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WO2018051345A1 - Matériau composite ignifuge biodégradable thermiquement stable et ses procédés de préparation - Google Patents

Matériau composite ignifuge biodégradable thermiquement stable et ses procédés de préparation Download PDF

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Publication number
WO2018051345A1
WO2018051345A1 PCT/IL2017/051039 IL2017051039W WO2018051345A1 WO 2018051345 A1 WO2018051345 A1 WO 2018051345A1 IL 2017051039 W IL2017051039 W IL 2017051039W WO 2018051345 A1 WO2018051345 A1 WO 2018051345A1
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Prior art keywords
composite material
app
plastic
amine
aldehyde
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Steve Daren
Pavel BASIN
Paul Antony Yianni
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Daren Laboratories & Scientific Consultants Ltd
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Daren Laboratories & Scientific Consultants Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials

Definitions

  • the present invention relates to a biodegradable flame retardant composite material having improved intumescent properties and thermal stability and processes for its preparation.
  • the present invention further relates to plastic materials comprising said flame retardant composite material and methods for their preparation.
  • FR additives In the field of industrial applications such as automotive, consumer electronics and home appliances, all plastic components must be flame retardant (FR). Many of the well-known FR additives contain halogens (e.g. chlorinated and brominated substances), and therefore are potentially harmful to human health and to the environment.
  • halogens e.g. chlorinated and brominated substances
  • Phosphorus-containing FRs are of reduced ecological impact, and their range is wide and versatile due to the several potential oxidation states of phosphorus (P) atom.
  • P phosphorus
  • a system containing such FRs should be well designed to prevent the migration of the phosphorous-based FR additive to the surface of the polymeric matrix.
  • Lignin is one of the most abundant organic substances on earth and is increasingly available as a by-product of cellulose production. Lignin-containing materials demonstrate the ability to prevent the material from dripping, forming a solid char upon exposure to high temperature and stays adhered to the exposed surface.
  • Physical barrier forming effect as described hereinabove is a known property of intumescent substances or systems comprising these substances.
  • an exposure to heat causes the material to swell, thus increasing the material's volume and decreasing its density.
  • the swollen phase constitutes a new interface between the heat source, oxygen and other fire-enhancing gases, and the material itself and slows the flame's progress.
  • Ammonium polyphosphate (APP) based systems are efficient halogen-free flame retardants, mainly used in polyolefins, polyethylene and polypropylene (PE and PP respectively), thermoset resins such as epoxy resins, polyurethane, unsaturated polyester phenolic resins and others.
  • APP is a non-toxic, environmentally friendly material and it does not generate additional quantities of smoke due to the unique mechanism of intumescence.
  • stable intumescent systems are very often difficult to produce, demanding a complex and involved formulation and/or compounding processes.
  • APP decomposition is about 275°C whereas the processing temperature for engineering plastics such as nylon (PA6) is over 300°C.
  • PA6 processing temperature for engineering plastics
  • APP therefore cannot be used as an additive in such systems.
  • Other materials can be used in such systems such as phosphinates and red phosphorous, but these are more expensive and have health and safety risks.
  • CN 103382281 discloses epoxy-lignin based FR laminates.
  • CN 102250360 discloses solvent lignin-cyanamide derivative FR and a method for its preparation.
  • CN 102585141 discloses FR material based on polyurethane foam in combination with lignin and a preparation method thereof.
  • CN 102757567 discloses nitrogen-based lignin FR agent and corresponding FR composite materials containing such agent.
  • US Patent No. 7, 129,291 discloses urea-bio based urethane FR compositions.
  • WO 2006/003421 discloses flexible FR nanocomposite based on polyurethane foams and clay.
  • US Patent Application US 20020158237 discloses FR based on amino-aldehyde- phosphate resins and copolymers, and their preparation methods.
  • CN 104493932 discloses water solutions of the products of the reactions between lignosulfonate (LS), melamine and formaldehyde as protective coatings to prevent fire in wooden buildings of historic value.
  • the present invention provides a biodegradable composite material, comprising a flame retardant (FR) of renewable resource, namely, lignin-based material, an aldehyde, an amine- containing compound and ammonium polyphosphate (APP), coupled together to give a synergistic intumescent effect.
  • FR flame retardant
  • the composite material of the invention is a solid material at room temperature and is characterized by low water solubility, a desired property it terms of environmental safety regulations. Furthermore, the composite material's distinct formulation gives rise to a chemically stable FR composite material, exhibiting high temperature resistivity.
  • the present invention is based in part on an unexpected finding that a chemically stable intumescent system can be formulated in a facile, convenient and cost-effective process.
  • the present invention provides methods for the preparation of the FR composite material of the invention.
  • the FR composite material of the invention can be incorporated into commonly used plastic materials as an additive, and improve their FR properties, without jeopardizing their mechanical properties.
  • the present invention further provides plastic materials comprising the FR composite material of the invention and processes for the incorporation of the FR composite material of the invention into plastic materials.
  • the plastic material is selected from bioplastics and synthetic thermoplastic and thermosetting materials.
  • the present invention provides a biodegradable flame retardant (FR) composite material comprising a lignin-based compound, an aldehyde, an amine- containing compound, phosphoric acid and ammonium polyphosphate (APP), wherein said composite material is in solid form at room temperature.
  • the FR composite material is a chemical adduct of a lignin-based compound, an aldehyde, an amine-containing compound, phosphoric acid and ammonium polyphosphate (APP).
  • the lignin-based FR is hgnosulfonate (LS).
  • the amine-containing compound is selected from the group consisting of ammonia, an alkyl amine, a diamine, a triamine, a polyamine, an alkanolamine, a cyclic amine and an amino acid.
  • the diamine is ethylene diamine.
  • the triamine is melamine.
  • the aldehyde is selected from the group consisting of paraformaldehyde, formaldehyde, acetaldehyde, furfural, hydroxymethyl furfural, butyraldehyde, 4-hydroxy-3- methoxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde and 2-hydroxybenzaldehyde.
  • the aldehyde is paraformaldehyde.
  • the composite material as described above is consisting of a lignin- based compound, an aldehyde, an amine containing compound, phosphoric acid and ammonium polyphosphate (APP).
  • the composite material as described above is consisting of a LS, paraformaldehyde, ethylene diamine or melamine, phosphoric acid and APP.
  • the present invention further provides a biodegradable FR composite material consisting essentially of a lignin-based compound, an aldehyde, an amine containing compound, phosphoric and ammonium polyphosphate (APP), wherein said composite material is in solid form at room temperature.
  • a biodegradable FR composite material consisting essentially of a lignin-based compound, an aldehyde, an amine containing compound, phosphoric and ammonium polyphosphate (APP), wherein said composite material is in solid form at room temperature.
  • the composite material of the invention comprises: from about 35 to about 75 wt% APP; from about 15 to about 35 wt% LS; from about 10 to about 35 wt% phosphoric acid; from about 1 to about 15 wt% ethylene diamine or melamine; and from about 1 to about 15 wt% p-formaldehyde.
  • the present invention further provides a plastic material comprising the FR composite material as described above.
  • the plastic material is of a natural origin.
  • the plastic material is selected from the group consisting of polyhydroxyalkanoate (PHA), polyethylene glycol (PEG), polyester, polyamide, polylactic acid (PLA), polybutylene succinate (PBS), poly p- phenylene (PPP), polytrimethylene tetraphthalate (PTT), polyethylene (PE), and combinations thereof, with each possibility represents a separate embodiment of the present invention.
  • the plastic is polyhydroxyalkanoate (PHA).
  • the plastic is polyhydroxybutyrate (PHB).
  • the plastic material is of a synthetic origin.
  • the plastic material is selected from the group consisting of a thermoplastic material, a thermosetting material and an engineering plastic.
  • the thermoplastic material is polypropylene.
  • the thermosetting material is selected from the group consisting of polyurethane, epoxy resin and unsaturated polyester.
  • the engineering plastic is selected from the group consisting polyamide (PA) and polybutylene terephthalate (PBT).
  • the present invention further provides methods for the preparation of a biodegradable composite material as described above.
  • the method for the preparation of the biodegradable composite material comprises the steps of: (i) mixing, with optional heating, lignin-based compound with amine-containing compound and an aldehyde; (ii) adding phosphoric acid; (iii) drying and optionally grinding the material obtained in step (ii); (iv) mixing with optional heating, of the material obtained in step (iii) with APP; and (v) optionally grinding the material obtained in step (iv) to obtain a solid, water-insoluble FR composite material.
  • the heating in step (i) is carried at a temperature of between about 70 to about 150 °C.
  • the drying in step (iii) is carried at a temperature of between about 80 to about 150 °C.
  • the heating in step (iv) is carried at a temperature of between about 200 to about 300 °C.
  • the APP and the material obtained in step (ii) were mixed together in step (iv) in a 1: 1 weight ratio.
  • the lignin-based compound is lignosulfonate (LS).
  • the amine-containing compound is selected from the group consisting of ammonia, an alkyl amine, a diamine, a triamine, a polyamine, an alkanolamine, a cyclic amine and an amino acid.
  • the diamine is ethylene diamine.
  • the triamine is melamine.
  • the aldehyde is selected from the group consisting of paraformaldehyde, formaldehyde, acetaldehyde, furfural, hydroxymethyl furfural, butyraldehyde, 4-hydroxy-3- methoxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde and 2-hydroxybenzaldehyde.
  • the aldehyde is paraformaldehyde.
  • the method for the preparation of a biodegradable FR composite material comprises the steps of: (i) mixing, with optional heating, sulfite spent liquor (SSL) with an amine-containing compound, sulfuric acid and an aldehyde; (ii) separating the solid phase obtained in step (i); (iii) adding, with optional heating, phosphoric acid to the solid material obtained in step (ii); (iv) optionally drying and/or grinding the material obtained in step (iii); (v) mixing, with optional heating, of the material obtained in step (iii) with APP; and (vi) optionally grinding the material obtained in step (iv) to obtain a solid, water- insoluble FR composite material.
  • the heating in step (i) is carried at a temperature of between about 70 to about 150 °C. In another embodiment, the heating in step (v) is carried at a temperature of between about 200 to about 300 °C. In yet another embodiment, the APP and the material obtained in step (iv) were mixed together in step (v) in a 1 : 1 weight ratio.
  • the lignin-based compound is lignosulfonate (LS).
  • the amine-containing compound is selected from the group consisting of ammonia, an alkyl amine, a diamine, a triamine, a polyamine, an alkanolamine, a cyclic amine and an amino acid.
  • the diamine is ethylene diamine.
  • the triamine is melamine.
  • the aldehyde is selected from the group consisting of paraformaldehyde, formaldehyde, acetaldehyde, furfural, hydroxymethyl furfural, butyraldehyde, 4-hydroxy-3-methoxybenzaldehyde, 4- hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde and 2- hydroxybenzaldehyde.
  • the aldehyde is paraformaldehyde.
  • FIG. 1 illustrates a Thermogravimetric analysis (TGA) profile of neat FR materials, demonstrating the decomposition onset of samples comprising ammonium polyphosphate (APP) and/or modified lignosulfonate.
  • TGA Thermogravimetric analysis
  • FIG. 2 illustrates a Thermogravimetric analysis (TGA) profile of bioplastics comprising FR materials, demonstrating the decomposition onset of samples comprising ammonium polyphosphate (APP) and/or modified lignosulfonate.
  • TGA Thermogravimetric analysis
  • FIG 3 illustrates a Thermogravimetric analysis (TGA) profile of neat FR materials demonstrating the decomposition onset of samples comprising ammonium polyphosphate (APP) and/or modified lignosulfonate originated from spent sulfite liquor (SSL).
  • TGA Thermogravimetric analysis
  • FIG 4 illustrates a Thermogravimetric analysis (TGA) profile of bioplastics comprising FR materials, demonstrating the decomposition onset of samples comprising ammonium polyphosphate (APP) and/or modified lignosulfonate originated from spent sulfite liquor (SSL).
  • TGA Thermogravimetric analysis
  • Figure 5 depicts the enhanced intumescent effect demonstrated in a bioplastic comprising the composite material of the invention.
  • the black arrow points at the swollen black material resulted from heating the plastic in a TGA apparatus.
  • FIG. 6 illustrates a Thermogravimetric analysis (TGA) profile of neat modified LS FR originated from spent sulfite liquor (SSL).
  • TGA Thermogravimetric analysis
  • FIG. 7 illustrates a Thermogravimetric analysis (TGA) profile of neat modified LS FR originated from spent sulfite liquor (SSL) compared to a commercially available APP-based FR.
  • TGA Thermogravimetric analysis
  • Figure 8 depicts a Fourier transform infrared spectroscopy (FTIR) analysis of neat modified LS FR originated from spent sulfite liquor (SSL).
  • FTIR Fourier transform infrared spectroscopy
  • the bottom graph depicts the neat material before thermal treatment and the top graph depicts the material after treatment.
  • Figure 9 illustrates a Thermogravimetric analysis (TGA) profile of composite materials comprising different ratios of modified LS FR originated from spent sulfite liquor (SSL) and APP-based FR.
  • TGA Thermogravimetric analysis
  • FIG 10 illustrates a Thermogravimetric analysis (TGA) profile of composite materials comprising different ratios of modified LS FR originated from spent sulfite liquor (SSL) and water soluble APP.
  • TGA Thermogravimetric analysis
  • the present invention is directed to a biodegradable composite material, which is based on a natural flame retardant (FR) of renewable resource, namely, lignin-based FR, thereby promoting the use of discarded biomass products.
  • the composite material of the invention comprises a distinct combination of said renewable resource FR material, an aldehyde, an amine-containing compound and ammonium polyphosphate (APP), which give rise to enhanced intumescent properties of the resulted composite material.
  • the composite material of the invention is a solid material at room temperature, with low water solubility, thereby presents facile handling and environmentally friendly non-leaching characteristics.
  • the composite material's distinct formulation and preparation conditions promote the formation of a chemically stable FR composite material, exhibiting an enhance stability at high temperatures.
  • the biodegradable composite material of the invention demonstrate a unique combination between a biopolymer (lignin-based material), ammonium polyphosphate (APP), an aldehyde and amine-containing compound which yields a chemically stable material, characterized by a high concentration of hetero-atoms (non-carbon atoms) and therefore beneficial for use as a FR.
  • a biopolymer lignin-based material
  • APP ammonium polyphosphate
  • aldehyde aldehyde
  • amine-containing compound which yields a chemically stable material, characterized by a high concentration of hetero-atoms (non-carbon atoms) and therefore beneficial for use as a FR.
  • the present invention provides a biodegradable flame retardant (FR) composite material comprising a lignin-based compound, an aldehyde, an amine-containing compound, phosphoric acid and ammonium polyphosphate (APP), wherein said composite material is in solid form at room temperature.
  • FR biodegradable flame retardant
  • the composite material of the present invention is the chemical reaction product of a lignin-based compound, an aldehyde, an amine containing compound, phosphoric acid and ammonium polyphosphate (APP).
  • the chemical reaction product has distinctive chemical and physical properties, compared to the properties of the starting materials. Specifically, it has improved flame retardant properties.
  • the lignin-based FR, aldehyde, amine-containing compound, phosphoric acid and APP are covalently coupled.
  • the FR composite material is a chemical adduct of lignin-based FR, aldehyde, amine-containing compound, phosphoric acid and APP. Without being bound to by theory or mechanism, it is contemplated that at least some of the components are covalently coupled in the composite material of the invention.
  • the amine-containing compound is covalently bound to the phenolic ring of the lignin-based material by a condensation reaction involving the aldehyde.
  • the APP is covalently bound to the lignin-based material through at least one of the lignin-based hydroxyl groups.
  • the phosphoric acid forming a salt with the amine- containing compound.
  • the composite material as described above is consisting of a lignin- based compound, an aldehyde, an amine containing compound, phosphoric acid and ammonium polyphosphate (APP).
  • the amine-containing compound used in the composite material as described above is selected from the group consisting of ammonia, an alkyl amine, a diamine, a triamine, a polyamine, an alkanolamine, a cyclic amine and an amino acid.
  • the diamine is ethylene diamine.
  • the triamine is melamine.
  • the aldehyde used in the composite material as described above is selected from the group consisting of paraformaldehyde, formaldehyde, acetaldehyde, furfural, hydroxymethyl furfural, butyraldehyde, 4-hydroxy-3-methoxybenzaldehyde, 4- hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde and 2- hydroxybenzaldehyde.
  • the aldehyde is paraformaldehyde.
  • the composite material of the invention comprises: from about 35 to about 75 wt% APP; from about 15 to about 35 wt% LS; from about 10 to about 35 wt% phosphoric acid; from about 1 to about 15 wt% ethylene diamine or melamine; and from about 1 to about 15 wt% p-formaldehyde.
  • the composite material as described above is consisting of a LS, paraformaldehyde, ethylene diamine or melamine and APP.
  • the composite material of the invention comprises the reaction products formed by reacting: about 35 to about 75 wt% of APP; about 15 to about 35 wt% of LS; about 10 to about 35 wt% of phosphoric acid; about 1 to about 15 wt% of ethylene diamine or melamine; and about 1 to about 15 wt% of p-formaldehyde.
  • the composite material as described above is a product obtained by reacting the materials from the group consisting of a LS, paraformaldehyde, ethylene diamine or melamine and APP.
  • the present invention further provides a flame retardant (FR) composite material prepared from combining a lignin-based compound, an aldehyde, an amine containing compound, phosphoric acid and ammonium polyphosphate (APP), wherein said composite material is in solid form at room temperature.
  • FR flame retardant
  • the combination for preparing the flame retardant (FR) composite material comprises about 35 to about 75 wt% APP. In some embodiments, the combination comprises about 15 to about 35 wt% lignin-based compound. In some embodiments, the lignin-based compound is LS. In some embodiments, the combination comprises about 15 to about 35 wt% LS. In some embodiments, the combination comprises about 10 to about 35 wt% phosphoric acid. In some embodiments, the combination comprises about 1 to about 15 wt% amine containing compound. In some embodiments, the amine containing compound is ethylene diamine or melamine. In some embodiments, the combination comprises about 1 to about 15 wt% ethylene diamine or melamine.
  • the combination comprises about 1 to about 15 wt% aldehyde. In some embodiments, the aldehyde is p-formaldehyde. In some embodiments, the combination comprises about 1 to about 15 wt% p-formaldehyde.
  • the weight percentages above refer to the weight of the recited ingredient divided by the total weight of the combination.
  • the term about, as used herein refers to ⁇ 20% of a recited value. Preferably the term refers to ⁇ 10% of the value.
  • the phrase "the combination comprises about 1 to about 15 wt% p-formaldehyde” means that the weight of the p-formaldehyde is in the range of 0.8% to 18% based on the total weight of the combination used for preparing the FR material.
  • the present invention further provides a biodegradable FR composite material consisting essentially of a lignin-based compound, an aldehyde, an amine containing compound, phosphoric acid and ammonium polyphosphate (APP), wherein said composite material is in solid form at room temperature.
  • a biodegradable FR composite material consisting essentially of a lignin-based compound, an aldehyde, an amine containing compound, phosphoric acid and ammonium polyphosphate (APP), wherein said composite material is in solid form at room temperature.
  • the present invention is based in part on an unexpected finding that a chemically stable intumescent system can be formulated in a facile, convenient and cost-effective process.
  • the present invention provides methods for the preparation of the composite material of the invention.
  • the preparation of the composite FR material is carried by mixing of a lignin-based compound, an aldehyde, an amine containing compound, phosphoric acid and ammonium polyphosphate (APP) in the conditions appropriate to achieve said composite material, as described herein below.
  • the present invention utilizes an economically favored and abundant starting material, namely, lignin-based material, which is available as a by-product of large scale cellulose production processes.
  • the lignin-based compound is a lignin derivative or a modified lignin molecule.
  • the lignin-based compound is a molecule having lignin attached to said molecule's backbone chain as a side group.
  • said molecule's backbone chain comprise additional side groups or moieties.
  • the lignin- based FR is lignosulfonate (LS).
  • the lignin-based compound is a component in a composition comprising the lignin-based compound.
  • the composition comprises technical lignins.
  • the composition is selected from Spent Sulfite Liquor (SSL), Black Liquor (BL) and a combination thereof.
  • the composition is SSL.
  • the composition is BL.
  • SSL spent sulfite liquor
  • wood chips or other lignocellulose are cooked under pressure in sulfite liquor so that lignins of the lignocellulose are solubilized and thereby separable from the insoluble cellulose, in a process generally known as pulping.
  • the cellulose is then separated from the liquor, the liquor resulting from the separation is known as spent sulfite liquor (SSL).
  • liquors include lignosulfonates and wood sugars (e.g. xylose, mannose, galactose, glucose).
  • SSL is composed of 55% total solids (about 35% lignosulfonates and 20% sugars w/w).
  • the Kraft process is another process for conversion of wood into wood pulp. It entails treatment of wood chips with a hot mixture of water, sodium hydroxide, and sodium sulfide that breaks the bonds that link lignin, hemicellulose, and cellulose. In the process the wood chips are cooked in pressurized vessels. The solid pulp (about 50% by weight of the dry wood chips) is then collected and washed. At this point the pulp is known as brown stock because of its color. The separated combined liquids are waste known as black liquor (BL). They contain lignin fragments, carbohydrates from the breakdown of hemicellulose, sodium carbonate, sodium sulfate and other inorganic salts. Typically, the composition of BL concentrate (i.e.
  • the lignin-based composition comprises about 10% to about 60% lignosulfonates, or about 20% to about 50% lignosulfonates, or about 25% to about 40% lignosulfonates, or about 10% to about 40% lignosulfonates.
  • the preparation of a mixture comprising lignosulfonate (LS), amine containing compound and an aldehyde, which is referred to as modified lignosulfonate (mod-LS) can be carried utilizing neat lignosulfonate, by a direct extraction route from black liquor (BL), or by a direct extraction route from sulfite spent liquor (SSL).
  • the mod-LS prepared from SSL biomass or from BL biomass may further comprise residual organic materials originated in said biomass, for example proteins, peptides, nucleic acid fragments and lipids, or residual inorganic salts.
  • the modified-LS is further mixed with APP or APP-based composition to achieve the composite FR material of the invention.
  • APP-based composition refers to a composition in which the main ingredient is APP, and it may further contain stabilizers such as alcohols, in particular alcohols containing a plurality of hydroxyl groups.
  • the method for the preparation of the biodegradable FR composite material comprises the steps of: (i) mixing, with optional heating, lignin-based compound with an amine-containing compound and an aldehyde; (ii) adding phosphoric acid; (iii) drying and optionally grinding the material obtained in step (ii); (iv) mixing with optional heating, of the material obtained in step (iii) with APP; and (v) optionally grinding the material obtained in step (iv) to obtain a solid, water-insoluble FR composite material.
  • the heating in step (i) is carried at a temperature of between about 70 to about 150 °C. In other embodiments, the drying in step (iii) is carried at a temperature of between about 80 to about 150 °C. In some additional embodiments, the heating in step (iv) is carried at a temperature of between about 200 to about 300 °C. In yet some other embodiments, the APP and the material obtained in step (ii) were mixed together in step (iv) in a 1: 1 weight ratio. In some related embodiments, the modified LS is prepared directly from SSL.
  • the method for the preparation of modified LS comprises the steps of: (i) mixing, with optional heating, sulfite spent liquor (SSL) with ethylene diamine or melamine, sulfuric acid and paraformaldehyde; (ii) separating the solid phase obtained in step (i); (iii) adding, with optional heating, phosphoric acid to the solid material obtained in step (ii); and (iv) optionally drying and/or grinding the material obtained in step (iii).
  • the heating in step (i) is carried at a temperature of between about 70 to about 150 °C.
  • the resultant modified LS is further mixed with APP or an APP -based composition to form the solid composite FR material of the invention.
  • the method for the preparation of a biodegradable FR composite material comprises the steps of: (i) mixing, with optional heating, sulfite spent liquor (SSL) with ethylene diamine or melamine, sulfuric acid and paraformaldehyde; (ii) separating the solid phase obtained in step (i); (iii) adding, with optional heating, phosphoric acid to the solid material obtained in step (ii); (iv) optionally drying and/or grinding the material obtained in step (iii); (v) mixing, with optional heating, of the material obtained in step (iii) with APP; and (vi) optionally grinding the material obtained in step (iv) to obtain a solid, water-insoluble FR composite material.
  • the heating in step (i) is carried at a temperature of between about 70 to about 150 °C. In another embodiment, the heating in step (v) is carried at a temperature of between about 200 to about 300 °C. In yet another embodiment, the APP and the material obtained in step (iv) were mixed together in step (v) in a 1 : 1 weight ratio.
  • the lignin-based compound used for the preparation of the FR composite material of the invention is lignosulfonate (LS).
  • the amine-containing compound used for the preparation of the FR composite material of the invention is selected from the group consisting of ammonia, an alkyl amine, a diamine, a triamine, a polyamine, an alkanolamine, a cyclic amine and an amino acid.
  • the diamine is ethylene diamine.
  • the triamine is melamine.
  • the aldehyde used for the preparation of the FR composite material of the invention is selected from the group consisting of paraformaldehyde, formaldehyde, acetaldehyde, furfural, hydroxymethyl furfural, butyraldehyde, 4-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3,5- dimethoxybenzaldehyde, 4-hydroxybenzaldehyde and 2-hydroxybenzaldehyde.
  • the aldehyde is paraformaldehyde.
  • the preparation of the composite material of the invention can be carried out using APP which is water soluble.
  • APP which is water soluble.
  • Low molecular weight APP having a molecular weight of less than 10,000 g/mol is often used in agriculture as a fertilizer and is highly water soluble and hydroscopic.
  • the composite material of the invention comprises low molecular APP and modified LS. Upon thermal treatment of the resultant composite material, the later may present lower solubility of APP incorporated within the composite material and lower hygroscopic nature.
  • Plastic material comprising the composite material
  • the composite material of the invention can be incorporated into commonly used plastic materials as an additive in order to improve their FR properties without jeopardizing their mechanical properties.
  • the beneficial thermal stability obtained by the unique composition of the composite material of the invention allows the use of both bioplastics and engineering plastics for the generation of improved plastic materials in terms of FR properties.
  • the present invention provides a plastic material comprising the FR composite material as described above.
  • the plastic material is of a natural origin.
  • the plastic material is selected from the group consisting of polyhydroxyalkanoate (PHA), polyethylene glycol (PEG), polyester, polyamide, polylactic acid (PLA), polybutylene succinate (PBS), poly p-phenylene (PPP), polytrimethylene tetraphthalate (PTT), polyethylene (PE), and combinations thereof, with each possibility representing a separate embodiment of the present invention.
  • the plastic is polyhydroxyalkanoate (PHA).
  • the plastic is polyhydroxybutyrate (PHB).
  • the plastic material is of a synthetic origin.
  • the plastic material is selected from the group consisting of a thermoplastic material, a thermosetting material and an engineering plastic.
  • the thermoplastic material is polypropylene.
  • the thermosetting material is selected from the group consisting of polyurethane, epoxy resin and unsaturated polyester.
  • the engineering plastic is selected from the group consisting polyamide (PA) and polybutylene terephthalate (PBT).
  • polymer refers to a molecule composed primarily of a plurality of repeating units. It is to be understood that the names of the abovementioned polymers refer to the repeating units which make up the majority of the structure of the polymers, and are not meant to exclude the presence of additional functional groups in the polymer.
  • FR flame retardant
  • lignin- based FR refers to a FR that is achieved by anchoring molecules bearing heteroatoms to lignin polymer groups. The anchoring can be carried by means of physical or chemical interactions or bonding.
  • biodegradable refers to materials which are capable of degrading or decomposing upon interaction with the environment over a period of time.
  • Biodegradable materials can undergo degradation from the action of naturally occurring microorganisms such as bacteria, fungi, and algae. Additional factors affecting the rate of the degradation include pH, temperature, pressure, water presence, etc.
  • the degradation of biodegradable materials results in natural byproducts such as gases (C0 2 , N 2 ), water, biomass, and inorganic salts.
  • the approximated period of time for compounds to biodegrade can vary between about 1 to about 100 years. According to some embodiments, the composite material of the present invention undergoes biodegradation in about 1 to about 50 years.
  • said composite material undergoes biodegradation in about 1 to about 20 years, or from about 20 to about 50 years, or from about 50 to about 70 years, or from about 70 to about 100 years. In still further embodiments, said composite material undergoes biodegradation in about 1 to about 10 years.
  • chemical reaction product refers to a compound or a plurality of compounds, which is formed by a chemical reaction and includes atoms and/or chemical fragments derived from the starting components, which lead to its formation.
  • the chemical reactions leading to the chemical reaction product may be, for example, a condensation(s), leading to a condensate(s), an acid-base netralization and/or addition (s), leading to an adduct(s).
  • modified-LS and “mod-LS” are used interchangeably and refer to chemically modified lignosulfonate (LS).
  • the chemical modification can be carried by anchoring molecules bearing heteroatoms to lignosulfonate polymer groups.
  • the anchoring can be carried by means of physical or chemical interactions or bonding.
  • composite material refers to a composition combining two or more materials from an organic and/or inorganic origin, which might differ in their chemical and/or physical properties, in a certain way to produce a new material with advantageous characteristics.
  • the composite material can have a different set of properties from the individual components used for its formation.
  • thermal treatment and “annealing” are used interchangeably and refer to the optional heating of the composite material as a part of the preparation process.
  • the heating may take place upon mixing modified LS and APP or after the two components are mixed together.
  • cyclic amine refers to heterocycles comprising one or more secondary amine.
  • cyclic amines include but not limited to aziridine, pyrrolidine, piperidine and piperazine.
  • hygroscopic refers to the tendency of a material to absorb water from the atmosphere.
  • low weight APP is hygroscopic as it absorbs water molecules in an amount that can increase its initial mass in about 5%.
  • bioplastic refers to a plastic material derived from a renewable biomass source.
  • plasticizer refers to a material that improves the plasticity or fluidity of another material. The addition of such materials into plastic or bioplastic can increase the flexibility of the plastic and its durability.
  • plasticizers are: citrate esters (e.g. CITROFOLTM), bioplasticizers (e.g. LAPOLTM), monoglycerides of hydrogenated castor oil (e.g. DANISCOTM).
  • nucleant refers to a material promoting the crystallization of semi- crystalline polymers. Examples of possible nucleants are: saccharin, talc, boron nitride and ammonium chloride.
  • chain extender and “cross-linking agents” refers to low molecular weight hydroxyl and/or amine terminated compounds that play an important role in polymer morphology. These materials can react through their hydroxyl and/or amine terminal groups with an existing polymer to enhance mechanical properties, increase viscosity and compatibility of plastic alloys. Examples of possible cross-linking agents are: isocyanates and aromatic carbodiimides (e.g. BIOADIMIDETM).
  • lubricant refers to a compound that can be inserted into a plastic and reduces the material's friction and wear, especially during processing, and increase the plastic's life.
  • antioxidant refers to a compound which helps to prevent the polymer reaction with oxygen. Oxidation can cause loss of impact strength, elongation, surface cracks and discoloration.
  • thermoplastic materials is understood in the art and used herein to denote compositions and materials that are generally capable of repeatedly softening when appropriately heated and hardening when subsequently cooled. Thermoplastic materials are generally in a solid or form stable state below the melting point or softening range, while generally being in a plastic or flowable state above the melting point or softening range.
  • thermoplastic material as used herein further is understood to mean any thermoplastic polymer, including thermoplastic elastomers, and blends thereof.
  • thermosetting material refers to a high polymer that solidifies or “sets” irreversibly when heated. This property is typically associated with a cross-linking reaction of the molecular constituents induced by heat or irradiation. Phenolics, alkyds, amino resins, polyesters, epoxides, and silicones are usually considered to be thermosets.
  • engineering plastics refers to a group of plastic materials that have better mechanical and/or thermal properties than the more widely used commodity plastics. "Engineering plastics” usually refers to thermoplastic materials rather than thermosetting ones. Examples of engineering plastics include, but are not limited to, acrylonitrile-butadiene styrene (ABS), polycarbonates and polyamides (nylons).
  • ABS acrylonitrile-butadiene styrene
  • nylons polyamides
  • Example 1 composite material preparation
  • modified hgnosulfonate can be performed utilizing neat Hgnosulfonate or by a direct extraction route from sulfite spent liquor (SSL) a waste stream from the extraction of cellulose from wood pulp by the sulfite process.
  • SSL sulfite spent liquor
  • Exolit 766 (Clariant) and mod-LS powder prepared according to either process A or B, were mixed in a weight ratio of 1: 1.
  • the mixture was heated to 250°C for 3 hours (annealing) and the obtained solid mass was ground to powder. A weight loss of -10-20% was observed during the annealing process.
  • the FR composite material as described above was shown to be insoluble in water.
  • TGA Thermo gravimetric analysis
  • the TGA analyses were obtained at a scan rate of 10°C per minute and the samples were heated from 36°C to 400 °C under nitrogen.
  • the preparation process was carried out in two steps: Dry blending and Compounding.
  • the FR composite material as prepared in Example 1 (path A or B) was mixed with PHB and polybutylene succinate (PBS) to form a bioplastic material.
  • PBS polybutylene succinate
  • the resulting material is then discharged and cut to form pellets which can be further molten and injected into the desired mold.
  • PHB powder and several commonly used additives such as plasticizer, nucleant, lubricant, antioxidant, chain extender, and a crosslink agent, were dry-blended in a turbomixer to obtain a homogeneous mixture of the PHB formulation.
  • the turbomixer was also connected to a vacuum pump to remove any possible moisture during the mixing stage.
  • the composite material of as described above was mixed with the PHB and PBS.
  • a vacuum pump was implemented in order to extract the volatiles produced during the compounding process.
  • Example 4 High-temperature stability of PHB comprising the composite FR material TGA was used in order to determine the onset decomposition temperature of different bioplastic materials comprising the composite FR material of the invention as follows:
  • Example 5 High-temperature stability of neat FR material, wherein the mod-LS is originated from spent sulfite liquor (SSL)
  • TGA was used in order to determine the onset decomposition temperature of different FR materials.
  • the LS component was produced directly from sulfite spent liquor (SSL) biomass as described in Example 1 process B.
  • SSL sulfite spent liquor
  • the TGA analysis obtained at a scan rate of 10°C per minute and was samples were heated from room temperature to 400 °C.
  • the TGA results demonstrate the improvement in thermal stability of neat mod-LS (obtained from SSL) achieved by a short heating of mod-LS. Additionally, the results show that the conjugation of mod-LS and APP is more stable than the neat mod-LS, but the composite material is not as stable as the neat APP system.
  • An important and surprising finding can was detected at about 360°C, where a sharp change in the thermogram was observed for the composite material due to an enhanced intumescent effect (Figure 3). This effect was further investigated in a PHB formulation comprising such composite material, as presented in example 6.
  • Example 6 High-temperature stability of PHB comprising composite material FR material TGA was used in order to determine the onset decomposition temperature of different bioplastic materials comprising the composite material FR material of the invention.
  • the LS component was produced directly from sulfite spent liquor (SSL) biomass as described in Example 1 process B. The samples measured were as follows:
  • the TGA analysis obtained at a scan rate of 5°C per minute and samples were heated from 36°C to 350 °C.
  • the TGA results demonstrate an improvement in thermal stability of a PHB-based plastic material upon the insertion of APP intumescent system, compared with neat PHB (Figure 4). Furthermore, the stability of 1 : 1 PHB with mod-LS prepared from SSL has a higher onset decomposition temperature than both neat PHB and 1: 1 PHB : APP systems (weight ratio).
  • An additional effect can be detected in the beneficial combination of PHB and the composite FR material of the invention, demonstrating both high onset decomposition temperature and reduced decomposition level, which without being bound by any theory or mechanism is contemplated to be a result of the enhanced intumescent effect achieved by the unique composite material composition.
  • a photograph of the resulted intumescent effect occurred in sample 4 comprising the composite FR material is presented in Figure 5.
  • a modified LS was prepared as described in Example 1 paragraph 2 (utilizing process B) and analyzed using inductive couple plasma (ICP) and elemental analysis (Table 1).
  • the material was heated to 300°C for 1 hour and was analyzed chemically and thermally before and after the annealing process.
  • the TGA analysis obtained at a scan rate of 10°C per minute and the samples were heated from 35°C to 400 °C.
  • the annealed material demonstrated a significant thermal stability, where the decomposition of the material starts only around 300°C as demonstrated in Figure 6.
  • FTIR Fourier transform infrared spectroscopy
  • Example 8 Different possible formulations of FR composite material and their related thermal stability properties
  • the composite materials 1-4 were heated in the oven at 250 °C for 3 hours. During this time a slight release of ammonia was observed by wet pH paper (depicted pH ⁇ 9). The resultant solids were ground to powders. The TGA analysis obtained at a scan rate of 10°C per minute and the samples were heated from 36°C to 400 °C under nitrogen.
  • Example 9 preparation of composite material utilizing agricultural grade ammonium polyphosphate
  • Agricultural grade ammonium polyphosphate is a water soluble, low molecular weight ammonium polyphosphate that is commonly used as a fertilizer.
  • the composite materials were annealed for 3 hours at 250 °C.
  • the TGA analysis obtained at a scan rate of 10°C per minute and the samples were heated from 35°C to 400 °C under nitrogen.
  • the obtained composite materials demonstrated an enhanced thermal stability, especially compared with the neat APP -based material (sample 4). Additionally, a strong intumescent effect was detected upon heating the samples to 400 °C. The resulted composites were also less hydroscopic than the neat APP.
  • Example 10 preparation of thermoplastic material comprising the composite material of the invention
  • Modified- LS prepared according to Example 1A was dried in an oven in 100°C for 24h with moisture content ⁇ 1%. Initial moisture was about 5% and final moisture about 0.5%. APP and mod-LS were mixed to create the composite of the invention. The composite was further mixed with Triazine in order to increase the heteroatom content. The mixture was then further homogenized in a PLASMEC turbo-mixer for 5min at lOOOrpm under vacuum before compounding.
  • the compounding process was carried out in a EURLAB PRISM twin screw extruder with 16mm of screw diameter.
  • the polypropylene and coupling agent were pre- mixed and fed together into the extruder together with the composite material and additional amine source triazine.
  • a vacuum pump removed volatiles and residual moisture from the process.
  • the compounding process was carried out using a reverse profile temperature from 210 to 190°C, at 200 rpm and 1.5kg/h.
  • the molten strand was cooled in a water bath and cut into pellets with a strand pelletizer.
  • the obtained pellets were dried after drying for 4h at 80°C and bagged under vacuum to prevent moisture absorption.
  • the obtained formulations were injected in an ENGEL Victory 50 hydraulic injection molding machine with a 25 mm screw diameter and camping force of 50 Ton.
  • the samples were injected using a profile temperature of 180 to 210°C and mold temperature of 30°C at 800 - 900 bars of injection pressure.
  • the composite material of the invention prepared according to the procedure in Example 1 path A) was added together with antioxidant and lubricant in a PLASMEC turbo-mixer for 5 min at lOOOrpm under vacuum before compounding.
  • the compounding process was carried out in a COPERION ZSK26 twin screw extruder with 26mm of screw diameter, and equipped with two side feeders. Glass fiber was fed in the second side feeder to avoid the breakage of the glass fibres. A vacuum pump removed volatiles and residual moisture from the process.
  • the compounding process was carried out using a profile temperature from 220 to 270°C, at 200 rpm and lOkg/h. The molten strand was cooled in a water bath and cut into pellets with a strand pelletizer.
  • the obtained pellets were dried after compounding for 4h at 80°C and bagged under vacuum to prevent moisture absorption.
  • the obtained formulations were injected in a KraussMaffei Ex 160-750 electric injection molding machine with a 50mm screw diameter and camping force of 160 Ton.
  • the samples were injected using a profile temperature of 220 to 260°C and mold temperature of 80°C at 1300 - 800 bars of injection pressure.
  • the formulations with LSmod showed lower injection molding pressures.
  • the composite of the invention was prepared as described in Example 1 (path A) and was further mixed with antioxidant and chain extender.
  • PBT was compounded with the composite mixture and glass fibers in the Coperion ZSK26 twin screw extruder. The compounding process was carried out using a profile temperature from 220 to 275 °C, at 200 rpm and lOkg/h.
  • the obtained formulations were injected in a KraussMaffei Ex 160-750 electric injection molding machine with a 50mm screw diameter and camping force of 160 Ton.
  • the samples were injected using a profile temperature of 210 to 250°C and mold temperature of 80°C at 1800 - 2000 bars of injection pressure.

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Abstract

La présente invention concerne un matériau composite ignifuge biodégradable présentant des propriétés intumescentes améliorées et une stabilité thermique améliorée, et des procédés servant à sa préparation. La présente invention concerne en outre des matériaux plastiques contenant le matériau composite ignifuge de l'invention et des procédés de préparation directe et facile et le mélange de tels matériaux plastiques ignifuges améliorés.
PCT/IL2017/051039 2016-09-15 2017-09-14 Matériau composite ignifuge biodégradable thermiquement stable et ses procédés de préparation Ceased WO2018051345A1 (fr)

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Cited By (7)

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US11225608B2 (en) 2017-09-13 2022-01-18 Daren Laboratories & Scientific Consultants Ltd. Lignin based flame retardant compositions and processes for the preparation thereof
CN111286008A (zh) * 2020-02-17 2020-06-16 南京工业大学 一种生物基环氧树脂固化剂及其制备方法
CN111286008B (zh) * 2020-02-17 2021-03-16 南京工业大学 一种生物基环氧树脂固化剂及其制备方法
WO2022148738A1 (fr) * 2021-01-05 2022-07-14 Universiteit Maastricht Composition de polymère ignifuge
CN113278229A (zh) * 2021-04-27 2021-08-20 台州学院 一种具有阻燃性的epdm发泡保温材料及其制备方法
CN118459958A (zh) * 2024-07-09 2024-08-09 台州黄岩泽钰新材料科技有限公司 一种聚乳酸-聚羟基脂肪酸酯基可降解复合材料及其制备方法
CN119286102A (zh) * 2024-12-13 2025-01-10 烟台亮彩塑料科技有限公司 一种改性塑料母粒及其制备方法

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