EP2760923A2 - Vernetztes mikrozelliges material aus industriellem lignin und verfahren zu seiner herstellung - Google Patents

Vernetztes mikrozelliges material aus industriellem lignin und verfahren zu seiner herstellung

Info

Publication number
EP2760923A2
EP2760923A2 EP12775776.3A EP12775776A EP2760923A2 EP 2760923 A2 EP2760923 A2 EP 2760923A2 EP 12775776 A EP12775776 A EP 12775776A EP 2760923 A2 EP2760923 A2 EP 2760923A2
Authority
EP
European Patent Office
Prior art keywords
phase
dispersant
interconnected
solvent
microcellular material
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Withdrawn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
EP12775776.3A
Other languages
English (en)
French (fr)
Inventor
Hervé DELEUZE
Claire FORGACZ
Marc Birot
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.)
Centre National de la Recherche Scientifique CNRS
Universite de Bordeaux
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite de Bordeaux
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 Centre National de la Recherche Scientifique CNRS, Universite de Bordeaux filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP2760923A2 publication Critical patent/EP2760923A2/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • C08J2397/00—Characterised by the use of lignin-containing materials

Definitions

  • the invention relates to a microcellular material, a process for preparing this material from residues of the paper industry of low value, as well as its use for the manufacture of articles such as catalysts, filters or absorbent elements.
  • the microcellular materials according to the invention are porous monoliths of centimeter size whose porosity is characterized by the presence of spherical cavities also called "cells", which have a diameter generally ranging between 1 and 100 ⁇ m, in particular about 2 ⁇ m. pm at about 50 ⁇ , and preferably from about 5 ⁇ m to about 20 ⁇ m. These cells are generally all interconnected with their close neighbors by openings or "windows" smaller than them. These interconnect windows are of variable size and have a diameter of from about 0.5 to about 10 ⁇ m, particularly from about 50 nm to about 1000 nm, and preferably from about 250 nm to about 500 nm.
  • the interconnected microcellular materials according to the invention have a particularly low density of 0.02 to 0.2 gcm- 3 .
  • the existing interconnected microcellular materials are generally obtained by the polyHIPE (Polymerization of a Hg /? Internai Phase Emulsion) process. Such materials are, for example, described in application FR 2 932 184.
  • the polyHIPE process consists in the polymerization of a highly concentrated emulsion which is composed of a dispersed internal phase whose volume percentage is greater than that of the dispersant external phase.
  • the volume percentage of the dispersed internal phase must theoretically be greater than or equal to 74% relative to the total volume of the emulsion.
  • This threshold of 74% corresponds to the maximum volume occupied by spherical drops internal phase uniforms dispersed and arranged so that they do not undergo deformation. Above 74%, the drops are compressed against each other.
  • the threshold for obtaining, after polymerization, an interconnected porous structure may be less than the theoretical value of 74%.
  • the outer dispersing phase of the polyHIPE process constitutes the continuous phase and mainly comprises monomers capable of polymerizing and a surfactant in solution in a solvent.
  • the dispersed inner phase consists mainly of a solvent immiscible with the monomers and / or the solvent of the continuous phase.
  • microcellular materials Due to their structure and physical properties, interconnected microcellular materials are of increasing interest and their use has been proposed in many areas, including the manufacture of disposable absorbent articles, thermal, acoustic, electrical or mechanical insulation of membranes, filters or carriers for inks, dyes and catalysts.
  • the interconnected microcellular materials are obtained from polymerizable precursors mainly of petroleum origin or of synthetic origin, that is to say non-plant and non-renewable raw materials.
  • polymerizable precursors mainly of petroleum origin or of synthetic origin, that is to say non-plant and non-renewable raw materials.
  • the recovery of renewable materials to replace them has become a priority.
  • the object of the invention is therefore to provide an interconnected microcellular material, preferably from the polyHIPE process, while meeting certain sustainable development concerns and retaining the advantageous properties of current polyHIPE materials.
  • the present invention therefore relates to a process for preparing this interconnected microcellular material using as raw material lignin.
  • This raw material is derived from lignocellulosic biomass.
  • Lignocellulosic biomass is one of the most abundant renewable resources on earth. Lignin is of significant interest because of its abundance and is the subject of much research for valuations other than its current uses in lumber and fuels.
  • lignin results from the oxidative polymerization of at least three types of phenolic alcohols: p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol.
  • p-coumaryl alcohol the phenolic alcohols
  • coniferyl alcohol the phenolic alcohols
  • sinapyl alcohol the phenolic alcohols
  • its structure depends on the botanical origin, the age of the plant, the type of tissue, the cells and the parietal layers in which it is found. This strong natural variability associated with variations in analytical methods makes it difficult to present the structure of lignins.
  • lignin is a generic name which denotes a set of polyphenolic polymers of high molecular mass, composition and variable and complex structure.
  • lignins are separated from cellulose by chemical processes that significantly alter their structure.
  • the residual lignins henceforth referred to as "industrial lignins"
  • cooking liquors which may also comprise hemicellulose monomers.
  • cooking liquors are either strongly basic in the Kraft process or in acidic solutions comprising sulfonated derivatives in the case of the bisulphite process.
  • Industrial lignins can be mined and are a by-product of a significant amount of waste with more than 50,000 tonnes per year worldwide.
  • organosolines lignins resulting from an extraction process using organic oxidants
  • the raw material of the process according to the invention is one of the main by-products of the paper industry, currently available in very large quantities and very poorly valued, namely the "black liquor”.
  • Black liquor or Kraft black liquor is the baking liquor from Kraft paper making. It is in the form of a strongly basic aqueous solution consisting mainly of Kraft lignin and hemicellulose residues dissolved from the pulp, as well as other inorganic chemical compounds used in the dissolution process. Black liquor is mainly used locally as a liquid fuel to supply energy to paper mills.
  • the subject of the invention is therefore a process for preparing an interconnected microcellular material by polymerization of a concentrated emulsion comprising:
  • an outer dispersant phase comprising, in a solvent, a surfactant and a solution comprising at least one polymerizable monomer contained in industrial lignin, and
  • a dispersed internal phase comprising a solvent immiscible with said polymerizable monomer and / or with the solvent of the dispersant external phase.
  • at least one polymerizable monomer contained in industrial lignin is meant a polymerizable monomer which originates from industrial lignins as defined above.
  • the solid material is preferably subjected to one or more washing and drying steps.
  • the invention also relates to interconnected microcellular materials, obtainable by the polymerization of a concentrated emulsion as described above.
  • the volume percentage of the dispersed inner phase of the concentrated emulsion is greater than or equal to about 55%.
  • microcellular materials having an interconnected porous structure according to the invention are capable of being obtained by polymerization of a concentrated emulsion comprising a percentage by volume in dispersed internal phase less than the theoretical threshold of 74% of the polyHIPE emulsions.
  • the concentrated emulsion according to the invention is preferably an "oil-in-water” emulsion, that is to say having as dispersant outer phase an aqueous phase and dispersed organic phase an organic phase.
  • the outer dispersing phase comprises a solution containing the monomers contained in the industrial lignin, as described above, which will then polymerize.
  • This solution can be a cooking liquor, especially the black liquor itself.
  • Kraft lignin is the main constituent of the black liquor, which makes it possible to use it in a privileged manner as main constituent of the dispersant external phase of a concentrated oil-in-water type emulsion according to the invention, and that without prior modification.
  • the solvent of the dispersing external phase is derived from this liquor.
  • the raw material used in the context of the invention is black liquor comprising in particular from about 20% to about 80% by weight of dry matter, preferably from about 40% to about 60% mass of dry matter.
  • the preferred mass percentage for obtaining interconnected microcellular materials according to the invention is 45% by mass of dry matter in the black liquor.
  • the dispersed internal phase of the emulsion according to the invention can be formed of any oil, and in particular, an oil soluble in common solvents and inexpensive to facilitate the washing of solids.
  • Other types of oil can be used as the dispersed internal phase of the emulsion according to the invention.
  • oils having a melting point between about 10 ° C and about 40 ° C and preferably close to room temperature may also be used.
  • the monomers capable of polymerization come from Kraft lignin and hemicelluloses.
  • the polymerizable monomers contained in the outer dispersant phase may be crosslinked to obtain a rigid solid.
  • the outer phase of the concentrated emulsion may then further comprise a crosslinking agent, such as, for example, epichlorohydrin and cyanuric chloride.
  • the crosslinking makes it possible to create covalent bonds between the polymer chains by means of the reactive chemical functions present on the lignin chains (aliphatic alcohols and phenols) as well as on the hemicellulose chains possibly present (aliphatic alcohols only), in aqueous basic medium and at a moderate temperature.
  • the preferred crosslinking agent is epichlorohydrin.
  • the reaction of epichlorohydrin with Kraft lignin from black liquor has the advantage of being catalyzed in a strong basic medium at a moderate temperature of 60.degree.
  • the concentrated emulsion can be polymerized at a temperature below 100 ° C and preferably from about 40 ° C to about 80 ° C.
  • a surfactant having a strong hydrophilic character is preferably added to the dispersant outer phase.
  • the surfactant may thus be selected from hydrophilic anionic surfactants and nonionic hydrophilic surfactants.
  • an anionic surfactant will be used, the hydrophilic head may be a carboxylate, sulfate or sulfonate group.
  • the apolar part may consist of a long linear or branched alkyl chain, simple or functionalized, or a long linear or branched alkylbenzene chain.
  • sodium dodecyl sulphate (SDS) triethanolamine stearate
  • sodium lauryl sulphate and triethanolamine lauryl sulphate can be used, for example, to form the emulsion according to the invention.
  • SDS will be used because it is inexpensive and can be used in a wide variety of formulations.
  • the surfactant may also be selected from nonionic surfactants.
  • HLB hydrophilic-lipophilic balance
  • a wide variety of high hydrophilic-lipophilic balance (HLB) surfactants can be envisioned, including alkyl polyethoxylates, ethoxylated alkylphenols, polyethylene and polypropylene oxide complex polymers, octylphenols, and the like.
  • the porous morphology of the interconnected microcellular materials according to the invention can be characterized by the porosity but also by the distribution of the mean diameters of the cells, the average diameter of the windows of the interconnections or the specific surface.
  • the analysis of this porous morphology also includes the determination of the origin of the porosity which comes from the imprint of the dispersed internal phase or the elimination of the water possibly contained in the dispersant external phase.
  • An indicator of the dispersion of the distribution of the U-cell diameters can in particular be used to determine whether this distribution is polydisperse or even monodisperse.
  • This factor U is defined by the following expression:
  • ri is the number of cells of diameter d and d * the median diameter, namely the diameter for which the volume fraction of the smaller sizes is equal to 0.5. It is generally considered that a monodisperse distribution (i.e. where the cell diameters are homogeneous) is obtained when U is less than or equal to 0.3.
  • This porous morphology can be, in particular, modulated according to the nature and the amount of surfactant or the emulsification time.
  • the interconnected microcellular material according to the invention then has a polydisperse or monodisperse distribution.
  • the modulation of the experimental parameters thus makes it possible to obtain interconnected microcellular materials according to the invention having a more or less broad distribution of cell diameters (monodisperse or polydisperse).
  • the invention also relates to the interconnected microcellular materials, obtainable by the method described above.
  • These interconnected microcellular materials may in particular have a porosity greater than or equal to about 60%. This porosity value is sufficient to obtain high permeability materials while maintaining the mechanical strength required for the intended applications.
  • the invention also relates to the use of a concentrated emulsion comprising at least one polymerizable monomer contained in industrial lignin, as defined above, for the preparation of an interconnected microcellular material.
  • the industrial lignin as described above may, in particular, be present in a cooking liquor, in particular black liquor.
  • the invention also relates to an emulsion useful for the preparation of a microcellular material as defined above. This emulsion is preferably monodisperse.
  • the emulsion according to the invention comprises:
  • an outer dispersant phase comprising, in a solvent, a surfactant and a solution comprising at least one polymerizable monomer contained in industrial lignin, and
  • a dispersed internal phase comprising a solvent immiscible with said monomer and / or with the solvent of the dispersant external phase.
  • the invention relates to any article consisting of all or part of the interconnected microcellular material described above such as, for example, a filter, a thermal insulation article, an acoustic insulation article, an insulation article. electric or mechanical, a disposable absorbent article, or a carrier for inks, dyes and catalysts.
  • Example 1 relates to the preparation of concentrated emulsions based on black liquor.
  • Example 2 describes the preparation of microcellular materials interconnected by the polymerization of the outer dispersant phase of the emulsions prepared in Example 1.
  • Example 3 relates to the analysis of the porous morphology of the microcellular materials obtained in Example 2, in particular as a function of the nature and amount of the surfactant.
  • Example 4 relates to the analysis of the porous morphology of microcellular materials obtained in Example 2 as a function of the emulsification time.
  • the emulsification is carried out using a system consisting of a metal tube of 10 mm diameter divided into two chambers connected by a small diameter channel (1 mm), and closed at both ends by pistons waterproof.
  • the tube is immobilized on a bench.
  • a regular back and forth motion is applied to the pistons that close the tube by a crank / crank system operated by a motor.
  • the mixture to be emulsified is thus forced to pass alternately from one chamber to another through the small junction channel. This creates a strong shear of the mixture to be emulsified, which is favorable for obtaining monodisperse emulsions.
  • crosslinking agent epichlorohydrin (Acros Organics)
  • the metal tube is closed using the two pistons and fixed with screws on the bench.
  • the mixture to be emulsified is then stirred by reciprocating the pistons for 80 min at a constant speed of 15 rpm.
  • ⁇ is defined as the volume percentage approximated in the internal phase dispersed in the emulsion.
  • Example 1 The emulsions of Example 1 are molded into hermetically sealed 2.80 cm ⁇ 4.30 cm polytetrafluoroethylene (PTFE) molds and are heated to a temperature of 60 ° C. for 48 hours.
  • the rigid solids obtained after this step are placed with their mold in an ethanol bath at room temperature for 24 hours. During this period, a portion of the castor oil constituting the dispersed phase of the emulsion and a portion of the water of the outer dispersant phase are entrained by the ethanol. This causes a slight contraction of the solid which allows easy demolding and without risk of deterioration of the solid.
  • PTFE polytetrafluoroethylene
  • the solids are placed in a Soxhlet extractor and continuously extracted with ethanol for four days to completely remove castor oil remaining in the solid. Once washed, the solids are placed in an ether bath for 24 hours at room temperature in order to exchange the ethanol contained in the solid with this more volatile solvent. Finally, the solids are dried in ambient air for four days.
  • FIG. 1 corresponds to the image obtained for the interconnected microcellular material A based on 4% by mass of Triton X-405.
  • FIG. 2 corresponds to the image obtained from the interconnected microcellular material C based on 4% by mass of Cremophor EL.
  • Example 2 An image analysis of the interconnected microcellular materials obtained according to Example 2, completed by a statistical analysis on a significant sample of cells (between 100 and 150 cells) are also carried out. This study makes it possible to determine the mean diameter of the cells, as well as the dispersion factor of these U diameters. The results are shown in Table 2 below.
  • the nature of the surfactant has an influence on the average diameter of the interconnections. This is 300 nm for microcellular materials A and B, Triton® X-405, and 800 nm for microcellular materials C and D, Cremophor® EL.
  • the nature and proportion of surfactant also influences the average cell diameter and the dispersion of the values of these diameters.
  • the average cell diameter is thus 6 ⁇ m and the distribution is monodisperse for Triton® X-405, 4% and 11 ⁇ m and the distribution is polydisperse for Triton® X-405, 8%.
  • the average cell diameter is 9 ⁇ m and the monodisperse distribution for Cremophor® EL 4%; and 16 ⁇ m and the polydisperse distribution for Cremophor® EL 8%.
  • Cremophor® EL used in the same 4% proportion, the decrease in the emulsification time results in a decrease in the mean diameter of the cells and a greater dispersion of these values (U increases).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Catalysts (AREA)
  • Processing Of Solid Wastes (AREA)
EP12775776.3A 2011-09-29 2012-09-27 Vernetztes mikrozelliges material aus industriellem lignin und verfahren zu seiner herstellung Withdrawn EP2760923A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1158752A FR2980797B1 (fr) 2011-09-29 2011-09-29 Materiau microcellulaire interconnecte a base de lignine industrielle et son procede de preparation
PCT/FR2012/052188 WO2013045848A2 (fr) 2011-09-29 2012-09-27 Matériau microcellulaire interconnecte a base de lignine industrielle et son procédé de préparation

Publications (1)

Publication Number Publication Date
EP2760923A2 true EP2760923A2 (de) 2014-08-06

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EP12775776.3A Withdrawn EP2760923A2 (de) 2011-09-29 2012-09-27 Vernetztes mikrozelliges material aus industriellem lignin und verfahren zu seiner herstellung

Country Status (6)

Country Link
US (1) US9290633B2 (de)
EP (1) EP2760923A2 (de)
JP (1) JP2014530275A (de)
CA (1) CA2846782A1 (de)
FR (1) FR2980797B1 (de)
WO (1) WO2013045848A2 (de)

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Publication number Priority date Publication date Assignee Title
CA2963691C (en) * 2014-10-30 2022-08-30 Cellutech Ab Cnf cellular solid material
US10907020B2 (en) 2014-10-30 2021-02-02 Cellutech Ab CNF cellular solid material with anionic surfactants
CN108794798A (zh) * 2018-05-18 2018-11-13 金学芳 一种多孔吸油树脂的制备方法
CN111905643A (zh) * 2020-08-17 2020-11-10 重庆化工职业学院 木质素羧基甜菜碱表面活性剂的制备方法
EP4492417A1 (de) * 2023-07-10 2025-01-15 Universite De Bordeaux Verfahren zur herstellung eines porösen monolithischen kohlenstoffhaltigen materials, nach diesem verfahren hergestelltes poröses monolithisches kohlenstoffhaltiges material und dessen verwendung als superkondensatorelektrode

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US3313745A (en) * 1962-02-22 1967-04-11 Klug Oluf Walther Henry Process for producing foam bodies from sulfite waste liquor and a foam product produced according to the process
US3857830A (en) * 1972-11-13 1974-12-31 Georgia Pacific Corp Process for preparation of lignin epoxide compositions and composition thereof
US4168371A (en) * 1977-02-04 1979-09-18 Westvaco Corporation Process for making lignin gels in bead form
JP2675997B2 (ja) * 1988-05-16 1997-11-12 工業技術院長 新規なポリウレタンの製造方法
FI104834B (fi) * 1997-01-14 2000-04-14 Neste Chemicals Oy Ligniinipohjaiset sideaineet ja niiden valmistusprosessi
FR2932184B1 (fr) 2008-06-09 2010-07-30 Commissariat Energie Atomique Materiau polyhipe a haute tenue mecanique, son procede de preparation, emulsion utile pour sa preparation et article constitue d'un tel materiau
CN102272313B (zh) * 2008-12-17 2014-11-05 鲍利葛股份公司 木质纤维素生物质转化
JP2011184643A (ja) * 2010-03-11 2011-09-22 Kawasaki Kasei Chem Ltd ポリエステルポリオール及び硬質ポリウレタンフォームの製造方法
CN102174164B (zh) * 2011-01-31 2013-01-09 中国农业大学 利用造纸废液提取物合成生物质基聚氨酯泡沫材料的方法

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Also Published As

Publication number Publication date
CA2846782A1 (fr) 2013-04-04
US9290633B2 (en) 2016-03-22
FR2980797B1 (fr) 2013-11-01
WO2013045848A2 (fr) 2013-04-04
WO2013045848A3 (fr) 2014-04-03
US20140228460A1 (en) 2014-08-14
JP2014530275A (ja) 2014-11-17
FR2980797A1 (fr) 2013-04-05

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