WO2015165588A1 - Composition comprenant des fibres de cellulose et des agents de réticulation, des éthers de cellulose réticulés hydrosolubles et leur procédé de production - Google Patents

Composition comprenant des fibres de cellulose et des agents de réticulation, des éthers de cellulose réticulés hydrosolubles et leur procédé de production Download PDF

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WO2015165588A1
WO2015165588A1 PCT/EP2015/000880 EP2015000880W WO2015165588A1 WO 2015165588 A1 WO2015165588 A1 WO 2015165588A1 EP 2015000880 W EP2015000880 W EP 2015000880W WO 2015165588 A1 WO2015165588 A1 WO 2015165588A1
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cellulose
crosslinking agent
composition
formula
cellulose fibres
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PCT/EP2015/000880
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English (en)
Inventor
Ove Bartholsen
Hans Henrik ØVREBØ
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Borregaard As
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Priority to EP15721122.8A priority Critical patent/EP3137507A1/fr
Publication of WO2015165588A1 publication Critical patent/WO2015165588A1/fr

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    • 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
    • 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]
    • 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
    • C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/005—Crosslinking of cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/10—Crosslinking of cellulose

Definitions

  • the present invention relates to cellulosic fibrous products, and more particularly to a composition comprising cellulose fibres and one or more crosslinking agent(s), and a process for the preparation thereof.
  • the cellulose fibrous products are useful in the production of various cellulose based products, and in particular in the production of cross- linked cellulose derivatives, specifically cellulose ethers.
  • the present invention further relates to crosslinked cellulose derivatives and the production thereof from a composition of cellulose fibres and crosslinking agent(s).
  • cellulose and cellulose derivatives in particular cellulose ethers and cellulose esters
  • an alkali metal hydroxide solution is used to pre-treat and activate the cellulose before derivatization by etherification.
  • the etherifica- tion is then typically performed with one or more alkyl halides and/or alkylene oxides and/or alkylating reagents having ionic functionalities, e.g. carboxylic residues such as halogen substituted carboxylic acids, e.g. chloroacetic acid or it's sodium salt.
  • crosslinking of cellulose may be performed in the finishing process of cot- ton fabric with the objective to provide wrinkle resistance.
  • Crosslinked cellulose fibres are also used in other consumer articles, such as disposable diapers, to improve the absorption capacity and in paper towels to improve the "wet strength”.
  • Crosslinked cellulose ethers are also used in pharmaceutical applications for controlled release of drugs. These examples of crosslinking of cellulose ethers frequently result in non- (or poorly) water soluble cellulose ethers, since the degree of crosslinking is high.
  • Exemplary cellulose ethers of particular commercial interest are: sodium carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose, and mixtures of at least two components thereof.
  • These cellulose ethers, and others, are useful in a wide range of household and industrial products such as construction materials, cosmetics, foods, coatings, paints, binders and controlled-release pharmaceuticals, e.g. for their properties as viscosity modifiers, water retention agents, film forming agents, foaming agents and/or binding agents.
  • cellulose raw materials Although a wide range of cellulose raw materials can be used, two preferred raw materials for production of cellulose ethers are purified wood pulp (often denoted speciality cellulose) and cotton linters pulp.
  • the properties of cellulose ethers are characterised by several parameters, wherein water retention capacity, viscosity and shear thinning of their solutions are particularly relevant parameters. Among others, specifically these pa- rameters may be advantageously affected by crosslinking the cellulose ether.
  • US 4,321 ,367 (The Dow Chemical Company) describes preparation of crosslinked polysaccharide ethers such as cellulose ethers crosslinked with polyhalohydrocarbon entities such as 1 ,2-dichloroethane, 1 ,3-dibromopropane and 1 ,4-dichlorobutane. Tables I and II therein show that all products contain amounts of solid materials.
  • US 6,958,393 (Wolff Cellulosics GmbH & Co. K.G.) describes cellulose derivatives such as cellulose ethers crosslinked with a crosslinking agent. The products are described as having gel-like rheological properties in aqueous solution.
  • the crosslinker used by the inventors is epichlorohydrine, which is a reagent of high reactivity that forms rather short crosslinks and is known to lead to poorly soluble cellulose ether products.
  • JP 2004155806 (Shinetsu Chemical Co.) teaches crosslinked cellulose ethers where named crosslinkers used are e.g. ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether.
  • the crosslinked cellulose ethers are held to be excellent in salt re- sistance, have tackiness and biodegradability, and are feasible for use as additives to absorbent material to increase the absorption power and water holding capacity.
  • the crosslinked products appear to contain solid material, since Table 1 (4 th and 7 th column) show that the viscosity decreases with the amount crosslinker added.
  • WO 2008/034176 (Ultraceuticals R&D PTY Ltd.) describes crosslinked gels of hyaluronic acid where the crosslinker is 1 ,4-butanediol diglycidyl ether and where a masking agent (e.g. glycidol) is preferably added.
  • the objective is to produce hyaluronic acid gels for pharmaceuticals or cosmetic use, that are resistant to hyaluronidase degradation under physiological conditions.
  • WO 2009/127605 (Akzo Nobel N.V.) aims to produce cellulose ethers with an increased viscosity in aqueous solutions by the use of phosphate crosslinking agents.
  • a disadvantage of using phosphate crosslinking agents is that the phosphonate ester linkages that are created between the cellulose backbones, are more labile to alkali and acidic environment than ether linkages.
  • US 2006/0142561 discloses the manufacture of carboxyalkyl cellulose which may be crosslinked in a subsequent step. It is known from the art, in principle, that crosslinked cellulose derivatives such as cellulose ethers have useful rheological properties such as enhanced viscosity, improved water retention capacity and improved shear thinning properties. For example, the viscosity of a solution of cellulose ethers is mainly determined by the degree of polymerisation of the cellulose raw material. Other parameters affecting the viscosity of cellulose ether solutions are the manufacturing conditions of the cellulose ethers, as well as type and amount of the substituted ether groups.
  • the raw material with the highest degree of polymerisation available appears to be cotton linters pulp.
  • Use of wood pulp as raw material for cellulose derivatives is beneficial from several aspects, like cost, availability, and for avoiding the use of genetically modified raw material.
  • cellulose derivatives such as cellulose ethers with high solution viscosity
  • use of high molecular weight cellulose derivatives such as cellulose ethers with high solution viscosity is beneficial, e.g. in order to lower the amount of cellulose ethers needed in a given application, for example for special applications, such as paints and paper coating, and for control of the hydration rate. Therefore, for more than half a century, there have been efforts within this industry to find technical solutions to increase the viscosity of solutions of cellulose derivatives. These efforts include grafting of hydrophobic groups onto the cellulose ether backbones as well as various attempts to crosslink cellulose ether molecules with each other.
  • crosslinked cellulosic ethers are not uniform and may contain non-homogenous areas and/or hard lumps, both when the product is in solid form or in soluble or gel form. Such lack of uniformity is generally unwanted.
  • the lack of uniformity often encountered in these processes may be caused by concentration gradients of the crosslinker(s) in the cellulose matrix or in the cellulose pulp, which may occur when low amounts of crosslinker(s) are mixed with the cellulose.
  • concentration gradients of the crosslinker(s) in the cellulose matrix or in the cellulose pulp which may occur when low amounts of crosslinker(s) are mixed with the cellulose.
  • crosslinked cellulose derivatives are also challenging when using a slurry process, which is often used to produce the cellulose derivatives sodium carboxymethyl cellulose and hydroxyethyl cellulose, wherein the cellulose fibres are dispersed in a relatively large volume of diluting solvent as reaction medium.
  • the challenge is based on the fact that the added crosslinker will be dispersed or dissolved in a relatively large volume of solvent, which may result in unwanted side reactions and a significantly reduced level of crosslinks in the obtained cellulose ether.
  • the cellulose starting materials in the form of cellulose fibres used to produce cellulose ethers are usually obtained from cellulose pulp manufacturers.
  • the cellulose fibres are provided in the form of a web, sheet or roll, or in fluff form, in particular in the form of cellulose sheets.
  • Weyerhaeuser discloses in US2002/0031971 (WO 00/65146) that crosslinked cellulose fibres have a relatively low strength and cannot easily be transported in rolled form. Weyerhaeuser therefore proposes to avoid the transport problem by providing crosslink- able cellulosic fibrous product containing cellulose fibres and a crosslinking agent, which can be transported in rolled or sheet form. The crosslinkable fibrous product can then be converted to the crosslinked cellulosic product, e.g. by heating the cellulose with the applied crosslinker at the production site.
  • Cellulose to be etherified and optionally crosslinked is frequently provided in sheets or rolls to the manufacturer of cellulose derivatives such as cellulose ethers. It would be a benefit for the producers if the producers could use their standard production equipment for the production of cellulose ethers in the production of crosslinked cellulose ethers. However, as explained above, this may not be possible due to the challenge of achieving sufficient mixing of the added crosslinking agent in the cellulose fibrous product. Furthermore, it would be beneficial to avoid additional reaction steps in the etherification process, e.g. an additional step where the cellulose fibrous product is reacted with the crosslinking agent. Still further, it would simplify the production for the cellulose derivative producer to be provided with a cellulose product that can be processed according to the same established procedures, irrespective of whether the cellulose is to be crosslinked or not.
  • the crosslinked ethers should be capable of being pro- Defined, at an industrial scale, in a similar or the same way as used when producing non- crosslinked product.
  • the equipment used for producing non-crosslinked cellulose ethers should also be used for production of the crosslinked ethers.
  • Another object of the present invention is to provide crosslinked cellulose derivatives such as ethers that are water soluble, and have increased viscosity and/or other desirable Theological properties compared to the corresponding non-crosslinked cellulose ethers, when the cellulose ethers are in solution, thus to provide crosslinkable cellulose products in the form of a composition of one or more crosslinking agent(s) and cellulose fibres, and method for its production, and to provide essentially water soluble crosslinked cellulose ethers that can be produced from a cellulose fibrous starting material in an easy, controllable and versatile manner.
  • the present invention relates to cellulosic fibrous products, and more particular to a composition comprising cellulose fibres and one or more crosslinking agent(s), and a process for preparation thereof.
  • the cellulosic fibrous product is a crosslinkable cellulosic product, meaning that the product contains substantially no covalent bonds between the cellulose fibres and the crosslinking agent(s).
  • the cellulose fibrous products according to the invention are useful in the production of various cellulose based products, and in particular in the production of crosslinked cellulose derivatives, specifically cellulose ethers.
  • the present invention further relates to crosslinked cellulose derivatives and the production thereof from a composition of cellulose fibres and crosslinking agent(s). More specifically, the crosslinked cellulose derivatives are crosslinked cellulose ethers and contain substantially no solid particles, or only a small amount of solid particles. The eel- lulose ethers are therefore predominantly, preferably essentially in water soluble form.
  • the crosslinks in the crosslinked cellulose ethers are substantially covalent bonds formed between the hydroxyl groups of the anhydroglucose (AGU) of the backbones of the cellulose fibres, and a binding site of the crosslinking agent. Other bonds such as e.g. hydrogen bonds are usually also present to a certain extent in the crosslinked product according to the invention.
  • AGU anhydroglucose
  • Cellulose ethers according to the invention relate to cellulose in which the hydroxyl (OH) groups of said cellulose AGU units have been partially or fully reacted with chemical rea- gents to substitute the proton of substantially all or of some of said hydroxyl groups.
  • cellulose fibres relate to cellulose that has been processed and dried in a device typically used in the cellulose pulp industry.
  • the composition of cellulose fibres and crosslinking agent(s) according to the invention is a crosslinkable cellulosic fibre material.
  • the cellulose fibres are in dried or partly dried form and may be in the form of a web, sheet or roll, or in fluff form.
  • Crosslinking agent(s) also denoted “crosslinkers” or “linkers” are chemical entities which, in the context of the present invention, are capable of cellulose fibre crosslinking.
  • At least one of the objects addressed above is achieved with a composition comprising cellulose fibres and at least one crosslinking agent, and with crosslinked cellulose ethers being obtainable from a composition comprising cellulose fibres and at least one crosslinking agent.
  • the manufacture of the composition and use of the composition in the manufacture of cellulose derivatives is also included, as well as a process for the production of crosslinked cellulose ethers.
  • the present invention relates to a composition
  • a composition comprising cellulose fibres and at least one crosslinking agent of Formula (I) below, wherein the composition has a solvent content of less than 20 weight%, and wherein substantially no covalent bonds are formed (including: have been formed) between the cellulose fibres and the crosslinking agents.
  • Said composition is defined in independent claim 1 and claims 2 to 10 depending thereon.
  • the present invention relates to a process for the manufacture of the composition according to the first aspect. Said process is defined in independent claim 1 1 and claims 12 to 14 depending thereon.
  • the present disclosure describes water soluble crosslinked cellulose ethers obtainable from a composition comprising cellulose fibres and one or more crosslinking agent(s), preferably a composition according to the first aspect of the invention.
  • the present invention relates to the use of a composition as defined in the first aspect in the manufacture of the water soluble crosslinked cellu- lose ethers as defined in the third aspect. Said use is defined in independent claim 15 and claim 16 depending thereon.
  • the present invention relates to a process for the manufacture of crosslinked cellulose ethers as defined in the third aspect. Said process is de- fined in independent claim 17 and claim 18 depending thereon.
  • Figures 1 to 3 show "flow curves" for crosslinked and non-crosslinked cellulose ethers in terms of viscosity ⁇ as a function of shear rate 7.
  • composition comprising cellulose fibres and at least one crosslinking agent as defined in claims 1 to 10
  • composition of the invention contains no or only a non-substantial amount of cova- lent bonds between the crosslinking agent(s) and the cellulose fibres and may therefore be denoted a "crosslinkable composition" .
  • crosslinkable composition due to the nature of the cellulose fibres and the crosslinker, the crosslinker may form hydrogen bonds with the cellulose backbones, in the state as described in the composition according to the invention (crosslinker physically admixed with the cellulose fibers).
  • said composition contains no or only limited amounts, in particular not more than 10 weight %, preferably not more than 5 weight %, more preferably not more than 2 weight %, in particular not more than 1 weight % of cellulose fibers in crosslinked form, based on the total amount of cellulose fibres.
  • said composition contains substantially no cellulose fibres in crosslinked form, i.e. the number of such covalent bonds is approaching 0%.
  • composition of the cellulose fibres and the crosslinking agent(s), in accordance with the present invention is useful as starting material for the production of crosslinked cellulose products, in particular in the production of crosslinked cellulose ethers, preferably water soluble cellulose ethers.
  • cellulose encompasses any type of cellulose. No restrictions exist in regard to the type of cellulose that can be used in the composition and process according to the present invention.
  • cellulose raw material for the present invention main sources for cellulose ethers are cotton linters pulp and wood pulp.
  • other sources like cellulose from fruit or vegetable origin, such as citrus, orange, lemon or tomato, cellulose from agricultural waste such as bagasse, and the like, cellulose from annual plants or energy crops, or cellulose with bacterial origin may also be used as the cellulose raw material.
  • These types of cellulose are known in the art and any mixture of these or others may be used.
  • Preferred sources of cellulose are fibres derived from cotton linters pulp and either hard- wood or softwood pulps, or mixtures thereof.
  • the pulping operation is preferably a sulphite or a Kraft process.
  • Particularly preferred is cellulose derived from cotton linters pulp and from softwood pulp, in particular from spruce, from a sulphite pulping process.
  • the cellulose from the cellulose pulping operation is further treated, preferably by washing and bleaching steps as required from a utility point of view, and may be partially de- watered and dried to the desired cellulose fibre and solvent content, and may be provided in the form of a web, sheet or roll, or in fluff form, the fluff form preferably being dried as loose fibres, more preferably delivered compressed into bales.
  • the cellulose fibre and solvent content is provided in the form of a web or sheet.
  • the composition comprising the cellulose fibres and one or more crosslinking agent(s) is dried to reach a suitable solvent content that should be below about 20 weight% based on the weight of the dried finished composition, preferably to less than 10 weight%, and particularly preferred from 6 to 8 weight.%, preferably wherein the solvent is water or comprises water.
  • solvent means any solvent used in the process of producing the cellulose fi- bres as such, as well as any solvent that is used in the process of producing the claimed composition.
  • the solvent will consist predominantly of water.
  • cellulose fibre in accordance with the present invention relates to cellulose fibres that may also contain minor amounts of other substances, e.g. from the raw mate- rial such as lignin and hemicelluloses, and chemicals added and products formed during the pulping process such as lignosulfonates and sulfuric acid.
  • cellulose fibre content' also includes cellulose fibres and minor amounts of other substances.
  • the cellulose fibre content is frequently also denoted the "dry content of the cellulose fibre sheets.
  • a suitable process is e.g. known from WO 2004/003290 A1 (EP 1 18 018 B1 ) and reference is made to this application, in this context, in particular in regard to cellulose fibers and dry content.
  • the cellulose fibres are preferably in the form of a web, sheet or roll, or in fluff form, more preferably in the form of cellulose sheets and are usually in a "dried" form such that the claimed composition formed from the cellulose fibres and the crosslinking agent has a solvent content of less than 20 weight%, as outlined above.
  • the crosslinkable cellulosic fibrous product material comprising the composition of cellulose fibres in the form of a web, sheet or roll, or in fluff form, and the crosslinking agent(s), preferably has a cellulose fibre content of at least 80 weight%, and at least one crosslinking agent and a solvent.
  • crosslinker(s)/crosslinking agent(s) as used in accordance with the present invention relates to one or more crosslinking agent(s), unless specified otherwise.
  • the expressions crosslinking agent(s) and crosslinker(s) are used interchangeably, herein.
  • the crosslinking agent(s) are applied to the cellulose fibres to obtain the composition of cellulose fibres and crosslinking agent(s). Most preferably, one selected crosslinker is applied.
  • the crosslinking agent(s) selected from the compounds of Formula (I) must be capable of forming covalent bonds between the carbohydrate polymer backbone of an- hydroglucose units (AGU) of cellulose, by reacting with the functional groups of the cellu- lose backbone (hydroxyl groups), when the cellulose fibres containing the crosslinking agent(s) are exposed to crosslinking reaction conditions (in subsequent step).
  • substantially no such crosslinking should take place when the composition of cellulose fibres and crosslinking agent(s) according to the present invention is transported and stored under normal conditions, i.e. at temperatures typically from 0°C to 30°C and at moderate humidity (less than 60%, preferably less than 40%) as typically ensured in industry and transport operations settings.
  • normal conditions also imply the absence of reactive chemicals, in particular hydroxides.
  • the process of forming the composition of the cellulose fibres and the crosslinking agent(s) is performed most conveniently in an aqueous solution, it is preferred that the at least one crosslinker is soluble or at least dispersible in water.
  • crosslinking agent(s) should be stable and sufficiently reactive when exposed to the crosslinking conditions, e.g. when exposed to the strong alkali used to pre-treat the cellulose with the crosslinking agent(s) prior to the etherification reaction.
  • the crosslinking agent(s) should also have acceptable toxicity both as reagent and in the final cellulose fibrous product.
  • Crosslinking agent(s) that are suitable for performing the crosslinking reaction in the same stage as the derivatization reaction is/are preferred, since such compounds may render superfluous the need of a subsequent (separate) etherification step in the manufacture of the final cellulose product.
  • any crosslinking agent known in the art to be capable of crosslinking cellulose may be used within the ambit of the subject invention.
  • the at least one crosslinking agent is selected from the group of compounds of Formula (I):
  • composition comprising cellulose fibres and the at least one crosslinking agent, in accordance with the present invention, is produced by applying a solution or suspension of crosslinker(s) to the cellulose fibre and, if necessary, to adjust the solvent content of the composition to less than 20 weight%.
  • crosslinking agent(s) is/are selected from Formula (la)
  • Y denotes a C-i-C-u straight or branched alkylene group, which may be interrupted by O, carbonyls, NH and/or S entities, and/or may contain a C 3 -C 6 carbocyclic group, and/or may be substituted by OH, NH 2 , SH, epoxide and/or glycidyl units.
  • crosslinker agents are selected from the group of diglycidyl ethers of the formula (lb)
  • the compound 1 ,4-butandioldiglycidyl ether (BDE) is particularly preferably used as crosslinking agent.
  • crosslinkers mentioned above are found to have properties that make them particularly suited to prepare the composition according to the present invention, including that they are sufficiently soluble or dispersible in water and that they can be spread along the cross-section of the cellulose fibres, and that they have a suitable reactivity, and therefore provide uniform crosslinked cellulose products, when (once) subjected to crosslinking conditions.
  • the amount of crosslinking agent(s) is of particular relevance and should be carefully controlled.
  • the amount of crosslinker(s) employed is dependent, among others, on the properties desired for the crosslinked cellulose end product. The amount is dependent on several factors such as the reactivity and selectivity of the crosslinker itself, and also on reactivity of additional reactants, e.g. the reactants used to form cellulose ethers.
  • the amount of crosslinker(s) is from 0.0001 to 0.1 molar equivalents relative to the anhydroglucose units (AGU) of the cellulose fibres. More preferred, the crosslink- ing agent is applied in an amount of from 0.0005 to 0.05 molar equivalents, more preferred from 0.0007 to 0.03 molar equivalents relative to the anhydroglucose units (AGU) of the cellulose.
  • the amount of crosslinker(s) is from 0.0001 to 0.005 molar equivalents, relative to the anhydroglucose units (AGU) of the cellulose fibres, more preferably from 0.0003 to 0.005 molar equivalents, more preferred from 0.0007 to 0.005 molar equivalents.
  • the crosslinking agent(s) is substantially uniformly distributed along or in the cellulose fibres and substantially not covalently bound to the cellulose fibres.
  • the crosslinking agent(s) should be applied to the cellulose fibres in a way that secures a most even and uniform distribution of the crosslinker in the resulting cellulose fibrous material, the composition of the present invention.
  • even and uniform distribution means that the distribution of the crosslinking agent(s) is substantially the same in two dimensions, i.e. on the surface, and/or in the depth of the material, i.e. in one further dimension, e.g. when the material is in the form of a web or a sheet.
  • the term "even and uniform distribution” encompasses a distribution, wherein preferably at least 90 weight% of the crosslinker(s), based on the total amount of crosslinker(s), preferably more than 95 %, more preferred 98 %, of the crosslinker show substantially the same concentration/amount in two dimensions, i.e. on the surface, and/or in the depth of the material, i.e. in one further dimension, e.g. when the material is in the form of a web or a sheet.
  • the crosslinking agent(s) can be added to the cellulose material in any conceivable way, including addition of the crosslinking agent in aqueous solution or suspension to the cellulose material by spraying, dipping and/or soaking of the cellulose fibres.
  • the crosslinking agent is applied to a suspension of fibres in water, this is preferably done after the last bleaching step of the process of making the cellulose fibers ("pulping"), and even more preferred just before the drying step.
  • the crosslinker When added after the forming of a sheet or web, the crosslinker is preferably added "at the wire" or close to the drying machine press section, preferably close to the drying ma- chine press section.
  • a solution or suspension of the crosslinking agent in a suitable solvent, preferably water is conveniently applied to the cellulose sheet by spraying and/or dipping the cellulose sheet with the crosslinker. The application may be performed on one side or both sides of the sheet.
  • the crosslinker may also be applied to dried, commercial cellulose prior to the crosslinking reaction.
  • crosslinker(s) Said addition or application of the crosslinker(s) to the cellulose material is carried out in a manner to make sure that substantially the same amount of crosslinker(s) is added or applied per unit 2 surface, preferably per mm 2 or cm 2 surface, and/or per unit depth, preferably per mm of depth.
  • the application of the crosslinking agent(s) will preferably be conducted during the drying process including the dewatering process of the cellulose pulp, i.e. after a sheet or web or similar of the cellulose fibres is formed.
  • cellulose pulp with a low concentration of cellulose fibres is distributed over a pre-selected area, i.e. a continuously formed area, and the water is partially removed e.g.
  • the crosslinker is applied.
  • the cellulose is preferably exposed to pressure, preferably to a pressure (slightly) above ambient pressure, in order to secure uniform distribution of the crosslinker throughout the entire amount of the cellulose.
  • pressure preferably to a pressure (slightly) above ambient pressure
  • the crosslinking agent is applied to the cellulose material, preferably in web or sheet form, when the solvent, preferably usually predominantly water, content of the sheet is from about 70 to 35 weight% of solvent, preferably about 60 to 35 weight% of solvent.
  • the composition of the cellulose material with the crosslinking agent added is dried to reach a pre-selected dryness.
  • the composition of cellulose fibres impregnated with crosslinking agent(s) should be stable to such an extent that the cross- linking agents will not, or only to a non-significant extent, covalently react with the cellu- lose during the drying stage of the cellulose, or during storage and transportation of the composition.
  • the temperature employed during the drying process step should be high enough to provide for effective drying, preferably about or above 100 °C, to facilitate evaporation of water, but not so high that the crosslinker is affected, or reacts with the cellulose fibre, in any significant amount
  • the composition of the cellulose fibres and crosslinking agent(s) is dried to a suitable water and/or solvent content, which solvent content should preferably be below about 20 weight% based on the total weight of the composition, preferably below 10 weight%, and more preferred from 6 to 8% of water and/or solvent or even below.
  • the solvent will usually consist predominantly of water.
  • composition of the present invention comprising cellulose fibres, e.g. in sheet or web form, with crosslinking agent(s) as the starting material for the production of cellulose derivatives
  • the producers of cellulose derivatives are able to obtain a uniform product and avoid the known production challenges outlined in the Background section.
  • producers of cellulose ethers do not need to implement any, or only very small changes, in their usual process for producing non-crosslinked cellulose ethers. In particular, they do not need to dose and add any crosslinking agent and also do not need to provide additional equipment to ensure sufficient mixing of the crosslinking agent(s) with the cellulose.
  • the customer will use the composition of cellulose fibres containing the desired crosslinking agent(s) in the desired amount and treat the fibres with strong alkali, optionally after having performed a process, in which the cellulose sheets are grinded or milled to a desired degree.
  • the crosslinking agent tolerates the alkali treatment of cellulose performed prior to the conversion to crosslinked cellulose ethers, and will not decompose or lose its functionality.
  • the formation of ether linkages between the cellulose backbones and the crosslinking agents entails that the crosslinks are stable over a large pH region and will not be easily destroyed in, e.g., alkaline environments.
  • composition of cellulosic fibres and crosslinking agent(s) to cross- linked cellulose ethers is performed in processes known from the state of art, similar to the production of non-crosslinked cellulose ethers. Further, the preparation of crosslinked cellulose ethers from the said composition is also illustrated in the Example section.
  • the etherification reactions are preferably performed by adding one or more etherification agent(s) directly to the alkalized composition of cellulose fibre and crosslinking agent, either simultaneously or in a sequential manner, and isolating and purifying the cross- linked cellulose ether from the reaction mixture.
  • the present disclosure relates to water soluble cross- linked cellulose derivatives such as cellulose ethers that are obtainable by providing a composition comprising cellulose fibres and at least one crosslinking agent, and wherein the at least one crosslinking agent is substantially uniformly distributed in the cellulose fibres and substantially covalently unbound to the cellulose fibres, and to crosslink and etherify the cellulose fibres by reaction(s) with one or more suitable derivatization agents and with the at least one crosslinker.
  • the resulting crosslinked cellulose ethers may be purified and the concentration may be adjusted.
  • the crosslinked cellulose ether may also be dried.
  • cellulose derivatives encompasses cellulose ethers, cellulose esters and cellulose containing nitro groups.
  • the preferred cellulose derivatives according to the present invention are cellulose ethers.
  • the term "substantially uniformly distributed' has the meaning as defined in the second aspect of the invention
  • the starting material in the form of the composition of cellulose fibres and one or more crosslinking agent(s) is manufactured by applying a solution or suspension of crosslink- ing agent(s) to cellulose fibres.
  • the mode of application of the crosslinking agent(s) to the cellulose fibres can be by spraying, dipping and/or soaking the cellulose fibres, which are preferably in the form of a web, sheet or roll or in fluff form, with the crosslinking agent(s).
  • the cellulose fibres are treated by pressing and/or drying.
  • the crosslinking agents should be uniformly spread in the cellulose fibres.
  • the crosslinking and etherification reactions as such can be conducted using processes known from the state of the art.
  • the manufacture of the water soluble, crosslinked cellulose ethers is usually initiated by treating the composition with one or more alkalizing agents, e.g. alkali or alkali earth metal hydroxides such as NaOH, KOH and/or Ca(OH) 2 , to activate the cellulose fibres.
  • alkalizing agents e.g. alkali or alkali earth metal hydroxides such as NaOH, KOH and/or Ca(OH) 2
  • Etherifying agent(s) are then added, either simultaneously or in a sequential manner.
  • the temperature of the reaction may also be controlled, preferably at temperatures between 60 and 100 °C.
  • crosslinking and etherification is performed at least partially simultaneously, preferably completely simultaneously.
  • This embodiment excludes that the cellulose fibres are crosslinked in a first step and then etherified in a second, subsequent step, or are etherified in a first step and are crosslinked in a second, subsequent step.
  • the inventors of the present invention have surprisingly discovered that the at least partially simultaneous, preferably completely simultaneous, crosslinking and etherification results in more or essentially completely water-soluble crosslinked cellulose ethers, which have beneficial properties in terms of viscosity and homogeneity. This renders these products particularly advantageous for uses that are addressed in the" Background and Objectives" section.
  • the etherifying agent(s) can be chosen among those known from the art. No limitations exist in regard to which chemical reagents are used for the etherification. Common etherification agents are alkyl halides and alkylene oxides and alkylating reagents having ionic functionalities. Preferably, the alkyl and alkylene moieties have from 1 to 6 carbon atoms, more preferred from 1 to 3 carbon atoms.
  • Particularly preferred alkyl halides for etherification are methyl chloride and ethyl chloride.
  • Particularly preferred alkylene oxides for etherification are ethylene oxide and pro- pylene oxide.
  • Particularly preferred alkylating reagent for etherification having ionic functionalities is monochloroacetic acid.
  • the crosslinking agent(s) may be any crosslinker that provide crosslinked cellulose ethers being water soluble and provided that the crosslinking agent(s) are sufficiently water soluble or water dispersible to be applied to the cellulose fibrous material and distributed in the cellulose material in a uniform manner.
  • the crosslinker(s) is/are the crosslinking agents as defined in the first aspect of the invention.
  • the present disclosure includes crosslinked cellulose ethers being wa- ter soluble and being obtainable by a process comprising at least the following steps (a) and (b) and optionally step (c):
  • crosslinking agent(s) are substantially uniformly distributed in the cellulose fibres and substantially covalently unbound to the cellulose fibres
  • crosslinking agent(s) may be any crosslinker that provides cross- linked cellulose derivatives being water soluble.
  • the crosslinking agent(s) should be sufficiently water soluble or water dispersible to be applied to the cellulose material and distributed in the cellulose material in a uniform manner.
  • the amount of crosslinkers is from 0.0001 to 0.1 molar equivalents relative to the anhydroglucose units (AGU) of the cellulose, further preferably as described above in the first aspect.
  • AGU anhydroglucose units
  • composition comprising cellulose fibres and at least one crosslinking agent should contain substantially no covalent bonds between the cellulose fibres and the crosslinkers before the composition is subjected to the ether manufacturing process.
  • the crosslinked cellulose ethers formed should also be sufficiently stable for the intended use, and have desired properties such as rheological properties.
  • a class of suitable crosslinking agents are those of Formula (la):
  • crosslinkers of Formula (I) or Formula (la) wherein Y denotes the entity -CH 2 -0-Y'-0- CH 2 -, wherein Y' denotes a C 2 -C 6 straight alkylene group or branched alkylene group, or a straight alkylene group interrupted by oxygen, or denotes a cyclohexyl entity, and/or may be substituted by OH, methyl, and/or glycidyl ether units.
  • crosslinkers of Formula (I) or Formula (la) wherein Y denotes - CH 2 -0-Y'-0- CH 2 -, and wherein Y' denotes an entity selected from C 2 -C 6 straight al- kylene, and preferably C -C 6 straight alkylene groups.
  • Y denotes a C 2 -C 6 straight alkylene group or branched alkylene group, or a straight alkylene group interrupted by oxygen, or denotes a cyclohexyl entity, and/or may be substituted by OH, methyl, and/or glycidyl ether units.
  • crosslinkers are 1 ,4-butanediol diglycidyl ether (BDE) and 1 ,6- hexanediol diglycidyl ether, in particular BDE.
  • the amount of crosslinkers selected from diepoxy compounds of Formula (I) are preferably from 0.0001 to 0.1 molar equivalents relative to the anhydroglucose units (AGU) of the cellulose. More preferred, the crosslinking agent(s) are applied in an amount of from 0.0005 to 0.05 molar equivalents, and even more preferred from 0.0007 to 0.03 molar equivalents relative to the anhydroglucose units (AGU) of the cellulose.
  • the crosslinked cellulose ethers of the invention are essentially water soluble and contain only a small, preferably an insignificant amount of solid material, e.g. solid particles.
  • the crosslinked cellulose ether products, in accordance with the present invention have good water solubility, as evidenced by an essentially transparent liquid product, which displays a comparatively high optical transmittance. The method of measuring the optical transmittance is described below in the Experimental Section.
  • the water-soluble crosslinked cellulose ether has an optical transmittance, as measured with a UVA IS spectrometer at 457 nm and in a solution of 1 % of crosslinked cellulose ether in water, of at least 50%, preferably at least 70%, further preferably at least 90% of the transmittance of the corresponding non-crosslinked cellulose ether, as measured under the same conditions.
  • Preferred crosslinked cellulose ethers are those as discussed above, i.e. cellulose ethers where the cellulose ether entity is chosen from the group of sodium carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and ethyl cellulose.
  • the producers of cellulose ethers can obtain a uniform product and avoid the known production challenges outlined above in the "Background and Objectives" section.
  • producers of cellulose ethers for example, do not need to implement any, or only small changes to their usual process for producing non crosslinked cellulose ethers. In particular they do not need to dose and add the crosslinking agent and also do not need to provide additional equipment to ensure sufficient mixing of the crosslinking agent(s) with the cellulose.
  • well known procedures from the state of art are easily adapted.
  • the customer will use the cellulose fibres containing the desired crosslinking agent(s) in the desired amounts and treat the fibres with strong alkali, optionally after having performed a process where the cellulose material, e.g. the cellulose sheets, are grinded or milled to a desired degree.
  • the cross- linking agent tolerates the alkali treatment of cellulose performed prior to the conversion to cellulose derivative, and will not decompose or lose its functionality.
  • the covalent crosslinks, e.g. ether bonds, formed between the cellulose backbones and the crosslinking agent(s) should not be easily destroyed in e.g. alkali environments.
  • the etherifica- tion reactions are preferably performed by adding the one or more etherification agents directly to the alkalized cellulose, either simultaneously or in a sequential manner, and isolating and purifying the cellulose ether from the reaction mixture.
  • the etherification and crosslinking reactions may then take place concurrently or in a sequential manner, dependent on the reactivity of the reagents and the reaction conditions employed, pref- erably at least partially simultaneously.
  • the manufacture of the crosslinked cellulose ethers is performed using a semidry process, preferably being performed using a Lodige® reactor. In another embodiment, the manufacture of the crosslinked cellulose ethers is performed using a slurry process.
  • the etherifying agent(s) can be chosen among those known from the state of the art. No limitations exist in regard to which chemical reagents are used for the etherification. Common etherification agents are alkyl halides and alkylene oxides and alkylating reagents having ionic functionalities. Preferably, the alkyl and alkylene moieties have 1 to 6 carbon atoms, more preferred have 1 to 3 carbon atoms. Particularly preferred alkyl halides are methyl chloride and ethyl chloride. Particularly preferred alkylene oxides are ethylene oxide and propylene oxide. Particularly preferred alkylating reagent having ionic functionalities is monochloroacetic acid. In a further embodiment, additional etherification agents may be added in one or more further reaction steps. In such steps, the etherification agents can be the same or different from the etherification agents initially used.
  • the product obtained may be purified by methods well known from the art, e.g. by wash- ing.
  • the concentration may be optionally regulated and/or the product may be optionally dried.
  • the present invention reads on the use, or a method of use, of the composition comprising the cellulose fibres and one or more crosslinking agent(s) as defined in the first aspect in the manufacture of water soluble crosslinked cellulose ethers.
  • the present invention also relates to the use of a composition comprising cellulose fibres and one or more crosslinking agent(s) of formula (I)
  • the present invention provides a process for the manufacture of water soluble, crosslinked cellulose ethers defined above, where the process at least comprises the following steps (a) and (b) and optionally step (c):
  • crosslinking agent(s) is/are substantially uniformly distributed in the cellulose fibres and substantially covalently unbound to the cellulose fibres, (b) crosslinking and etherifying the cellulose fibres, and
  • the one or more crosslinking agent(s) is/are of Formula (la)
  • PO - propylene oxide % denotes weight% if not specified otherwise.
  • Example 1 Cellulose material from spruce pulp with 1,4-butandiol diglycidyl ether crosslinker
  • the pulping process includes e.g. the process steps of cooking, bleaching and drying of the cellulose pulp.
  • BDE was added to the cellulose pulp at the drying machine by spraying BDE, diluted in water, onto the cellulose pulp.
  • the amount of added BDE was 2 kg / ADMT cellulose. This results in a composition in accordance with claim 1.
  • the cellulose sheets were milled in a conventional way, using a sieve with the mesh size of 0.315 mm.
  • the intrinsic viscosity of the cellulose powder in cupriethylenediamine was 1640 ml/g.
  • Example 2 Cellulose from spruce pulp with 1, 4-butanediol diglycidyl ether cross/inker
  • Example 1 was repeated with an amount of added BDE of 3,5 kg / ADMT cellulose.
  • the cellulose pulp was milled in a conventional way as in example 1.
  • the intrinsic viscosity of the cellulose powder in cupriethylenediamine was 1640 ml/g.
  • Example 3 Comparative Example - Cellulose from spruce pulp without crosslinker Example 1 was repeated but without the addition of crosslinker.
  • the cellulose pulp was milled in a conventional way as in example 1 .
  • the intrinsic viscosity of the cellulose powder in cupriethylenediamine was 1640 ml/g., i.e. the same as for the corresponding composition of Examples 1 and 2 (with crosslinker added)
  • Example 4 Cotton /inters pulp with 1,4-butandiol diglycidyl ether crosslinker
  • BDE was added to a sample of CLP.
  • the addition of BDE was done in laboratory scale by spraying BDE, diluted in water, onto a wetted sample of the CLP.
  • the amount of added BDE was 2,3 kg / ADMT CLP.
  • the CLP sheets were milled in a conventional way, using a sieve with the mesh size of 0.25 mm, before conversion to carboxymethyl cellulose was performed.
  • the intrinsic viscosity of the cellulose powder in cupriethylenediamine was 1770 ml/g.
  • Example 5 Comparative Example - Cotton /inters pulp without crosslinker
  • Example 4 was repeated but without the addition of crosslinker.
  • the cellulose pulp was milled in a conventional way as in example 4.
  • the intrinsic viscosity of the cellulose powder in cupriethylenediamine was 1770 ml/g. This composition is in accordance with claim 1.
  • Example 6 Conversion of the cellulose material to methyl hydroxypropyl cellulose ether
  • Methyl hydroxypropyl cellulose ether was produced using the cellulose material de- scribed in Examples 1 and 3.
  • Example 7 Conversion of the cellulose material to a carboxymethyl cellulose ether
  • the cellulose ether carboxymethyl cellulose was produced using the cellulose material described in Examples 1 to 5.
  • Example 8 Addition of cross/inker during the process of converting the cellulose material to carboxymethyl cellulose ether
  • Cellulose ether carboxymethyl cellulose was produced using cellulose pulp produced from spruce wood in a conventional sulphite process. The cellulose sheets were milled in a conventional way, using a sieve with the mesh size of 0.250 mm. The intrinsic viscosity of the cellulose powder, as measured in cupriethylenediamine, was 1520 ml/g.
  • the carboxymethyl cellulose was produced according to the process decribed in example 7, but with BDE added to the solution of caustic soda before the mixed solution was added to the pulp. The amount of added BDE was 0.8 kg / ADMT cellulose.
  • Example 9 Addition of cross/inker during the process of converting the cellulose mate- rial to carboxymethyl cellulose ether
  • Example 8 was repeated with an amount of added BDE of 2.4 kg / ADMT cellulose.
  • Example 10 Comparative Example - Addition of crosslinker during the process of converting the cellulose material to carboxymethyl cellulose ether
  • Example 8 was repeated without the addition of BDE, as a reference example.
  • Example 11 Addition of crosslinker during the process of converting the cellulose material to carboxymethyl cellulose ether
  • Cellulose ether carboxymethyl cellulose was produced using cellulose pulp produced from spruce in a conventional sulphite process. The cellulose sheets were milled in a conventional way, using a sieve with the mesh size of 0.250 mm. The intrinsic viscosity of the cellulose powder in cupriethylenediamine was 1620 ml/g.
  • the carboxymethyl cellulose was produced according to the process described in exam- pie 7, but after the addition of NaOH and the following stirring for 60 minutes, BDE was added and mixed with the alkalised cellulose for 2 hours at 60 °C before the procedure followed with addition of MCA. The amount of added BDE was 4.0 kg / ADMT cellulose.
  • Example 12 Comparative Example - Addition of crosslinker during the process of con- verting the cellulose material to carboxymethyl cellulose ether
  • Example 1 1 was repeated without the addition of BDE, as a reference example.
  • Example 13 Cellulose material from spruce pulp with 1 ,3-dichloropropane-2-ol cross- linker
  • Cellulose pulp was produced from spruce in a conventional sulphite process.
  • the pulping process includes e.g. the process steps of cooking, bleaching and drying of the cellulose pulp.
  • DCP was added to the pulp sample.
  • the addition of DCP was done in laboratory scale by soaking the sheets into a bath of DCP in water.
  • the amount of added DCP was 2,5 kg / ADMT pulp
  • the cellulose sheets were milled in a conventional way, using a sieve with the mesh size of 0.25 mm.
  • the intrinsic viscosity of the cellulose powder in cupriethylenediamine was 1640 ml/g
  • Example 14 Addition of crosslinker during the process of converting the cellulose material to carboxymethyl cellulose ether
  • the carboxymethyl cellulose was produced according to the process decribed in exam- pie 7, but after the addition of NaOH and the following stirring for 15 minutes, DCP was added and mixed with the alkalised cellulose for 10 min before the procedure followed with addition of MCA. The amount of added DCP was 2.5 kg / ADMT cellulose.
  • Example 4 was repeated, but with the addition on DCP as crosslinker
  • the amount of added DCP was 2.5 kg / ADMT cellulose.
  • Example 16 Comparative Example - Addition of crosslinker during the process of converting the cellulose material to carboxymethyl cellulose ether
  • Example 14 was repeated without the addition of DCP, as a reference example. Performance Characteristics
  • the rheological characterisations of the aqueous solutions of methyl hydroxypropyl cellulose and carboxymethyl cellulose prepared in Examples 6 to 16 were performed on a rheometer (Anton Paar Physica MCR 301 ). The temperature for the measurements was 20°C and a cone-plate geometry was used (diameter: 75 mm, angle: 2°). The type of rheological measurement performed was rotational viscosity measurements, where the viscosity was measured as a function of the shear rate. The reported viscosity was determined at shear rates of 0.01 , 1 .0 and 2.5 s ⁇ 1 .
  • the transmittance measurements were performed on a Perkin-Elmer UV VIS spectrome- ter. Reported transmittance readings were obtained at 457 nm and in a 1 % solution of the cellulose ether, with water as the solvent. A high transmittance value indicates that the amount of insoluble material in the solution is low.
  • Figure 1 presents flow curves of MHPC samples prepared from Examples 1 and 3 [- downward pointing triangle- Example 1 ; -open circles- Example 3 ( comparative)]
  • Figure 2 presents flow curves of CMC samples prepared from Examples 1 , 2 and 3 [- downward pointing triangle- Example 2; -open square- Example 1 ; - open circles- Example 3 ( comparative)]
  • Figure 3 presents flow curves of CMC samples prepared from Examples 4 and 5 [-open circles- Example 4; -downward pointing triangles- Example 5 (comparative)]
  • the crosslinked MHPC sample prepared from composition of cellulose fibres with cross- linker of Example 1 displays good solubility in water. As shown in Table 1 there is little difference in transparency measured by transmittance between the crosslinked ether from the material of Example 1 and the reference ether from the material of Example 3.
  • Table 1 Viscosity and transmittance of aqueous solutions of methyl hydroxypropyl cellu- lose (MHPC) made from softwood sulphite pulp
  • Example 1 Example 6 2,0 kg 30.7 1.37 77
  • Example 3 Example 6 5.3 1.67 82
  • Table 3 shows the viscosity and turbidity measurements of CMC ethers prepared from the cellulose of examples 4 and 5. These measurements show that a very large increase in viscosity is observed in the CMC ether prepared from cellulose impregnated with crosslinker, and a good solubility in water is observed. The flow curves obtained from these samples are displayed in Figure 3.
  • Table 3 Viscosity and transmittance of aqueous solutions of carboxymethyl cellulose (CMC) made from cotton /inters pulp
  • Table 4 shows the viscosity of CMC ethers prepared according to examples 8 to 12, where the crosslinker was added at two different stages during the process to convert the cellulose to carboxymethyl cellulose.
  • adding BDE mixed with the caustic soda shows no increase in measured CMC viscosity by means of adding a cross-linker at this stage.
  • the same lack of effect was found when dosing BDE after the mercerication step but before addition of MCA, see Examples 1 1 and 12.
  • Example 8 Example 8 0.8 kg 38
  • Example 8 Example 9 2.4 kg 36
  • Example 11 Example 11 4.0 66
  • Example 1 1
  • Example 12 no cross-linker 68
  • Examples 1 to 7 described above demonstrate that the ethers produced from the compositions of cellulose fibres and crosslinking agent have higher solution viscosity than the corresponding cellulose ethers prepared from cellulose fibres without crosslinking agent.
  • the dosing of crosslinker in the cellulose fibres allows for adjusting the viscosity of the resulting cellulose derivatives.
  • the composition containing cellulose and crosslinking agent results in cellulose ethers with good water solubility, wherein no significant difference in water solubility is detected compared to the reference cellulose ethers.
  • Examples 8 to 12 show, surprisingly, that the addition of the crosslinker directly to the slurry meant to be etherified in a slurry-based cellulose ether process (i.e. not adding the crosslinker earlier to the cellulose fibers, as is the case for the compositions and pro- Switchs and uses according to the present invention) results in no significant increase of the viscosity of the resulting cellulose ether, at the claimed dosage levels.
  • the crosslinker essentially stays in the solvent (interacts with the solvent) in this case, and therefore does not affect the cellulose ether viscosity.
  • the crosslinker effectively "sticks" to the cellulose fibers and can exert the viscosity increasing crosslinking effect in the subsequent etherification and crosslinking reaction, even in a slurry process.
  • Examples 13 to 16 show that the effect of adding crosslinker to the sheets, compared to addition to the reactor, also applies when DCP is used as crosslinker.
  • the claimed invention has a superior effect with regard to obtaining in- creased cellulose ether viscosity, in particular for cellulose ethers produced by means of using a solvent based slurry process, which is the process of choice for the production of carboxymethyl cellulose and hydroxyethyl cellulose, among others. Furthermore, the effect is present for an array of different crosslinkers.

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Abstract

La présente invention concerne une composition comprenant des fibres de cellulose et un ou plusieurs agents de réticulation ainsi qu'un procédé de préparation correspondant. L'invention concerne en outre des éthers de cellulose réticulés hydrosolubles pouvant être obtenus à partir d'une composition comprenant des fibres de cellulose et un ou plusieurs agents de réticulation ainsi que leur fabrication.
PCT/EP2015/000880 2014-05-02 2015-04-29 Composition comprenant des fibres de cellulose et des agents de réticulation, des éthers de cellulose réticulés hydrosolubles et leur procédé de production WO2015165588A1 (fr)

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WO2020223037A1 (fr) * 2019-05-01 2020-11-05 Dow Global Technologies Llc Procédé de production d'un éther de cellulose réticulé
CN112523004B (zh) * 2020-12-17 2022-05-17 河南千卡绘纸制品有限公司 一种彩色触感珠光纸的制造方法
CN112523004A (zh) * 2020-12-17 2021-03-19 河南千卡绘纸制品有限公司 一种彩色触感珠光纸的制造方法
CN117164728A (zh) * 2023-09-06 2023-12-05 山东扬子生物科技有限公司 一种淤浆法制备锂电池用cmc的生产工艺

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