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    • 专利摘要:
    METHOD FOR INCREASING LIGNIN REACTIVITY The present invention relates to a method for increasing lignin reactivity, in which the method comprises the following steps: a) forming, under heating at a temperature of 30 - 70 ° C, a dispersion aqueous which comprises alkali and lignin, wherein the alkali comprises an alkali metal hydroxide; and b) heating the dispersion formed in step a) to a temperature of 50 - 95 ° C for the production of alkylated lignin.
    公开号:BR112014010004B1
    申请号:R112014010004-7
    申请日:2013-03-28
    公开日:2020-12-01
    发明作者:Suvi Pietarinen；Okko Ringena；Kati Oinonen；Sanna Valkonen
    申请人:Upm-Kymmene Corporation；
    IPC主号:
    专利说明:

    [0001] [0001] The invention relates to a method for increasing the reactivity of lignin and the additional use of such lignin. BACKGROUND OF THE INVENTION
    [0002] [0002] Lignin is a natural polymer, which can be extracted, for example, from wood. As lignin is a natural biopolymer, its use as a glue component instead of synthetic materials has been investigated in order to obtain a more environmentally friendly adhesive composition. In particular, the ability to replace synthetic phenol in phenolic resins, such as phenol formaldehyde resin, has been the subject of the prior art.
    [0003] [0003] Adhesive compositions of different types, such as phenolic glues, can be used with wood products. Examples of such adhesives include compositions comprising phenol formaldehyde resin. Traditionally, synthetic formaldehyde phenol resins are produced by polymerization of phenol and formaldehyde in the presence of a catalyst. Examples of such catalysts are sodium hydroxide (NaOH) and acids. The method for producing phenol formaldehyde resin comprises adding formaldehyde in a gradual form to a phenol composition and, therefore, increasing the temperature of the formed composition to 80-90 ° C. The composition is baked at this temperature until a desired viscosity of the length of the formed resin or polymer chain is achieved.
    [0004] [0004] Lignin can be used for the purpose of decreasing the amount of synthetic phenol in a resin composition. Lignin was previously used to replace phenol during the production of lignin - phenol - formaldehyde resin.
    [0005] [0005] It was possible to replace up to 30% of the synthetic phenol in the final resin, for example, phenol formaldehyde resin, with lignin, but greater substitutions result in unsatisfactory properties of the glue produced.
    [0006] [0006] The inventors recognized, therefore, a need for a method, which could result in a greater substitution of phenol in the composition and, therefore, in a more environmentally friendly binder composition having properties suitable for use in different applications. PURPOSE OF THE INVENTION
    [0007] [0007] The purpose of the invention is to provide a new method to increase the reactivity of lignin. In addition, the purpose of the invention is to provide a new type of method, in which the more reactive lignin is used to replace at least part of the amount of synthetic materials used during the production of a binder composition. Especially the purpose is to produce a more environmentally friendly binder composition to be used, for example, in adhesive applications. SUMMARY
    [0008] [0008] The method for increasing the reactivity of lignin according to the present invention is characterized by the fact that it is presented in claim 1.
    [0009] [0009] The lignin obtained by the method according to the present invention is characterized by the fact that it is presented in claim 12.
    [0010] [0010] The method for producing a binder composition according to the present invention is characterized by the fact that it is presented in claim 13.
    [0011] [0011] The binder composition according to the present invention is characterized by the fact that it is presented in claim 18.
    [0012] [0012] The adhesive composition according to the present invention is characterized by the fact that it is presented in claim 19.
    [0013] [0013] The uses according to the present invention are characterized by the fact that it is presented in claims 20 and 21. BRIEF DESCRIPTION OF THE DRAWINGS
    [0014] [0014] The accompanying drawings, which are included to provide a better understanding of the invention and form a part of this specification, illustrate some embodiments of the invention and together with the description helps to explain the principles of the invention. In the drawings:
    [0015] [0015] Fig. 1 is a flow diagram illustration of a method for increasing the reactivity of lignin and the use of lignin having increased reactivity according to an embodiment of the present invention;
    [0016] [0016] Fig. 2 shows the result of differential scanning calorimetry (DSC) measurement of a binder component (resin) produced using alkylated lignin according to the present invention; and
    [0017] [0017] Fig. 3 shows the DSC measurement result of a binder composition (resin) produced using treated lignin according to comparative example 1 DETAILED DESCRIPTION OF THE INVENTION
    [0018] a) formar, sob aquecimento a uma temperatura de 30 -70°C, uma dispersão aquosa que compreende álcali e lignina, em que o álcali compreende um hidróxido de um metal alcalino; e b) aquecer a dispersão formada na etapa a) a uma temperatura de 50 - 95°C para a produção de lignina alquilada. [0018] The present invention relates to a method for increasing the reactivity of lignin, the method of which comprises the following steps: a) forming, under heating at a temperature of 30-70 ° C, an aqueous dispersion comprising alkali and lignin, wherein the alkali comprises an alkali metal hydroxide; and b) heating the dispersion formed in step a) to a temperature of 50 - 95 ° C for the production of alkylated lignin.
    [0019] [0019] A disadvantage of different methods for separating or isolating lignin from, for example, biomass is that lignin is condensed during the process due to the low pH environment used. Thus, the separated lignin has a very low reactivity and a heterogeneous nature, which affects reactions with other reactive components during, for example, the production of a binder composition. The low reactivity of lignin has been one of the reasons that prevents a higher level of substitution, for example, of synthetic phenol in binder compositions with bio-based lignin. It has been recognized that the properties of currently available binder compositions, in which up to 50 - 60% of the synthetic phenol has been replaced with lignin, are not acceptable for, for example, bonding applications. For example, the strength of glued joints was not at the required level.
    [0020] [0020] The inventors have surprisingly found that the reactivity of lignin can be increased by the method of the present invention and that a higher level of substitution of, for example, synthetic phenol in binder compositions can be achieved when using this type of activated lignin during the production of the binder composition.
    [0021] [0021] The term "lignin having increased reactivity" should be understood in this specification, unless otherwise indicated, as referring to the lignin that was treated by the method according to the present invention. The treatment of lignin with the method according to the present invention activates lignin making it more suitable for use in other applications. The reactivity of lignin is thus increased compared to lignin, which has not been treated by the method according to the present invention.
    [0022] [0022] In this specification, unless otherwise stated, the term "lignin" is to be understood as any suitable lignin for use in the present invention.
    [0023] [0023] Lignin may include essentially pure lignin, as well as lignin derivatives and lignin modifications.
    [0024] [0024] The term "essentially pure lignin" should be understood as at least 90% pure lignin, preferably at least 95% pure lignin. In an embodiment of the present invention, essentially pure lignin comprises a maximum of 10%, preferably a maximum of 5%, of other components. Extracts and carbohydrates, such as hemicelluloses, can be mentioned as examples of these other components.
    [0025] [0025] In one embodiment of the present invention, the lignin to be treated by the method according to the present invention is selected from a group consisting of lignin kraft, biomass from lignin, lignin from the alkaline pulping process, lignin from soda process, lignin from the pulping of organosolvents and combinations thereof.
    [0026] [0026] Different components of lignin can have different properties, for example, molecular weight, molar mass, polydispersity, hemicellulose and extractive contents. In one embodiment of the present invention, lignin includes water, but no solvent.
    [0027] [0027] "Lignin kraft" should be understood in this specification, unless otherwise stated, lignin that originates from black kraft liquor. Black liquor is an aqueous alkaline solution of lignin, hemicellulose and inorganic chemicals used in a kraft pulping process. The black liquor from the pulping process comprises components from different species of softwood and hardwood in various proportions. Lignin can be separated from black liquor by different techniques including, for example, precipitation and filtration. Lignin generally starts by precipitating at pH values below 11 - 12. Different pH values can be used to precipitate fractions of lignin with different properties. These lignin fractions differ from each other by a molecular weight distribution, for example, Mw and Mn, polydispersity, hemicellulose and extractive contents. The molar mass of lignin precipitated at a higher pH value is greater than the molar mass of lignin precipitated at a lower pH value. In addition, the molecular weight distribution of a lignin fraction with a lower pH value is wider than that of the precipitated lignin fraction at a higher pH value. Thus, the properties of lignin can be varied, depending on the end use of the bonding application.
    [0028] [0028] The precipitated lignin can be purified from inorganic impurities, hemicellulose and wood extracts using acid washing steps. Additional purification can be achieved by filtration.
    [0029] [0029] In one embodiment of the present invention, the dry matter content of lignin is below 98%, preferably 40 - 80%, and more preferably 50 -70%.
    [0030] [0030] In one embodiment of the present invention, lignin is separated from pure biomass. The separation process can begin with the liquidization of the biomass with strong alkali, followed by a neutralization process. After treatment with alkali, lignin can be precipitated in a similar manner, as shown above. In one embodiment of the present invention, the separation of lignin from biomass comprises an enzyme treatment step. The enzyme treatment modifies the lignin to be extracted from the biomass. Lignin separated from pure biomass is sulfur-free and, therefore, valuable in further treatment.
    [0031] [0031] The alkali comprises an alkali metal hydroxide. In one embodiment of the present invention, alkali is selected from the group consisting of sodium hydroxide, potassium hydroxide and mixtures thereof. In an embodiment of the present invention, the alkali is sodium hydroxide.
    [0032] [0032] In an embodiment of the present invention, the alkali concentration is 5 - 50% by weight, and preferably 10 - 25% by weight based on the total weight of the dispersion in step a).
    [0033] [0033] In one embodiment of the present invention, the concentration of lignin in step a) is 10 - 50% by weight, preferably 20 - 50% by weight, and more preferably 20 - 45% by weight based on the total weight of the dispersion in step a).
    [0034] [0034] In an embodiment of the present invention, the temperature in step a) is preferably 50 - 65 ° C.
    [0035] [0035] In an embodiment of the present invention, the temperature in step b) is preferably 60 - 75 ° C.
    [0036] [0036] In an embodiment of the present invention, step b) is carried out for 15 minutes - 24 hours, preferably during the period of 5 hours, and more preferably for 0.5 - 1.5 hours.
    [0037] [0037] The method according to the present invention, and especially the alkylation steps a) and b) result in the lignin being activated. As discussed above, lignin is condensed during the processes of acid isolation or separation. Without limiting the invention to any specific theory as to why the alkylation of lignin results in the formation of a more reactive lignin, it must be considered that the alkylation opens the macromolecular structure of the lignin through which the steric hindrance, which generally deactivates the reactive groups in the structures of lignin, is removed. Alkylation can also add charged groups to the lignin macromolecule. The disadvantage of using alkylated lignin, for example, for the production of a binder composition is that the reaction behavior and compatibility are much better than in the normal case, where the untreated lignin has been used in the cooking or cooking stage. polymerization.
    [0038] [0038] In an embodiment of the present invention, the method comprises, before step a), step i) of reacting lignin with a compound selected from the class of phenols. In an embodiment of the present invention, the compound is selected from a group consisting of phenol, cresol, resorcinol and combinations thereof. In one embodiment of the present invention, the compound is phenol. By allowing the aliphatic part of lignin to react with, for example, phenol, the number of phenolic OH groups attached to the aliphatic part of lignin is increased. As the number of OH groups increases, the reactivity of lignin during, for example, the cooking step of a binder production method with other components of the reagent is increased. The alkylation advantage of phenolated lignin is that, in addition to having new phenolic OH groups attached to lignin, the lignin structure will be opened as discussed above. The increased reactivity of lignin has the advantage of allowing the replacement of a higher amount of synthetic reagents, such as phenol, with bio-based lignin in the final binder composition.
    [0039] [0039] In an embodiment of the present invention, step i) is carried out at a temperature of 100 - 140 ° C for 1 - 3 hours in the presence of a catalyst. In one embodiment of the present invention, the catalyst used in step i) is an acid, preferably, sulfuric acid (H2SO4).
    [0040] [0040] In an embodiment of the present invention, the method comprises, after step b), step ii) of adding an aldehyde, an aldehyde derivative, or a combination thereof to the dispersion formed in step b). In an embodiment of the present invention, the derivative of an aldehyde is paraformaldehyde. In an embodiment of the present invention, the alkylated lignin is reacted with an aromatic aldehyde, or glyoxal. In one embodiment of the present invention, the aromatic aldehyde is furfuryl aldehyde. In one embodiment of the present invention, the aldehyde is formaldehyde.
    [0041] [0041] In an embodiment of the present invention, the alkylated lignin is reacted with an aldehyde, for example, formaldehyde, in order to form hydroxymethylated lignin. By allowing the alkylated lignin to react with, for example, formaldehyde, the reactivity of lignin is also increased since hydroxymethyl groups are increased, whose groups react easily with the other components of the reagent during, for example, the resin cooking step.
    [0042] [0042] In an embodiment of the present invention, in step ii), the weight ratio of aldehyde to lignin in the dispersion from step b) is 0.2 - 0.7, and preferably 0.3 - 0 , 6.
    [0043] [0043] The present invention also relates to lignin that can be obtained by the method of the present invention. In one embodiment of the present invention, the lignin obtainable by the method of the present invention can be the lignin that has been subjected to alkylation; phenolation and alkylation; alkylation and hydroxymethylation; or to phenolation, alkylation and hydroxymethylation.
    [0044] [0044] The present invention also relates to a method for the production of a binder composition, wherein the method comprises the step of: (iii) cooking an aqueous composition comprising reactive components, including lignin treated in accordance with the present invention, a polymerizable substance and a crosslinking agent in the presence of a catalyst at a temperature of 60 - 95 ° C for polymerization of the reactive components to a binder composition with a predetermined viscosity value will be formed.
    [0045] [0045] In one embodiment of the present invention, the lignin used in the method for producing a binder composition is lignin, which has been alkylated in accordance with the present invention. In one embodiment of the present invention, the lignin used in the method for producing a binder composition is the lignin that has been phenolized and alkylated in accordance with the present invention. In one embodiment of the present invention, the lignin used in the method for producing a binder composition is the lignin that has been alkylated and hydroxymethylated in accordance with the present invention. In one embodiment of the present invention, the lignin used in the method for producing a binder composition is the lignin that has been phenolized, alkylated and hydroxymethylated in accordance with the present invention.
    [0046] [0046] In an embodiment of the present invention, the predetermined viscosity value of the final binder composition is at least 40 cP, preferably at least 50 cP, and more preferably, at least 80 cP. In one embodiment of the present invention, the viscosity value of the final binder composition is at least 40 but not more than 250 cP, preferably at least 50 cP, but not more than 150 cP, and more preferably, at least 80 cP but no more than 120 cP.
    [0047] [0047] In an embodiment of the present invention, the predetermined viscosity value of the final binder composition is at least 250 cP, preferably at least 300 cP, and more preferably, at least 500 cP. In one embodiment of the present invention, the predetermined viscosity value of the final binder composition is at least 250 cP, but not more than 1500 cP, preferably at least 300 cP, but not more than 1200 cP, and more preferably, at least 500cP, but not more than 1,000cP. Viscosity is measured at 25 ° C using a rotating viscome. The predetermined viscosity value of the final binder composition may vary, depending on the specific application in which the binder composition is to be used.
    [0048] [0048] The precise order of the combination and / or addition of the components necessary for the production of binder composition can vary depending, for example, on the required properties of the binder composition formed. The choice of the sequence of the combination and / or addition of the required components is within the knowledge of the person skilled in the art. The precise amount of the components used for the production of the binder composition can vary and the choice of the amounts of the different components is within the knowledge of the person skilled in the art based on this specification. The temperature can be controlled during the production of the binder composition by cooling and / or heating the composition.
    [0049] [0049] The essential feature of the binder production method is that the reactive components, for example, lignin treated in accordance with the present invention, the crosslinking agent and the polymerizable substance, are allowed to react with each other in an aqueous environment in the presence of a catalyst and under heating, in such a way that the reactive components are truly synthesized together and not just physically mixed together.
    [0050] [0050] The method of the present surprising invention results in a more environmentally friendly binder composition since in the binder production method, the natural polymer lignin, which is a phenolic polymer, replaces at least part of the synthetic phenol substance normally used in the production of phenolic compositions, such as phenol formaldehyde resin. Without limiting the invention to any specific theory as to why the process of the present invention results in the above-mentioned advantage, it should be considered that the suitability of substituting at least a part of, for example, phenol with lignin is due to the fact of lignin, whose reactivity was increased by the method of the present invention, to react effectively with an aldehyde, such as formaldehyde, in a very similar way as phenol.
    [0051] [0051] In an embodiment of the present invention, the aqueous composition further comprises tannin as a reactive component.
    [0052] [0052] In one embodiment of the present invention, the tannin used comes from any wood species. The tannin can come, for example, from bark or heartwood. The quebracho tree, beech tree and acacia tree are presented as examples of possible sources of tannin. In one embodiment of the present invention, the tannin used comes from the soft wood bark. In one embodiment of the present invention, the tannin is separated from the soft wood bark of debarking units in sawmills or cellulose plants. The separation process can be combined with an ethanol extraction process, a hot water extraction process, a hot steam extraction process or a soft wood bark water-ethanol extraction process. In one embodiment of the present invention, the tannin is condensed tannin. Condensed tannin has a high dry matter content and is therefore suitable for use in the present invention. The dry matter content of condensed tannins can vary between 40 - 100% and is suitably between 60 - 90% and, preferably, between 70 - 80%. Tannin with a dry matter content can be easily dispersed, whereby good reactivity with the other components of reagents is achieved. The tannin can also be hydrolyzable tannin.
    [0053] [0053] In an embodiment of the present invention, step (iii) comprises cooking the composition, preferably at a temperature of 65 - 90 ° C, and more preferably at a temperature of 75 - 85 ° C.
    [0054] [0054] In one embodiment of the present invention, the crosslinking agent is selected from a group consisting of an aldehyde, an aldehyde derivative, an aldehyde-forming compound and combinations thereof. In an embodiment of the present invention the derivative of an aldehyde is hexamethylene tetramine, para-formaldehyde or trioxane. In one embodiment of the present invention, the crosslinking agent is selected from a group consisting of an aromatic aldehyde, glyoxal, furfuryl alcohol, caprolactam and glycol compounds. The aldehyde can be formaldehyde. The aromatic aldehyde can be furfuryl aldehyde. In one embodiment of the present invention, the cross-linking agent is a bio-based cross-linking agent. In one embodiment of the present invention, the cross-linking agent is an aldehyde, and preferably formaldehyde.
    [0055] [0055] In one embodiment of the present invention, the polymerizable substance is selected from a group consisting of phenol, cresol, resorcinol and combinations thereof. In one embodiment of the present invention the polymerizable substance is phenol. In one embodiment of the present invention, the polymerizable substance is selected from a group consisting of bio-based hydroxyphenols and their derivatives. In one embodiment of the present invention, the polymerizable substance is a bio-based polymerizable substance. In one embodiment of the present invention, the polymerizable substance is selected from a group consisting of lignin and tannin.
    [0056] [0056] In one embodiment of the present invention, the catalyst in step iii) comprises an alkali metal salt or hydroxide. In one embodiment of the present invention, the catalyst in step iii) is selected from the group consisting of sodium hydroxide, potassium hydroxide, acids and any mixture thereof. In one embodiment of the present invention, the catalyst in step iii) is sodium hydroxide.
    [0057] [0057] In one embodiment of the present invention, the relationship between the amounts of lignin, catalyst / solvent, polymerizable substance, and crosslinking agent, based on their dry content, used to produce the binder composition is as follows: 18-70 % by weight, preferably 26-45% by weight of crosslinking agent and catalyst / solvent, and 82-30% by weight, preferably 74-55% by weight, of the polymerizable substance and lignin.
    [0058] [0058] The present invention also relates to a binder composition that can be obtained by the method of the present invention.
    [0059] [0059] The present invention also relates to an adhesive composition comprising the binder composition according to the present invention. The adhesive composition may further comprise one or more adhesive components selected from a group consisting of other binders, diluents, additives, catalysts and fillers. A binder is a substance, which is primarily responsible for creating the growth and crosslinking of polymers and thus helps in curing polymer systems. A diluent is a substance that helps the binder by adjusting its physical properties, for example, by adjusting the humidity. The additive can be a polymer or an inorganic compound, which helps with properties such as filling, softening, reducing costs, adjusting humidity, increasing rigidity and increasing flexibility. The catalyst is a substance, which generally strengthens and adjusts the cure speed. By "substance" is here to be understood as including a compound or composition. The binder composition of the present invention can serve as a binder, diluent, additive, catalyst and / or filler in the adhesive composition.
    [0060] [0060] The present invention also relates to the use of the binder composition in an impregnation application, such as a coating, for the reinforcement of plastic, for the production of a compressed molding, a molding, a laminate or a lacquer, or for gluing a wooden product. The binder composition of the present invention can also be used for bonding combinations of plastic and wood.
    [0061] [0061] The present invention also relates to the use of the adhesive composition of the present invention for bonding a wood product.
    [0062] [0062] In one embodiment of the present invention, the wooden product is selected from a group consisting of a wooden plate, a wooden laminate, and a wooden bar.
    [0063] [0063] In one embodiment of the present invention, a layered composite structure can be formed of two or more layers including at least one layer of wood laminate, in which the layers are arranged one above the other and combined by means of gluing with the binder composition according to the present invention and / or the adhesive composition according to the present invention. In this specification, unless otherwise indicated, the term "wood laminate" is used to treat a laminate, which can be formed of any material, for example, wood-based material, fiber material, composite material or the like. In this context, the thickness of the wood laminate can be varied. Typically, the thickness of the wood laminate is less than 3 mm.
    [0064] [0064] In one embodiment of the present invention, the layered composite structure is selected from a group consisting of a wood panel product, a plywood product, a composite product, and a pressed panel product. The layered composite structure can be formed by a series of layers, preferably layers of wood laminate, in which the layers are placed on top of each other and glued together.
    [0065] [0065] The modalities of the invention described here can be used in any combination with each other. Several of the embodiments can be combined together to form another embodiment of the invention. A method, composition or use, to which the invention is related, may comprise at least one of the embodiments of the invention described hereinbefore.
    [0066] [0066] An advantage of the method according to the present invention is that the reactivity of lignin, for example, separated from biomass can be significantly increased and also the heterogeneous nature of lignin can be decreased.
    [0067] [0067] An advantage of the present invention is that the reactivity of lignin can be increased by the method, and especially the alkylation step, according to the present invention. Lignin treated with the method according to the present invention has a greater number of reactive groups along the lignin structure compared to untreated lignin.
    [0068] [0068] An advantage of the method according to the present invention is that, using lignin, the reactivity of which has been increased by the method of the present invention, as a reactive component during the production of a binder composition a more environmentally favorable binder composition is achieved. Surprisingly, it has been found that when using this type of lignin as a reagent component, the amount of the polymerizable substance, such as the synthetic phenol substance, for example, phenol, can be significantly decreased during the binder production process. As phenol is a synthetic compound and lignin is a natural polymer, it is advantageous to be able to minimize the amount of phenol present in the final binder composition. The advantage of reducing the amount of synthetic materials is that a higher level of bio-based components is achieved in the final binder composition.
    [0069] [0069] An advantage of the present invention is that, using lignin having increased reactivity compared to untreated lignin, the properties of the final binder composition are more favorable for bonding applications. Lignin treated with the method according to the present invention increases the cure, adhesion and tensile strength performance of the binder composition. An advantage of the present invention is that the bonding performance of the binder composition or adhesive composition produced is suitable for using the composition, for example, in outdoor applications.
    [0070] [0070] An advantage is that when using lignin, which has a greater reactivity than normal, untreated lignin results in even better compatibility and reaction behavior of the binder production method according to the present invention. EXAMPLES
    [0071] [0071] Reference will now be made in detail to the modalities of the present invention, an example of which is illustrated in the attached drawings.
    [0072] [0072] The description that follows describes some embodiments of the invention in detail so that one skilled in the art is able to use the invention based on disclosure. Not all stages of the modalities are discussed in detail, as many of the stages will be obvious to the person skilled in the art based on this specification.
    [0073] [0073] Figure 1 illustrates a method according to some modalities of the present invention to increase the reactivity of lignin and the additional use of lignin.
    [0074] [0074] Fig. 1 shows different combinations of treatment steps, which can be used to increase the reactivity of lignin. Fig. 1 illustrates the phenolation step i), the alkylation steps a) and b) and the hydroxymethylation step ii) and combinations thereof for the treatment of lignin. Lignin having increased reactivity compared to untreated lignin can still be used in the synthesis of a binder composition, step iii) of Fig. 1, or can be used for any other suitable application, as illustrated in Fig. 1.
    [0075] [0075] Before any of the treatment steps the source of lignin is chosen. As shown above, lignin can be selected from kraft lignin, lignin from biomass, lignin from the alkaline pulping process, lignin from the soda process, the lignin from the organosolvent pulping, and combinations thereof. In addition, the other components and their quantities to be used in the method according to the invention are selected. If necessary, the components used in the method of Fig. 1 can be pretreated to be suitable for lignin treatment processes.
    [0076] [0076] After the various preparations and pretreatments, in one of the modalities of the present invention shown in Fig. 1, step i) is performed. Step i) comprises reacting lignin with a compound selected from the class of phenols in the presence of a catalyst. As a result of step i) of phenolation, the reactive phenolic OH groups are linked to the aliphatic portion of lignin.
    [0077] [0077] After step i), step a) must be performed. Alternatively, lignin can be treated directly according to step a), without first being treated according to step i), as shown in Fig. 1.
    [0078] [0078] Step a) comprises the formation of an aqueous dispersion comprising alkali and lignin under heating. The alkali comprises an alkali metal hydroxide. Then, step b) is carried out by heating the dispersion formed to a temperature of 50-95 ° C. Step a) and step b) result in the lignin being activated through alkylation.
    [0079] [0079] After step b) the fraction of alkylated lignin can be introduced in the cooking step of the binder composition production method, during which said lignin is polymerized with the other reagent components used in the binder composition production method ( step iii) of Fig. 1).
    [0080] Alternatively, the alkylated lignin from step b) can be further reacted with an aldehyde in step ii), before being introduced into the synthesis of the binder composition. Step ii) is carried out by adding, for example, formaldehyde to the alkylated lignin dispersion of step b), which results in the formation of a hydroxymethylated product.
    [0081] [0081] As a result of step iii) a binder composition having the desired properties and especially being mostly based on bio-based components is produced. This binder composition can be used as such for bonding applications or it can be further processed with other adhesive components to produce an adhesive composition.
    [0082] [0082] As shown above, in addition to using the alkylated lignin of step b) or the hydroxymethylated lignin of step ii) in a method for the production of a binder composition, the alkylated lignin or the hydroxymethylated lignin can be used as such in any another suitable application. EXAMPLE 1 - Alkylation
    [0083] [0083] In this example, the reactivity of lignin has been increased by the alkylation of lignin. The following components and their quantities were used:
    [0084] [0084] First, the water and NaOH were mixed and heating of the mixture was started. Then, the lignin was slowly dispersed in the mixture of alkali and water, with stirring and, simultaneously, the temperature was increased to 60 ° C. When all of the lignin was dispersed, the dispersion was heated to a temperature of about 75 ° C for 1.5 hours. As a result, lignin became alkylated.
    [0085] [0085] The lignin treated in accordance with Example 1 was then used for the production of a binder composition. 38 g of phenol (90%) was mixed with 105 g of alkylated lignin, after which 79 g of formaldehyde (37%) were added gradually. NaOH was used as a catalyst. The temperature was kept below 75 ° C. Thereafter, cooking was maintained at 85 - 90 ° C until the viscosity of the composition formed was about 415 cp (measured at a temperature of 25 ° C).
    [0086] [0086] The composition or binder resin formed was then subjected to DSC measurements, the results of which can be seen in Fig. 2.
    [0087] [0087] A comparative example 1 was formed using lignin which was treated as follows:
    [0088] [0088] The following components and their values were used:
    [0089] [0089] First, the water and NaOH were mixed and heating of the mixture was started. Then, the lignin was added to the mixture of alkali and water, with stirring, and, simultaneously, the temperature was increased to 95 ° C. When lignin was added, the mixture was heated to a temperature of about 90 ° C for 1 hour.
    [0090] [0090] The lignin of comparative example 1, was used to produce a comparative binder composition 1 in a similar manner as described above. The comparative binder composition formed was also subjected to DSC measurements.
    [0091] [0091] The results of the DSC measurements of comparative binder composition 1 are shown in Fig. 3.
    [0092] [0092] As can be seen from Fig. 2, the binder composition formed using alkylated lignin according to the present invention shows only a distinct peak. On the contrary, as can be seen from Fig. 3, the comparative binder composition showed several peaks.
    [0093] [0093] The distinct peak of Fig. 2 indicates that the alkylated lignin reacted with phenol and formaldehyde to form a homogeneous and uniform polymeric structure. The various distinct peaks in Fig. 3 indicate that phenol and formaldehyde react without a reaction with the alkylated lignin or only partially in conjunction with the alkylated lignin.
    [0094] [0094] Without limiting the invention to any specific theory as to why the alkylation of lignin according to the present invention results in this advantageous result, it should be considered that the alkylated lignin according to comparative example 1 remains in its form original particles or is agglomerated into larger clusters where the alkylation process is able to affect only the surface of such clusters or particles. The alkylation of lignin according to the present invention results in the lignin being well dispersed or dissolved when the alkylation process begins. Since a major part or area of lignin is alkylated, the reactivity of lignin is increased compared to the alkylated lignin according to the process of the comparative example. As lignin has an increased reactivity, it will easily react with the other reactive components during the production of the binder composition. EXAMPLE 2 - Alkylation, Low Temperature
    [0095] [0095] In this example, the reactivity of lignin was increased by alkylation of lignin. The following components and their values were used:
    [0096] [0096] First, the water and NaOH were mixed and heating of the mixture was started. Then, the lignin was slowly dispersed in the mixture of alkali and water, with stirring, and, simultaneously, the temperature was increased to 60 ° C. When all of the lignin was dispersed, the dispersion was heated to a temperature of about 60 ° C for about 1 hour. As a result, lignin became alkylated. EXAMPLE 3 - Alkylation, High Temperature
    [0097] [0097] In this example, the reactivity of lignin has been increased by the alkylation of lignin. The following components and their values were used:
    [0098] [0098] First, the water and NaOH were mixed and heating of the mixture was started. Then, the lignin was slowly dispersed in the mixture of alkali and water, with stirring, and, simultaneously, the temperature was increased to 60 - 70 ° C. When all the lignin was dispersed, the dispersion was heated to a temperature of about 90 - 95 ° C for about 1 hour. As a result, lignin became alkylated. EXAMPLE 4 - Phenolation in combination with alkylation and use of treated lignin for the production of a binder composition
    [0099] [0099] In this example, the reactivity of lignin was increased by phenolation and alkylation of the lignin, in which after the lignin was treated it was used to produce a binder composition.
    [0100] [0100] First, phenolation was performed. The following components and their values were used:
    [0101] [0101] Water, phenol and lignin were mixed under stirring for about 5 - 10 minutes after which H2SO4 was added. Then, the temperature was slowly increased to 135 ° C over a period of about 3 hours and maintained at that temperature for about an hour. Then, the mixture was cooled and the treatment ended resulting in phenolized lignin.
    [0102] [0102] The phenolated lignin was then alkylated. 430 g of phenolated lignin was mixed with 150 g of 50.0% NaOH under heating. Then, the dispersion was heated to a temperature of 75 ° C for about 1 hour.
    [0103] [0103] As a result of the above treatments, phenolated and alkylated lignin was formed.
    [0104] [0104] After the phenolation and alkylation treatments, 38 g of water and 38 g of phenol (90%) were added to the composition, after which 368 g of formaldehyde (39.3%) were added gradually. The temperature was kept below 75 ° C. Thereafter, cooking was continued at 85 - 90 ° C until the viscosity of the composition formed was about 415 cp (as measured at a temperature of 25 ° C). EXAMPLE 5 - Alkylation in combination with hydroxymethylation and use of treated lignin to produce a binder composition
    [0105] [0105] In this example, the reactivity of lignin was increased by alkylation and hydroxymethylation to lignin, where after the lignin was treated it was used to produce a binder composition. The following components and their values were used:
    [0106] [0106] First, the water and NaOH were mixed and heating of the mixture was started. Then, the lignin was slowly dispersed in the mixture of alkali and water, with stirring, and at the same time, the temperature was increased to about 75 ° C. When all the lignin was dispersed, the dispersion was heated to about 75 ° C for about 1 hour. As a result, lignin became alkylated. Then, formaldehyde was added to the dispersion and the reaction was allowed to continue for about 1 hour, resulting in the structure of the lignin being hydroxymethylated.
    [0107] [0107] The treated lignin was used to produce a binder composition. Phenol was added to the composition, followed by the addition of formaldehyde and then NaOH. The cooking of the formed composition was continued, with the addition of NaOH, at a temperature of 70-90 ° C until the viscosity of the formed composition was about 300 cp (as measured at a temperature of 25 ° C). EXAMPLE 7 - Preparation of an Adhesive Composition
    [0108] [0108] In this example, the binder composition produced in Example 4 was used to produce an adhesive composition. The binder composition was mixed with diluents, fillers, catalysts, additives, such as, for example, starch, wood flour and hardening agent (for example, tannins or carbonates), thus forming the adhesive composition. EXAMPLE 8 - Application of the Binder Composition for the Production of a Plywood Product
    [0109] [0109] Laminates of wood having a thickness below 3 mm were glued together with the binder composition produced in Example 5 for the production of a 7-plywood. The results showed that the bonding effect was good enough to glue wood veneers. EXAMPLE 9 - Application of the Adhesive Composition to Produce a Plywood Product
    [0110] [0110] In this example, the adhesive composition of Example 7 was applied to wood laminates. The wood laminates were joined by the adhesive composition to form a plywood. The dry matter content of the adhesive composition was between 45 and 55%. The laminated wood with the adhesive composition was pressed by the hot pressing technique, at a temperature between 120 - 170 ° C. The adhesive composition was cured simultaneously. The adhesive composition of the present invention was found to be suitable for bonding wood laminates together and thus for the manufacture of plywood. EXAMPLE 10 - Application of the Binder Composition for the Production of Laminates
    [0111] [0111] In this example, the binder composition as produced in Example 4 was used in an impregnation application. During the production of laminates the paper was impregnated with an alcoholic solution of the binder composition, after which the impregnated layers were transferred to an oven. The alcohol was volatilized and the binder composition was partially cured. The layers comprising such a semi-cured composition were arranged on top of each other and baked by a hot pressing technique in order to form uniform thick plates or laminates.
    [0112] [0112] In the binder production method presented in the examples above, phenol and formaldehyde are used. However, any other polymerizable substance or crosslinking agent can be used equally well in the method of producing binder composition, as will be obvious to the person skilled in the art based on this specification.
    [0113] [0113] It is obvious to a person skilled in the art that with the advancement of technology, the basic idea of the invention can be implemented in several ways. The invention and its modalities, therefore, are not limited to the examples described above; instead, they may vary within the scope of the claims.
    权利要求:
    Claims (16)
    [0001]
    Method for increasing the reactivity of lignin, characterized by the fact that the method comprises the following steps: a) forming, under heating at a temperature of 30-70 ° C, an aqueous dispersion comprising alkali and lignin, wherein the alkali comprises an alkali metal hydroxide; and b) heating the dispersion formed in step a) to a temperature of 50 - 95 ° C to produce alkylated lignin.
    [0002]
    Method according to claim 1, characterized by the fact that the alkali concentration is 5 - 50% by weight, based on the total weight of the dispersion in step a).
    [0003]
    Method according to claim 1 or 2, characterized by the fact that the temperature in step a) is 50 - 65 ° C.
    [0004]
    Method according to any one of claims 1 to 3, characterized in that the temperature in step b) is 60 - 75 ° C.
    [0005]
    Method according to any one of claims 1 to 4, characterized in that the method comprises, before step a), step i) of reacting lignin with a compound selected from the class of phenols.
    [0006]
    Method according to any one of claims 1 to 5, characterized in that the method comprises, after step b), step ii) of adding an aldehyde, an aldehyde derivative, or a combination thereof to the dispersion formed in step b).
    [0007]
    Lignin, characterized by the fact that it is obtainable by the method, as defined in any one of claims 1 to 6.
    [0008]
    Method for the production of a binder composition, characterized by the fact that the method comprises the step of: (iii) cooking an aqueous composition comprising reagent components including the lignin obtainable by the method, as defined in any one of claims 1 to 6, a polymerizable substance and a crosslinking agent in the presence of a catalyst at a temperature of 60 - 95 ° C for polymerization of the reactive components until a binder composition, with a predetermined viscosity value, is formed.
    [0009]
    Method according to claim 8, characterized in that step (iii) comprises cooking the composition at a temperature of 65 - 90 ° C.
    [0010]
    Method according to claim 8 or 9, characterized in that the crosslinking agent is an aldehyde.
    [0011]
    Method according to any of claims 8 to 10, characterized by the fact that the polymerizable substance is selected from a group consisting of phenol, cresol, resorcinol and combinations thereof.
    [0012]
    Method according to any one of claims 8 to 11, characterized in that the catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide and any mixture thereof.
    [0013]
    Binder composition, characterized by the fact that it is obtainable by the method, as defined in any one of claims 8 to 12.
    [0014]
    Adhesive composition, characterized by the fact that it comprises the binder composition, as defined in claim 13.
    [0015]
    Use of the binder composition, as defined in claim 13, characterized by the fact that it is for an impregnation application, such as a coating, for the reinforcement of plastic, for the production of a compressed impression, a laminate or a lacquer, or for the bonding of a wooden product.
    [0016]
    Use of the adhesive composition, as defined in claim 14, characterized by the fact that it is for gluing a wooden product.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/03/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-06-08| B17A| Notification of administrative nullity (patentee has 60 days time to reply to this notification)|Free format text: REQUERENTE DA NULIDADE: OTTO BANHO LICKS - 870210049476 - 31/05/2021 |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20125358|2012-03-29|
    FI20125358A|FI123936B2|2012-03-29|2012-03-29|A method for increasing the reactivity of lignin|
    PCT/FI2013/050353|WO2013144454A1|2012-03-29|2013-03-28|A method for increasing the reactivity of lignin|
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