EP2938781B1 - Lipophile anionische polymere auf glycerolbasis für organische abscheidungskontrolle in verfahren zur papierherstellung - Google Patents

Lipophile anionische polymere auf glycerolbasis für organische abscheidungskontrolle in verfahren zur papierherstellung Download PDF

Info

Publication number
EP2938781B1
EP2938781B1 EP13866663.1A EP13866663A EP2938781B1 EP 2938781 B1 EP2938781 B1 EP 2938781B1 EP 13866663 A EP13866663 A EP 13866663A EP 2938781 B1 EP2938781 B1 EP 2938781B1
Authority
EP
European Patent Office
Prior art keywords
glycerol
based polymer
anionic
branched
cyclic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13866663.1A
Other languages
English (en)
French (fr)
Other versions
EP2938781A4 (de
EP2938781A1 (de
Inventor
Xiaojin Harry Li
Paul Richardson
Qing Qing YUAN
Qun DONG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ChampionX LLC
Original Assignee
Nalco Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/730,003 external-priority patent/US8709209B2/en
Application filed by Nalco Co LLC filed Critical Nalco Co LLC
Publication of EP2938781A1 publication Critical patent/EP2938781A1/de
Publication of EP2938781A4 publication Critical patent/EP2938781A4/de
Application granted granted Critical
Publication of EP2938781B1 publication Critical patent/EP2938781B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • 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

Definitions

  • This invention relates to methods of reducing the deposition of organic contaminants, such as pitch and stickies, in papermaking processes.
  • organic contaminants such as pitch and stickies
  • the deposition of organic contaminants on process equipment, screens, and containment vessels in papermaking can significantly reduce process efficiency and paper quality.
  • Deposits on machine wires, felts, foils, headbox surfaces, screens, and instruments can result in costly downtime for cleaning to avoid the problems associated with poor process control, reduced throughput, and substandard sheet properties.
  • Such contaminants are generically referred to in the paper industry as either "pitch” or "stickies”.
  • Pitch deposits generally originate from natural resins present in virgin pulp, including terpene hydrocarbons, rosin/fatty acids or salts thereof, such as pimaric acid, pinic acid and abietic acid, glyceryl esters of fatty acid, sterols, etc.
  • Stickies and white pitch generally refer to the hydrophobic substances used in the manufacture of paper such as sizing agents, coating binders, and pressure sensitive or contact adhesives. Such substances can form deposits when reintroduced in recycled fiber systems.
  • Other common organic contaminants that are chemically similar to stickies and found in recycle applications include wax, which originates primarily from wax-coated old corrugated containers, and polyisoprene.
  • Pitch and stickies may also contain entrapped inorganic materials such as talc, calcium carbonate, or titanium dioxide.
  • Recycled fiber also refers to secondary fibers which are repulped to provide the papermaking furnish with raw material for the production of new papers.
  • the secondary fibers may be either pre-consumer or post-consumer paper material that is suitable for use in the production of paper products.
  • Sources of secondary fiber may include old newspaper (ONP), old corrugated containers (OCC), mixed office waste (MOW), computer printout (CPO), ledger, etc.
  • OCP old newspaper
  • OCC old corrugated containers
  • MOW mixed office waste
  • CPO computer printout
  • ledger etc.
  • These once-processed papers contain various types of adhesives (pressure sensitive, hot melts, etc.), inks, and coating binders.
  • Pitch and stickies are hydrophobic in nature and thus unstable as colloids in aqueous papermaking environments, thereby facilitating their deposition.
  • the major problems arising from deposition are as follows: (1) reduced throughput due to plugging of forming fabrics and press felts, (2) sheet holes or paper breaks due to large deposits breaking loose from the equipment, and (3) reduced sheet quality due to large particle contaminants incorporated in the final sheet.
  • Detackifiers passivate the exposed surfaces of pitch and sticky particles rendering them non-adhesive and unlikely to deposit.
  • a number of chemical are known to be effective detackifiers.
  • Effective organic detackifiers include polyvinyl alcohol, copolymer of vinyl alcohol and vinyl acetate, polyethylene oxide, polyacrylates, and waterborne globulins. In order for detackifiers to function well, it must satisfy two crucial functions: 1) it must selectively and sufficiently attach to the surface of the pitch or sticky surface, and 2) it must stabilize the resulting sticky/pitch-detackifier complex in water.
  • the WO 2011/112703 A2 discloses a method of improving the digestion of wood chips into pulp.
  • the method involves: adding a liphohydrophilic glycerol-based polymer additive to a solution used in the digestion process. This additive is unexpectedly effective at facilitating digestion.
  • At least one embodiment of the invention is directed towards a method of reducing the deposition of organic contaminants in papermaking processes, according to claim 1.
  • the anionic group may be one selected from the list consisting of phosphates, phosphonates, carboxylates, sulfonates, the like and any combination thereof.
  • the glycerol-based polymer may be an anionic lipohydrophilic glycerol based polymer.
  • the glycerol-based polymer may be branched, hyperbranched, dendritic, cyclic or any combination thereof,
  • the branched, cyclic glycerol-based polymer may be cross-linked.
  • the anionic branched, cyclic glycerol-based polymer may comprise a random arrangement of the monomeric units including R 1 indicated in the following formula: wherein:
  • the method may further comprise adding to the pulp or the papermaking system at least one component selected from the group consisting of fixatives, dispersants, and other detackifiers.
  • the organic contaminants may be pitch, stickies or combination thereof.
  • the composition may be added to a pulp slurry in a pulper, latency chest, reject refiner chest, disk filter or Decker feed or accept, whitewater system, pulp stock storage chest, blend chest, machine chest, headbox, saveall chest, or any combination thereof in the papermaking process.
  • the composition may be added to a surface in the papermaking process selected from a pipe wall, a chest wall, a machine wire, a press roll, a felt, a foil, an Uhle box, a dryer, or any combination thereof.
  • the anionic branched, cyclic glycerol-based polymer may be added to a pulp slurry in the papermaking process.
  • the effective amount of the anionic branched, cyclic glycerol-based polymer may be from about 5 ppm to about 300 ppm.
  • Acyl refers to a substituent having the general formula -C(O)R, wherein R is alkyl, alkenyl, alkynyl, aryl, heteroaryl or heterocyclyl, any of which may be further substituted
  • Alkyl refers a linear, branched, or cyclic saturated hydrocarbon group, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, cyclopentyl group, cyclohexyl group, and the like. Alkyl groups may be optionally substituted.
  • Branched means a polymer having branch points that connect three or more chain segments. The degree of branching may be determined by 13 C NMR based on a known literature method described in Macromolecules, 1999, 32, 4240 . As used herein, a branched polymer includes hyperbranched and dendritic polymers.
  • Cyclic means a polymer having cyclic or ring structures.
  • the cyclic structure units can be formed by intramolecular cyclization or any other ways.
  • Degree of branching or DB means the mole fraction of monomer units at the base of a chain branching away from the main polymer chain relative to a perfectly branched dendrimer, determined by 13 C NMR based on a known literature method described in Macromolecules, 1999, 32, 4240 . Cyclic units or branched alkyl chains derived from fatty alcohols or fatty acids are not included in the degree of branching. In a perfect dendrimer the DB is 1 (or 100%).
  • Degree of cyclization or DC means the mole fraction of cyclic structure units relative to the total monomer units in a polymer.
  • the cyclic structure units can be formed by intramolecular cyclization of the polyols or any other ways to incorporate in the polyols.
  • the cyclic structure units comprise basic structure units (V, VI and VII of FIG. 2 ) and the analogues thereof.
  • the degree of cyclization may be determined by 13 C NMR.
  • Glycerol-based polymers refers to any polymers containing repeating glycerol monomer units such as polyglycerols, polyglycerol derivatives, and a polymer consisting of glycerol monomer units and at least another monomer units to other multiple monomers units regardless of the sequence of monomers unit arrangements, glycerol-based polymers include but are not limited to alkylated, branched, cyclic polyglycerol esters, as well as those polymers disclosed in US Patent Applications 13/484,526 , 12/720,973 , and 12/582,827 .
  • Hyperbranched means a polymer, which is highly branched with three-dimensional tree-like structures or dendritic architecture.
  • Lipohydrophilic glycerol-based polymers means glycerol-based polymers having lipophilic and hydrophilic functionalities, for example, lipohydrophilic polyglycerols resulting from lipophilic modification of polyglycerols (hydrophilic) in which at least a part of and up to all of the lipophilic character of the polymer results from a lipophilic carbon bearing group engaged to the polymer, the lipophilic modification being one such as alkylation, and esterification modifications.
  • Multifunctional means a composition of matter having two or more functions such as selectively bonding to and forming a complex with a material and maintaining the stability of that complex in water.
  • Papermaking process means a method of making paper products from pulp comprising forming an aqueous cellulosic papermaking furnish, draining the furnish to form a sheet and drying the sheet. The steps of forming the papermaking furnish, draining and drying may be carried out in any conventional manner generally known to those skilled in the art.
  • the papermaking process may also include a pulping stage, i.e. making pulp from a lignocellulosic raw material and bleaching stage, i.e. chemical treatment of the pulp for brightness improvement.
  • Surfactant is a broad term which includes anionic, nonionic, cationic, and zwitterionic surfactants. Enabling descriptions of surfactants are stated in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 8, pages 900-912 , and in McCutcheon's Emulsifiers and Detergents, both of which are incorporated herein by reference.
  • Detackifiers means a process chemical that reduces tackiness other substances present in a papermaking process or which disperses otherwise undispersed tacky substances present in a papermaking process, when detackifiers reduce the tackiness of or disperse pitch and stickies, the pitch and stickies have less tendency to form agglomerates or deposit onto papermaking equipment or create spots or holes in the product.
  • deposition of pitch or stickies in papermaking process water is controlled by the addition of a novel detackifier composition into the process water.
  • the composition comprises an anionic lipophilic glycerol based polymer.
  • the polymer comprises a glycerol based polymer backbone which has undergone chemical modification with multifunctional groups.
  • the chemical modification of glycerol-based polymers is done with an anionic group and a lipophilic group.
  • the lipophilic group can be an aliphatic and/or aromatic hydrocarbon of 1 to 50 carbon atoms.
  • the anionic group can be selected from the list consisting of: phosphates, phosphonates, carboxylates, sulfonates, the like including acid and/or ionic salt forms and any combination thereof.
  • the anionic charge density can be1% to 99%.
  • the anionic modification of glycerol-based polymers is phosphorylation.
  • a representative example of such phosphorylation is described in US Patent 3,580,855 .
  • the anionic modification is phosphonation.
  • a representative example of such phosphonation is described in the scientific paper: Michael Additions to Activated Vinylphosphonates , by Tomasz Janecki et al., Synthesis, issue 8, pp. 1227-1254 (2009 ).
  • the anionic modification is carboxyalkylation. Representative examples of such carboxyalkylation are described in US Patent Applications 2004/0018948A1 and 2006/0047168A1 .
  • the anionic modification is sulfonation. A representative example of such sulfonation is described in GB Patent Specification 802325A .
  • the lipophilic modification glycerol-based polymers is via alkylation, alkoxylation, oxyalkylation, esterification or any combination thereof, such as described in US Patent Applications 13/560,771 , 13/484,526 , 12/720,973 and references therein.
  • anionic and lipophilic modifications of glycerol-based polymers are done together in one step, separately in two steps or combination thereof.
  • the lipophilic modification enhances the hydrophobic interaction between pitch/stickies and the anionic glycerol-based polymers.
  • the anionic functionality enhances the water solubility for dispersing of the pitch/stickies.
  • the anionic functionality chelates cationic ions commonly existed in water such as calcium and magnesium to increase the glass transition temperature of the pitch/stickies for preventing from being sticky in the papermaking processes.
  • the well-balanced modifications synergistically enhance the organic deposition control.
  • the glycerol-based polymer is a lipohydrophilic glycerol-based polymer, as illustrated in FIG. 1 , wherein: m, n, o, p, q and r are independently 0 to 700; R and R' are independently -(CH 2 ) x -, wherein each x is independently 0 or 1; and each R 1 is independently selected from hydrogen, acyl and alkyl, wherein at least R 1 is alkyl.
  • the composition may be added to a papermaking process involving virgin pulp, recycled pulp or combination thereof at any one or more of various locations during the papermaking process. Suitable locations may include pulper, latency chest, reject refiner chest, disk filter or Decker feed or accept, whitewater system, pulp stock storage chests (either low density ("LD"), medium consistency (MC), or high consistency (HC)), blend chest, machine chest, headbox, saveall chest, paper machine whitewater system, and combinations thereof.
  • LD low density
  • MC medium consistency
  • HC high consistency
  • the composition may be added to a pulp slurry in the papermaking process.
  • the composition may also be applied to a surface in the papermaking process, such as a metal, plastic, or ceramic surfaces such as pipe walls, chest walls, machine wires, press rolls, felts, foils, Uhle boxes, dryers and any equipment surfaces that contact with fibers during the paper process.
  • the method may include the step of contacting fibers with the composition.
  • the fibers may be cellulose fibers, such as recycled fibers, virgin wood cellulose fibers, or combinations thereof.
  • the composition is added to a papermaking process using recycled paper fibers.
  • the recycled fibers may be obtained from a variety of paper products or fiber containing products, such as paperboard, newsprint, printing grades, sanitary and other paper products. These products may comprise, for example, old corrugated containers (OCC), old newsprint (ONP), mixed office waste (MOW), old magazines and books, or combinations thereof. These types of paper products typically contain large amounts of hydrophobic contaminants.
  • the method may involve the use of pulp derived from softwood, hardwood or blends thereof.
  • Virgin pulp can include bleached or unbleached Kraft, sulfite pulp or other chemical pulps, and groundwood (GW) or other mechanical pulps such as, for example, thermomechanical pulp (TMP).
  • organic hydrophobic contaminants include what is known in the industry as "stickies” that may include synthetic polymers resulting from adhesives and the like, glues, hot melts, coatings, coating binders, pressure sensitive binders, unpulped wet strength resins and "pitch” that may include wood resins, rosin and resin acid salts. These types of materials are typically found in paper containing products, such as newsprint, corrugated container, and/or mixed office waste.
  • hydrophobic contaminants can have polymers present, such as styrene butadiene rubber, vinyl acrylate polymers, polyisoprene, polybutadiene, natural rubber, ethyl vinyl acetate polymers, polyvinyl acetates, ethylvinyl alcohol polymers, polyvinyl alcohols, styrene acrylate polymers, and/or other synthetic type polymers.
  • the method may control hydrophobic contaminants in papermaking processes, e.g., the deposition of hydrophobic contaminants on components of a papermaking process.
  • the method may control hydrophobic contaminants present in paper mill furnish.
  • the method may reduce, inhibit or eliminate the deposition of hydrophobic contaminants in a papermaking process.
  • the method may also reduce the size of contaminant particles through dispersion and suppressing agglomeration, and/or reduce the tackiness of the hydrophobic contaminants when compared to a papermaking process in which the composition is not employed.
  • the method may reduce the average size of contaminant particles by at least about 5% to about 40% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35% or 40%) when compared to a papermaking process in which the composition is not employed.
  • the method may reduce the deposition of hydrophobic contaminants by at least about 5% to about 95% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%) when compared to a papermaking process in which the composition is not employed.
  • the composition is added to a papermaking process in an amount of from about 5 ppm to about 330 ppm to reduce deposition of hydrophobic contaminants when compared to a papermaking process in which the composition is not employed.
  • the composition may be added to pulp slurry in an amount from about 10 ppm to about 300 ppm, e.g., from about 50 ppm to about 200 ppm, or 140ppm, 150ppm, 160ppm, 170ppm, 180ppm, 190ppm, to about 200 ppm.
  • the effective amount may reduce the deposition of hydrophobic contaminants by at least 5% to about 95% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%) when compared to a papermaking process in which the composition is not employed.
  • the method may further include adding to the papermaking system at least one component selected from the group consisting of fixatives, detackifiers and other dispersants.
  • the glycerol-based polymer may be any polymer containing repeating glycerol monomer units such as polyglycerols, polyglycerol derivatives, and polymers consisting of glycerol monomer units and at least one other monomer unit, regardless of the sequence of monomers unit arrangements.
  • other monomers may be polyols or hydrogen active compounds such as pentaerythrital, glycols, amines, etc. capable of reacting with glycerol or any polyglycerol structures.
  • the polymer may be linear, branched, hyperbranched, cyclic, dendritic, and any combination thereof and have sub-chains/sunregions characterized by any combination thereof.
  • the glycerol-based polymer is branched.
  • the branched structure increases the polymer dimensions for the effective interfacial interactions to result in exceptional organic deposit control. Branching may be particularly useful as it facilitates increased molecular weight of the glycerol-based polymers.
  • Branched polymers include both hyperbranched and dendritic structures.
  • the branched, cyclic glycerol-based polymer may have a degree of branching of at least about 0.10, e.g., from about 0.20 to about 0.75 or from about 0.30 to about 0.50.
  • a branched, cyclic glycerol-based polymer may have a degree of branching of about 0.10, about 0.15, about 0.20, about 0.25, about 0.30, about 0.35, about 0.40, about 0.45, about 0.50, about 0.55, about 0.60, about 0.65, about 0.70 or about 0.75.
  • the glycerol-based polymer is cyclic, i.e. has at least one cyclic or ring structure, or has at least one cyclic or ring structured polymer molecule in the polymer.
  • cyclic structures may be formed, for example, during the polymerization process via intramolecular cyclization reactions.
  • the rigidity of cyclic structures in the polymer backbone may uniquely extend the molecular dimensions and increase the hydrodynamic volume, to better act interfacially for dispersing pitch and stickies.
  • Cyclic glycerol-based polymers may have a degree of cyclization of about 0.01 to about 0.50.
  • the branched, cyclic glycerol-based polymer may have a degree of cyclization of at least 0.01, e.g., about 0.02 to about 0.19 or about 0.05 to about 0.15.
  • a branched, cyclic glycerol-based polymer may have a degree of cyclization of about 0.01, about 0.02, about 0.03, about 0.04, about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.10, about 0.11, about 0.12, about 0.13, about 0.14, about 0.15, about 0.16, about 0.17, about 0.18, or about 0.19.
  • Suitable branched, cyclic glycerol-based polymers include compounds as illustrated in FIG. 1 .
  • m, n, o, p, q and r are independently 0 to 700;
  • R and R' are independently -(CH 2 ) x -, wherein each x is independently 0 or 1; and each R 1 is independently selected from hydrogen, acyl, alkyl, acid and anionic groups.
  • the anionic groups may be in acid form in acidic condition, in anionic salt form in neutral or basic condition or any combination thereof.
  • the anionic group is selected from a list of phosphates -P(O)(OH) 2 or - (CH2) x OP(O)(OH) 2 , phosphonates -(CH 2 ) x P(O)(OH) 2 , carboxylates - (CH 2 ) x C(O)OH, sulfonates (CH 2 ) x S(O) 2 OH and combination thereof, where per H can be independently substituted by any other groups or atoms, and each x can independently be any number of integers from 0 to 50. Furthermore, it should be understood that the compounds illustrated in FIG. 1 are random polymers of the indicated monomeric units, including R 1 groups.
  • the monomeric units may be present in any order and not necessarily in the order illustrated in FIG. 1 .
  • m, n, o, p, q and r are each 2
  • the monomeric units may be present in any order, where the two "m” units may or may not be adjacent to each other, the two "n" units may or may not be adjacent to each other, and so on.
  • R 1 is H
  • two R 1 s are -P(O)(OH) 2 and another two R 1 s are dodecanol
  • any of the groups may or may not be on any of the end groups or non-end groups.
  • each m, n, o and p is independently 1-700, and each q and r is independently 0-700. In embodiments of the formula illustrated in FIG. 1 , each m, n, o and q is independently 1-700, and each p and r is independently 0-700. In embodiments of the formula illustrated in FIG. 1 , each m, n, o, p, q and r is independently selected from 0 to 50, 0 to 40, 0 to 30 or 0 to 25.
  • each of m, n, o, p, q and r are independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50 (or more).
  • each R 1 is independently selected from hydrogen, acyl and C 1 -C 50 alkyl.
  • R 1 is alkyl, it may be, for example, a C 1 -C 50 alkyl, C 1 -C 40 alkyl, C 1 -C 30 alkyl, C 1 -C 24 alkyl, C 6 -C 18 alkyl, C 10 -C 16 alkyl or C 12 -C 14 alkyl group.
  • each R 1 that is alkyl may independently be a Ci, C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20, , C 21 , C 22 , C 23 or C 24 alkyl group.
  • the R 1 group may be optionally substituted with other hydrocarbon-based groups, such as branched, cyclic, saturated, or unsaturated groups.
  • R 1 When R 1 is acyl, it may be, for example, a C1-C15 acyl group. When R 1 is acyl, it may be, for example, -C(O)CH(OH)CH 3 (lactate). In embodiments, lactate or lactic acid may be produced as a co-product during the synthesis of the branched, cyclic glycerol-based polymer, which may further react with the polymer.
  • the glycerol-based polymer may comprise at least two repeating units selected from at least one of the structures listed in FIG. 2 , including but not limited to linear structures I and II, branched structures III, IV and VIII, cyclic structures V, VI and VII, and any combination thereof. Any structure in FIG. 2 can be combined with any structure or structures including itself, in any order.
  • the cyclic linkages of any basic cyclic structures in FIG. 2 may contain any structure or structures as a part or parts of linkages.
  • each R 1 is independently selected from hydrogen, acyl, alkyl and anionic
  • each n and n' is independently 0 to 700.
  • the glycerol-based polymer may have a weight-average molecular weight of about 100 Da to about 1,000,000 Da.
  • the glycerol-based polymer may be crosslinked.
  • Crosslinked polymers include cross-linkages between one or more types of polymers which are: linear, branched, hyperbranched, cyclic, dendritic, and any combination thereof and have sub-chains/sub-regions characterized by any combination thereof.
  • the glycerol-based polymer may self-crosslink, and/or the polymer may be crosslinked via addition of a crosslinking agent.
  • Suitable crosslinking agents typically include at least two reactive groups such as double bonds, aldehydes, epoxides, halides, and the like.
  • a cross-linking agent may have at least two double bonds, a double bond and a reactive group, or two reactive groups.
  • Non-limiting examples of such agents are diisocyanates, N,N-methylenebis(meth)acrylamide, polyethyleneglycol di(meth)acrylate, glycidyl(meth)acrylate, dialdehydes such as glyoxal, di- or tri-epoxy compounds such as glycerol diglycidyl ether and glycerol triglycidyl ether, dicarboxylic acids and anhydrides such as adipic acid, maleic acid, phthalic acid, maleic anhydride and succinic anhydride, phosphorus oxychloride, trimetaphosphates, dimethoxydimethsilane, tetraalkoxysilanes, 1,2-dichloroethane, 1,2-dibromoethane, dichloroglycerols 2,4,6-trichloro-s-triazine and epichlorohydrin.
  • diisocyanates N,N-methylenebis(
  • the glycerol-based polymer used for the anionic and lipophilic modifications may be from a commercially available supplier, or synthesized according to known methods such as those described in U.S. Patent Nos. 3,637,774 , 5,198,532 and 6,765,082 B2 , and in U.S. Patent Application Publication Nos. 2008/0306211 and 2011/0092743 , or from any combination thereof.
  • a method of preparing a glycerol-based polymer for the modifications may include the step of: reacting a reaction mass comprising at least glycerol monomer in the presence of a strong base catalyst of a concentration above 2%, in a low reactivity atmospheric environment at a temperature above 200 °C, which produces a product comprising branched, cyclic polyols and a co-product comprising lactic acid, lactic salt, and any combination thereof.
  • a method can further comprise the steps of providing a catalyst above 3%.
  • the catalyst may be selected from the group consisting of: NaOH, KOH, CsOH, a base stronger than NaOH, and any combination thereof.
  • the strong base catalyst in the particular amount can be used with combining a base weaker than NaOH.
  • the atmospheric environment may be an atmospheric pressure of less than 760 mm Hg and/or may be a flow of an inert gas selected from the list of N 2 , CO 2 , He, other inert gases and any combination thereof and the flow is at a rate of 0.2 to 15 mol of inert gas per hour per mol of monomer.
  • the particular atmospheric environment profile applied can be steady, gradual increase, gradual decrease or any combination thereof.
  • the method of preparing the branched, cyclic glycerol-based polymer may produce glycerol-based polymer products selected from the group consisting of polyglycerols, polyglycerol derivatives, a polyol having both glycerol monomer units and non-glycerol monomer units and any combination thereof.
  • the branched, cyclic glycerol-based polymer products have at least two hydroxyl groups. At least a portion of the produced polymers may have both at least a 0.1 degree of branching and at least a 0.01 degree of cyclization.
  • the co-product may be at least 1% by weight.
  • the method of preparing the branched, cyclic glycerol-based polymer may make use of different forms of glycerol including pure, technical, crude, or any combination thereof. Such methods may further comprise other monomers selected from the group consisting of polyols such as pentaerythritol and glycols, amines, other monomers capable of reacting with glycerol or glycerol-based polyol intermediates and any combination thereof.
  • the monomer(s) and/or catalyst(s) can be mixed at the very beginning of the reaction, at any time during the reaction and any combination thereof.
  • the glycerol-based polyol products may be resistant to biological contamination for at least two years after synthesis.
  • the method may further comprise the steps of pre-determining the desired molecular weight of the produced polyglycerol and adjusting the atmospheric environment to match the environment optimum for producing the desired molecular weight.
  • the method may further comprise the steps of pre-determining the desired degree of branching and the desired degree of cyclization of the produced polyglycerol and the desired amount of co-product, and adjusting the atmospheric environment to match the environment optimum for producing the desired degree of branching, degree of cyclization and amount of co-product lactic acid and/or lactate salt.
  • Anionic, lipophilic glycerol-based polymer may be made from a lipophilic glycerol-based polymer.
  • the lipohydrophilic glycerol-based polymer may be produced from glycerol-based polymers, such as those that are commercially available or those described herein, according to known methods such as alkylation, esterification and any combinations thereof.
  • such polymers may be produced from glycerol-based polymers according to known methods such as alkylation, as described in German Patent Application No. 10307172 , in Canadian Patent No. 2,613,704 , in U.S. Patent Nos.
  • the glycerol-based polymers may be produced according to known methods such as esterification of glycerol-based polymers as described in U.S. Patent No. 2,023,388 , U.S. Patent Application Publication No. 2006/0286052 and the like.
  • the esterification may be carried out with or without a catalyst such as acid(s) or base(s).
  • Anionic, lipophilic glycerol-based polymers may be made from crosslinked polymers.
  • the crosslinked glycerol-based polymers may be produced in a continuous process under a low reactivity atmospheric environment according to a method described in US Patent Application No. 13/484,526, filed on May 31, 2012 .
  • the method may comprise the steps of: a) reacting a reaction mass comprising at least glycerol monomer in the presence of a strong base catalyst of a concentration of above 2% at a temperature above 200 degrees C which produces a first product comprising polyols which are both branched and cyclic, and a co-product comprising lactic acid, lactic salt, and any combination thereof, b) esterifying the first product in presence of an acid catalyst of a concentration above 5% at a temperature above 115 degrees C to produce a second product, c) alkylating the second product at a temperature above 115 degrees C to form a third product, and d) crosslinking the third product at a temperature above 115 degrees C to form an end product.
  • the resulting polymer may further react with the acid catalyst to form the desired anionic polymer.
  • polyglycerol PG2
  • polyphosphoric acid 116.2% by wt. relative to polylgycerol
  • the mixture was gradually heated to 130° C under nitrogen atmosphere while agitating whenever stirrable, and kept at this condition for hours to achieve the desired phosphorylation.
  • 1-hexanol 31.9% by wt. relative to polyglycerol
  • the mixture was gradually heated to 150° C under nitrogen atmosphere while stirring, and kept at this condition for hours to result in the final composition.
  • the ALPG was dissolved in water as 60% product.
  • file fold label (TopStick 4282) is used as adhesives, and baffle test method is used to evaluate the effectiveness of chemistry by deposition mass comparing to that of a blank test.
  • the topstick label (12.4 cm x 21.0 cm) is placed on a plain copy paper, and the paper with the adhesives is cut or torn into 2.5 cm square pieces and put in a disintegrator vessel. Plain copy paper without adhesives is also cut or torn in 2.5 cm square pieces and added to the disintegrator vessel to make up 18.75 g of paper material in total.
  • hot water is added to a total weight of 1875 g of the suspension, and the suspension is mechanically disintegrated for 30 minutes to result in pulp of 1% consistency.
  • the pulp is transferred to the baffle testing vessel, and diluted with 1875 g of hot water, followed by mixing to form the pulp in 0.5% consistency for the test.
  • the baffle testing vessel is heated on a hot plant and controlled at 50° C while mixing at 425 rpm. After 60 minutes at this temperature, the baffles (plastic strips) are removed, rinsed with cooled water and finally air dried. The weight increase of strips is the deposition mass of the blank test, which is without addition of any chemicals.
  • a chemical sample or product is added before heated to the testing temperature 50° C in the baffle test, and the deposition control effectiveness is calculated by the deposition mass difference from the blank divided by the deposition mass of the blank.
  • FIG. 3 graphically conveys the effectiveness of the invention (ALPG) as a superior detackifier of organic contaminants comparing to non-modified glycerol based polymer PG1 and a Nalco current product 64231 (a copolymer of vinyl alcohol and vinyl acetate).
  • APG invention
  • compositions and methods disclosed herein may comprise, consist of, or consist essentially of the listed components, or steps.
  • the term “comprising” means “including, but not limited to”.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Claims (14)

  1. Verfahren zum Verringern der Ablagerung von organischen Verunreinigungen in Papierherstellungsvorgängen, umfassend Hinzufügen von etwa 5 ppm bis etwa 300 ppm einer Zusammensetzung, die ein anionisches lipophiles verzweigtes cyclisches Polymer auf Glycerinbasis umfasst, zu einem Zellstoff oder einem Papierherstellungssystem, wobei sich die Zusammensetzung selektiv an die organischen Verunreinigungen bindet, um einen Komplex auszubilden, und der Komplex in Papierherstellungsvorgängen stabil ist.
  2. Verfahren nach Anspruch 1, wobei die anionische Gruppe eine ist, die ausgewählt ist aus der Liste bestehend aus Phosphaten, Phosphonaten, Carboxylaten, Sulfonaten und Ähnlichen und jeder beliebigen Kombination daraus.
  3. Verfahren nach Anspruch 1, wobei das Polymer auf Glycerinbasis ein anionisches lipohydrophiles Polymer auf Glycerinbasis ist.
  4. Verfahren nach Anspruch 1, wobei das Polymer auf Glycerinbasis verzweigt, hochverzweigt, dendritisch, cyclisch oder jede beliebige Kombination daraus ist.
  5. Verfahren nach Anspruch 1, wobei das verzweigte, cyclische Polymer auf Glycerinbasis vernetzt ist.
  6. Verfahren nach Anspruch 1, wobei das anionische verzweigte cyclische Polymer auf Glycerinbasis ein zufälliges Polymer der Monomereinheiten ist, einschließlich R1, in der folgenden Formel angegeben:
    Figure imgb0003
     wobei:
    m, n, o, p, q und r unabhängig 0 bis 700 sind;
    R und R' unabhängig -(CH2)x- sind, wobei jedes x unabhängig 0 oder 1 ist; und
    jedes R1 unabhängig ausgewählt ist aus Wasserstoff, Acyl, C1-C50-Alkyl und anionischen Gruppen.
  7. Verfahren nach Anspruch 6, wobei jedes R1 unabhängig ausgewählt ist aus Wasserstoff, C2-C18-Alkyl und -C(O)CH(OH)CH3.
  8. Verfahren nach Anspruch 6, wobei m, n, o, p, q und r unabhängig ausgewählt sind aus 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 und 50.
  9. Verfahren nach Anspruch 1, wobei das Polymer auf Glycerinbasis eine gewichtsgemittelte Molekülmasse von etwa 200 Da bis etwa 500.000 Da aufweist.
  10. Verfahren nach Anspruch 1, ferner umfassend das Hinzufügen wenigstens einer Komponente, ausgewählt aus der Gruppe bestehend aus Fixiermitteln, Dispergiermitteln und anderen Entklebungsmitteln, zu dem Zellstoff oder dem Papierherstellungssystem.
  11. Verfahren nach Anspruch 1, wobei die organischen Verunreinigungen Pech oder klebrige Verunreinigungen oder eine Kombination daraus sind.
  12. Verfahren nach Anspruch 1, wobei die Zusammensetzung in einem/einer Stofflöser, Latenzbehälter, Ausschuss-Refiner-Behälter, Scheibenfilter- oder Eindickerzufuhr oder -aufnahme, Rückwassersystem, Zellstoffvorratsbütte, Mischbehälter, Maschinenbütte, Stoffauflauf, Stofffängerbehälter oder jeder beliebigen Kombination daraus zu einer Zellstoffaufschlämmung im Papierherstellungsvorgang hinzugefügt wird.
  13. Verfahren nach Anspruch 1, wobei die Zusammensetzung zu einer Oberfläche im Papierherstellungsvorgang zugefügt wird, die ausgewählt ist aus einer Rohrwand, einer Behälterwand, einem Maschinendraht, einer Presswalze, einem Filz, einer Folie, einem Rohrsauger, einem Trockner oder einer beliebigen Kombination daraus.
  14. Verfahren nach Anspruch 1, wobei das anionische verzweigte cyclische Polymer auf Glycerinbasis einer Zellstoffaufschlämmung im Papierherstellungsvorgang hinzugefügt wird.
EP13866663.1A 2012-12-28 2013-12-16 Lipophile anionische polymere auf glycerolbasis für organische abscheidungskontrolle in verfahren zur papierherstellung Active EP2938781B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/730,003 US8709209B2 (en) 2010-03-10 2012-12-28 Anionic lipophilic glycerol-based polymers for organic deposition control in papermaking processes
PCT/US2013/075438 WO2014105489A1 (en) 2012-12-28 2013-12-16 Anionic lipophilic glycerol-based polymers for organic deposition control in papermaking processes

Publications (3)

Publication Number Publication Date
EP2938781A1 EP2938781A1 (de) 2015-11-04
EP2938781A4 EP2938781A4 (de) 2016-07-20
EP2938781B1 true EP2938781B1 (de) 2018-05-30

Family

ID=51021936

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13866663.1A Active EP2938781B1 (de) 2012-12-28 2013-12-16 Lipophile anionische polymere auf glycerolbasis für organische abscheidungskontrolle in verfahren zur papierherstellung

Country Status (5)

Country Link
EP (1) EP2938781B1 (de)
KR (1) KR102134245B1 (de)
CN (1) CN104884705B (de)
CA (1) CA2892629C (de)
WO (1) WO2014105489A1 (de)

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5032224A (en) * 1989-03-27 1991-07-16 Exxon Chemical Patent Inc. Method of producing pulp
US5667634A (en) * 1991-05-01 1997-09-16 Novo Nordisk A/S Method for controlling pitch deposits in papermaking process using lipase and polyelectrolyte
CA2427854A1 (en) * 2000-11-06 2002-05-10 Lonza Inc. Processes for preparing linear polyglycerols and polyglycerol esters
CN1312278C (zh) 2001-05-21 2007-04-25 诺维信公司 脂解酶在粘性物控制中的应用
WO2008013875A2 (en) * 2006-07-26 2008-01-31 Hercules Incorporated Hydrophobically modified poly(ethylene glycol) for use in pitch and stickies control in pulp and papermaking processes
JP5096952B2 (ja) 2007-02-26 2012-12-12 株式会社日新化学研究所 抄紙機汚れ付着防止剤組成物および抄紙機汚れ付着防止方法
US20100269989A1 (en) * 2009-04-28 2010-10-28 Enzymatic Deinking Technologies, L.L.C. Use of 1,3-selective lipases for pitch control in pulp and paper processes
US20110008637A1 (en) * 2009-07-09 2011-01-13 Broadus Katherine M Method for improving the performance of optical brightening agents
US9290620B2 (en) * 2009-10-21 2016-03-22 Nalco Company Production and composition of glycerol based polyols
US8101045B2 (en) * 2010-01-05 2012-01-24 Nalco Company Modifying agent for yankee coatings
US8366877B2 (en) 2010-03-10 2013-02-05 Nalco Company Lipohydrophilic glycerol based polymers as digestion aids for improving wood pulping processes
EP2402503A1 (de) 2010-06-30 2012-01-04 Akzo Nobel Chemicals International B.V. Prozess zur Herstellung eines Zelluloseproduktes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
KR20150103146A (ko) 2015-09-09
EP2938781A4 (de) 2016-07-20
CN104884705A (zh) 2015-09-02
CA2892629C (en) 2016-08-30
EP2938781A1 (de) 2015-11-04
CN104884705B (zh) 2016-12-14
CA2892629A1 (en) 2014-07-03
WO2014105489A1 (en) 2014-07-03
KR102134245B1 (ko) 2020-07-15

Similar Documents

Publication Publication Date Title
EP2044263B1 (de) Verfahren zur kontrolle von harzablagerungen und klebenden verunreinigungen in zellstoff- und papierherstellungsverfahren, unter verwendung von hydrophob modifiziertes poly(ethylenglycol)
FI121811B (fi) Uudet dispersiot ja menetelmä niiden valmistamiseksi
US4313790A (en) Additives for increased retention and pitch control in paper manufacture
WO2017057154A1 (ja) セルロース繊維と無機粒子の複合体
JP3158575B2 (ja) 製紙用ロジン系エマルジョンサイズ剤、サイジング紙及びサイジング方法
US11535985B2 (en) Method for manufacture of paper or board and paper or board obtained by the method
EP2877633B1 (de) Glycerinbasierte polymere zur reduzierung der ablagerung organischer verunreinigungen in papierherstellungsverfahren
US8709209B2 (en) Anionic lipophilic glycerol-based polymers for organic deposition control in papermaking processes
EP2938781B1 (de) Lipophile anionische polymere auf glycerolbasis für organische abscheidungskontrolle in verfahren zur papierherstellung
JP2009096834A (ja) 濾水性を向上させる方法及びセルロース系成形物
CN1986960A (zh) 用漆酶处理occ纸浆提高瓦楞箱板纸强度的技术
JP3158585B2 (ja) 製紙用ロジン系エマルションサイズ剤及びサイジング方法
JPH07229083A (ja) 中性抄紙用サイズ剤、その製造方法、サイジング方法及びサイジング紙
JP2002256150A (ja) ロジン系エマルション組成物、紙のサイジング方法及び紙
JPH07189173A (ja) ロジン系エマルション組成物、その製造方法、サイズ剤、サイジング方法及びサイズされた紙
JP3221062B2 (ja) ロジン系エマルション組成物、その製造方法、サイジング方法、サイズ剤及びサイズ紙
WO2024126892A1 (en) A surface size composition
JPH07119076A (ja) ロジン系エマルション組成物、その製造方法、サイズ剤、サイジング方法及びサイズされた紙

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150720

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20160617

RIC1 Information provided on ipc code assigned before grant

Ipc: D21H 17/33 20060101AFI20160613BHEP

Ipc: D21H 17/00 20060101ALI20160613BHEP

Ipc: D21H 17/63 20060101ALI20160613BHEP

17Q First examination report despatched

Effective date: 20170320

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20171214

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1003727

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013038414

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180530

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180830

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180830

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180831

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1003727

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013038414

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20181216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181216

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181216

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181231

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181216

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20131216

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180530

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180930

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231024

Year of fee payment: 11