• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a method of preparing grafted copolymers of lignin and/or cellulose, comprising the generation of macroradicals in situ by mechanical impact on the backbone of said lignin and/or cellulose of said lignin and/or cellulose containing material and grafting monomers and/or polymers to said backbone. Furthermore, the present invention relates to the grafted copolymers obtainable by said method, composite materials comprising said copolymers as well as to uses thereof.
    公开号:SE1651139A1
    申请号:SE1651139
    申请日:2016-08-24
    公开日:2018-02-25
    发明作者:Yijing Zhang Eric
    申请人:Biofiber Tech Sweden Ab；
    IPC主号:
    专利说明:

    METHOD OF PREPARING A GRAFTED COPOLYMER OF LIGNIN AND/ORCELLULOSE Field of the inventionThe present invention relates to a method of preparing grafted copolymers of lignin and/or cellulose, comprising the generation ofmacroradicals in situ by mechanical impact on the backbone of the ligninand/or cellulose in lignin and/or cellulose containing material and graftingmonomers and/or polymers to said backbone. Furthermore, the presentinvention relates to the grafted copolymers obtainable by said method,composite materials comprising said grafted copolymers as well as to uses thereof.
    BackgroundLignoce|u|osic fibers are hydrophilic and thus upon exposure to moisture they are highly susceptible to loss of mechanical properties. This isa disadvantage as paper and cardboard are not suitable for applicationswhich require a high degree of stability and mechanical strength.Paper and cardboard can be produced from mechanical pulp, which isa pulp in which the fibers in the lignocellulose material are reduced toconstituent fibers by mechanical means in one or more refiners. Traditionalmechanical pulping involves forcing wood against a revolving stone, whichgrinds the wood by abrasive action (stone ground wood). The production ofmechanical pulp results in little removal of lignin content, and consequentlyproduces paper and cardboard that is not of as high quality as other pulpingmethods that remove significant amounts of lignin.Examples of mechanical pulping processes include refiner mechancial pulps (RMP), thermomechanical pulp manufacturingprocess (TMP), chemithermomechanical pulp manufacturing process (CTMP)and the alkaline peroxide mechanical pulp manufacturing process (APMP).During the thermomechanical pulp manufacturing process, wood chips are 2 exposed to heat treatment by warm steam before entering refiners. Largeparts of the chemithermomechanical pulp manufacturing process are similarto the thermomechanical pulp manufacturing process. The main differencelies in pre-treating the |ignoce|u|ose material, normally wood chips, with somekind of chemical agent(s), such as commonly used sodium sulphite orhydrogen peroxide, for instance at a certain temperature and over a certainperiod of time. ln the case of hydrogen peroxide pre-treatments, the processis also called alkaline peroxide mechanical pulping process (APMP).
    Lignocellulose material, such as wood, can be used as startingmaterial in these processes. The wood is normally chopped initially in the pulpmanufacturing process into an indeterminate number of chips which aresubsequently subjected to further mechanical treatment.
    Any known refiner or refiners can be used to defiberate the fibers. Themajority of refiners comprise two refining discs, between which the material tobe treated is caused to pass. Normally, one disc remains stationary whilst theother rotates at high speed. ln another type of refiner, the two refining discsare counter-rotational. A third type of refiner comprises four refining discs inwhich a centrally placed rotor has refining discs mounted on both sidesthereof.
    Fibers obtained from mechanical pulp manufacturing processes arereferred to as mechanical fibers and are normally used in newsprint,magazine or other kind of publication papers and in packaging as a fillingmaterial. ln order to find new applications for mechanical fibers, the addition ofnew functionalities to the fibers is desired. Examples of such desirablefunctionalities include for example hydrophobicity, elasticity, threedimensional formability and fire retardency.
    Applications of mechanical pulp fibers in plastic composite materialshave been studied, but their application is strongly limited due to the poorinteractivity of the hydrophilic lignocellulosic materials with the hydrophobic plastic polymers. 3 US5741875 discloses ways of grafting lignin with alkene or alkynemonomers using organic solvents, such as dimethyl sulfoxide (DMSO) andhydrogen peroxides, under oxygen free environment, which oxygen freeenvironment is obtained by passing Ngthrough the reaction medium.US8679292 discloses similar reaction systems applied to mechanical pulpfibers, but in aqueous non-oxygen media. These reactions systems arehowever difficult to implement in industrial scale of pulp and papermanufacturing processes. As there is always oxygen air soluble in the pulpfiber water suspension, it is not practically feasible to spurge the suspensionwith nitrogen gas in pulp and paper industrial processes.
    Thus, there is a continued need in the field for a method for graftinglignin and/or cellulose containing material with new functional groups which can be efficiently applied at industrial scale.
    Summary of the invention lt is an object of the present disclosure to provide a method forpreparing a grafted copolymer of lignin and/or cellulose, which overcomes thelimitations and disadvantages of the prior art. lt is another object of present disclosure to provide a method forpreparing a grafted copolymer of lignin and/or cellulose, which can beimplemented into a mechanical pulp manufacturing process. lt is yet another object of the present disclosure to provide a graftedcopolymer of lignin and/or cellulose, which grafted copolymer possessesdesirable characteristics, such as hydrophobicity, elasticity, three dimensionalformability and/or fire retardency.
    Another object of the present disclosure is to provide a compositematerial comprising said grafted copolymer.
    Thus, in the first aspect of the present disclosure there is provided amethod of preparing a grafted copolymer of lignin and/or cellulose, wherein said method comprises the steps of: 4 o subjecting a lignin and/or cellulose containing material in the formof wood chips and/or defiberated wood chips in an oxygen reducedenvironment to a redox initiator, o exposing said lignin and/or cellulose material to mechanicalimpact, and o subjecting said lignin and/or cellulose containing material tomonomers and/or polymers before, during and/or immediately afterexposure to mechanical impact, wherein macroradicals are generated in situ by the mechanical impact on thebackbone of said lignin and/or cellulose of said lignin and/or cellulosecontaining material, and wherein the monomers and/or polymers are grafted to the backbone of saidlignin and/or cellulose.
    The present disclosure provides a novel chemical-mechanical methodto incorporate new functionalities into lignin and/or cellulose containingmaterials by graft polymerization of any carbon-carbon double or triple bondcontaining synthetic or natural occurring monomers and/or polymers. Theprocess is based on the mechanical refining of wood chips and/or defiberatedwood chips whereby lignin radicals and cellulose radicals are generated insitu by mechanical impact on the backbone of said lignin and/or cellulose.The radicals on the backbone of said lignin and/or cellulose can then reactwith added monomers and/or polymers via radical grafting reactions initiatedby redox initiators, such as hydrogen peroxide or other peroxide basedoxidants. lt will be appreciated that the above-mentioned steps of the method asdisclosed herein, may be performed in any order. For example, said ligninand/or cellulose containing material may be subjected to monomers and/orpolymers prior to, during or after mechanical impact.
    To clarify, grafting can occur between added monomers and the ligninand/or cellulose backbone. The monomer grafted to the backbone can itselfbe polymerized via radical reactions to form a polymer of its own repeating units, attached to the backbone. Grafting can also occur between the addedpolymers and the lignin and/or cellulose backbone. lmportantly, in the present method, the lignin and/or cellulosecontaining material is subjected to monomers and/or polymers before, duringand/or immediately after exposure to mechanical impact. Thus, the step ofsubjecting said material occurs prior to the formation of pulp in themechanical pulp manufacturing process.
    The yield and efficiency of the grafting process essentially depend onhow successful the generation of radicals is onto the backbone of ligninand/or cellulose, whereby macroradicals are formed.
    Wood is a porous and fibrous structural tissue found in the stems androots of trees, and other woody plants. lt is an organic material, a naturalcomposite of cellulose fibers (which are strong in tension) embedded in amatrix of lignin which resists compression.
    As used herein, the term “macroradicals” refers to lignin and/orcellulose itself where radicals have been generated on different sites on itsbackbone. These sites could be the potential radical generator functions inthe lignin molecules and/or the hydroxyl groups or the carbon atoms of thecarbinol groups of cellulose in lignocellulosic materials. Once themacroradicals are formed, the graft polymerization occurs, i.e. themacroradicals react with the desired monomers and/or polymers in theirproximity.
    As used herein, the term “grafting” refers to a process of co-polymerization wherein functional groups are imparted to a polymer. Graft co-polymerization can e.g. be initiated by chemical treatment.
    As used herein, the term “grafted copolymer” is a branched copolymerwhere the components of the side chain are structurally different than that ofthe main chain. lt is beneficial that that the monomers and/or polymers and the at leastone redox initiator are well mixed either during wood chip pre-treatmentstage(s), in the refining stage(s) or directly after the refining to ensure that the initiated monomer and/or polymer radicals are available to react with the 6 lignin and/or cellulose polymers radicals (macroradicals) immediately oncethey are generated by the mechanical impact.
    The material used in the present method may be wood chips and/ordefiberated wood chips, such as wood chips which are or have beensubjected to refining. Defiberated wood chips are compressionallydestructured wood chips with partially open structure to facilitate thesubsequent refining.
    Any lignocellulose material can be used as starting material. Examplesof such materials are wood, bamboo, straw, bagasse, kenaf, ramie, hemp,jute, sisal and cotton. Thus, in one embodiment of the present aspect, thelignin and/or cellulose containing material is selected from the groupconsisting of wood, bamboo, straw, bagasse, kenaf, ramie, hemp, jute, emptyfruit branches from oil palm, sisal and cotton. Wood is the preferred startingmaterial, and both softwoods and hardwoods can be beneficially used, eitherseparately or in combination. The wood is normally initially chopped in thepulp manufacturing process into an indeterminate number of chips. ln one embodiment of the present aspect, the lignin and/or cellulosecontaining material is hardwood or softwood. The term “hardwood” as usedherein refers to wood from deciduous trees and broad-leaf evergreen trees.Hardwood is contrasted to softwood, which comes from conifers, conebearing seed plants. Hardwoods are not always harder than softvvoods, balsawood being an example of this. Hardwood trees are more varied thansoftwoods and there are about hundred times more species of hardwood thanthere are softvvoods. Hardwoods usually have broad leaves. Hardwoods allhave enclosed nuts or seeds, where softwoods are gymnosperms, nakedseed plants. Non-limiting examples of hardwood include alder, ash, aspen,beech, birch, boxwood, cherry, cottonwood, elm, hackberry, hickory, hardmaple, horse chestnut, oak, sassafras, maple, olive tree, poplar, Americantulipwood, walnut and willow. The term “softwood” as used herein refers towood that comes from gymnosperm trees. These are conifers which includesmost evergreen trees. Softwood makes up about 80 % of the world's 7 production of lumber. The skilled person knows what is meant by hardwoodand softwood in the context of starting material for mechanical pulping. ln one particular embodiment, said lignin and/or cellulose containingmaterial is a lignin containing material, such as mechanical pulps, or semi-mechanical pulps. ln one particular embodiment, said lignin and/or cellulose containingmaterial is a cellulose containing material, such as sulfate chemical pulps,sulfite pulps, dissolving pulps, cellulose and cellulose derivatives.
    As used to herein, the term “wood chip” refers to a medium-sized solidmaterial made by cutting, or chipping, larger pieces of wood. Wood chips maybe produced by a wood chipper to a desirable size. Wood chips may be usedas a raw material for producing wood pulp.
    Wood chips used in the present method may be relatively uniform insize and free of bark. The optimum size varies with the wood species. lt isimportant to avoid damage to the wood chips as this is important for the pulpproperties. ln one embodiment of the present method, the wood chips ordefiberated wood chips used have a length in the range of 5-30 mm, athickness in the range of 3-25 mm and a width in the range of 3-25 mm. lnanother example, the wood chips or defiberated wood chips used have alength in the range of 10-20 mm, a thickness in the range of 5-15 mm and awidth in the range of 5-15 mm. However, the wood chips may have any chipsize which can enter the refining discs. ln one aspect of the present method, the wood chips or defiberatedwood chips are pre-treated, such as chemically pre-treated. The pre-treatment may comprise of chip washing, steaming, chemical treatment withchelating agent, such as EDTA or DTPA, sulfite or hydrogen peroxide, ozoneand others, and compressive mechanical treatment in a plug screw and/orother forms of compression screw. Furthermore, the pre-treatment may beperformed in one, two, three or more steps depending on the requirements ofthe mechanical pulp manufacturing process and the properties of the starting material. 8 ln one particular embodiment, the defiberated wood chips arecompressionally destructed wood chips with partially open structure. ln one embodiment, there is provided a method wherein the oxygenreduced environment is oxygen deficient. This may be advantageous asoxygen is a radical scavenger which can terminate the radical graftingreaction. By pre-steaming wood chips, the air present in the wood chips isdepleted by the saturated steams. Further in the refiner itself, chipscompression in combination with high steam pressure also leads to anoxygen deficient environment.
    According to the present disclosure, “oxygen reduced environment”means that the amount of oxygen is reduced compared to the amount ofoxygen present in air. ln one embodiment, the oxygen concentration in the oxygen reducedenvironment is reduced with at least 50 %, such as at least 75 %, such as atleast 80 %, such as at least 85 %, such as at least 90 %, such as at least96 %, such as at least 97 %, such as at least 98 % or such as at least 99 %compared to the oxygen concentration in air. ln one embodiment, about 1 %, such as about 2 %, such as about 5 %,such as about 10 %, or such as about 15 % of oxygen is present in theoxygen reduced environment. ln one embodiment, there is provided a method wherein the redoxinitiator is selected from the group consisting of hydrogen peroxide, peraceticacid, 2-hydroperoxy-1,4-dioaycyclohexane, 3,3-dimethyl-1,2-dioxybutane, 1-hydroperoxybenzene, 1-(2-hydroperoxypropyl)benzene, and anhydrous solidperoxides, such as magnesium peroxyphthalate, sodium peroxyborate andsodium percarbonate. ln one example, the redox initiator is a peroxidasebased redox initiator. ln one particular embodiment, said redox initiator isH2O2. Hydrogen peroxide is a commonly used bleaching chemical in pulp andpaper industry and is commercially easily available. ln some embodiments, other radical initiators may be used. Forexample ceric ammonium nitrate, Co (lll) acetylacetonate complex, other 9 Cu2+/|O4 - couples (such as potassium diperiodatocuprate (lll) and the likemay be used. ln yet other embodiments, a co-initiator may be used. The co-initiatorused in the copolymerization process is a reductant agent. As an example,iron (ll) could be used for this purpose. Copper manganese, chromium,vanadium or any other cation able to carry out oxidation-reduction reactionswith the initiator could likewise be used. The initiation process can be speedup by using acids that are able to dissociate into radicals, such as sulphuricacid or nitric acid. The co-initiators, such as iron (ll), may not need to beadded to the process since iron often exists in wood chips.
    As explained herein, the lignin and/or cellulose radicals (also referredto as macroradicals) are generated under mechanical impact in the presentmethod. ln one embodiment, said mechanical impact is grinding, milling,and/or refining. The mechanical impact has to be sufficient to generate saidmacroradicals. Thus, in one embodiment, said mechanical impact isperformed under a pressure in the range of 1-7 bars, a temperature in therange of 70-180 °C, and a specific energy consumption of 300- 2900 KWH/BDT (bone-dry ton). ln another example, the mechanical impact isperformed under a pressure in the range of 6-7 bars and a temperature in therange of 150-170 °C.
    The skilled person will appreciate that any kind of alkyl, aryl, vinyl, allyltypes or any double bond or trippel bond containing molecules can be usedas monomers in the context of the present method, provided that it can bepolymerized through radical polymerization. Non-limiting examples of suchmonomers include acrylamide, methyl acrylate, butyl acrylate, 4-vinylpyridine,acrylic acid, dimethylaminoethyl methacylate, acrylonitrile and butylmethacrylate. Also, molecules for example macromolecules that canpolymerize in situ are suitable as monomers in the invention. Acrylates,styrenes or butadienes are examples of possible monomers.
    Thus, in one aspect of present disclosure, there is provided a methodwherein the monomers used have at least one double or triple bond. ln one embodiment, said monomer is an alkyl, aryl vinyl or allyl. ln one embodiment, said monomer is selected from the groupconsisting of acrylamide, methyi acrylate, butyl acrylate, 4-vinylpyridine,acrylic acid, dimethyiaminoethyl methacylate, acrylonitrile and butylmethacrylate. ln one embodiment, said monomer is an acrylate, a styrene ora butadiene. ln one embodiment, said monomer is a vinyl monomer. ln oneembodiment, said vinyl monomer is selected from the group consisting ofmethyl methacrylate, butyl methacrylate, glycidyl methacrylate, acrylamide,methyi acrylate, butyl acrylate, 4-vinylpyridine, acrylic acid,dimethylaminoethyi methacyiate, acrylonitrile and butyl methacrylate.
    Tne ntonornera rnay he aikenes or aiirynes of the generai structure: Rz Rs | | o =o Ri-oao-Rz oH2=o-R6-o=oH2| | | | R1 R4 Rs R where Ri, wherein i='t, 2, 3, 4, 5, 6, or Tf, ie an organic or inorganio funotionaigroup tfvhioh does not interfere tfvitn free raciicai poiyrnerizatioit, often chosenfrorn arnong 1) hydrogen; 2) a haiogen; 3) the group consisting of an organicacid, an organic aiconoi, an aidehyde, an aikana, an aikene, an aikyne, anarnide, an arornatic, a cycioaikane, an eater, an etner, an organic naiogen, aketone, an organic nitriie, a phenoi, an organophosphate, and an organicsuifonic acid; 4) the group specified at 3) suhstituted in at ieast one,tetravaient carbon atom oy a divaient heteroatom with the atoniic eyrnooi S,Se, Te, Si, Ge, Sn, or Ph, a trivaient heteroatont with the atornic eyrnhoi N, F, As, So, Bi, or B, or a tetravaient neteroatom with the atornio ayrnboi S, Se, Te, Si, Ge, Sn, or Ph; and 5) the etructures of grotipe 3) and 4) further suostitutedby niernhers of such groups, Non~iirniting exarnpies of aricn nionornersinciude: 1~chioroethene; 'i,1Qßtetrafiuoroethene; “i-phenyietiterte; 1,2- diphenyietnene (atiiberiey Hilnaiophenyhetnerie where; is 2, 3, or 4 and the 11 haiide substitiient is fluorine, cnlerine, er brorniiwe; 'Lk-dietheriyiberizerie er k-etnenyipyridine, »where k=2, 3, or 4; i,3«bi.itadiene; Bbutenâ-one; 2~thio-3«butene; Z-methyi-i ß-biitadiene; ßcniora-'l ß-butadiene; â-propeiwoic acid; 2-propenn-al (acroieiny 2~propene nitrile; ëmetnyl-ßpropenoic acid; 1,1-dichioroethene; Lßdichleroethene; ßpropenamide; Nfiæiimethyi-Z»propenarftide; N,N«bis(2~prapenarnidcnmetnane; i~rnetnyl¥lphenyletiierie; 2-oxe-ísexyperita-ene; a 2~rnetnyl~3-o>
    权利要求:
    Claims (1)
    [1] 1. A method of preparing a grafted copolymer of lignin and/or cellulose, wherein said method comprises the steps of: o subjecting a lignin and/or cellulose containing material in the formof wood chips and/or defiberated wood chips in an oxygen reducedenvironment to a redox initiator, o exposing said lignin and/or cellulose containing material tomechanica| impact, and o subjecting said lignin and/or cellulose containing material tomonomers and/or polymers before, during and/or immediately afterexposure to mechanica| impact, wherein macroradicals are generated in situ by mechanica| impact on the backbone of the lignin and/or cellulose of said lignin and/or cellulose containing material, and wherein the monomers and/or polymers are grafted to the backbone of said lignin and/or cellulose. A method according to claim 1, wherein the oxygen reduced environment is oxygen deficient. A method according to any of the preceding claims, wherein the woodchips and/or defiberated wood chips are chemically pre-treated. A method according to any of the preceding claims, wherein the redoxinitiator is selected from the group consisting of hydrogen peroxide,peracetic acids, 2-hydroperoxy-1,4-dioaycyclohexane, 3,3-dimethyl-1,2-dioxybutane, 1-hydroperoxybenzene, 1-(2-hydroperoxypropyl)benzene, and anhydrous solid peroxides, such asmagnesium peroxyphthalate, sodium peroxyborate and sodiumpercarbonate. _ A method according to any of the preceding claims, wherein the redox initiator is hydrogen peroxide. _ A method according to claim 5, wherein the lignin and/or cellulose containing material is subjected to hydrogen peroxide at aconcentration of 1-5 wt% based on dry-bone wood. _ A method according to any of the preceding claims, wherein the mechanica| impact is grinding, mi|ing and/or refining. _ A method according to any of the preceding claims, wherein the monomers have at least one double or triple bond. _ A method according to any of the preceding claims, wherein the monomers are selected from the group consisting of styrenebutadiene, isoprene, chloroprene, methyl methacrylate, andmethacrylate. 10_A method according to any one of claims 1-7, wherein the polymers are selected from the group consisting of polyvinyl chloride,polyethylene, polypropylene, polyisoprene and polystyrene butadiene. 11_A method according to any of the preceding claims, wherein the monomers and/or polymers are added to the lignin and/or cellulosecontaining material with a charge rate in the range of 5-15 wt% basedon bone-dry wood. 12_A method according to any of the preceding claims, wherein the lignin and/or cellulose containing material is subjected to monomers and/or polymers during a pre-treatment step. 41 13.A method according to any of the preceding claims, wherein the lignin and/or cellulose containing material is subjected to monomers and/or polymers during a primary refining step and/or secondary refining step. 14.Grafted copolymer of lignin and/or cellulose obtainable by the methodaccording to any one of claims 1-13. 15.Use of the grafted copolymer of lignin and/or cellulose according toclaim 14 for applications in construction, packaging, furniture,household products, or in any lignin and/or cellulose fiber based composite materials. 16.Composite material comprising at least one grafted copolymer of ligninand/or cellulose according to claim 14.
    类似技术:
    公开号 | 公开日 | 专利标题
    Kumar et al.2017|Cellulose based grafted biosorbents-Journey from lignocellulose biomass to toxic metal ions sorption applications-A review
    US4022965A|1977-05-10|Process for producing reactive, homogeneous, self-bondable lignocellulose fibers
    US7326317B2|2008-02-05|Lignocellulose product
    US5169687A|1992-12-08|Supercritical fluid-aided treatment of porous materials
    US5741875A|1998-04-21|Biodegradable plastics and composites from wood
    Panesar et al.2013|Functionalization of lignin: Fundamental studies on aqueous graft copolymerization with vinyl acetate
    US20070163735A1|2007-07-19|Method for reducing brightness reversion of mechanical pulps and high-yield chemical pulps
    EP0434698A1|1991-07-03|Supercritical fluid-aided treatment of porous materials
    US20100300634A1|2010-12-02|Method of making medium density fiberboard
    SE1651139A1|2018-02-25|Method of preparing a grafted copolymer of lignin and / or cellulose
    Samal et al.1986|Graft copolymerization of cellulose, cellulose derivatives, and lignocellulose
    Mahdavi et al.2011|Optimized conditions for graft copolymerization of poly | onto rubberwood fibre
    WO1997022744A1|1997-06-26|Method for the production of highly absorbent hybrid fibres by ozoning and graft polymerizing and hybrid fibres produced through the method
    Abu‐Ilaiwi et al.2004|Optimized conditions for the grafting reaction of poly | onto rubberwood fiber
    Myja et al.2018|TEMPO mediated oxidation optimization on thermomechanical pulp for paper reinforcement and nanomaterial film production
    US5424382A|1995-06-13|Biodegradable plastics and composites from wood
    Asada et al.2020|Production of eco-refinery pulp from moso bamboo using steam treatment followed by milling treatment
    WO2002092669A8|2003-07-24|A method for preparation of absorbing substances
    US4534397A|1985-08-13|Method for producing chemimechanical high yield pulp using an oxygen alkali treatment followed by an oxygen mechanical defibration
    CA1115908A|1982-01-12|Process for manufacture of thermoformable panels
    Young1977|Modification of high-yield pulp fibers by the xanthate method
    Mašura1982|Alkaline degradation of spruce and beech wood
    Hakim et al.2022|The effect of alkali treatment on the surface and mechanical properties of fibrovascular bundles of Salacca sumatrana Becc. fronds
    Xiu et al.2012|Copolymerization Modification Process of OCC Fibers Grafted by Hexanelactam and Characterization of the Grafted Products
    Bagby et al.1977|Modification of High-Yield Pulp Fibers by the Xanthate Method
    同族专利:
    公开号 | 公开日
    CN109923261B|2022-01-11|
    US10889674B2|2021-01-12|
    CA3034509A1|2018-03-01|
    KR20190045910A|2019-05-03|
    WO2018038672A1|2018-03-01|
    US20190202956A1|2019-07-04|
    CN109923261A|2019-06-21|
    MX2019002060A|2019-07-01|
    SE540288C2|2018-05-22|
    RU2019106126A|2020-10-02|
    EP3504375A1|2019-07-03|
    BR112019003463A2|2019-05-21|
    CL2019000451A1|2019-05-03|
    AU2017314753A1|2019-03-28|
    PH12019500343A1|2019-06-17|
    EP3504375A4|2020-05-06|
    JP2019526715A|2019-09-19|
    RU2019106126A3|2020-12-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3330787A|1963-04-08|1967-07-11|Scott Paper Co|Graft polymerization using ferrated thioated cellulose substrate, products thereof and intermediates|
    US3607799A|1969-10-24|1971-09-21|Eastman Kodak Co|Processes for grafting vinyl-type compounds to cellulosic materials|
    LU76172A1|1976-11-11|1978-07-10|
    SE435520B|1980-05-07|1984-10-01|Mo Och Domsjoe Ab|CELLULOSAMASSA FOR USE IN CEMENT PLASTS AND SETS FOR ITS MANUFACTURING|
    CN1071436A|1988-12-19|1993-04-28|约翰·J·曼斯特|Xylogen-acrylamide-phenylethene grafted copolymer, method for making and application|
    US5138007A|1988-12-19|1992-08-11|Meister John J|Process for making graft copolymers from lignin and vinyl monomers|
    US5741875A|1991-11-08|1998-04-21|Meister; John J.|Biodegradable plastics and composites from wood|
    US5651861A|1995-12-18|1997-07-29|Rhone-Poulenc Inc.|Process for removing inks from waste paper|
    AU2003234058A1|2003-05-13|2004-12-03|Stazione Sperimentale Carta Cartoni E Paste Per Carte|Method for plasma treating paper and cardboards|
    EP2148001B1|2008-07-23|2016-02-24|Solenis Technologies Cayman, L.P.|Pulping of cellulosic material in the presence of a cationic polymer|
    WO2011147027A2|2010-05-26|2011-12-01|Fpinnovations|Hydrophobic lignocellulosic material and process therefor|
    JP5969262B2|2012-05-10|2016-08-17|国立大学法人群馬大学|Method for producing graft polymer-modified cellulose fiber|
    WO2015117106A1|2014-02-03|2015-08-06|Carnegie Mellon University|Polymer-grafted lignin surfactants|
    CN105642247B|2014-11-25|2018-03-30|山东大学（威海）|A kind of preparation method of new TEPA modified cellulose base heavy metal high-efficiency adsorbent|
    EP3491070A4|2016-07-27|2020-03-11|FPInnovations|Vacuum-assisted co-extrusion of flexible fibres and the moldable thermoplastic composites produced|CN113136038A|2021-03-31|2021-07-20|南京林业大学|Preparation method of micro-nano lignocellulose composite material, composite material and application|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1651139A|SE540288C2|2016-08-24|2016-08-24|Method of preparing a grafted copolymer of lignin and / or cellulose|SE1651139A| SE540288C2|2016-08-24|2016-08-24|Method of preparing a grafted copolymer of lignin and / or cellulose|
    PCT/SE2017/050853| WO2018038672A1|2016-08-24|2017-08-24|Method of preparing a grafted copolymer of lignin and/or cellulose|
    EP17844038.4A| EP3504375A4|2016-08-24|2017-08-24|Method of preparing a grafted copolymer of lignin and/or cellulose|
    MX2019002060A| MX2019002060A|2016-08-24|2017-08-24|Method of preparing a grafted copolymer of lignin and/or cellulose.|
    US16/326,744| US10889674B2|2016-08-24|2017-08-24|Method of preparing a grafted copolymer of lignin and/or cellulose|
    CA3034509A| CA3034509A1|2016-08-24|2017-08-24|Method of preparing a grafted copolymer of lignin and/or cellulose|
    JP2019510774A| JP2019526715A|2016-08-24|2017-08-24|Process for preparing lignin and / or cellulose graft copolymers|
    BR112019003463-3A| BR112019003463A2|2016-08-24|2017-08-24|method of preparing a grafted lignin and / or cellulose copolymer|
    RU2019106126A| RU2019106126A3|2016-08-24|2017-08-24|
    CN201780051544.2A| CN109923261B|2016-08-24|2017-08-24|Method for preparing graft copolymers of lignin and/or cellulose|
    KR1020197006456A| KR20190045910A|2016-08-24|2017-08-24|Process for producing graft copolymers of lignin and / or cellulose|
    AU2017314753A| AU2017314753A1|2016-08-24|2017-08-24|Method of preparing a grafted copolymer of lignin and/or cellulose|
    PH12019500343A| PH12019500343A1|2016-08-24|2019-02-18|Method of preparing a grafted copolymer of lignin and/or cellulose|
    CL2019000451A| CL2019000451A1|2016-08-24|2019-02-19|Method for preparing a grafted copolymer of lignin and / or cellulose.|
    [返回顶部]