 475 times
  • Fig. 8 shows an SEM image of a unidirectional fabric made from the two-component linear structure according to Fig. 7 at a magnification of 109 times
  • Fig. 9 shows the DSC curves of the individual components of the hierarchically structured selfreinforcing composite system according to the invention formed using the unidirectional fabric according to Fig. 8
  • Fig. 10a shows an SEM image of the fracture surface of this hierarchically structured self-reinforcing composite system at a magnification of 158 times
  • Fig. 10b shows a detail of an interphase interface at the fracture surface in Fig. 10a.
  • Fig. 11 shows an SEM image of one variant of sc-PLA nanofibers at a magnification of 15,000 times
  • Fig. 12 shows an SEM image of the two- component linear structure with the multifilament yam core and the sheath formed by the layer of sc-PLA nanofibers according to Fig. 11 at the point of rupture at a magnification of 183 times
  • Fig. 13 shows an SEM image of fabric consisting of the two-component linear structure according to Fig. 12 at a magnification of 125 times
  • Fig. 14 shows the DSC curves of the individual components of the hierarchically structured self-reinforcing composite system according to the invention formed using the fabric according to Fig. 13, Fig.
  • FIG. 15a shows an SEM image of the fracture surface of this hierarchically structured self-reinforcing composite system at a magnification of 630 times
  • Fig. 15b shows a detail of the interphase interface at the fracture surface in Fig. 15a at a magnification of 2,520 times.
  • Fig. 16 shows an SEM image of a second variant of sc-PLA nanofibers at a magnification of 25,000 times
  • Fig. 17 shows an SEM image of the two- component linear structure with the monofilament yarn core and the sheath formed by the layer of sc-PLA nanofibers according to Fig. 11 at the section point at a magnification of 416 times
  • Fig. 18 shows an SEM image of unidirectional fabric made from the two-component linear structure according to Fig. 17 at a magnification of 85 times
  • Fig. 19 shows the DSC curves of the individual components of the hierarchically structured self-reinforcing composite system according to the invention formed using fabric according to Fig. 18, Fig.
  • FIG. 20a shows an SEM image of the fracture surface of this hierarchically structured selfreinforcing composite system at a magnification of 349 times
  • Fig. 20b shows a detail of the interphase interface at the fracture surface in Fig. 20a at a magnification of 4,320 times.
  • Fig. 21 shows an SEM image of a third variant of sc-PLA nanofibers at a magnification of 5,200 times
  • Fig. 22 shows an SEM image of the two-component linear structure with the multifilament yarn core and the sheath formed by the layer of sc-PLA nanofibers according to Fig. 21 at the section point at a magnification of 611 times
  • Fig. 23 shows an SEM image of twill fabric made of the two-component linear structure according to Fig. 22 at a magnification of 84 times
  • Fig. 24 shows the DSC curves of the individual components of the hierarchically structured self-reinforcing composite system according to the invention formed using the fabric according to Fig. 23, Fig.
  • FIG. 25a shows an SEM image of the fracture surface of this hierarchically structured self-reinforcing composite system at a magnification of 500 times
  • Fig. 25b shows a detail of the interphase interface at the fracture surface in Fig. 25a at a magnification of 2,540 times
  • Fig. 26 is an SEM image of a fourth variant of sc-PLA nanofibers at a magnification of 25,000 times
  • Fig. 27 shows an SEM image of the two- component linear structure with the monofilament yarn core and the sheath formed by the layer of sc-PLA nanofibers according to Fig. 26 at the section point at a magnification of 191 times
  • FIG. 28 shows an SEM image of plain weave fabric made from the two-component linear structure according to Fig. 27 at a magnification of 124 times
  • Fig. 29 shows the DSC curves of the individual components of hierarchically structured self-reinforcing composite system according to the invention formed using the fabric according to Fig. 28
  • Fig. 30a shows an SEM image of the fracture surface of this hierarchically structured selfreinforcing composite system at a magnification of 405 times
  • Fig. 30b shows a detail of the interphase interface at the fracture surface in Fig. 30a at a magnification of 3,100 times.
  • Fig. 31 shows an SEM image of a fifth variant of sc-PLA nanofibers at a magnification of 14,800 times
  • Fig. 32 shows an SEM image of a two-component linear structure with a multifilament yarn core and a sheath formed by a layer of sc-PLA nanofibers according to Fig. 31 at the section point at a magnification of 396 times
  • Fig. 33 shows an SEM image of twill fabric made from the two- component linear structure according to Fig. 32 at a magnification of 221 times
  • Fig. 34 shows the DSC curves of the individual components of the hierarchically structured self-reinforcing composite system according to the invention formed using the fabric according to Fig. 33, Fig.
  • FIG. 35a shows an SEM image of the fracture surface of this hierarchically structured self-reinforcing composite system at a magnification of 821 times
  • Fig. 35b shows a detail of the interphase interface on the fracture surface in Fig. 35a at a magnification of 2,550 times.
  • PLA biopolymers, compounds, mixtures and fabrics are dried for at least 12 hours in a vacuum dryer at a temperature of 80 °C to prevent their degradation due to hydrolytic reactions.
  • Additives added are similarly dried at a temperature of 50 °C.
  • DCM dichloromethane
  • DMSO dimethyl sulfoxide
  • PY pyridine
  • DCM has a specific mass of 1320 kg/m 3 , a molar mass of 85 g/mol and a chemical purity of 99.88 %
  • DMSO has a specific mass of 1100 kg/m 3 , a molar mass of 78.13 g/mol, and a chemical purity of 99.88 %
  • PY has a specific mass of 983 kg/m 3 , a molar mass of 79.1 g/mol and a chemical purity of 99.5 %.
  • PLA monofilament (trade name 6101, Perlon) was used as a fibrous core 2, with a diameter of 0.22 mm, a melting temperature Tm of 170 °C, a fineness of 48 Tex, or PLA multifilament (trade name PLA-DTY dtex 76 f 32, Trevira) was used as a fibrous core 2.
  • This multifilament consisted of 32 elementary fibers having a fineness of 7.6 Tex and a melting temperature Tm of 180 °C.
  • PLA biopolymers modified with additives e.g., plasticizers, impact modifiers, nucleating agents, lubricants
  • other biopolymers e.g., polyester-based thermoplastic elastomer - TPE
  • the matrix of the composite was prepared from plates of PLA biopolymer or sc-PLA having dimensions of 145 x 145 x 2 mm prepared by injection molding technology; the mold being cooled to a temperature of 20 °C.
  • the resulting hierarchically structured self-reinforcing composite systems were subsequently prepared by inserting at least one layer of fabric between two PLA or sc-PLA plates followed by hot pressing on a heated press.
  • Table 1 shows some mechanical parameters of the individual components of the structured self-reinforcing composite system and of the structured selfreinforcing composite systems according to Examples 1 to 6 for comparison.
  • PLLA poly(L-lactide)
  • Luminy L130 Total Corbion PLA
  • Mw weight average molar mass
  • Tm 180 °C
  • L-enantiomer content of at least 99 % was dissolved under constant stirring at a temperature of 23 ⁇ 1 °C in 63 g of dichloromethane (DCM).
  • DCM dichloromethane
  • DMSO dimethyl sulfoxide
  • PY pyridine
  • the polymer solution prepared by this process which contained 10 wt. % of PLLA and 90 wt. % of the solvent mixture (70 % DCM, 20 % DMSO, and 10 % PY) was homogenized under constant stirring for 12 hours and then spun by electric spinning.
  • the plume was fed into the working space of the device, where it was continuously wound onto a core made from PLA monofilament yam which was unwound at a speed of 60 m/min.
  • a two-component yam was prepared with a core consisting of PLA monofilament yam and a sheath formed by a layer of PLLA nanofibers, see Fig. 7, which is an SEM image of this yam at a magnification of 475 times, showing its structure.
  • the two-component core yam thus prepared showed a fineness of 53 tex.
  • the two-component core yam thus prepared was subsequently made into a unidirectional fabric - see Fig. 8, which shows an SEM image of this fabric at a magnification of 109 times, in which both the cores and the nanofibrous sheaths of the individual two-component core yams are visible.
  • the plates were made by thermoplastic injection technology at temperatures ranging from 160 °C to 190 °C, and their dimensions were 145 x 145 x 2 mm.
  • Unidirectional fabric made from two-component core yam was inserted between these two PLLA plates, and the thus prepared structure was tempered for 5 minutes in a press in contact mode at a temperature of 160 °C.
  • the co-PLA plates melt and the co-PLA fabric is saturated with the matrix; however, there is no melting of the core and the sheath of the two-component core - see Fig. 9, which shows the DSC curves of the individual components of the hierarchically structured self-reinforcing composite, from which it is clear that only the material of the plates melted at a temperature of 160 °C.
  • the temperature was then increased to 170 °C and after reaching it, pressing took place for 20 seconds with a clamp force of 160 kN.
  • the result of the process was a hierarchically structured self-reinforcing composite system based on PLA biopolymers with different melting temperatures.
  • the unidirectional fabric layer in this case constituted 9 ⁇ 1 % of the weight of this system.
  • Fig. 10a shows an SEM image of the fracture surface of the above- mentioned structured self-reinforcing composite system at a magnification of 158 times and Fig. 10b shows an SEM image of a detail of the interphase interface on the fracture surface at a magnification of 968 times. It can be seen from the two images that neither the core nor the sheath of the two-component core yarn melted during the heat treatment.
  • the polymer solutions thus prepared were mixed and to the mixture formed 23 g of DMSO and 13.8 g of PY was added.
  • the polymer solution prepared by this process which contained 8 wt. % of PLA biopolymers (PLLA 90 % and PDLA 10 %) and 92 wt. % of the solvent mixture (60 % DCM, 25 % DMSO, and 15 % PY) was homogenized under constant stirring on a magnetic stirrer for 12 hours and then spun by electric spinning. Alternating current (AC) with a voltage of 20 kV and a frequency of 60 Hz was applied to the spinning electrode, while the polymer solution described above was supplied to its spinning surface at a rate of 15 mL/min. Spinning took place at a laboratory temperature of 23 ⁇ 1 °C and a relative humidity of 35 %.
  • AC Alternating current
  • a spatial hollow plume consisting of nanofibers with a diameter of 310 ⁇ 43 nm was formed - see Fig. 11 , which shows an SEM image of these nanofibers at a magnification of 15,000 times.
  • the plume was fed into the working space of the device, where it was continuously wound onto a core made from PLA multifilament yarn which was unwound at a speed of 50 m/min.
  • a two-component yam was prepared with a core consisting of PLA multifilament yam and a sheath formed by a layer of sc-PLA nanofibers (PLLA 90 % and PDLA 10 %) with a fineness of 10 tex - see Fig. 12, which shows an SEM image of this yam at a magnification of 183 times and in which the structure of this yam is visible.
  • Two PLLA plates with a content of 15 wt % plasticizer - acetyl tributy I citrate (ATBC, CITROFLEX* A-4, Vertellus LLC) were used for the preparation of the matrix of the composite.
  • the plates were made by thermoplastic injection technology at temperatures ranging from 170 °C to 200 °C, and their dimensions were 145 x 145 x 2 mm.
  • the temperature was then increased to 170 °C and after reaching it, pressing took place for 30 seconds with a clamp force of 170 kN. This was followed by non-isothermal cooling while maintaining the clamp force of 170 kN until a temperature of 50 °C was reached; the following cooling process was already without applying clamp force.
  • the result of the process was a hierarchically structured self-reinforcing composite system based on PLA biopolymers with different melting temperatures. In this case, the layers of plain weave fabric constituted 13 ⁇ 1 % of the weight of this system.
  • Fig. 15 shows an SEM image of the fracture surface of the above- mentioned hierarchically structured self-reinforcing composite system at a magnification of 630 times and Fig. 15b shows an SEM image of a detail of the interphase interface on this fracture surface at a magnification of 2,520 times. It can be seen from the two images that neither the core nor the sheath of the two- component core yarn melted during the heat treatment.
  • the polymer solutions thus prepared were mixed and 27.6 g of DMSO and 13.8 g of PY was added to the mixture obtained.
  • the thus obtained polymer solution which contained 8 wt. % of PLA biopolymers (PLLA 80 % and PDLA 20 %) and 92 wt. % of the solvent mixture (55 % DCM, 30 % DMSO and 15 % PY) was left to homogenize under constant stirring for 12 hours and then spun by electric spinning.
  • the plume was fed into the working space of the device, where it was continuously wound onto a core made from PLA monofilament yam which was unwound at a speed of 40 m/min.
  • a two-component yarn was prepared with a core made from PLA monofilament yarn and a sheath formed by a layer of sc-PLA nanofibers - see Fig. 17, which shows an SEM image of this yarn at a magnification of 416 times and from which its structure is visible.
  • the two-component core yarn prepared in this way showed a fineness of 57 tex.
  • the two-component core yam thus prepared was subsequently made into a unidirectional fabric - see Fig. 18, which shows an SEM image of this fabric at a magnification of 85 times, in which both the cores and the nanofibrous sheaths of the individual two-component core yarns are visible.
  • TPE thermoplastic elastomer
  • the temperature was increased to 175 °C, and after reaching it, pressing took place for 40 seconds with a clamp force of 185 kN.
  • the result of the process was a hierarchically structured self-reinforcing composite system with a crystalline structure based on PLA biopolymers with different melting temperatures.
  • the layers of unidirectional fabric constituted 19 ⁇ 1 % of the weight of the above-mentioned system.
  • Fig. 20a shows an SEM image of the fracture surface of the above- mentioned structured self-reinforcing composite system at a magnification of 349 times
  • Fig. 20b shows an SEM image of a detail of the interphase interface on the fracture surface at a magnification of 4,320 times. It can be seen from the two images that neither the core nor the sheath of the two-component core yarn melted during the heat treatment. Furthermore, the morphology of the matrix is visible in the two images, where TPE is dispersed in co-PLA in the form of spherical particles.
  • PDLA poly(D-lactide)
  • Luminy D120 Total Corbion PLA
  • the polymer solutions thus prepared were mixed and to the mixture obtained, 27.9 g DMSO and 18.6 g PY was added.
  • the thus prepared polymer solution which contained 7 wt. % of PLA biopolymers (PLLA 70 % a PDLA 30 %) and 93 wt. % of the solvent mixture (50 % DCM, 30 % DMSO, and 20 % PY) was left to homogenize under constant stirring for 12 hours and then spun by electris spinning.
  • a two-component yam was prepared with a core consisting of PLA multifilament yam and a sheath formed by a layer of sc-PLA nanofibers - see Fig. 22, which shows an SEM image of this yam at a magnification of 611 times, and from which its structure is visible.
  • the two-component core yam thus prepared showed a fineness of 14 tex.
  • twill fabric was then formed - see Fig. 23, which shows an SEM image of this fabric at a magnification of 84 times, in which both the cores and the nanofibrous sheaths of the individual two-component core yams are visible.
  • Two PLLA plates (trade name Luminy 130, Total Corbion PLA) containing a PLA-based impact modifier (masterbatch) were used to prepare the matrix of the composite.
  • the impact modifier content was 10 wt. %.
  • the plates were made by thermoplastic injection technology at temperatures ranging from 170 °C to 200 °C, and their dimensions were 145 x 145 x 2 mm.
  • the temperature was then increased to 180 °C, and after reaching it, pressing took place for 30 seconds with a clamp force of 190 kN. This was followed by non-isothermal cooling while maintaining the clamp force of 190 kN until a temperature of 100 °C was reached. At this temperature, the composite crystallized isothermally for 2 minutes. Subsequently, non-isothermal cooling continued while maintaining the clamp force of 190 kN until a temperature of 50 °C was reached; the following cooling process was already without applying clamp force.
  • the result of the process was a hierarchically structured self-reinforcing composite system with a crystalline structure based on PLA biopolymers with different melting temperatures. In this case, the layers of twill fabric constituted 21 ⁇ 2 % of the weight of the above-mentioned system.
  • Fig. 25a shows an SEM image of the fracture surface of this structured self-reinforcing composite system at a magnification of 500 times
  • Fig. 25b shows an SEM image of a detail of the interphase interface on the fracture surface at a magnification of 2,540 times. It can be seen from the two images that neither the core nor the sheath of the two-component core yarn melted during the heat treatment. Furthermore, the morphology of the matrix with cavities caused by the addition of the masterbatch can be seen in both images.
  • the polymer solutions thus prepared were mixed and 28.2 g of DMSO and 23.5 g of PY was added to the mixture obtained.
  • the thus prepared polymer solution which contained 6 wt. % of PLA biopolymers (PLLA 60 % and PDLA 40 %) and 93 wt. % of the solvent mixture (50 % DCM, 30 % DMSO, and 20 % PY) was left to homogenize under constant stirring for 12 hours and then spun by electric spinning.
  • the plume was fed into the working space of the device, where it was continuously wound onto a core made from PLA monofilament yam which was unwound at a speed of 25 m/min.
  • a two-component yam was prepared with a core consisting of PLA monofilament yam and a sheath formed by a layer of sc-PLA nanofibers - see Fig. 27, which shows an SEM image of this yam at a magnification of 191 times and from which its structure is visible.
  • PLLA plates (trade name Luminy 130, Total Corbion PLA) containing 0.3 wt.% of the nucleating agent - orotic acid monohydrate (OA, Merck) were used.
  • the plates were made by thermoplastic injection moulding at temperatures ranging from 160 °C to 200 °C, and their dimensions were 145 x 145 x 2 mm.
  • the temperature was then increased to 180 °C, and after reaching it, pressing took place for 40 seconds with a clamp force of 200 kN. This was followed by non-isothermal cooling while maintaining the clamp force of 200 kN until a temperature of 90 °C was reached. At this temperature, the composite crystallized isothermally for 3 minutes. Subsequently, non-isothermal cooling continued while maintaining the clamp force of 190 kN until a temperature of 50 °C was reached; the following cooling process was already without applying clamp force.
  • the result of the process was a hierarchically structured self-reinforcing composite system with a crystalline structure based on PLA biopolymers with different melting temperatures.
  • the layers of twill fabric constituted 30 ⁇ 1 % of the weight of the above-mentioned system.
  • Fig. 30a shows an SEM image of the fracture surface of the above- mentioned structured self-reinforcing composite system at a magnification of 405 times
  • Fig. 30b shows an SEM image a detail of the interphase interface on the fracture surface at a magnification of 3,100 times. It can be seen from the two images that neither the core nor the sheath of the two-component core yarn melted during the heat treatment. Furthermore, the morphology of the matrix with a nucleating agent based on orotic acid can be seen in the two images.
  • the polymer solutions thus prepared were mixed and 33.3 g of DMSO and 28.5 g of PY was added to the mixture obtained.
  • the thus prepared polymer solution which contained 5 wt. % of PLA biopolymers (PLLA 50 % and PDLA 50 %) and 95 wt. % of the solvent mixture (35 % DCM, 35 % DMSO, and 20 % PY) was left to homogenize under constant stirring for 12 hours and then spun by electric spining.
  • the plume was fed into the working space of the device, where it was continuously wound onto a core made from PLA multifilament yarn which was unwound at a speed of 20 m/min.
  • a two-component yam was prepared with a core made from PLA multifilament yarn and a sheath formed by a layer of sc-PLA nanofibers - see Fig. 32, which shows an SEM image of this yarn at a magnification of 396 times and from which its structure is visible.
  • twill weave fabric was formed from the two-component core yarn thus prepared - see Fig. 33, which shows an SEM image of this fabric at a magnification of 221 times, on which both the cores and the nanofibrous sheaths of the individual two-component core yarns are visible.
  • Two PLLA plates (trade name Luminy 130, Total Corbion PLA) with a content of 0.5 wt. % of a lubricant based on N,N'-Ethylenebis(stearamide) (EBS, Merck) were used for the preparation of the composite of the matrix.
  • the plates were made by thermoplastic injection technology at temperatures ranging from 180°C to 210°C, and their dimensions were 145 x 145 x 2 mm.
  • twill weave fabric made from two-component core yarn, rotated relative to each other by 45°, were inserted, and the thus prepared structure was tempered for 5 minutes in a press in contact mode at a temperature of 170 °C.
  • the PLLA plates melt and the co-PLLA fabric is saturated with the matrix; however, there is no melting of the core and the sheath of the two-component core - see Fig. 34, which shows the DSC curves of the individual components of the hierarchically structured self-reinforcing composite, from which it is visible that at a temperature of 170 °C only the material of the plates melted.
  • the temperature was then increased to 180 °C, and after reaching it, pressing took place for 60 seconds with a clamp force of 220 kN. This was followed by non-isothermal cooling while maintaining the clamp force of 220 kN until a temperature of 110 °C was reached. At this temperature, the composite crystallized isothermally for 1 minute. Subsequently, non-isothermal cooling continued while maintaining the clamp force of 220 kN until a temperature of 50 °C was reached; subsequent cooling was without force.
  • the result of the process was a hierarchically structured self-reinforcing composite system with a crystalline structure based on PLA biopolymers with different melting temperatures. In this case, the layers of twill fabric constituted 27 ⁇ 1 % of the weight of this system.
  • Fig. 35a shows an SEM image of the fracture surface of the above- mentioned structured self-reinforcing composite system at a magnification of 821 times and Fig. 35b shows an SEM image of a detail of the interphase interface on the fracture surface at a magnification of 2,550 times. It can be seen from the two images that neither the core nor the sheath of the two-component core yarn melted during the heat treatment.
  • the tensile test of two-component nanofibrous core yams according to Examples 1 to 6 was carried out according to ISO 2062, the standard is intended for threads on packages and determines the breaking strength and elongation at break of individual threads using an apparatus with a constant elongation rate.
  • the results of the test are the values of modulus of elasticity in tension (Et), ultimate tensile strength (Om) and nominal relative elongation at break (stb).
  • Et modulus of elasticity in tension
  • Om ultimate tensile strength
  • stb nominal relative elongation at break
  • the tensile test of the hierarchically structured self-reinforcing biocomposites according to Examples 1 to 6 was conducted according to ISO 527-4, the standard is intended for isotropic and orthotropic plastic composites reinforced with fibrous filler.
  • the result of the test was modulus of elasticity in tension (Et), ultimate tensile strength (Om) and nominal relative elongation at break (stb).
  • a preload of 2 N was used to measure the samples.
  • a speed of 1 mm/min was used, and a speed of 5 mm/min was used to determine the ultimate strength and ultimate tensile strength.
  • the impact strength test of the hierarchically structured self-reinforcing biocomposites according to Examples 1 to 6 was carried out according to standard ISO 179-1 and complement ISO 179-1 Z1 fll by the Charpy method with a nominal hammer energy of 5 J.
  • Determination of the temperature of deflection of the hierarchically structured self-reinforcing biocomposites of Examples 1 to 6 under load (HDT) was performed according to ISO 75-2, method A using a bending stress of 1.8 MPa at a heating rate of 120 °C/h.
  • Transition temperatures and enthalpies, ratios of homo- and stereocomplex crystallites were obtained from differential scanning calorimetry (DSC) measurements according to ISO 11357, which describes thermoanalytical DSC testing methods. A heating rate of 10 °C/min was selected.
  • Table 1 shows the mechanical properties of the two-component nanofibrous core yams used in Examples 1 to 6, and Table 2 shows the mechanical properties of the hierarchically structured self-reinforcing composite systems based on polylactic acid biopolymers according to Examples 1 to 6 created using these two-component nanofibrous core yams.
  • able 1 part 1/2
  • able 2 part 1/6
  • able 2 part 2/6)
  • able 2 part 3/6)
  • able 2 part 4/6) able 2 (part 5/6) able 2 (part 6/6)

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Abstract

L'invention concerne un procédé de préparation de systèmes composites autorenforçants structurés hiérarchiquement à base de biopolymères d'acide polylactique, dans lequel une solution polymère est préparée, contenant de 5 à 15 % en poids de poly(L-lactide) ou de mélanges symétriques ou asymétriques de poly(L-lactide) et de poly(D-lactide) et de 85 à 95 % en poids d'un système de solvant constitué d'un mélange de dichlorométhane, de diméthylsulfoxyde et de pyridine selon le rapport (3 à 7,5):(1,5 à 4):(0,5 à 3,5). Cette solution est transformée en nanofibres de poly(L-Lactide) ou de mélanges de poly(L-lactide) et de poly(D-lactide) par filage, ces nanofibres, après leur formation, étant déposées sur la surface d'une âme fibreuse (2) constituée d'un biopolymère d'acide polylactique, qui tourne ou s'enroule autour de son axe longitudinal, un fil d'âme à deux composants à base d'acide polylactique étant ainsi préparé. Ensuite, un tissu uni est formé à partir de ce fil, au moins une couche du tissu uni étant déposée à une température et à une pression élevées dans une matrice (5) à base d'un biopolymère d'acide polylactique présentant une température de fusion inférieure ou égale à la température de fusion d'une gaine nanofibreuse (3) du fil d'âme à deux composants, lors du dépôt, la structure du tissu uni étant saturée avec la matrice (5), ce qui crée un système composite autorenforçant structuré hiérarchiquement à base de biopolymères d'acide polylactique, qui est constitué de 5 à 35 % en poids d'un fil d'âme à deux composants à base d'acide polylactique.
EP22760646.4A 2022-06-29 2022-06-29 Procédé de préparation de systèmes composites autorenforçants structurés hiérarchiquement à base de biopolymères d'acide polylactique, et de tels systèmes composites Pending EP4355938A1 (fr)

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