EP3189095A1 - Composition polymère thermoplastique - Google Patents

Composition polymère thermoplastique

Info

Publication number
EP3189095A1
EP3189095A1 EP15781421.1A EP15781421A EP3189095A1 EP 3189095 A1 EP3189095 A1 EP 3189095A1 EP 15781421 A EP15781421 A EP 15781421A EP 3189095 A1 EP3189095 A1 EP 3189095A1
Authority
EP
European Patent Office
Prior art keywords
proteic
hydrolysate
fleshing
composition
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15781421.1A
Other languages
German (de)
English (en)
Inventor
Sandra VITOLO
Monica PUCCINI
Maurizia SEGGIANI
Domenico CASTIELLO
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.)
Generale Per La Gestione Del Polo Tecnologico Conciario Societa Consortile A Responsabilita Limitata (poTeCo SCRL) Soc
Universita di Pisa
Original Assignee
Generale Per La Gestione Del Polo Tecnologico Conciario Societa Consortile A Responsabilita Limitata (poTeCo SCRL) Soc
Universita di Pisa
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 Generale Per La Gestione Del Polo Tecnologico Conciario Societa Consortile A Responsabilita Limitata (poTeCo SCRL) Soc, Universita di Pisa filed Critical Generale Per La Gestione Del Polo Tecnologico Conciario Societa Consortile A Responsabilita Limitata (poTeCo SCRL) Soc
Publication of EP3189095A1 publication Critical patent/EP3189095A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
    • 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
    • C08J2489/00—Characterised by the use of proteins; Derivatives thereof
    • C08J2489/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08J2489/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Definitions

  • the present invention relates in general to the field of thermoplastic polymeric materials, and more precisely it relates to novel thermoplastic; polymeric compositions defined better herein after that are useful for the manufacture, by hot melt extrusion, of biodegradable artefacts and packaging, compostable and having at the same time performances and costs comparable to those of the products obtained with the traditional non-biodegradable thermoplastic polymeric materials, such as the polyoleflns.
  • biodegradable material it is meant a material which can be decomposed by microorganisms until its complete transformation into simple chemical compounds, which means for the processes of aerobic degradation into carbon dioxide and water, while for the anaerobic processes of degradation mainly into methane and carbon dioxide.
  • the biodegradability of a material therefore has a high added value in the context of the characteristics of that material, in particular for the end of life management of products made with that materia!, because their biodegradability makes them compatible with any route of disposal, including routes of disposal of the existing organic waste, for instance by treatment in composting plants for the production of compost, or by treatment in a plant for anaerobic digestion for production of biogas or in a plant for the biological treatment of wastewater.
  • This is the case of food packaging, which is increasingly used, but which, when made with biodegradable materials, compared to traditional non-biodegradable plastics, has the advantage of being able to be disposed directly with the organic fraction of waste, without further separation operations from food residue, and without onerous cost of recovery and disposal.
  • the synthetic polymer polycaprolactone that is per se biodegradable, may be used in mixture with a proteic hydro!ysate material coming from the operations of fleshing out/shaving of animal pelts in tanning industry, to obtain a novel thermoplastic polymer composition, hot processable by means of extrusion or filming known procedures, for the manufacture of a wide range of products that have been shown as completely biodegradable, compostable and as having performances and costs comparable to those of the traditional thermoplastic polymeric materials based on non-biodegradable polymers.
  • the aforesaid components of the novel composition namely polycaprolactone and proteic hydroiysate
  • the proteic hydroiysate of the present compositions is a hydrolysed animal collagen originating from a waste of the tanning industry, or a proteic hydrolysate from wastes and/or by-products of other industrial processes, whose reuse for the preparation of the compositions of the invention, in addition to not burden the manufacturing costs of the compositions, represents a valorisation of a waste product or by product, otherwise to be treated as industrial waste, or having up to now limited possibilities of use or recycling.
  • thermoplastic polymeric composition obtainable by mixing molten polycaprotactone and proteic hydrolysate in powder having average molecular weight lower than 10,000 g/moi, as defined in the first of the claims herein after.
  • the percentages of a product are to be considered as weight percentages of that product with respect to the total weight of the composition containing it
  • polycaprolactone or "PCL” is meant, in the present invention, the synthetic polyester poly-E-caprolactone, obtainable from polymerisation of ⁇ -caprolactone.
  • the PCL is endowed with good characteristics of biocompatibiiity, and with a high thermal stability; its modest mechanical properties and its relatively high manufacture cost up to date have meant that the use of the PCL did not go beyond the production of objects for biomedical applications.
  • It is a biodegradable synthetic product that, for the scopes of the invention, is preferably used in the form of granules or pellets, of dimensions for instance of about 3 mm, whose properties are summarised in the following Table 1 :
  • hydrolysed or “proteic hydroiysed”, indicated herein sometimes by the acronym “HYD”, is meant a natural organic product in the form of a powder, obtained by hydrolysis of the animal fleshing, that is the waste product in the phase of mechanical removal of the subcutaneous tissue from the dermis, called fleshing out, or obtained by treatment of the processing residues of the operations of shaving of the pelts.
  • the animal fleshing is a product mainly formed by fats and collagen fibres rather relaxed and degraded.
  • the fleshing out is that mechanical operation in the tanning process during which the flesh and subcutaneous tissue residues are removed from the skin, it is carried out immediately downstream of the phase so called of "liming" (during which hair and epidermis are removed) because in this phase the skin swells and therefore the fleshing out process is easier and stress less the collagen fibres. From this processing the “fleshed” skin is obtained, which is then conveyed to the subsequent processing, and a waste product called “fleshing” enriched in proteins (mainly collagen) and in fats.
  • the skins are subjected to the process of shaving in order to equalize the thickness of the skin.
  • the shaving is carried out with the shaving machine whose principle of operation is similar to that of the fleshing machine.
  • the hides treated in this phase of the tanning process provide residues mainiy consisting of subcutaneous tissue (rich in collagen), of fats and of a smaller amount of salts with respect to the fleshing, since the skin has undergone numerous intermediate washings.
  • the residues of shaving obtained from tanned skins contain subcutaneous tissue and collagen, in particular, less degraded compared to that constituted by fleshing.
  • hydrolysate or "proteic hydrolysate”.
  • proteic hydrolysate is moreover meant a natural organic product in the form of powder, obtained by any treatments of hydrolysis of any proteic substrate of vegetal or animal origin, such as milk serum or soya.
  • the production processes of hydrolysis industrially applicable on this type of proteic matrix may be processes of:
  • the process for obtaining the proteic hydrolysate may comprise, in addition to the actual hydrolysis step, a preliminary step of homogenization of the proteic substrate used as a raw materia!, white after the hydrolysis it may comprise one or more operations to standardize, purify and/or stabilize the obtained product, and consisting for example of drying, screening, cooling, etc.
  • any person skilled in the art can easily vary and diversify the characteristics of the obtainable proteic hydrolysate, such as the degree of hydrolysis, degree of racemization, distribution of molecular masses, and the content of free amino acids, modifying the phase of hydrolysis selected (chemtcal/thermai/enzymatic hydrolysis or their combination) and the related parameters of the process, according to the knowledge and procedures known to any person skilled in the field.
  • the proteic hydrolysate from fleshing or from the shaving residue of animal pelts is obtained by subjecting a substrate, before the hydrolysis, to milling, then the milled substrate is hydroSysed under conditions of acid pH at temperature of about 70-80°C.
  • the fatly phase and the protein phase which stratify during hydrolysis, may be then separated; more particularly, the saponified fatty phase, less dense, is touched on the surface to be separately recovered, white the peat protein is taken from the bottom of the separator and possibly let to pass through a special grid to eliminate the not dissolved coarser pieces, then subjected to sterilisation.
  • the sterilisation is preferably carried out at a temperature of 133°C, 3 bars of pressure for a minimum time of 20 minutes.
  • the obtainment of the proteic hydrolysate In powder, useful for preparing the polymer compositions of the present invention includes a last drying phase, carried out for instance by concentration in a system of multiple-effect evaporators and atomization. Before drying, if necessary, the sterilised product is filtered to eliminate the insoluble organic component, and then subjected to oxidation in order to eliminate sulphides and then subjected to decalcification.
  • the proteic hydrolysate used to obtain the present compositions can therefore advantageously be obtained from the proteic substrate by chemical hydrolysis (alkaline or acid) and/or thermal and/or enzymatic hydrolysis under such conditions that result in a product having average molecular weight lower than 10,000 g/moi, and typically ranging between 1,000 and 5,000 g/mol, which is then subjected to degreasing and drying, preferably to atomisation, to obtain a solid product, substantially free of water, to be used in the form of powder.
  • chemical hydrolysis alkaline or acid
  • thermal and/or enzymatic hydrolysis under such conditions that result in a product having average molecular weight lower than 10,000 g/moi, and typically ranging between 1,000 and 5,000 g/mol, which is then subjected to degreasing and drying, preferably to atomisation, to obtain a solid product, substantially free of water, to be used in the form of powder.
  • the so obtained hydroiysed product having average molecular weight in the range indicated above ensures the best compatibility between PCL and the hydrolysate, and consequently allows obtaining a composition having optimal homogeneity for a better processabi!ity of the material.
  • the molecular weight of the proteic hydrolysate is meant the average molecular weight which was determined by size exclusion chromatography (SEC-HPLC).
  • compositions essentially consist of proteic hydrolysate and potycaproiaclone, with no need to add any kind of additive, thus guaranteeing the complete biodegradabifity of the obtained products, as also shown in the following experimental part. It is meant that the compositions in the molten state as well as the compositions in the solid state are compnsed in the scope of the present invention.
  • the surprising aspect of the present compositions is the possibility to be easily hot processed, for instance by extrusion or filming, with no need of compatibilising additives or other additives of any kind, to obtain artefacts in different forms, from pellets to thin films, ail having the stability and the mechanical characteristics required to the material of that form.
  • This is surprising given the scarce thermoplastic properties of the pure PCL, which is not processable by hot extrusion or filming; on the contrary, the two products together, in a wide range of weight ratios, have shown a surprising ability to be hot processed, producing stable solid artefacts or resistant and flexible thin films.
  • the present compositions may have percentages of proteic hydrolysate ranging for instance between 5 and 60% by weight with respect to the total weight of the composition, and preferably ranging between 10 and 30%.
  • the weight ratios polycaprolactone: proteic hydrolysate according to the invention are for example of 90:10, 80:20, 70:30 and 60:40.
  • the proteic hydrolysate used in the present compositions may be a hydrolysate coming from fleshing out, from shaving or it may be a mixture of such two types of hydrolysate, or it may be a hydroiysate coming from the treatment of other proteic organic substrates different from fleshing or from the residues of processing of animal pelts, and identified above; according to a preferred embodiment of the invention it is a proteic hydrolysate coming from fleshing out animal hides.
  • the process for obtaining the present compositions includes the hot extrusion of moiten PCL with a powder of proteic hydrolysate at temperatures ranging for example between about 90°C at the inlet of the extruder and about 130°C at the output. It is essentia! that the temperature at the inlet of the extruder is lower than the degradation temperature of the proteic hydrolysate, for example lower than 120°C, to avoid the degradation of the hydrolysate.
  • the initial temperature or the temperature at the input of the extruder will therefore be advantageously comprised between about 90°C and about 120°C.
  • the PCL and the proteic hydrolysate powder are blended before entering the extruder, and are processed in a twin screw extruder that allows a uniform and effective mixing in the moiten state of the material fed.
  • the extruded matenai may be formed of the desired size and shape by moulding according to procedures known to any expert in the sector, including moulding with 3D printers, to obtain a solid plastic material of desired shape and size, or it may be sent to an apparatus for filming, for example for blown film extrusion, which allows to obtain thin films consisting of the present composition.
  • compositions of the invention various kinds of articles may be obtained, for instance thin films, films for packaging in general, pipes, wires, packets, bags or bottles.
  • the polymer compositions of the invention have been obtained in the form of pellets by mixing in the molten state pellets of PCL with powder of proteic hydrolysate, coming from fleshing out or shaving, previously lyophilised, by using a twin screw extruder (model Thermo PRISM TSE 16/28mmTC).
  • the twin screw extruder allows a very efficient mixing thanks to the interaction between the polymer and the screws, in particular the mixing involves the entire mass fed, which melts quickly and uniformly in a space of very limited length and allows to obtain very high-performance results in short times, thus allowing shorter residence times and lower thermal stress for the materials under processing.
  • the twin screw extruder used for producing the mixtures was equipped with a single nozzle for the exit of polymer, from which flowed the extruded product, referred to as "spaghetti", air-coo!ed up to the cutter with which it was reduced to pellets.
  • compositions with various ratios between PCL and proteic hydrolysate were thus prepared, in particular with 10, 20. 30 and 40% by weight of hydrolysate compared to the total weight of the composition, without adding any type of additive.
  • the speed of the screws was set to values between 30 and 60 revolutions per minute, whiie the temperature profile has been adapted to the pelieiizing process by studying the suitable degree of homogeneity and viscosity of the strand produced by the machine.
  • the extrusion temperatures for the mixtures produced with the thermoplastic polymer matrix in PCL and the charge of proteic hydrolysate are reported in the Table 3 below. In the first part it is important to maintain a sufficiently low temperature, since the proteic hydrolysate, already at 120°C, tends to deteriorate losing the volatile components and compacting, thereby preventing an optimum mixing even with the twin-screw extruder.
  • film blowing is an industrial process used for the production of polymer thin films biaxially oriented, it is a continuous process for the production of a tubular film in a single operation and allows the adjustment of the circumference and of the thickness of the film by controlling the volume of air blown into the bubble, the parameters of the extrusion process and the speed of draw of the film in the course of the process.
  • the polymer fed to the equipment through a hopper is conveyed and me!ted in an extruder; with a constant speed of flow of the mass, it is forced to enter inside a die of annular form to form a continuous "tube”; an internal pressure and an axial draw concur, instead, to the biaxiai extension of the film.
  • the properties of the film thus formed are controlled by the molecular orientation and by the stress induced by the crystallisation.
  • An important requirement for this type of processing is the stability of the bubble in order to allow continuous process operations and the production of a film with satisfactory properties.
  • the equipment chosen for the experimentation is a singie-screw extruder Rheomex 19/25 Thermo Scientific QC, equipped with a system of winding of the film produced.
  • Such equipment allows evaluating the processabiiity of the materials for blow extrusion, by faithfuliy replicating the industrial extrusion process.
  • Figure 1 it is shown the SEM image, i.e. the image obtained by scanning electron microscopy, of the surface (part A) and of the section ⁇ part B) of a film sample of pure PCL, obtained by bubble extrusion; the surface and the section of the thermoplastic matrix are homogeneous and free from impurities.
  • SEM image i.e. the image obtained by scanning electron microscopy, of the surface (part A) and of the section ⁇ part B) of a film sample of pure PCL, obtained by bubble extrusion; the surface and the section of the thermoplastic matrix are homogeneous and free from impurities.
  • Such images are shown herein by way of comparison with the compositions of the invention, demonstrating the fact that the addition of the organic charge of proteic hydrolysate to the PCL does not alter the homogeneity, even when the compositions are used to form thin films.
  • thermogravimetric analysis A sample of PCL (approx. 50 mg) was placed in a platinum sample holder, subjected to a nitrogen flow (100 mL/min) and heated from room temperature to a temperature of 600°C with a heating rate of 10°C/min.
  • the weight variations of the sample tested thermogravimetric curves TG
  • the related speed DTG
  • the proteic hydrolysate after the initial loss of weight around 100°C due to moisture, shows a first peak around 170°C linked to the loss of the lightest volatile components and a high loss of weight with peak around 300°C .
  • the amplitude of this range of temperature depends on the composition of the proteic hydrolysate. consisting of more or less long peptide chains and of free amino acids.
  • the residual weight at end of the test (27%) is constituted by the residua! carbonaceous matrix and by the inorganic salts contained in the hydrolysate.
  • the curve related to the PCL biodegradable polymer matrix shows instead a thermal stability up to 320°C and a single peak for weight ioss around 410°C, corresponding to the degradation of the polymer.
  • thermogravimetric analyses on the compositions of the invention consisting of polymer matrix of polycaprolactone and hydrolysate are shown in Figure 4.
  • the compositions in the form of pellets with the PCL with 10% or 20% by weight of hydrolysate were tested, obtained as described above in Example 1.
  • the standard tensile test allows establishing the strength and stiffness of a material.
  • the instrument used to perform the test with the compositions of the invention was composed of a base on which was placed a fixed clamp and two columns on which flows the bar which supports a second clamp. These clamps are self-locking, i.e. their grip increases with the progress of the deformation by the action of a pneumatic control.
  • the sample must be aligned with the direction in which the strain is applied so as to avoid rotatory movements that may induce the specimen to scroii.
  • the distance between the clarnps is varied and. through a load cell placed between the upper jaw and the guide, it is recorded the effort that the specimen offers in terms of resistance.
  • the software that manages the tool allows adjusting the rale of deformation and the different criteria for the calculation of the mechanical characteristics of the tested material. To perform the test it is necessary to characterize the specimen from the geometrical point of view, because this information is used by the software to normalise the results obtained.
  • a representation of the tensile test and the geometry of the specimen used in the tests is illustrated in Figure 5.
  • P is the load and A0 is the initial section of the unloaded specimen (i.e. of the portion with constant, section) and
  • ⁇ L is the variation of length caused by the load and L 0 is the initial length of the useful part of the specimen.
  • the point A in Figure 6 represents the elastic limit. This value indicates the maximum stress that the material can withstand if it is desired that it returns exactly to its original size after unloading, if it is urged over the edge A, the material undergoes a deformation at least partially plastic.
  • the point A corresponds to the limit of proportionality, defined by the value of the stress for which the graph deviates from a straight line.
  • the proportionality constant between stress and strain (given by the slope of the curve in the part between the origin and the point A) is called the modulus of normal elasticity or Young's modulus (E).
  • the mechanical analyses have been carried out by using the Instron Model 5564, testing twelve samples for each type of material; the values shown in the Table 5 below were obtained as the arithmetic mean of the valid tests.
  • the mechanical properties of the specimens were evaluated both in the longitudinal direction and in the transverse direction of the film formation.
  • the biodegradability test determines the amount of carbon dioxide released from the bioiogicai decomposition of the organic carbon contained in the tested specimen, due to the action of a microbial population present in a soil sample, used as solid substrate and inoculum.
  • the test was conducted, for a comparison, also on portions of paper, used as a positive control, and only on the soil: as a matter of fact, the paper is a biodegradable material, and it allows verifying that, inside the receptacles, the microorganisms are able to implement the degradative processes and, as the soil contributes to the production of CO 2 , being an excellent substrate for the microorganisms, it is necessary to quantify this carbon dioxide in order to calculate then by difference the amount of CO 2 actually produced by the tested samples.
  • Figure 7 shows a scheme of the system for the evaluation of the biodegradability of the materials produced.
  • the sample is placed in contact with the soil placed in a sealed flask, inside of a test tube, perforated in the upper part, it is contained a solution of KOH: in this way the CO 2 developed by biodegradation processes reacts with the potassium hydroxide and the subsequent titration to determine the residual KOH allows to quantify the carbon dioxide produced. Titrations are repeated at precise time frames taking into account the estimated daily production of CO 2 and of the amount of O 2 inside the container.
  • Figure 8 shows the results obtained in about five months of experiments, in terms of cumulative production of CO 2 (expressed in mg) over time.
  • the trend of the values for the paper biodegradation is indicative of the presence, in the system used, of appropriate conditions able to ensure the development of microorganisms.
  • the mixtures containing HYD from fleshing and 20% of HYD from shaving exhibit a greater tendency to be degraded, even higher than that of the
  • biodegradability index based on the amount of carbon dioxide that the samples could produce in theory, calculated on the basts of the weight of the samples and of the content of organic carbon in them.
  • the paper has reached an index close to 30%.
  • the films obtained with the compositions of the invention have a biodegradability index fairly high, comparable to the value obtained for the paper and higher than that of the commercial material.
  • proteic hydrolysate in mixture with poiycaprolactone makes possible the processability by hot extrusion, also obtaining a fully biodegradable material, having good mechanical and thermal properties, properties that are considerably improved compared to those of the polymer matrix of PCL alone.
  • This also allows the advantageous disposal of a waste material of the leather tanning industry, such as the proteic hydrolysate obtained from fleshing out or from shaving of cowhides to be submitted to tanning.
  • the present invention was herein described with reference to a preferred embodiment, it is to be understood that there may be other embodiments afferent to the same inventive core, as defined by the scope of protection of the claims set out beiow.

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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Dermatology (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

La présente invention concerne des compositions polymères thermoplastiques, hautement biodégradables, basées sur une polycaprolactone et un matériau d'hydrolysat protéique, qui sont utiles pour le prototypage rapide avec des imprimantes 3D et pour la fabrication de produits semi-finis sous la forme de filaments, de pastilles et de films minces par extrusion à chaud.
EP15781421.1A 2014-09-03 2015-09-02 Composition polymère thermoplastique Withdrawn EP3189095A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITFI20140199 2014-09-03
PCT/IB2015/056660 WO2016035021A1 (fr) 2014-09-03 2015-09-02 Composition polymère thermoplastique

Publications (1)

Publication Number Publication Date
EP3189095A1 true EP3189095A1 (fr) 2017-07-12

Family

ID=51753310

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15781421.1A Withdrawn EP3189095A1 (fr) 2014-09-03 2015-09-02 Composition polymère thermoplastique

Country Status (2)

Country Link
EP (1) EP3189095A1 (fr)
WO (1) WO2016035021A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3321002A1 (fr) * 2016-11-15 2018-05-16 Höganäs AB Charge d'alimentation d'un procédé de fabrication additive, procédé de fabrication additive l'utilisant, et article ainsi obtenu
CN107266884B (zh) * 2017-05-26 2019-03-15 吴新贤 一种完全可生物降解的3d打印材料及其制备方法
IT201800003401A1 (it) * 2018-03-09 2019-09-09 Conceria Lufran S R L Procedimento di produzione di materiale similpelle e materiale così ottenuto.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2168652T3 (es) * 1996-08-12 2002-06-16 Novamont Spa Composicion biodegradable.
US6632925B1 (en) * 1999-05-04 2003-10-14 Iowa State University Research Foundation, Inc. Biodegradable plant protein composites and related methods
SI2004753T1 (sl) * 2006-03-13 2010-06-30 Becker & Co Naturinwerk Termoplastični sestavki na osnovi kolagenskega prahu in kolagena za pripravo oblikovanih teles
EP3747632A1 (fr) * 2010-10-27 2020-12-09 Rize Inc. Procédé et appareil permettant de fabriquer des objets en trois dimensions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2016035021A1 *

Also Published As

Publication number Publication date
WO2016035021A1 (fr) 2016-03-10

Similar Documents

Publication Publication Date Title
Seggiani et al. Processing and mechanical performances of Poly (Butylene Succinate–co–Adipate)(PBSA) and raw hydrolyzed collagen (HC) thermoplastic blends
WO2016035021A1 (fr) Composition polymère thermoplastique
US8623249B2 (en) Method for producing leather pellets and compound granules, and use thereof
CN105838047A (zh) 一种可生物降解改性木质素颗粒及其制造方法
US7649036B2 (en) “Green” materials from soy meal and natural rubber blends
EP0961805A1 (fr) Composant pour la production de melanges polymeres a base d'amidon, et procede de production de ce composant
Haroun Preparation and characterization of biodegradable thermoplastic films based on collagen hydrolyzate
Li et al. Unveiling the reinforcement effects in cottonseed protein/polycaprolactone blend biocomposites
US20070155863A1 (en) Novel "green" materials from soy meal and natural rubber blends
CN109096506B (zh) 一种羽毛角蛋白/pva复合膜的制备方法
CN110922725A (zh) 生物全降解薄膜组合物、生物全降解薄膜及其制法和应用
CN102675840A (zh) 一种可完全生物降解塑料薄膜的制备方法
US9416255B2 (en) Compositions comprising polylactic acid, bentonite, and gum arabic
Jaya et al. The Influences of Chicken Feather Loading on Tensile and Physical Properties of R-Hdpe/Eva/Cff Composites
CA2949145A1 (fr) Polylactide polymere thermoformable
CN114605798A (zh) 一种可降解的高分子材料薄膜的生产工艺
US20130131225A1 (en) Compositions comprising polylactic acid and gum arabic
CN113773624A (zh) 一种聚乳酸类共混改性材料及其制备方法
Puccini et al. Novel thermoplastic materials from wastes of the leather industry
CN112322053A (zh) 一种可生物降解的化妆品软管及其制备方法
Kaewkannetra et al. Quality improvement and characteristics of polyhydroxyalkanoates (PHAs) and natural latex rubber blends
Seggiani et al. PROCESSING AND MECHANICAL PERFORMANCES OF POLY (BUTYLENE SUCCINATE-CO-ADIPATE)(PBSA) AND RAW COLLAGEN HYDROLYSATE (HC) THERMOPLASTIC BLENDS
JP2004083734A (ja) 耐水性に優れた生分解性成形品とその製造方法
CN107603017A (zh) 一种塑料食品包装袋及其制备方法
Petrucci et al. Mechanical and thermal characterisation of poly (ethylene) and thermoplastic starch filled with keratin horn powder from bovine claws

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20170321

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20200529

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20201009