EP3445753A1 - Difunctional grafting agent based on phenolic backbone from lignin - Google Patents

Difunctional grafting agent based on phenolic backbone from lignin

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Publication number
EP3445753A1
EP3445753A1 EP17720902.0A EP17720902A EP3445753A1 EP 3445753 A1 EP3445753 A1 EP 3445753A1 EP 17720902 A EP17720902 A EP 17720902A EP 3445753 A1 EP3445753 A1 EP 3445753A1
Authority
EP
European Patent Office
Prior art keywords
group
alkyl
hydrogen
epoxide
agent
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.)
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Application number
EP17720902.0A
Other languages
German (de)
French (fr)
Inventor
Joseph Samec
Alexander OREBOM
Maxim GALKIN
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.)
KAT2BIZ AB
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KAT2BIZ AB
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Filing date
Publication date
Application filed by KAT2BIZ AB filed Critical KAT2BIZ AB
Publication of EP3445753A1 publication Critical patent/EP3445753A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids

Definitions

  • the present invention relates to a grafting agent where said agent is a difunctional molecule, and the preparation of the grafting agent and the use of the same.
  • the agent may be used for cross linking various substrates.
  • BACKGROUND Grafting of molecules or polymer on to a substrate alters the properties of the substrate. This provides a strategy to tailor the properties of the substrate concerning for example mechanical properties, solubility, permeability, wettability, melting or softening temperatures and so on.
  • Bisphenol A is a compound used to prepare plastics and epoxy resins and is used today in a wide variety of applications. However the suitability of bisphenol A in certain applications have been questioned due to that it exhibits hormone like properties.
  • the object of the present invention is to present an effective grafting or cross-linking agent derived from a renewable source.
  • the present invention relates to a grafting agent having the formula wherein Rl is selected from substituted or unsubstituted epoxide group, aldehyde group, alkene, alkyl, alkyl aryl, thiol, an alkoxy, hydroxyl or a carboxylic acid group, R2 is hydrogen, alkyne group, alkoxy group, alkyl group, alkyl aryl group, thiol, hydroxyl or an alkyl epoxide group, R3 is hydrogen, alkyne group, alkene group, alkyl hydroxyl group, alkyl group, epoxide or an alkyl epoxide group and R4 is hydrogen or a methoxy group; and wherein the grafting agent is derived from lignin.
  • the present invention relates to a method of preparing a grafting agent having the formula of
  • R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group
  • R2 is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group comprising a.
  • R3 is a hydrogen or an alkyl group such as a methyl group.
  • step b product of step b; and f. Isolating the obtained diepoxide.
  • the present invention relates to a method of preparing a grafting agent having the formula of
  • R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group and R3 is selected from a hydrogen or an alkyl group such as a methyl group; wherein the method comprises a. Treating lignin using a transition metal catalyst, a solvent and heat to provide a compound having the formula of
  • R2 is hydrogen; b. Letting the compound react with a vinyl alcohol in the presence of a transition metal catalyst; c. Optionally isolating the product of step b; d. Rearranging the compound using Claisen rearrangement conditions; e. Optionally isolating the product of step d; f. Adding a weak oxidizing agent together with a ketone solvent such as acetone to the product of step d; g. Letting the oxidizing agent and the ketone solvent react with the
  • the present invention relates to a method of grafting a substrate using the grafting agent according to the present invention wherein the method comprises a. Providing the grafting agent according to the present invention; b. Providing a substrate having at least one hydroxyl groups; c. Bringing the grafting agent and the substrate into contact and letting the functional groups of the grafting agent reaction with the hydroxyl group of the substrate.
  • the present invention relates to a paper comprising cellulose grafted or cross-linked with the agent according to the present invention.
  • Figure 1 a schematic view of the reaction scheme for preparing the grafting agent according to the present invention.
  • Figure 2 H-NMR of an epoxide according to the present invention.
  • the present invention relates to a grafting agent or a cross-linking agent grafting agent having the formula
  • Rl is selected from substituted or unsubstituted epoxide group, aldehyde group, alkene, alkyl, alkyl aryl, thiol, an alkoxy, hydroxyl or a carboxylic acid group
  • R2 is hydrogen, alkyne group, alkoxy, alkyl, alkyl aryl thiol, hydroxyl or an alkyl epoxide group
  • R3 is hydrogen, alkyne, alkene, alkyl hydroxyl, alkyl, epoxide or an alkyl epoxide group
  • R4 is hydrogen or a methoxy group.
  • the agent is derived from a renewable source such as lignin.
  • Rl is a substituted epoxide group
  • the epoxide may be substituted with an alkoxy group, an alkyl group or an alkyl aryl group.
  • At least one of Rl to R3 is an alkyl epoxide or an epoxide group. In one embodiment R3 is an alkyl epoxide.
  • At least one of R2 and R3 is an epoxide group or an alkyl epoxide group.
  • the agent is an epoxide having the general structure according to (l)
  • R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group
  • R2 is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group or an alkyl epoxide group
  • R3 is hydrogen, alkyl group or an alkyl epoxide group. In one embodiment at least one of R2 and R3 is an alkyl epoxide group.
  • the R group is in one embodiment hydrogen or a C1-C3 alkyl group such as a methyl or ethyl group. In one embodiment the R group is a methyl group.
  • the R2 group is in one embodiment hydrogen or an alkoxy group such as methoxy or ethoxy group. In one embodiment R2 is a methoxy group. In one embodiment the R2 is an alkyl epoxide group such as a methyl epoxide.
  • R3 group is in one embodiment hydrogen.
  • R3 is an alkyl epoxide group such as a methyl epoxide or ethyl epoxide.
  • the agent is (2a) or (2b)
  • R2 is selected from hydrogen, an alkyl group or an alkyl aryl group.
  • R2 is hydrogen.
  • R2 is a methoxy group.
  • the grafting agent according to the present invention is derived from lignin which may be determined using C14 dating methods known to a person skilled in the art.
  • the agent according to the present invention may be prepared based on a renewable source such as biomass for example wood or lignin.
  • biomass When starting from biomass the biomass may be in particulate form such as powder, sawdust or chips and the biomass should containing lignin.
  • the biomass may be ground to small size particles or powder using any suitable technique. The size of the particles may be 10 cm or less, or 5 cm or less, or 2 cm or less, or 5 mm or less, or 1 mm or less, or 500 ⁇ or less.
  • the biomass may also be in the form of black or red liquor or isolated lignin.
  • the biomass is mixed with a solvent mixture
  • the starting compound may be prepared by the method described in WO2015080660 which is incorporated by reference.
  • the obtained mixture is heated, preferably to at least 80°C, and the depolymerized product is optionally isolated.
  • One of the products obtained by this step has the general structure of 1
  • R' is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group, an alkenyl group, an aldehyde or a carboxylic acid, and wherein R2 to R4 are as defined above.
  • R2 is a methoxy group.
  • the product 1 have the general structure of (4)
  • R is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group.
  • the compound 1 may be isolated using any suitable method such as liquid liquid extraction and the compound or the organic phase may be washed with an aqueous solution.
  • Biomass includes, but is not limited to wood, fruits, vegetables, processing waste, chaff, grain, grasses, com, com husks, weeds, aquatic plants, hay, paper, paper products, recycled paper, shell, algae, straw, bark or nut shells, lignocellulosic material and any cellulose containing biological material or material of biological origin.
  • the biomass is wood, preferably particulate wood such as saw dust or wood chips.
  • the wood may be any kind of wood, hard or soft wood, coniferous tree or broad-leaf tree.
  • a non-limiting list of woods would be pine, birch, spruce, maple, ash, mountain ash, redwood, alder, elm, oak and beech.
  • the present inventors have found that the depolymerization of the lignin according to the present invention is much more effective if the lignin is not chemically pre-treated or modified for example reduced or oxidized. For example kraft lignin or
  • the biomass contains lignin where the chemical structure or chemical composition of the lignin has essentially not been modified.
  • the biomass is organosolv lignin, i.e. lignin obtained from an organosolv process.
  • the biomass is mixed with an organic solvent or a mixture comprising at least one organic solvent.
  • a solvent mixture comprising an organic solvent and water is used.
  • the organic solvent may be an oxygenate such as an alcohol, ester, ketone, ether or furane or furfural based solvent.
  • Preferred solvents are C1 -C10 alcohols, C2-C10 ethers, C2-C10 carboxylic acids, C3-C10 ketones and C2-C10 esters, for example methanol, ethanol, propanol, isopropanol, butanol, glycerol, acetone and butyl ether such as tert-butyl methyl ether; diethyl ether, diglyme, diisopropyl ether, dimethoxyethane, diethylene glycol diethyl ether, polyethylene glycol 1 ,4-dioxane, acetic acid, and tetrahydrofuran.
  • C1 -C10 alcohols for example methanol, ethanol, propanol, isopropanol, butanol, glycerol, acetone and butyl ether such as tert-butyl methyl ether; diethyl ether, diglyme, diisopropyl
  • the solvent is selected from water, methanol, ethanol, butanol, propanol or acetone or a combination thereof.
  • Preferred C1 -C10 esters are organic esters, aromatic or non-aromatic esters, examples of esters are benzyl benzoate, various acetates such as methyl acetate, ethyl acetate and butyl acetate, various lactates such as ethyl lactates.
  • the solvent comprises a combination of C1-C10 alcohols, C2-C10 ethers, C2-C10 carboxylic acids and C2- CIO esters.
  • the solvent comprises two CI -CIO alcohols for example ethanol and glycerol, and in another embodiment the solvent comprises propanol and glycerol.
  • the solvent comprises polyethylene glycol and a CI -CIO alcohol.
  • the solvent comprises furfural or furfuryl alcohol.
  • the solvent is a mixture of an organic solvent and water the mixture may contain methanol and water, ethanol and water, isopropanol and water, acetic acid and water or ethyl acetate and water, preferably ethanol and water,
  • the ratio between the organic solvent and water may be from 1: 10 to 10: 1 (organic solvent:water weight ratio), such as 1:8 to 8: 1 preferably 1:4 to 4: 1 , or 1:2 to 2: 1 preferably around 1 : 1.
  • the solvent mixture comprises 40-60 weight% of organic solvent and 40-60 weight% of water.
  • the substrate, or biomass, concentration in the solvent may be 0.1 wt% or more, or 0.5 wt% or more, or 1 wt% or more, or 2 wt% or more, or 5 wt% or more, or 10 wt% or more, or 20 wt% or more, or 30 wt% or more and may be 70 wt% or less or 50 wt% or less.
  • the method may be performed without water, for example by using only an organic solvent, but by adding water the method becomes more suitable for large scale production due to the reduced risk of explosions. There is no need to add any base or any additional base to the reaction.
  • a transition metal catalyst is used to treat the biomass and the transition metal may be selected from or based on but not limited to palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh) nickel (Ni), iron (Fe), copper (Cu), chromium (Cr), molybdenum (Mo), tungsten (W), preferably Pd, Pt, Fe, Ni or Cu.
  • the catalyst is Pd.
  • the catalyst is Pt.
  • the catalyst is W or W/C.
  • the catalyst is Fe.
  • the catalyst is Ni based such as Raney Nickel.
  • the catalyst is Cu.
  • the catalyst may also be a combination of said metals or bi-metallic catalyst comprising at least one of said metals.
  • the catalyst is a palladium and / or platinum doped metal catalyst.
  • the doped metal catalyst may be a copper, nickel or iron based catalyst which has been doped with palladium or platinum.
  • the catalyst may be in the form of a powder, grains, coated surface or a solid material. In one embodiment the catalyst is selected from Pd, Pd 2 (dba)3
  • Pd(PPh 3 ) 4 Tetrakis(triphenylphosphine)palladium(O)
  • Pd(P t Bu 3 ) 2 Bisitri-tert- butylphosphine)palladium(O)) or Pd/C (Palladium on charcoal).
  • the catalyst is Pt, platinum black or Pt0 2 .
  • the catalyst is Rh/C.
  • the catalyst is Ru / C.
  • the catalyst is Fe(CO) or other Fe(O) sources.
  • the catalyst is a Fe(II) or Fe(III) source.
  • the catalyst is based on Mn.
  • the catalyst is based on Mo.
  • the catalyst is based on Co.
  • the catalyst is based on Ni.
  • the catalyst may be pre-activated prior to use for example by removal of oxygen or oxides through the use of a reducing agent.
  • the catalyst may be added in at least catalytic amounts.
  • the amount of catalyst is 0.5 mol% or more, or 1 mol% or more, or 3 mol% or more, or 5 mol% or more, or 7 mol% or more, or 10 mol% or more, or 100 mol% or less, or 50 mol% or less, or 25 mol% or less, or 15 mol% or less, or 12 mol% or less, in relation to the lignin content. It is believed that when using Pd or Pt based catalysts or catalysts doped with Pd or Pt the method becomes insensitive or at least less sensitive to water. It is preferred that the catalyst is in contact with the substrate or the biomass during the reaction.
  • the biomass and the catalyst forms a slurry or a mixture in the solvent and the mixture is heated to at least 80°C, or at least 120°C, preferably 130°C or higher, or 140°C or higher, or 150°C or higher, or 160°C or higher, or 170°C or higher, or 180°C or higher, or 190°C or higher, or 250°C or lower, or 230°C or lower, or 210°C or lower, or 200°C or lower.
  • the treatment time is dependent on the solvent used and the volume to be treated.
  • the mixture of biomass and catalyst in the solvent may be heated during 30 minutes or more, or 1 hour or more, or 1.5 hours or more, or 2 hours or more when treating a volume of 3 ml.
  • the treatment, or the reaction is fast and may be terminated after 1 hour or less, or after 3 hours or less, or after 10 hours or less.
  • the reaction may be performed in a closed or sealed container creating an autogenous pressure.
  • the reaction is preferably conducted during continuous mixing.
  • the pressure during the depolymerization may be around 100 bar or less, or 50 bar or less, or 45 bar or less, or 35 bar or less, or 25 bar or less, or 10 bar or less, for example 8 bar or less, or 5 bar or less, or 2 bar or less, or 1 bar or more.
  • the pressure during the depolymerization is 5-45 bar, such as 20- 35 bar.
  • one major advantage of the present invention is that no hydrogen gas is needed.
  • the reaction may also be performed during reflux.
  • the treatment, or reaction may be performed in air, or in an atmosphere with reduced oxygen pressure, or in an inert atmosphere such as nitrogen or argon.
  • an inert atmosphere such as nitrogen or argon.
  • the depolymerized lignin may be isolated by filtration, evaporation, distillation or centrifugation or any suitable technique. It is believed that the cellulose or the hemi-cellulose will not be affected or at least only slightly depolymerized.
  • Figure 1 is only disclosing the schematic reaction scheme of the formation of a diepoxide agent where the starting compound is 1.
  • the starting compound is not limited to this specific compound where R2 and R3 are as defined above.
  • route b the epoxide formation on the starting compound 1 is achieved via the formation of an allylic side chain 2 and a Claisen rearrangement product 3, followed by a reaction of the double bond together with a weak oxidation agent and a ketone solvent to generate the diepoxide compound 4.
  • step b l) the starting compound 1 is reacted with a vinyl alcohol in the presence of a transition metal catalyst to form compound 2 having an allylic side chain.
  • step b2) the compound 2 is rearranged via a Claisen rearrangement.
  • the Claisen rearrangement may be conducted under any suitable Claisen rearrangement conditions known to a person skilled in the art.
  • the temperature is 50°C or higher, or 70°C or higher, or 100°C or 150°C or higher, or 200°C or higher such as 100-300°C or 150-250°C.
  • a catalyst is present such as a transition metal catalyst.
  • the Claisen rearrangement requires that Rl is hydrogen.
  • the vinyl groups of compound 3 are then treated with a weak oxidation agent and a ketone solvent to form the diepoxide compound 4.
  • the halohydrin may be epichlorohydrin or any other suitable halohydrin.
  • the reaction cl) may be conducted at an elevated temperature such as 60° C or higher, or 80°C or higher.
  • a base is added to the reaction mixture.
  • the amount of base may be 0.5-2 equivalents to the starting compound 1, preferably 1- 1.5 equivalents.
  • the base may be any suitable base such as NaOH (aq), KOH (aq) or ammonia.
  • the monoepoxidized product 5 may be isolated by liquid-liquid extraction using any suitable solvent such as toluene.
  • the formed organic phase may be washed with water or a basic aqueous solution or brine or a combination thereof. The washing may be performed in several steps.
  • the solvent may be evaporated and the product 5 may be further purified by chromatography for example.
  • Reaction b3) and c2) are conducted in an emulsion together with a weak oxidation agent and a ketone solvent.
  • the emulsion is obtained by a mixture of an organic solvent, besides the ketone solvent, and water.
  • Suitable organic solvents are for example toluene, dichlorom ethane or chloroform.
  • suitable ketone solvents are acetone, acetophenone, isophorone and mesityl oxide.
  • the ketone solvent is acetone.
  • the reaction is preferably conducted in the presence of a weak base such as sodium biocarbonate.
  • the reaction is preferably conducted in the presence of tetrabutylammonium hydrogensulphate.
  • the reaction may be left for 10-90 minutes such as 30-60 minutes.
  • the organic phase is then removed from the aqueous phase.
  • the organic phase may be washed with water, basic aqueous solution or brine and the washing may be performed in several steps using different washing liquids.
  • the solvents and washing liquids may be evaporated and the final products 4 and 6 may be dried.
  • the present grafting or cross linking agent may comprise a mono or diepoxy functionality and may be used to graft substrates comprising at least one
  • nucleophilic group such as a hydroxyl group, an amine, a thiol.
  • substrate is an anhydride which can be used to generate a thermoset.
  • the grafting or the cross linking may be done by bringing the agent in contact with the substrate.
  • the reaction may be performed neat (without solvent) and the temperature may be 20-200°C, preferably between 70- 140°C or 90- 120°C.
  • the reaction may be performed under basic or neutral conditions.
  • the nucleophile is an amine
  • the reactions may be performed under neutral conditions.
  • the diepoxide is reacted with an anhydride a 1 : 1 ration may be applied, and an imidazole or aromatic amine may be added as a catalyst 0.01 -0. 1 equivalent.
  • the present grafting or cross linking agent comprises a hydroxyl (nucleophilic) and epoxy, aldehyde or carboxylic acid (electrophilic) functionality it may be used to graft substrates comprising one nucleophilic group such as a hydroxyl group, an amine, a thiol, or one electrophilic group such as an epoxide, carboxylic acid or an aldehyde, or may be react with itself to produce a material.
  • the present grafting or cross linking agent comprises a thiol (nucleophilic) and / or alkyne or alkene (electrophilic) functionality it may be used to graft substrates comprising one nucleophilic group such as a thiol, alkene or alkyne group.
  • the substrate having both the thiol and alkene or alkyne
  • these reactions may be performed at temperatures ranging from 20- 100 degrees Celsius using UV irradiation or a radical initiator.
  • the substrate is cellulose. In another embodiment the substrate is hemicellulose. In another embodiment the substrate is a mixture of cellulose and hemicellulose. In another embodiment the substrate is an anhydride. In another embodiment the substrate is a diamine. In another embodiment the substrate is a diol. In another embodiment the substrate is a thiol. In another embodiment the substrate is the agent.
  • the monoepoxide and the diepoxide were analyzed with H-NMR, Figure 2 and 3 respectively.
  • Example 2 The following compounds may be prepared
  • R4 is selected from hydrogen or an alkyl group
  • R2 is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group.
  • step b Optionally isolating the product of step b;
  • step d optionally isolating the product of step d;
  • Obtained mono epoxied could undergo self polymerisation prior to grafting or during grafting step.
  • the agent according to the present invention may be prepared based on a renewable source such as biomass for example wood or lignin.
  • the starting compound may be prepared by the method described in WO2015080660 which is incorporated by reference.
  • To obtained compounds where R4 is hydrogen or alkyl group the starting solution used for the pulping processes preferable should be acidified to pH 5-0 better pH 4-3 with mineral or organic acid.
  • To obtained compounds where R4 is alkyl group pulping liquor should contain corresponding alcohol (e.g. Methanol for R4 is Methyl, Ethanol for R4 is ethyl).

Abstract

The present invention relates to a grafting agent derived from lignin having the general formula of wherein R1 is selected from substituted or unsubstituted epoxide group, aldehyde group, alkene group, thiol, hydroxyl or a carboxylic acid group, R2 is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group, thiol, hydroxyl or an alkyl epoxide group, R3 is hydrogen, alkyne group, an alkene group, alkyl hydroxyl group or an alkyl epoxide group and R4 is hydrogen or a methoxy group.

Description

DIFUNCTIONAL GRAFTING AGENT BASED ON PHENOLIC BACKBONE FROM
LIGNIN
FIELD OF THE INVENTION The present invention relates to a grafting agent where said agent is a difunctional molecule, and the preparation of the grafting agent and the use of the same. The agent may be used for cross linking various substrates.
BACKGROUND Grafting of molecules or polymer on to a substrate alters the properties of the substrate. This provides a strategy to tailor the properties of the substrate concerning for example mechanical properties, solubility, permeability, wettability, melting or softening temperatures and so on.
Bisphenol A is a compound used to prepare plastics and epoxy resins and is used today in a wide variety of applications. However the suitability of bisphenol A in certain applications have been questioned due to that it exhibits hormone like properties.
The demand for renewable chemistry and renewable materials is increasing.
Therefore there is a need for grafting and cross linking agents derived from renewable sources.
SUMMARY OF THE INVENTION
The object of the present invention is to present an effective grafting or cross-linking agent derived from a renewable source.
In a first aspect the present invention relates to a grafting agent having the formula wherein Rl is selected from substituted or unsubstituted epoxide group, aldehyde group, alkene, alkyl, alkyl aryl, thiol, an alkoxy, hydroxyl or a carboxylic acid group, R2 is hydrogen, alkyne group, alkoxy group, alkyl group, alkyl aryl group, thiol, hydroxyl or an alkyl epoxide group, R3 is hydrogen, alkyne group, alkene group, alkyl hydroxyl group, alkyl group, epoxide or an alkyl epoxide group and R4 is hydrogen or a methoxy group; and wherein the grafting agent is derived from lignin.
In a second aspect the present invention relates to a method of preparing a grafting agent having the formula of
wherein R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group, R2 is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group comprising a. Treating lignin using a transition metal catalyst, a solvent and heat to provide a compound having the formula of
wherein R3 is a hydrogen or an alkyl group such as a methyl group. b. Letting the compound react with an epihalohydrin; c. Optionally isolating the product of step b; d. Adding a weak oxidizing agent together with a ketone solvent such as acetone to the product of step b; e. Letting the oxidizing agent and the ketone solvent react with the
product of step b; and f. Isolating the obtained diepoxide.
In a third aspect the present invention relates to a method of preparing a grafting agent having the formula of
wherein R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group and R3 is selected from a hydrogen or an alkyl group such as a methyl group; wherein the method comprises a. Treating lignin using a transition metal catalyst, a solvent and heat to provide a compound having the formula of
wherein R2 is hydrogen; b. Letting the compound react with a vinyl alcohol in the presence of a transition metal catalyst; c. Optionally isolating the product of step b; d. Rearranging the compound using Claisen rearrangement conditions; e. Optionally isolating the product of step d; f. Adding a weak oxidizing agent together with a ketone solvent such as acetone to the product of step d; g. Letting the oxidizing agent and the ketone solvent react with the
product of step d; and h. Isolating the obtained diepoxide. In a fourth aspect the present invention relates to a method of grafting a substrate using the grafting agent according to the present invention wherein the method comprises a. Providing the grafting agent according to the present invention; b. Providing a substrate having at least one hydroxyl groups; c. Bringing the grafting agent and the substrate into contact and letting the functional groups of the grafting agent reaction with the hydroxyl group of the substrate.
In a fifth aspect the present invention relates to a paper comprising cellulose grafted or cross-linked with the agent according to the present invention.
All the embodiments mentioned below are applicable to all aspects.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1, a schematic view of the reaction scheme for preparing the grafting agent according to the present invention. Figure 2, H-NMR of an epoxide according to the present invention.
Figure 3, H-NMR of an epoxide according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a grafting agent or a cross-linking agent grafting agent having the formula
wherein Rl is selected from substituted or unsubstituted epoxide group, aldehyde group, alkene, alkyl, alkyl aryl, thiol, an alkoxy, hydroxyl or a carboxylic acid group, , R2 is hydrogen, alkyne group, alkoxy, alkyl, alkyl aryl thiol, hydroxyl or an alkyl epoxide group, R3 is hydrogen, alkyne, alkene, alkyl hydroxyl, alkyl, epoxide or an alkyl epoxide group and R4 is hydrogen or a methoxy group. The agent is derived from a renewable source such as lignin.
When Rl is a substituted epoxide group the epoxide may be substituted with an alkoxy group, an alkyl group or an alkyl aryl group.
In one embodiment at least one of Rl to R3 is an alkyl epoxide or an epoxide group. In one embodiment R3 is an alkyl epoxide.
In one embodiment at least one of R2 and R3 is an epoxide group or an alkyl epoxide group.
In one embodiment the agent is an epoxide having the general structure according to (l)
wherein R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group, R2 is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group or an alkyl epoxide group and R3 is hydrogen, alkyl group or an alkyl epoxide group. In one embodiment at least one of R2 and R3 is an alkyl epoxide group.
The R group is in one embodiment hydrogen or a C1-C3 alkyl group such as a methyl or ethyl group. In one embodiment the R group is a methyl group. The R2 group is in one embodiment hydrogen or an alkoxy group such as methoxy or ethoxy group. In one embodiment R2 is a methoxy group. In one embodiment the R2 is an alkyl epoxide group such as a methyl epoxide.
The R3 group is in one embodiment hydrogen. In another embodiment R3 is an alkyl epoxide group such as a methyl epoxide or ethyl epoxide.
In one embodiment the agent is (2a) or (2b)
In one embodiment the agent has the general structure according to
wherein R2 is selected from hydrogen, an alkyl group or an alkyl aryl group. In embodiment R2 is hydrogen. In another embodiment R2 is a methoxy group.
The grafting agent according to the present invention is derived from lignin which may be determined using C14 dating methods known to a person skilled in the art.
Preparing the grafting agent or cross-linking agent 1. Preparing the starting compound 1
Figure 1 - step a. The agent according to the present invention may be prepared based on a renewable source such as biomass for example wood or lignin. When starting from biomass the biomass may be in particulate form such as powder, sawdust or chips and the biomass should containing lignin. The biomass may be ground to small size particles or powder using any suitable technique. The size of the particles may be 10 cm or less, or 5 cm or less, or 2 cm or less, or 5 mm or less, or 1 mm or less, or 500 μπι or less. The biomass may also be in the form of black or red liquor or isolated lignin. The biomass is mixed with a solvent mixture
comprising an organic solvent and water, and a transition metal catalyst. The starting compound may be prepared by the method described in WO2015080660 which is incorporated by reference. The obtained mixture is heated, preferably to at least 80°C, and the depolymerized product is optionally isolated. One of the products obtained by this step has the general structure of 1
wherein R' is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group, an alkenyl group, an aldehyde or a carboxylic acid, and wherein R2 to R4 are as defined above. In one embodiment R2 is a methoxy group. In one
embodiment the product 1 have the general structure of (4)
wherein R is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group.
The compound 1 may be isolated using any suitable method such as liquid liquid extraction and the compound or the organic phase may be washed with an aqueous solution.
Biomass includes, but is not limited to wood, fruits, vegetables, processing waste, chaff, grain, grasses, com, com husks, weeds, aquatic plants, hay, paper, paper products, recycled paper, shell, algae, straw, bark or nut shells, lignocellulosic material and any cellulose containing biological material or material of biological origin. In one embodiment the biomass is wood, preferably particulate wood such as saw dust or wood chips. The wood may be any kind of wood, hard or soft wood, coniferous tree or broad-leaf tree. A non-limiting list of woods would be pine, birch, spruce, maple, ash, mountain ash, redwood, alder, elm, oak and beech. The present inventors have found that the depolymerization of the lignin according to the present invention is much more effective if the lignin is not chemically pre-treated or modified for example reduced or oxidized. For example kraft lignin or
lignosulfonate treated according to the present invention will be less depolymerized in comparison with saw dust or wood chips or organosolv lignin treated with the method according to the present invention. In one embodiment the biomass contains lignin where the chemical structure or chemical composition of the lignin has essentially not been modified. In one embodiment the biomass is organosolv lignin, i.e. lignin obtained from an organosolv process.
The biomass is mixed with an organic solvent or a mixture comprising at least one organic solvent. In one embodiment a solvent mixture comprising an organic solvent and water is used. The organic solvent may be an oxygenate such as an alcohol, ester, ketone, ether or furane or furfural based solvent. Preferred solvents are C1 -C10 alcohols, C2-C10 ethers, C2-C10 carboxylic acids, C3-C10 ketones and C2-C10 esters, for example methanol, ethanol, propanol, isopropanol, butanol, glycerol, acetone and butyl ether such as tert-butyl methyl ether; diethyl ether, diglyme, diisopropyl ether, dimethoxyethane, diethylene glycol diethyl ether, polyethylene glycol 1 ,4-dioxane, acetic acid, and tetrahydrofuran. In one
embodiment the solvent is selected from water, methanol, ethanol, butanol, propanol or acetone or a combination thereof. Preferred C1 -C10 esters are organic esters, aromatic or non-aromatic esters, examples of esters are benzyl benzoate, various acetates such as methyl acetate, ethyl acetate and butyl acetate, various lactates such as ethyl lactates. In one embodiment the solvent comprises a combination of C1-C10 alcohols, C2-C10 ethers, C2-C10 carboxylic acids and C2- CIO esters. In one embodiment the solvent comprises two CI -CIO alcohols for example ethanol and glycerol, and in another embodiment the solvent comprises propanol and glycerol. In one embodiment the solvent comprises polyethylene glycol and a CI -CIO alcohol. In one embodiment the solvent comprises furfural or furfuryl alcohol. When the solvent is a mixture of an organic solvent and water the mixture may contain methanol and water, ethanol and water, isopropanol and water, acetic acid and water or ethyl acetate and water, preferably ethanol and water,
isopropanol and water and methanol and water. The ratio between the organic solvent and water may be from 1: 10 to 10: 1 (organic solvent:water weight ratio), such as 1:8 to 8: 1 preferably 1:4 to 4: 1 , or 1:2 to 2: 1 preferably around 1 : 1. In one embodiment the solvent mixture comprises 40-60 weight% of organic solvent and 40-60 weight% of water. The substrate, or biomass, concentration in the solvent may be 0.1 wt% or more, or 0.5 wt% or more, or 1 wt% or more, or 2 wt% or more, or 5 wt% or more, or 10 wt% or more, or 20 wt% or more, or 30 wt% or more and may be 70 wt% or less or 50 wt% or less. The method may be performed without water, for example by using only an organic solvent, but by adding water the method becomes more suitable for large scale production due to the reduced risk of explosions. There is no need to add any base or any additional base to the reaction.
A transition metal catalyst is used to treat the biomass and the transition metal may be selected from or based on but not limited to palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh) nickel (Ni), iron (Fe), copper (Cu), chromium (Cr), molybdenum (Mo), tungsten (W), preferably Pd, Pt, Fe, Ni or Cu. In one embodiment the catalyst is Pd. In one embodiment the catalyst is Pt. In one embodiment the catalyst is W or W/C. In one embodiment the catalyst is Fe. In one embodiment the catalyst is Ni based such as Raney Nickel. In one embodiment the catalyst is Cu. The catalyst may also be a combination of said metals or bi-metallic catalyst comprising at least one of said metals. In another embodiment the catalyst is a palladium and / or platinum doped metal catalyst. The doped metal catalyst may be a copper, nickel or iron based catalyst which has been doped with palladium or platinum. The catalyst may be in the form of a powder, grains, coated surface or a solid material. In one embodiment the catalyst is selected from Pd, Pd2(dba)3
(Tris(dibenzylideneacetone)dipalladium(O)), Pd(OAc)2 (Palladium (II) acetate),
Pd(PPh3)4 (Tetrakis(triphenylphosphine)palladium(O)), Pd(PtBu3)2 (Bisitri-tert- butylphosphine)palladium(O)) or Pd/C (Palladium on charcoal). In another embodiment the catalyst is Pt, platinum black or Pt02. In another embodiment the catalyst is Rh/C. In another embodiment the catalyst is Ru / C. In another embodiment the catalyst is Fe(CO) or other Fe(O) sources. In another embodiment the catalyst is a Fe(II) or Fe(III) source. In another embodiment the catalyst is based on Mn. In another embodiment the catalyst is based on Mo. In another embodiment the catalyst is based on Co. In another embodiment the catalyst is based on Ni. The catalyst may be pre-activated prior to use for example by removal of oxygen or oxides through the use of a reducing agent. The catalyst may be added in at least catalytic amounts. In one embodiment the amount of catalyst is 0.5 mol% or more, or 1 mol% or more, or 3 mol% or more, or 5 mol% or more, or 7 mol% or more, or 10 mol% or more, or 100 mol% or less, or 50 mol% or less, or 25 mol% or less, or 15 mol% or less, or 12 mol% or less, in relation to the lignin content. It is believed that when using Pd or Pt based catalysts or catalysts doped with Pd or Pt the method becomes insensitive or at least less sensitive to water. It is preferred that the catalyst is in contact with the substrate or the biomass during the reaction.
The biomass and the catalyst forms a slurry or a mixture in the solvent and the mixture is heated to at least 80°C, or at least 120°C, preferably 130°C or higher, or 140°C or higher, or 150°C or higher, or 160°C or higher, or 170°C or higher, or 180°C or higher, or 190°C or higher, or 250°C or lower, or 230°C or lower, or 210°C or lower, or 200°C or lower. The treatment time is dependent on the solvent used and the volume to be treated. As an example the mixture of biomass and catalyst in the solvent, may be heated during 30 minutes or more, or 1 hour or more, or 1.5 hours or more, or 2 hours or more when treating a volume of 3 ml. The treatment, or the reaction, is fast and may be terminated after 1 hour or less, or after 3 hours or less, or after 10 hours or less.
The reaction may be performed in a closed or sealed container creating an autogenous pressure. The reaction is preferably conducted during continuous mixing. The pressure during the depolymerization may be around 100 bar or less, or 50 bar or less, or 45 bar or less, or 35 bar or less, or 25 bar or less, or 10 bar or less, for example 8 bar or less, or 5 bar or less, or 2 bar or less, or 1 bar or more. In one embodiment the pressure during the depolymerization is 5-45 bar, such as 20- 35 bar. However one major advantage of the present invention is that no hydrogen gas is needed. The reaction may also be performed during reflux.
In certain applications the use of hydrogen gas may sometimes be advantageous.
The treatment, or reaction, may be performed in air, or in an atmosphere with reduced oxygen pressure, or in an inert atmosphere such as nitrogen or argon. When a palladium catalyst is used the use of an inert atmosphere gives better results but is not necessary.
After the treatment the depolymerized lignin may be isolated by filtration, evaporation, distillation or centrifugation or any suitable technique. It is believed that the cellulose or the hemi-cellulose will not be affected or at least only slightly depolymerized. This makes the present invention also an interesting method for producing high quality pulp and hemi-cellulose. By first treating the lignocellulosic feedstock according to organosolv processes followed by the method according to the present invention, high quality pulp and hemi-cellulose as well as
depolymerized lignin may be obtained. 2. Epoxidation of the starting compound
Figure 1 is only disclosing the schematic reaction scheme of the formation of a diepoxide agent where the starting compound is 1. The starting compound is not limited to this specific compound where R2 and R3 are as defined above.
Figure 1 - route b, step bl-b3. In route b the epoxide formation on the starting compound 1 is achieved via the formation of an allylic side chain 2 and a Claisen rearrangement product 3, followed by a reaction of the double bond together with a weak oxidation agent and a ketone solvent to generate the diepoxide compound 4.
In step b l) the starting compound 1 is reacted with a vinyl alcohol in the presence of a transition metal catalyst to form compound 2 having an allylic side chain. In the next step b2) the compound 2 is rearranged via a Claisen rearrangement. The Claisen rearrangement may be conducted under any suitable Claisen rearrangement conditions known to a person skilled in the art. In one embodiment the temperature is 50°C or higher, or 70°C or higher, or 100°C or 150°C or higher, or 200°C or higher such as 100-300°C or 150-250°C. In one embodiment a catalyst is present such as a transition metal catalyst. The Claisen rearrangement requires that Rl is hydrogen. The vinyl groups of compound 3 are then treated with a weak oxidation agent and a ketone solvent to form the diepoxide compound 4.
Figure 1 - route c, step cl-c2. In route c the epoxide formation on the starting compound 1 is achieved by the reaction with a halohydrin where the first epoxide group is formed 5 followed by the reaction of the double bond on a side chain together with a weak oxidation agent and a ketone solvent to form compound 6.
The halohydrin may be epichlorohydrin or any other suitable halohydrin. The reaction cl) may be conducted at an elevated temperature such as 60° C or higher, or 80°C or higher. In one embodiment a base is added to the reaction mixture. The amount of base may be 0.5-2 equivalents to the starting compound 1, preferably 1- 1.5 equivalents. The base may be any suitable base such as NaOH (aq), KOH (aq) or ammonia. The monoepoxidized product 5 may be isolated by liquid-liquid extraction using any suitable solvent such as toluene. The formed organic phase may be washed with water or a basic aqueous solution or brine or a combination thereof. The washing may be performed in several steps. The solvent may be evaporated and the product 5 may be further purified by chromatography for example.
Reaction b3) and c2) are conducted in an emulsion together with a weak oxidation agent and a ketone solvent. The emulsion is obtained by a mixture of an organic solvent, besides the ketone solvent, and water. Suitable organic solvents are for example toluene, dichlorom ethane or chloroform. A non-limiting list of suitable ketone solvents are acetone, acetophenone, isophorone and mesityl oxide. In one embodiment the ketone solvent is acetone. The reaction is preferably conducted in the presence of a weak base such as sodium biocarbonate. The reaction is preferably conducted in the presence of tetrabutylammonium hydrogensulphate. The reaction may be left for 10-90 minutes such as 30-60 minutes. The organic phase is then removed from the aqueous phase. The organic phase may be washed with water, basic aqueous solution or brine and the washing may be performed in several steps using different washing liquids. The solvents and washing liquids may be evaporated and the final products 4 and 6 may be dried.
Grafting or cross linking of substrate
The present grafting or cross linking agent may comprise a mono or diepoxy functionality and may be used to graft substrates comprising at least one
nucleophilic group such as a hydroxyl group, an amine, a thiol. In another embodiment the substrate is an anhydride which can be used to generate a thermoset.
The grafting or the cross linking may be done by bringing the agent in contact with the substrate. The reaction may be performed neat (without solvent) and the temperature may be 20-200°C, preferably between 70- 140°C or 90- 120°C.
In certain applications, as when the nucleophile on the substrate is a hydroxyl group, the reaction may be performed under basic or neutral conditions. When the nucleophile is an amine, the reactions may be performed under neutral conditions. When the diepoxide is reacted with an anhydride a 1 : 1 ration may be applied, and an imidazole or aromatic amine may be added as a catalyst 0.01 -0. 1 equivalent.
When the present grafting or cross linking agent comprises a hydroxyl (nucleophilic) and epoxy, aldehyde or carboxylic acid (electrophilic) functionality it may be used to graft substrates comprising one nucleophilic group such as a hydroxyl group, an amine, a thiol, or one electrophilic group such as an epoxide, carboxylic acid or an aldehyde, or may be react with itself to produce a material.
When the present grafting or cross linking agent comprises a thiol (nucleophilic) and / or alkyne or alkene (electrophilic) functionality it may be used to graft substrates comprising one nucleophilic group such as a thiol, alkene or alkyne group. In one application the substrate (having both the thiol and alkene or alkyne) can react with itself to produce a material. These reactions may be performed at temperatures ranging from 20- 100 degrees Celsius using UV irradiation or a radical initiator.
In one embodiment the substrate is cellulose. In another embodiment the substrate is hemicellulose. In another embodiment the substrate is a mixture of cellulose and hemicellulose. In another embodiment the substrate is an anhydride. In another embodiment the substrate is a diamine. In another embodiment the substrate is a diol. In another embodiment the substrate is a thiol. In another embodiment the substrate is the agent. EXAMPLES Example 1
A mixture of isoeugenol (10.00 g, 60.90 mmol, 1 eq) and epichlorohydrin (19.0 ml, 0.243 mol, 4 eq) were stirred and heated to 80 °C under argon. A solution of NaOH (2.62 g, 65.5 mmol, 1.08 eq) in water (3 ml) was added over 15 minutes and the reaction was continued for 3 hours at 80 °C. Toluene (70 ml) was added and organic phase was washed with water (20 ml), 10% NaOH (20 ml), brine (20 ml) and dried over Na2S04. After evaporation of the solvent the residue was purified by column chromatography on silica (pentane: ethyl acetate 90: 10 to 80:20) to give 9.35 g (69.7%) of semi solid white product.
To an ice bath cooled and vigurously stirred solution of the alkene 5 (4.50 g, 20.43 mmol, 1 eq) in dichloromethane (75 ml) and water (75 ml) was added NaHCOfe (8.55 g, 0.102, 5 eq), tetrabutylammonium hydrogensulphate (347 mg, 1.02 mmol, 0.05 eq) and acetone (15 ml, 0.204 mol, 10 eq). To the resulting emulsion was added a solution of Oxone® (18.84, 61.29 mmol, 3 eq) in water (150 ml) over 30 min.
After 3 hours the organic phase was separated. The aqueous phase was extracted with toluene (200 ml) and after combining the dichloromethane and toluene phases the dichloromethane was evaporated and the remaining toluene phase was washed with water (2x50 ml), brine (50 ml) and dried over N aSC . Evaporation of the solvent afforded 2.62 g of the diepoxide as an oil.
The monoepoxide and the diepoxide were analyzed with H-NMR, Figure 2 and 3 respectively.
Example 2 The following compounds may be prepared
wherein R4 is selected from hydrogen or an alkyl group, R2 is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group.
a. Providing a compound having the general structure of
b. Letting the compound react with an epihalohydrin;
c. Optionally isolating the product of step b;
d. Remove or exchange R4 if R4 is not hydrogen
e. Optionally isolating the product of step d;
Obtained mono epoxied could undergo self polymerisation prior to grafting or during grafting step.
The agent according to the present invention may be prepared based on a renewable source such as biomass for example wood or lignin. The starting compound may be prepared by the method described in WO2015080660 which is incorporated by reference. To obtained compounds where R4 is hydrogen or alkyl group the starting solution used for the pulping processes preferable should be acidified to pH 5-0 better pH 4-3 with mineral or organic acid. To obtained compounds where R4 is alkyl group pulping liquor should contain corresponding alcohol (e.g. Methanol for R4 is Methyl, Ethanol for R4 is ethyl).
A more detailed description of the synthesis of compound A is found in Example 1.

Claims

1. A grafting agent having the formula
wherein Rl is selected from substituted or unsubstituted epoxide group, aldehyde group, alkene group, thiol, hydroxyl or a carboxylic acid group, R2 is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group, thiol, hydroxyl or an alkyl epoxide group, R3 is hydrogen, alkyne group, an alkene group, alkyl hydroxyl group or an alkyl epoxide group and R4 is hydrogen or a methoxy group, with proviso that at least one of the Rl- R3 contains an epoxide group; and wherein the grafting agent is derived from lignin.
2. The grafting agent according to claim 1 having the formula
wherein R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group, R2 is selected from hydrogen, an alkoxy group, an alkyl group, an alkyl aryl group or an alkyl epoxide group and R3 is hydrogen or an alkyl epoxide group.
3. The agent according to claim 1 or 2 wherein R2 is an alkyl epoxide group such as methyl epoxide.
4. The agent according to claim 1 or 2 wherein R3 is an alkyl epoxide group such as methyl epoxide.
5. The agent according to claim 1 wherein the compound has the formula
6. The agent according to claim 1 wherein the compound has the formula
wherein R2 is selected from hydrogen, an alkoxy group, an alkyl group or alkyl aryl group.
The agent according to claim 6 wherein R2 is selected from hydrogen or a methoxy group.
8. A method of preparing a grafting agent having the formula of wherein R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group and R2 is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group comprising a. Providing a compound having the formula of
wherein R3 is a hydrogen or an alkyl group such as a methyl group. b. Letting the compound react with an epihalohydrin; c. Optionally isolating the product of step b; d. Adding a weak oxidizing agent together with a ketone solvent such as acetone to the product of step b; e. Letting the oxidizing agent and the ketone solvent react with the
product of step b; and f. Isolating the obtained diepoxide.
9. A method of preparing a grafting agent having the formula of
wherein R is selected from hydrogen, an alkoxy group, an alkyl group or an alkyl aryl group and R3 is selected from a hydrogen or an alkyl group such as a methyl group; wherein the method comprises a. Providing a compound having the formula of
wherein R2 is hydrogen; b. Letting the compound react with a vinyl alcohol in the presence of a transition metal catalyst; c. Optionally isolating the product of step b; d. Rearranging the compound using Claisen rearrangement conditions; e. Optionally isolating the product of step d; f. Adding a weak oxidizing agent together with a ketone solvent such as acetone to the product of step d; g. Letting the oxidizing agent and the ketone solvent react with the
product of step d; and h. Isolating the obtained diepoxide.
10. A method of grafting a substrate using the grafting agent according to any one of claims 1 to 7 wherein the method comprises a. Providing the grafting agent according to any one of claims 1 to 7; b. Providing a substrate having at least one hydroxyl group; c. Bringing the grafting agent in contact with the substrate and letting the functional groups of the grafting agent react with the hydroxyl group of the substrate.
11. The method according to claim 11 wherein the substrate is cellulose.
12. A paper comprising cellulose grafted or cross-linked with the agent according to any one of claims 1 to 7.
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