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WO2016131790A1 - Procédé de fabrication de matériau cellulosique hydrophobe - Google Patents

Procédé de fabrication de matériau cellulosique hydrophobe Download PDF

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Publication number
WO2016131790A1
WO2016131790A1 PCT/EP2016/053205 EP2016053205W WO2016131790A1 WO 2016131790 A1 WO2016131790 A1 WO 2016131790A1 EP 2016053205 W EP2016053205 W EP 2016053205W WO 2016131790 A1 WO2016131790 A1 WO 2016131790A1
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WIPO (PCT)
Prior art keywords
acid chloride
carboxylic acid
aliphatic carboxylic
kpa
process according
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Ceased
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PCT/EP2016/053205
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English (en)
Inventor
Hubertus Kroener
Jochen GATTERMAYER
Christian Eichholz
Lukas WENGELER
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BASF SE
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BASF SE
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Publication of WO2016131790A1 publication Critical patent/WO2016131790A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
    • C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/02—Chemical or biochemical treatment
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the current invention relates to a process for manufacturing a hydrophobic cellulosic material by reacting a cellulosic material with an aliphatic carboxylic acid chloride in supercritical carbon dioxide.
  • Cellulosic materials based on cellulosic fibers are typically hydro- philic. Changing this towards hydrophobic is in several technical areas of interest. For example, aqueous printing inks are spreading over a cellulosic material due to its hy- drophilic surfaces. In case of a paper, a certain reduction of this hydrophilicity can improve printability, e.g. an accentuated contrast by increasing the ratio between a penetration of the ink into the paper and spreading over the paper surface. Another example is the soaking of a cellulosic material, if it gets in contact with water.
  • US 6342268 discloses a method for treating a solid material, which possesses reactive protogenic hydrophilic functions.
  • a grafting reagent with a hydrophobic group which is liquid under atmospheric pressure at a temperature of at least 200 °C and can react with the hydrophilic functions, is made part of a micro-dispersion.
  • the micro-dispersion is produced on at least one part of the solid material.
  • a gas stream which is neutral to the grafting reaction of the grafting reagent, is applied at a temperature below the boiling point of the grafting reagent to carry out the grafting reaction by diffusion of the grafting reagent.
  • stearic acid chloride is often employed and either applied purely or as a pentane solution. In case of pentane or other solvents in its examples, evaporation of the solvent takes place prior to the grafting reaction.
  • US 2013/0236647 discloses a machine for treatment via chromatogenous grafting of a hydroxylated substrate and a process carried out by means of said machine. It refers to an equivalent of US 6342268, i.e. WO 99/08784 A for grafting by chromatogenic chemistry. It states that the reaction is made without a solvent, which contacts the substrate and the reagent and traps the released hydrochloric acid.
  • the process for treatment by chromatogenous grafting of a substrate having a hydroxylated face comprises (a) the application on the hydroxylated face a grafting reagent, (b) development of the grafting reaction by a heating roller, (c) extraction of the emitted hydrochloric acid and (d) application of a hot air knife on the treated face of the substrate so as to evacuate the residual grafting agent.
  • a proposed grafting reagent is a fatty acid chloride with stearic acid chloride being named.
  • EP 2164647 A discloses a method for preparing a superhydrophobic surface on a solid substrate by adding a hydrophobic substance to a pressurized fluid, dissolving the hydrophobic substance in the pressurized fluid, causing the pressurized solution to flow in an expansion chamber with a lower pressure and depositing the formed particles of the hydrophobic substance on the substrate to obtain a superhydrophobic surface.
  • the substrates is chosen for example from paper, plastics, glass, metal, wood, cellulose, silica, carbon tape, textile and paint.
  • supercritical carbon dioxide is employed to inter alia deposit alkylketenedimer on paper.
  • Raising the temperature could be one technical measure to help overcoming one or both of the two hurdles, but cellulosic fibers are sensitive to an increased temperature especially if an acidic reaction product is present. Furthermore, a reactive hydrophobization agent is itself also prone to degrade at an elevated temperature.
  • a high degree of hydrophobization is indicated by reduced water absorption in comparison to the untreated cellulosic material. It is further beneficial, if in addition also the mechanical stability of the cellulosic material in a wet stage is improved versus the untreated cellulosic material. In addition, it is desirable that the hydrophobization is achieved by the process with a low degree of degradation of other properties of the cellulosic material.
  • the mechanical stability of the single cellulosic fibers themselves or the mechanical stability of an assemblage of several cellulosic fibers should not or only to a low degree be reduced.
  • a mild reaction temperature e.g. one which is relatively close to room temperature, is desirable.
  • a simple conduction of the process is desirable.
  • the object is achieved, according to the invention, by a process for manufacturing a hydrophobic cellulosic material, which comprises the steps of
  • step (a) providing a cellulosic material, which is based on cellulosic fibers, wherein the fibers possess hydroxyl groups at their surface; (b) reacting the material from step (a) with a first aliphatic carboxylic acid chloride or a mixture, which comprises the first aliphatic carboxylic acid chloride, a second aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride, and optionally one or more further aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chloride, in supercritical carbon dioxide at an operating pressure above 7382 kPa and an operating temperature above 31.0 °C;
  • step (c) separating the reacted material from step (b) from the reaction to obtain the hydrophobic cellulosic material.
  • carbon dioxide is present as a supercritical fluid. In this stage, there is neither a commonly liquid nor a gaseous phase of the carbon dioxide.
  • a cellulosic material which is based on cellulosic fibers and wherein the fibers possess hydroxyl groups at their surface, is for example a cellulosic fiber such as a cotton fiber or a bacterial cellulosic fiber. In case of two or more fibers, a combination thereof is possible. It is also a pulp such as a mechanical pulp, a brown mechanical pulp, a chemo-thermo-mechanical pulp (CTMP), a semi-bleached pulp, a deinked pulp (DIP), a wood pulp or a combination thereof. A combination of a cellulosic fiber and a pulp is also possible.
  • the cellulosic fibers can originate from a recycling process or represent fresh fibers.
  • the cellulosic material is in the form of a sheet of fibrous material, for example a paper or a cardboard, a plywood or a cotton fabric.
  • Paper or cardboard are both common expressions for a plane material produced basically from plant fibers with a grammage for example up to 600 g/m 2 .
  • the expression paper is used typically more for a grammage up to 225 g/m 2
  • the expression cardboard is used typically more for a grammage above 150 g/m 2 .
  • the lower limit of the grammage is for example 5 g/m 2 , in particular 20 g/m 2 .
  • at least one of the two surfaces of the paper or the cardboard is uncoated, preferably both surfaces are uncoated.
  • a coating a coating with a polymer containing hydroxyl groups is preferred.
  • An example for a paper or a cardboard is a crude corrugated paper, a packaging paper, a sanitary paper, a tissue paper, a printing paper, a writing paper, a paper pulp or a combination thereof, especially in the form of a composite.
  • Preferred is a process, wherein the cellulosic material is a paper or a cardboard.
  • the cellulosic material can additionally contain a further ingredient, for example an in- organic pigment, a colourless organic pigment, fines such as for example a hemicellu- lose, a fluorescent whitener, a soluble dye, an insoluble dye for example in the form of a pigment, or a further chemical additive such as a retention aid, a fastener, a wet fixa- tive, a dry fixative, a defoamer, an impurity scavenger such as a cationic starch, or a sizing agent, in particular in an amount low enough that a sufficient amount of hydroxyl groups at the surface is left, for example at least 60% of the originally available ones in the unsized state.
  • a further ingredient for example an in- organic pigment, a colourless organic pigment, fines such as for example a hemicellu- lose, a fluorescent whitener, a soluble dye, an insoluble dye for example in the form of a pigment, or a further chemical additive such as a
  • the cellulosic material contains at least 60% by weight of cellulosic fibers based on the weight of the cellulosic material, especially at least 80% by weight, in particular at least 95% by weight and very particular at least 99% by weight.
  • the cellulosic material is a paper or a cardboard and contains at least 60% by weight of cellulosic fibers based on the weight of the cellulosic material.
  • the initial water content of the provided cellulosic material is below 8% by weight based on the weight of the cellulosic material, especially below 6% by weight, in particular below 2% by weight, very particular below 1 % by weight and most particular below 0.5% by weight.
  • the water content is defined by subtraction of the solids content of the cellulosic material measured as stated according to DIN EN ISO 3251 from the initial weight of the cellulosic material. In a practical manner, the determination is con- ducted at a test sample of the cellulosic material. For reduction of an originally high water content to the initial water content, i.e.
  • a drying step can be conducted prior to providing the cellulosic material, for example by infra-red irradiation or by a gas flow.
  • the initial water content can also or further be lowered prior to step (b) by a or a further drying step, for example by purg- ing with an inert gas and optionally interrupted by applying vacuum.
  • An example is applying carbon dioxide at a drying pressure between 105 kPa and 500 kPa and at a temperature of 23 °C, followed by reducing the pressure until an atmospheric pressure is reached again.
  • the cellulosic material is a paper or a cardboard and contains at least 60% by weight of cellulosic fibers based on the weight of the cellulosic material and the water content of the cellulosic material is below 8% by weight based on the weight of the cellulosic material, especially below 6% by weight.
  • Aliphatic carboxylic acid chlorides are partially commercially available. Especially aliphatic carboxylic acid chlorides, which are non-commercial or fragile might be prepared by transchlorination with a suitable reagent, for example with acetyl chloride or oxalyl chloride.
  • a first aliphatic carboxylic acid chloride is for example an alkanoyl chloride, which does not contain an aromatic or heteroaromatic moiety, or an alkenoyl chloride, which does not contain an aromatic or heteroaromatic moiety.
  • An alkanoyl chloride is for example hexanoyl chloride, octanoyl chloride, 2-ethylhexanoyl chloride, nonanoyl chloride, 2- methyloctanoyl chloride, decanoyl chloride, lauric acid chloride, tridecanoyl chloride, iso-tridecanoyl chloride, palmitic acid chloride, stearic acid chloride, icosanoyl chloride, docosanoyl chloride, tetracosanoyl chloride, hexacosanoyl chloride or triacontanoyl chloride.
  • alkenoyl chloride is for example hex-5-enoyl chloride, (E)-hex-2-enoyl chloride, sorbic acid chloride, oleic acid chloride, elaidic acid chloride, linoleic acid chloride, linolenic acid chloride, eleostearic acid chloride or erucic acid chloride.
  • the first aliphatic carboxylic acid chloride is a C6-C3o-alkanoyl chloride or a C6-C3o-alkenoyl chloride, especially a Cs-C22-alkanoyl chloride or a Cs-C22-alkenoyl chloride and very especially a Ci2-Cis-alkanoyl chloride or a Ci2-Cis-alkenoyl chloride.
  • the first aliphatic carboxylic acid chloride is very preferably lauric acid chloride, palmitic acid chloride or stearic acid chloride.
  • Preferred is a process, wherein the first aliphatic carboxylic acid is lauric acid chloride, palmitic acid chloride or stearic acid chloride.
  • the same preferences as listed for the first aliphatic carboxylic acid chloride apply and are independently chosen from the first aliphatic carboxylic acid chloride with the proviso that the second aliphatic carboxylic acid chloride is different to the first aliphatic carboxylic acid chloride.
  • the second aliphatic carboxylic acid chloride is defined by the same preference as the first aliphatic carboxylic acid chloride.
  • the same preferences as listed for the first aliphatic carboxylic acid chloride apply and are independently chosen from the first aliphatic carboxylic acid chloride and from the second aliphatic carboxylic acid chloride with the proviso that the one or more further aliphatic carboxylic acid chloride is different to the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chloride.
  • more further aliphatic carboxylic acid chloride means at least two further aliphatic carboxylic acid chlorides. These are different to each other.
  • the process can be conducted with the first aliphatic carboxylic acid chloride as the sole aliphatic carboxylic acid chloride, which is present at step (b).
  • the process can also be conducted with a mixture, which comprises the first aliphatic carboxylic acid chloride, the second aliphatic carboxylic acid chloride and optionally one or more fur- ther aliphatic carboxylic acid chloride. Accordingly, the mixture is present at step (b) and the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chloride are both reacted.
  • the mixture comprises also one or more further aliphatic carboxylic acid chloride, which is also reacted.
  • Preferred is a process, wherein at step (b) only the first aliphatic carboxylic acid chloride is present.
  • Preferred is a process for manufacturing a hydrophobic cellulosic material, which comprises the steps of
  • step (b) reacting the material from step (a) with a first aliphatic carboxylic acid chloride in supercritical carbon dioxide at an operating pressure above 7382 kPa and an operating temperature above 31.0 °C;
  • step (c) separating the reacted material from step (b) from the reaction to obtain the hydrophobic cellulosic material.
  • the first aliphatic carboxylic acid chloride is defined as the aliphatic carboxylic acid chloride with the highest content in percentage by weight based on the total weight of all aliphatic carboxylic acid chlorides, which are present at step (b).
  • the second aliphatic carboxylic acid chloride is defined as the aliphatic carboxylic acid chloride with the second highest content in percentage by weight based on the total weight of all aliphatic carboxylic acid chlorides.
  • the aliphatic carboxylic acid chlo- ride with the higher number of carbon atoms is defined as the first aliphatic carboxylic acid chloride.
  • the first carboxylic acid chloride is the one with the most saturated bonds, followed by the one with the most carbon atoms in a main chain.
  • the second aliphatic carboxylic acid chloride is defined in analogy versus an optionally present further aliphatic carboxylic acid chloride.
  • step (b) reacting the material from step (a) with a mixture, which comprises a first aliphatic carboxylic acid chloride, a second aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride, and optionally one or more further aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chlo- ride, in supercritical carbon dioxide at an operating pressure above 7382 kPa and an operating temperature above 31.0 °C;
  • the weight ratio of the first aliphatic carboxylic acid chloride to the second aliphatic carboxylic acid chloride is between 1 and 4.
  • the latter boundary represents accordingly 4 parts of the first aliphatic carboxylic acid chloride and 1 part of the second aliphatic carboxylic acid chloride.
  • the weight ratio is especially between 1 and 2.
  • Preferred is a process, wherein the content of the first aliphatic carboxylic acid chloride in the mixture is more than 40% by weight based on the weight of the mixture.
  • Preferred is a process, wherein the content of the second aliphatic carboxylic acid chloride in the mixture is more than 20% by weight based on the weight of the mixture.
  • Preferred is a process, wherein the sum of the content of the first aliphatic carboxylic acid chloride, the content of the second aliphatic carboxylic acid chloride and the content of the optional one or more further aliphatic carboxylic acid chloride is more than 20% by weight based on the weight of the mixture.
  • Preferred is a process, wherein the sum of the content of the first aliphatic carboxylic acid chloride, the content of the second aliphatic carboxylic acid chloride and the content of the optional one or more further aliphatic carboxylic acid chloride is more than 90% by weight based on the weight of the mixture.
  • Preferred is a process for manufacturing a hydrophobic cellulosic material, which comprises the steps of
  • step (b) reacting the material from step (a) with a first aliphatic carboxylic acid chloride or a mixture, which consists of the first aliphatic carboxylic acid chloride, a second aliphatic carboxylic acid chloride, which is different to the first aliphatic car- boxylic acid chloride, and optionally one or more further aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chloride, in supercritical carbon dioxide at an operating pressure above 7382 kPa and an operating temperature above 31.0 °C;
  • step (c) separating the reacted material from step (b) from the reaction to obtain the hydrophobic cellulosic material.
  • Preferred is a process for manufacturing a hydrophobic cellulosic material, which com- prises the steps of
  • step (b) reacting the material from step (a) with a first aliphatic carboxylic acid chloride or a mixture, which consists of the first aliphatic carboxylic acid chloride, a sec- ond aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride, and one or more further aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chloride, in supercritical carbon dioxide at an operating pressure above 7382 kPa and an operating temperature above 31.0 °C;
  • step (c) separating the reacted material from step (b) from the reaction to obtain the hydrophobic cellulosic material.
  • Preferred is a process for manufacturing a hydrophobic cellulosic material, which comprises the steps of
  • step (b) reacting the material from step (a) with a mixture, which consists of a first aliphatic carboxylic acid chloride, a second aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride, and optionally one or more further aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chloride, in supercritical carbon dioxide at an operating pressure above 7382 kPa and an operating temperature above 31.0 °C;
  • step (c) separating the reacted material from step (b) from the reaction to obtain the hydrophobic cellulosic material.
  • Preferred is a process for manufacturing a hydrophobic cellulosic material, which comprises the steps of
  • step (b) reacting the material from step (a) with a mixture, which consists of a first aliphatic carboxylic acid chloride, a second aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride, and one or more further aliphatic carboxylic acid chloride, which is different to the first aliphatic carboxylic acid chloride and the second aliphatic carboxylic acid chloride, in supercritical carbon dioxide at an operating pressure above 7382 kPa and an op- erating temperature above 31.0 °C;
  • step (c) separating the reacted material from step (b) from the reaction to obtain the hydrophobic cellulosic material.
  • the process is preferably conducted in a reaction vessel with an inner containment.
  • the reaction vessel is for example an autoclave, which is suited for the high pressure and the temperature and which is resistant to hydrogen chloride and preferably also to hydrochloric acid. The latter one might be formed by traces of humidity from hydrogen chloride.
  • the reaction vessel possesses preferably a pressure control and a temperature control. The latter one can be achieved by a heating and cooling jacket, whereas the pressure control can be achieved by an inlet valve and an outlet valve. Both valves are mounted on the top of the autoclave. Pressure is externally increased by addition of carbon dioxide and reduced by opening of the outlet valve. An increase of the temperature leads to an internal increase of the pressure until the pressure control reacts sufficiently.
  • the reaction vessel is preferably closed with the exception of a pressure increase by addition of carbon dioxide or a pressure reduction by release of mainly carbon dioxide via the outlet valve.
  • the cellulosic material is mounted in a gadget, which leaves a distance between the bottom of the inner containment and the provided cellulosic material.
  • the distance is chosen large enough to avoid contamination of the hydro- phobized cellulosic material with residuals at step (c).
  • the gadget is for example a wired cage.
  • the cellulosic material is in the form of a sheet of fibrous material, the sheet can be placed in the inner containment as without being coiled or in the form of a roll.
  • step (b) takes place in a reaction vessel with an inner containment.
  • step (b) Since recirculation occurs during the process, a homogenous distribution of the aliphat- ic carboxylic acid chlorides is enabled during step (b). Furthermore, in contrast to the chromatogenic grafting, the process avoids that for each individual aliphatic carboxylic acid chloride an own optimum of temperature applies. This is especially relevant in case of a mixture of aliphatic carboxylic acid chlorides. The process avoids also that parts of the aliphatic carboxylic acid chloride are lost by diffusion from the overall amount of aliphatic carboxylic acid chloride. Since stirring at step (b) supports a homogenous distribution of the aliphatic carboxylic acid chlorides, stirring is preferred at step (b), in particular at step (b) and at step (c). The stirring is preferably by a mechanical stirrer, for example a magnetic stirrer.
  • step (b) takes place in the inner containment of the reaction vessel, wherein the operating pressure varies by less than 15% over the diameters of the inner containment at a certain point in time and the operating temperature varies by less than 15% over the diameters of the inner containment at the certain point in time.
  • the variations of the operating pressure and the operating temperature are both less than 5%, in particular less than 2%.
  • the initial pressure is between 101 kPa and 2000 kPa
  • the initial pressure is between 101 kPa and 3000 kPa
  • the initial pressure is between 101 kPa and 4000 kPa
  • the initial pressure is between 101 kPa and 5000 kPa
  • the initial pressure is between 101 kPa and 6000 kPa.
  • the process has the advantage that a solvent in addition to carbon dioxide is not oblig- atory.
  • the solvent is being defined herein as a solubilising substance, which is in the liquid state at 23°C and at 101 .013 kPa, and which is different to the first aliphatic carboxylic acid chloride, the second aliphatic carboxylic acid chloride, the optional one or more further aliphatic carboxylic acid chloride and water.
  • a weight percentage for the solubilising substance equals in case of two or more solubilising substances the sum of all weight percentages of all solubilising substances, which individually fulfill the definition of the solubilising substance.
  • a solubilising substance which is in the liquid state at 23°C and at 101 .013 kPa, and which is different to the first aliphatic carboxylic acid chloride, the second aliphatic carboxylic acid chloride, the optional one or more further aliphatic carboxylic acid chloride and water, is present in less than 20% by weight based on the higher one out of the weight of the first aliphatic carboxylic acid chloride and the sum of the weight of the first aliphatic carboxylic acid chloride, the second aliphatic carboxylic acid chloride and the optional one or more further aliphatic carboxylic acid chloride.
  • the solubilising substance is present in an amount of less than 10% by weight, especially less than 5% by weight and very especially less than 1 % by weight based on the higher one out of the weight of the first aliphatic carboxylic acid chloride and the sum of the weight of the first aliphatic carboxylic acid chloride, the second aliphatic carboxylic acid chloride and the optional one or more further aliphatic carboxylic acid chloride.
  • the solubilising substance is present in an amount of less than 10% by weight, especially less than 5% by weight and very especially less than 1 % by weight based on the weight of the first aliphatic carboxylic acid chloride.
  • a base is for example a suitable basic neutralization agent, which is non-nucleophilic to avoid an alternative reaction with the carboxylic acid chloride.
  • a base is an organic basic agent.
  • Suitable organic agents are for example monocyclic or polycyclic compounds, which possess at least one nitrogen atom, which is basic. Basic means that this compound in its non-protonated form leads to a pH value above 7 once it is added to an aqueous solution at a temperature of 25°C at a concentration of 0.1 mol of basic nitrogen atoms per liter.
  • the operating pressure is preferably above 7382 kPa and below 25000 kPa, in particu- lar above 7382 kPa and below 20000 kPa. Surprisingly, a higher temperature does not lead necessarily to a higher degree of hydrophobization.
  • the operating temperature is above 31.0 °C and below 100 °C, in particular above 31 .0°C and below 85°C, especially above 31 .0°C and below 55 °C, very especially above 31.0 °C and below 45 °C.
  • the operating temperature is above 32.0°C, in particular above 33.0°C
  • the operating pressure is above 7400 kPa, in particular above 7500 kPa.
  • Preferred is a process, wherein the operating pressure is above 7400 kPa and the operating temperature is above 32.0 °C.
  • Preferred is a process, wherein the operating pressure is above 7400 kPa and below 25000 kPa and the operating temperature is above 32.0 °C and below 100 °C.
  • Preferred is a process, wherein the operating pressure is above 7400 kPa and below 25000 kPa and the operating temperature is above 32.0 °C and below 55 °C
  • the concentration of the aliphatic carboxylic acid chlorides is defined in the superfluidic stage by the amount of the aliphatic carboxylic acid chlorides divided by the reaction volume.
  • the reaction volume is in case of a reaction vessel with an inner containment the free, i.e. not occupied by equipment, volume of the inner containment.
  • the concentration of the first aliphatic carboxylic acid chloride or in case of a mixture the sum of the first aliphatic carboxylic acid chloride, the second aliphatic carboxylic acid chloride and the optional one or more further aliphatic carboxylic acid chloride is between 1 g/L and 45 g/L, in particular between 2 g/L and 35 g/L, especially between 3 g/L and 26 g/L and very especially between 10 g/L and 20 g/L.
  • the weight ratio between the weight of the provided cellulosic material and the weight of the first aliphatic carboxylic acid chloride or the weight of all aliphatic carboxylic acid chlorides in case of a mixture varies preferably between 0.05 to 25.
  • the latter boundary represents accordingly 25 parts of the provided cellulosic material and 1 part of the aliphatic carboxylic acid chlorides.
  • the weight ratio is in particular between 0.1 to 25, especially between 0.3 to 20 and very especially 0.4 to 10.
  • Separating the reacted material at the step (c) from the step (b) can easily be conduct- ed for example by first reducing the pressure, for example via the outlet valve of the autoclave, and secondly lowering the temperature. Hydrogen chloride is concomitantly removed together with exhausting carbon dioxide.
  • a further embodiment of the invention is a hydrophobic cellulosic material, which is obtained by the process as described above.
  • the preferences for the process as described above lead to preferred hydrophobic cellulosic materials, which are obtained through the processes.
  • the obtained hydrophobized cellulosic material is in case of a paper or a cardboard especially useful for manufacturing of a corrugated cardboard.
  • An article with desired water-repellent properties is for example a box for fruits or vegetables.
  • Solids contents are measured according to DIN EN ISO 3 251 (determination of non- volatile matter of paints and varnishes as well as binders for paints and varnishes) by the infrared-heated balance Mettler Toledo HR 83. The average of two measurements is taken.
  • Pa paper The used paper is a brown unsized testliner from Thurpapier (a Model AG company, Weinfelden, Switzerland) with a base weight of 130 g/m 2 and a Cobb6o value of 156 g/m 2 .
  • the initial water content of the applied paper sample is around 4-5% as defined by subtraction of the solids content of a test paper sample measured as stated accord- ing to DIN EN ISO 3251 from the initial weight of the test paper sample.
  • LACI lauric acid chloride (dodecanoyl chloride)
  • the used stearic acid [CAS No. 57-1 1-4] is an analytical standard grade from Fluka Inc.
  • the used stearic acid chloride contains essentially 92% stearic acid chloride and 8% palmitic acid chloride.
  • the used lauric acid chloride [CAS No. 1 12-16-3] is a commercial grade from Alrich Inc.
  • the used tallow acid chloride contains essentially 50% stearic acid chloride and 50% palmitic chloride.
  • Example Pa-1 untreated paper
  • untreated paper is used as a reference for the treated paper samples.
  • the hydrophobization agent in a defined amount of 5 g (unless stated otherwise) is dosed into the autoclave using a spatula in case of a solid or a pipette in case of a liquid.
  • a magnetic stirrer is positioned on the bottom of the autoclave.
  • An untreated paper sample with a weight of around 1 g is uprightly fixed in a wire cage as sample holder, which is mounted in the autoclave.
  • the autoclave is closed and flushed three times with CO2 gas at 2 bar to remove moisture and inert gas.
  • the CO2 pressure is increased to an initial pressure of 50 bar (unless stated otherwise) at 23 °C and the temperature is increased to the desired operating temperature of 40°C (unless stated otherwise).
  • Stearic acid is used as hydrophobization agent.
  • Tallow acid chloride is used as hydrophobization agent.
  • Example Pa-5 Tallow acid chloride is used as hydrophobization agent.
  • Stearic acid chloride is used as hydrophobization agent.
  • Example Pa-6 Stearic acid chloride is used as hydrophobization agent.
  • Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the amount of the hydrophobization agent is 1 .5 g and the initial pressure is changed to 100 bar.
  • Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the operating temperature is changed to 60 °C.
  • Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the operating temperature is changed to 80 °C.
  • Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the amount of the hydrophobization agent is 1 .5 g.
  • Example Pa-10 Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the amount of the hydrophobization agent is 1 .5 g.
  • Example Pa-10 Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the amount of the hydrophobization agent is 1 .5 g.
  • Example Pa-10 Example Pa-10:
  • Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the amount of the hydrophobization agent is 7.5 g and the operating temperature is changed to 80 °C.
  • Tallow acid chloride is used as hydrophobization agent, but different to the general treatment procedure, the amount of the hydrophobization agent is 10 g and the operating temperature is changed to 80 °C.
  • Table 1-A provides an overview of the parameters of the examples Pa-1 to Pa-1 1.
  • the contact angle of the sample is an angle that quantifies the wettability of the solid surface by water as a liquid according to Young's equation. It is determined from a microscopic picture by drop shape analysis of a sessile drop of deionized water on the surface. A high contact anlge indicates less tendency of a liquid, i.e. herein water, to spread on the cellulosic material's surface. The higher the contact angle of a sample versus water, the higher is the sample's hydrophobicity.
  • the wet tensile strength is measured in analogy to EN ISO 1924 05/2009 using a Zwick Roell TYP BX 2.5 / TS1 S-006 with software TextXpert 2 after submersing the paper sample (1 .5 cm x 5 cm) for 30 min in water. For better comparability, all values are normalized to the value of the untreated paper sample. The higher the percentage above 100, the higher is the mechanical strength in comparison to the chosen reference.
  • Table 2-A shows physical properties of the hydrophobized papers.

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Abstract

L'invention concerne un procédé de fabrication d'un matériau cellulosique hydrophobe, qui comprend les étapes suivantes consistant à : (a) fournir un matériau cellulosique qui est basé sur des fibres cellulosiques, les fibres possédant des groupes hydroxyles au niveau de leur surface ; (b) faire réagir le matériau de l'étape (a) avec un chlorure d'acide carboxylique aliphatique ou un mélange, qui comprend des chlorures d'acide carboxylique aliphatiques, dans du dioxyde de carbone supercritique ; (c) séparer le matériau ayant subi la réaction de l'étape (b) à partir de la réaction pour obtenir le matériau cellulosique hydrophobe.
PCT/EP2016/053205 2015-02-18 2016-02-16 Procédé de fabrication de matériau cellulosique hydrophobe Ceased WO2016131790A1 (fr)

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Publication number Priority date Publication date Assignee Title
FR3075071A1 (fr) * 2017-12-20 2019-06-21 Centre Technique Du Papier Procede pour conferer un caractere hydrophobe a un substrat solide comportant des fonctions hydrophiles reactives
CN110131315A (zh) * 2019-06-04 2019-08-16 宁波达尔机械科技有限公司 一种自润滑合金高耐磨轴承
SE1951393A1 (en) * 2019-12-04 2021-06-05 Stora Enso Oyj Water-resistant cellulose-based substrate with improved repulpability
SE2050194A1 (en) * 2020-02-21 2021-08-22 Stora Enso Oyj Water-resistant multilayered cellulose-based substrate
CN114127361A (zh) * 2019-07-09 2022-03-01 斯道拉恩索公司 包含生物阻隔物的纸板和层压物

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WO1999008784A1 (fr) 1997-08-14 1999-02-25 Daniel Samain Procede de traitement d'un materiau solide pour le rendre hydrophobe, materiau obtenu et applications
EP2164647A1 (fr) 2007-06-29 2010-03-24 Swetree Technologies Ab Procédé de préparation de surfaces superhydrophobes sur des corps solides par des solutions d'expansion rapide
US20130236647A1 (en) 2010-11-16 2013-09-12 Centere Technique Du Papier Machine and treatment process via chromatogenous grafting of a hydroxylated substrate
US20130345415A1 (en) * 2012-06-25 2013-12-26 Yagna Limited Methods for biocompatible derivitization of cellulosic surfaces

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WO1999008784A1 (fr) 1997-08-14 1999-02-25 Daniel Samain Procede de traitement d'un materiau solide pour le rendre hydrophobe, materiau obtenu et applications
US6342268B1 (en) 1997-08-14 2002-01-29 Daniel Samain Method for treating a solid material to make it hydrophobic, material obtained and uses
EP2164647A1 (fr) 2007-06-29 2010-03-24 Swetree Technologies Ab Procédé de préparation de surfaces superhydrophobes sur des corps solides par des solutions d'expansion rapide
US20130236647A1 (en) 2010-11-16 2013-09-12 Centere Technique Du Papier Machine and treatment process via chromatogenous grafting of a hydroxylated substrate
US20130345415A1 (en) * 2012-06-25 2013-12-26 Yagna Limited Methods for biocompatible derivitization of cellulosic surfaces

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3075071A1 (fr) * 2017-12-20 2019-06-21 Centre Technique Du Papier Procede pour conferer un caractere hydrophobe a un substrat solide comportant des fonctions hydrophiles reactives
CN110131315A (zh) * 2019-06-04 2019-08-16 宁波达尔机械科技有限公司 一种自润滑合金高耐磨轴承
CN114127361A (zh) * 2019-07-09 2022-03-01 斯道拉恩索公司 包含生物阻隔物的纸板和层压物
EP3997269A4 (fr) * 2019-07-09 2023-07-19 Stora Enso Oyj Carton et stratifié comprenant une barrière biologique
SE1951393A1 (en) * 2019-12-04 2021-06-05 Stora Enso Oyj Water-resistant cellulose-based substrate with improved repulpability
WO2021111357A1 (fr) * 2019-12-04 2021-06-10 Stora Enso Oyj Substrat à base de cellulose résistant à l'eau ayant une repulpabilité améliorée
SE2050194A1 (en) * 2020-02-21 2021-08-22 Stora Enso Oyj Water-resistant multilayered cellulose-based substrate
WO2021165898A1 (fr) * 2020-02-21 2021-08-26 Stora Enso Oyj Substrat à base de cellulose multicouche résistant à l'eau
CN115066527A (zh) * 2020-02-21 2022-09-16 斯道拉恩索公司 耐水的基于纤维素的多层基材
SE544899C2 (en) * 2020-02-21 2022-12-27 Stora Enso Oyj Water-resistant multilayered cellulose-based substrate

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