• 专利附录
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    • 专利摘要:
    USE OF LIGNINE OF LOW MOLECULAR WEIGHT WITH LIGNIN FOR THE PRODUCTION OF A PHENOL-FORMALDEHYDE BINDING COMPOSITION. The present invention relates to a method for producing a binder composition, wherein the method comprises the following steps: (i) forming an aqueous composition comprising reagent components that include lignin molecules from 11 to 60 units of lignin , lignin molecules from 1 to 10 lignin units, polymerizable substance and crosslinking agent in the presence of a catalyst; and (ii) cooking the composition at a temperature of 60 to 95 (degrees celsius) to polymerize the reagent components until a binder composition with a predetermined viscosity value is formed.
    公开号:BR112014023873B1
    申请号:R112014023873-1
    申请日:2013-03-28
    公开日:2021-02-02
    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:

    FIELD OF THE INVENTION
    [001] The invention relates to a method for the production of a binder composition, to a binder composition and to applications other than the binder composition. BACKGROUND OF THE INVENTION
    [002] Lignin is a natural polymer, which can be extracted from, for example, wood. Since lignin is a natural biopolymer, its use as a component in glues instead of synthetic materials has been investigated in order to present a more environmentally friendly adhesive composition. In particular, the ability to replace synthetic phenol in phenolic resins, such as phenol formaldehyde resin, was the aim of the prior art.
    [003] Different types of adhesive compositions, such as phenolic glues, can be used with wood products. Examples of such adhesives include compositions that comprise phenol formaldehyde resin. Traditionally, synthetic phenol formaldehyde resins are produced by polymerizing 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 stepwise manner to a phenol composition and thereafter increasing the temperature of the formed composition to 80 to 90 ° C. The composition is baked at this temperature until a desired viscosity of the formed resin or a polymer chain length is reached.
    [004] 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.
    [005] It was possible to replace up to 30% of the synthetic phenol in the final resin, for example, the phenol formaldehyde resin, with lignin, but the superior substitution resulted in unsatisfactory properties of the glue produced.
    [006] The inventors recognized, therefore, a need for a method, which can result in a superior phenol substitution in the composition and consequently in a more ecological binder composition that has properties suitable for use in different applications. PURPOSE OF THE INVENTION
    [007] The purpose of the invention is to provide a new type of method to replace at least part of the amount of synthetic materials used during the production of a binder composition. In particular, the purpose is to produce a more environmentally friendly binder composition to be used, for example, in adhesive applications. SUMMARY
    [008] The method according to the present invention is characterized by what is presented in claim 1.
    [009] The binder composition according to the present invention is characterized by what is presented in claim 16.
    [010] The adhesive composition according to the present invention is characterized by what is presented in claim 17.
    [011] The uses according to the present invention are characterized by what is presented in claims 18 and 19. BRIEF DESCRIPTION OF THE DRAWINGS
    [012] The attached drawings, which are included to provide a better understanding of the invention and form a part of this specification, illustrate some modalities of the invention and together with the description help to explain the principles of the invention. In the drawings:
    [013] Figure 1 is a flowchart illustration of a method according to an embodiment of the present invention; and
    [014] Figure 2 is a flowchart illustration of a method according to another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION
    [015] The present invention relates to a method for the production of a binder composition, wherein the method comprises the following steps:
    [016] (i) forming an aqueous composition comprising the reagent components which include lignin molecules from 11 to 60 units of lignin, lignin molecules from 1 to 10 units of lignin, the polymerizable substance and the crosslinking agent in the presence of a catalyst; and
    [017] (ii) baking the composition at a temperature of 45 to 95 ° C to polymerize the reagent components until a binder composition with a predetermined viscosity value is formed.
    [018] The term “lignin molecules from 11 to 60 units of lignin” should be understood in this specification, unless otherwise indicated, as referring to high molecular weight lignin. The term “lignin molecules from 1 to 10 units of lignin” should be understood in this specification, unless otherwise indicated, as referring to low molecular weight lignin.
    [019] The present invention relates to a method for the production of a binder composition, in which the method comprises the following steps:
    [020] (i) forming an aqueous composition comprising reagent components which include high molecular weight lignin, low molecular weight lignin, the polymerizable substance and the crosslinking agent in the presence of a catalyst; and
    [021] (ii) baking the composition at a temperature of 45 to 95 ° C to polymerize the reagent components until a binder composition with a predetermined viscosity value is formed;
    [022] where the high molecular weight lignin comprises lignin molecules of 11 to 60 units of lignin, and where the low molecular weight lignin comprises lignin molecules of 1 to 10 units of lignin.
    [023] The term “high molecular weight lignin” should be understood in this specification, unless otherwise indicated, as comprising the lignin molecules of 11 to 60 units of lignin.
    [024] The term “low molecular weight lignin” should be understood in this specification, unless otherwise indicated, as comprising lignin molecules of 1 to 10 units of lignin.
    [025] The term “lignin unit” should be understood in this specification, unless otherwise indicated, as phenylpropane. Phenylpropane can comprise OH and / or OMe groups attached to it. The lignin units are cross-linked to each other via ether bonds. A phenylpropane comprises nine carbon atoms.
    [026] A disadvantage of different methods for separating or isolating lignin from biomass, for example, is that lignin is condensed during the procedure due to the low pH environment used. Consequently, the separated lignin has a very low reactivity and a heterogeneous nature, which affects reactions with other reagent components during the production of a binder composition. The low reactivity of lignin was one of the reasons that prevents a higher level of substitution of synthetic phenol, for example, in bio-based lignin binder compositions. It has been recognized that the properties of currently available binder compositions, in which up to 50 to 60% of the synthetic phenol has been replaced by lignin, are not acceptable, for example, for bonding applications. For example, the strength of glued joints was not at the required level.
    [027] The inventors surprisingly observed that using low molecular weight lignin in combination with a fraction of high molecular weight lignin during the production of a binder composition, a higher substitution level, for example, of synthetic phenol in binder compositions can be achieved. It has been found that the use of low molecular weight lignin, which is recognized as more reactive compared to high molecular weight lignin, for example, intensifies the reactions that occur during the composition of binder production.
    [028] In one embodiment of the present invention, high molecular weight lignin is separated from black liquor, kraft lignin, biomass origin lignin, alkaline pulping process lignin, soda process lignin, organosolv pulping lignin or a combination of them. In one embodiment of the present invention, low molecular weight lignin is separated from black liquor, kraft lignin, biomass origin lignin, alkaline pulping process lignin, soda process lignin, organosolv pulping lignin or a combination of themselves.
    [029] Low molecular weight lignin as well as high molecular weight lignin can be separated from different sources using different types of methods or procedures. Low molecular weight lignin can be separated, for example, from lignin kraft by ultrafiltration, nanofiltration or by sequential precipitation. Low molecular weight lignin can also be separated from black liquor, for example, by ultrafiltration.
    [030] In this specification, unless otherwise indicated, the term "lignin" should be understood as any lignin suitable for use in the present invention.
    [031] Lignin may include essentially pure lignin as well as lignin derivatives and modifications of lignin.
    [032] 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. Extractives and carbohydrates such as hemicelluloses can be mentioned as examples of such other components.
    [033] By "kraft lignin", this specification should be understood, unless otherwise indicated, for 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 that originate from different hardwood and softwood species in various proportions. Lignin can be separated from black liquor by different techniques that include, for example, precipitation and filtration. Lignin normally starts to precipitate at pH values below 11 to 12. Different pH values can be used to precipitate fractions of lignin with different properties. These lignin fractions differ by molecular weight distribution, for example, Mw and Mn, levels of polydispersity, hemicellulose and extracts. 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. Furthermore, the molecular weight distribution of the precipitated lignin fraction at a lower pH value is wider than that of the precipitated lignin fraction at a higher pH value. Consequently, the properties of lignin can be varied depending on the end use of the bonding application.
    [034] The precipitated lignin can be purified from organic impurities, hemicellulose and wood extracts with the use of acid washing steps. In addition, purification can be achieved by filtration.
    [035] In one embodiment of the present invention, the dry matter content of lignin, for example, lignin, is below 98%, preferably 40 to 80% and more preferably 50 to 70%.
    [036] In one embodiment of the present invention, lignin is separated from pure biomass. The separation process can begin with liquefying the biomass with strong alkali followed by a neutralization process. After alkaline treatment, 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 biomass. Lignin separated from pure biomass is sulfur-free and, consequently, valuable in further processing.
    [037] 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 predetermined 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 but no more than 120 cP.
    [038] 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 1,500 cP, preferably at least 300 cP but not more than 1,200 cP, and more preferably at least 500 but not more than 1000 cP. Viscosity is measured at 25 ° C using a rotation viscometer. 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.
    [039] In one embodiment of the present invention, high molecular weight lignin is alkylated before being used in the method for producing a binder composition. In one embodiment of the present invention, the low molecular weight lignin is alkylated before being used in the method for producing a binder composition. Alkylation of lignin makes lignin more reactive. In one embodiment, the alkylation comprises forming, under heating at a temperature of 30 to 70 ° C, an aqueous dispersion comprising alkali and lignin, and heating the dispersion formed at a temperature of 50 to 95 ° C for 15 minutes - 2 hours to produce alkylated lignin. The alkali may comprise an alkali metal hydroxide. The treatment of lignin by alkylation activates lignin, making it more suitable for use in additional applications.
    [040] In one embodiment of the present invention, the weight ratio of lignin molecules from 11 to 60 lignin units to lignin molecules from 1 to 10 lignin units is 0.1 to 20, preferably 0.2 to 10, and most preferably 0.5 to 5.
    [041] In one embodiment of the present invention, step (i) of forming the aqueous composition comprises the following steps:
    [042] (ia) form a dispersion comprising lignin molecules of 11 to 60 units of lignin; and
    [043] (ib) combining the polymerizable substance and the crosslinking agent with the dispersion to form the aqueous composition.
    [044] In an embodiment of the present invention, step (ib) comprises adding the catalyst.
    [045] In one embodiment of the present invention, step (i) of forming the aqueous composition comprises, after step (ib), the following steps:
    [046] (ic) baking the formed composition until the composition has a viscosity, which corresponds to 15 to 70% of a predetermined viscosity value of the final binder composition; and
    [047] (id) add lignin molecules from 1 to 10 units of lignin as a reagent component to the composition.
    [048] In one embodiment of the present invention, step (ia) and / or step ib) comprises adding the lignin molecules from 1 to 10 units of lignin as a reagent component.
    [049] In an embodiment of the present invention, step (ia) comprises dissolving the lignin in a solvent. In one embodiment of the present invention, the solvent comprises sodium hydroxide. In an embodiment of the present invention, step (ia) comprises adding water.
    [050] The temperature of the dispersion may increase during stage (ia) from room temperature up to 70 ° C.
    [051] In one embodiment, the entire amount of the polymerizable substance, for example, phenol, used is added at once to the composition. In one embodiment of the present invention, the crosslinking agent, for example, aldehyde, is added in a stepwise manner. The addition of the aldehyde in a stepwise manner ensures that the temperature of the composition is not raised too much or too quickly.
    [052] In an embodiment of the present invention, step (i) comprises maintaining the composition at a maximum temperature of 75 ° C.
    [053] In an embodiment of the present invention, step (ic) comprises maintaining the temperature of the composition between 40 to 95 ° C, preferably between 50 to 85 ° C, and more preferably between 60 to 80 ° C.
    [054] In an embodiment of the present invention, the temperature of the composition is decreased below 85 ° C, and preferably below 65 ° C before step (id).
    [055] In an embodiment of the present invention, step (ii) comprises baking the composition preferably at a temperature of 50 to 85 ° C, and more preferably at a temperature of 60 to 80 ° C.
    [056] In an embodiment of the present invention, the temperature of the composition is increased to 45 to 95 ° C, preferably to 50 to 85 ° C, and more preferably to 60 to 80 ° C, before, during or after the step (id ).
    [057] The temperature can be controlled during the production of the binder composition by cooling and / or heating the composition.
    [058] In one embodiment of the present invention, the weight ratio of lignin molecules from 11 to 60 lignin units and lignin molecules from 1 to 10 lignin units to the polymerizable substance is at least 0.2, preferably at least minus 1, and more preferably at least 5.
    [059] In an embodiment of the present invention, the amount of lignin molecules from 1 to 10 units of lignin is 1 to 95%, preferably 3 to 60%, and more preferably 5 to 30%, of the amount of lignin molecules of 11 to 60 lignin units.
    [060] In one embodiment of the present invention, the relationship between the quantities of lignin molecules from 11 to 60 lignin units, catalyst / solvent, polymerizable substance, crosslinking agent and lignin molecules from 1 to 10 lignin units, with based on their dry contents used for the production of the binder composition is as follows: 18 to 60% by weight, preferably 26 to 45% by weight, crosslinking agent and catalyst / solvent, and 82 to 40% by weight , preferably 74 to 55% by weight, of the polymerizable substance, lignin molecules of 11 to 60 units of lignin and lignin molecules of 1 to 10 units of lignin.
    [061] In one embodiment of the present invention, the crosslinking agent is selected from the 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 hexamethylenetetramine, paraformaldehyde or trioxane. In one embodiment of the present invention, the cross-linking agent is selected from the 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.
    [062] In one embodiment of the present invention, the polymerizable substance is a compound selected from the class of phenols. In one embodiment of the present invention, the polymerizable substance is selected from the 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 the group consisting of bio-based hydroxyphenols and derivatives thereof. 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 the group consisting of lignin and tannin.
    [063] In an embodiment of the present invention, step (i) comprises tannin as a reagent component.
    [064] In one embodiment of the present invention, the tannin used originates from any type of wood. Tannin can originate, for example, from bark or heartwood. The Quebracho, beech and acacia trees are presented as examples of possible sources of tannin.
    [065] In one embodiment of the present invention, the tannin used originates from soft wood bark. In one embodiment of the present invention, the tannin is separated from soft wood bark from debarking units in sawmills or pulp mills. The separation process can be combined with an ethanol extraction process, a hot water extraction process, a hot steam extraction process or a coniferous bark water-ethanol extraction process.
    [066] In one embodiment of the present invention, the tannin is condensed tannin. Condensed tannin has a high dry content and is therefore suitable for use in the present invention. The dry matter content of condensed tannin can vary between 40 to 100% and is suitably between 60 to 90% and preferably between 70 to 80%. Tannin with such a dry matter content can be easily dispersed, whereby good reactivity with the other reagent components is achieved. The tannin can also be hydrolyzable tannin.
    [067] In one embodiment of the present invention, the method comprises dispersing the tannin before adding it to the composition. If the amount of tannin to be used in the production of the binder composition is greater than 3%, preferably greater than 5%, more preferably greater than 8% of the total dry matter content of the components to be used for the production of the binder composition, then the tannin is dispersed before it is added to the composition.
    [068] The method of the present invention surprisingly results in a more environmentally friendly binder composition since, in the method, natural polymer lignin, which is a phenolic polymer, has replaced at least part of the synthetic phenol substance normally used in the production of compositions phenolic compounds such as formaldehyde phenol resin. Without limiting the invention to any specific theory as to why the method of the present invention results in the aforementioned advantage, it should be considered that the suitability of replacing at least part of, for example, phenol with lignin is due to the fact that the lignin reacts with an aldehyde, such as formaldehyde, in a very similar way as phenol. The use of especially low molecular weight lignin as a reactive additive in the method of the present invention enhances the bonding properties of this type of lignin-based phenolic composition.
    [069] In one embodiment of the present invention, the catalyst comprises an alkali metal salt or hydroxide. In one embodiment of the present invention, the catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, acids and combinations thereof. In one embodiment of the present invention, the catalyst is sodium hydroxide.
    [070] The precise order of combining and / or adding the components necessary for the production of binder composition can vary depending, for example, on the required properties of the formed binder composition. The choice of the sequence of combination and / or addition of the required components is within the knowledge of the individual versed on the basis of this specification. The precise amount of the components used for the production of the binder composition can vary and the choice of the quantities of the different components is within the knowledge of the skilled person based on this specification.
    [071] When determining the order of mixing and combining components together to be used in the production of the binder composition, it should be considered that low molecular weight lignin is more reactive than high molecular weight lignin. Therefore, high molecular weight lignin can preferably be cooked in the aqueous composition for a longer period of time than low molecular weight lignin. In this way, it is guaranteed that the high molecular weight lignin has enough time to react with the crosslinking agent, for example, the aldehyde.
    [072] The present invention further relates to a binder composition obtainable by the method according to the present invention.
    [073] The present invention further relates to an adhesive composition comprising the binder composition according to the present invention. The adhesive composition may additionally comprise one or more adhesive components selected from the group consisting of other binders, extenders, additives, catalysts and fillers. A binder is a substance, which is mainly responsible for creating the growth and crosslinking of polymer and consequently assists in curing polymer systems. An extender is a substance that helps the binder by adjusting its physical properties, for example, by binding to moisture. The additive can be a polymer or an inorganic compound, which helps with properties such as filling, softening, cost reduction, humidity adjustment, increase rigidity and increase flexibility. The catalyst is a substance, which normally intensifies and adjusts the curing speed. By "substance" is meant in this document to include a compound or composition. The binder composition of the present invention can serve as a binder, an extender, an additive, a catalyst and / or a filler in the adhesive composition.
    [074] In one embodiment of the present invention, a layered composite structure can be formed of two or more layers that include at least one veneer layer of wood, 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 veneer” is used to encompass a veneer, which can be formed from any material, for example, wood-based material, fiber material, composite material or similar. In this context, the thickness of the wood veneer can be varied. Typically, the thickness of wood veneer is below 3 mm.
    [075] In one embodiment of the present invention, the layered composite structure is selected from the 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 of several layers, preferably veneered layers of wood, in which the layers are arranged on top of each other and glued together.
    [076] The present invention further relates to the use of the binder composition in an impregnation application, such as a coating, to reinforce plastic, for the production of a compressed coating, a molding, a laminate or a lacquer, or for the bonding of a wooden product. The binder composition of the present invention can be used additionally for bonding combinations of plastic and wood.
    [077] The present invention additionally relates to the use of the adhesive composition for bonding a wood product.
    [078] In one embodiment of the present invention, the wooden product is selected from the group consisting of a wooden plate, a wooden veneer and a wooden bar.
    [079] The modalities of the invention described above in this document can be used in any combination between them. Several of the embodiments can be combined together to form an additional 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 above in this document.
    [080] An advantage of the method according to the present invention is that, using both high molecular weight lignin and low molecular weight lignin as reagent components during the production of a binder composition, a binder composition more environmentally friendly is achieved. Surprisingly, it has been found that when using both high molecular weight lignin and low molecular weight lignin as reagent components, the amount of the polymerizable substance, such as the synthetic phenol substance, for example, phenol, can be decreased significantly during the binder production process. As phenol is a synthetic compound and lignin is a natural polymer, they are advantageous in having the ability to minimize the amount of phenol present in the final binder composition.
    [081] An advantage of the method according to the present invention is that, using low molecular weight lignin in the binder production method, the compatibility and reaction behavior of the formed binder composition is better than in use of high molecular weight lignin only.
    [082] An advantage of the method according to the present invention is that the use of the most reactive low molecular weight lignin in the binder composition improves, for example, the curing and adhesion properties, and the tensile strength performance of the composition of binder. That is, the overall performance of the formed binder composition is advantageous.
    [083] Consequently, an advantage of the present invention is that a higher level of bio-based components is achieved in the final binder composition. This advantage can be achieved by using the specific process steps of the present invention and especially when low molecular weight lignin is added to the composition. EXAMPLES
    [084] Reference will now be made in detail to the modalities of the present invention, the example of which is illustrated in the attached drawing.
    [085] The description below reveals some embodiments of the invention in such detail that an individual skilled in the art is able to use the invention based on the 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.
    [086] Figure 1 illustrates a method according to an embodiment of the present invention for producing a binder composition.
    [087] Before forming an aqueous composition that includes the reagent components, the source and quantities of the components are chosen in order to prepare a binder composition with the desired properties. In particular, the quantities and the source of high molecular weight lignin and low molecular weight lignin are selected.
    [088] Following various preparations, step (i) and especially step (ia) of said step are carried out by forming an aqueous dispersion comprising lignin. In the modality of Figure 1, both the high molecular weight lignin, that is, the lignin molecules of 11 to 60 units of lignin, and the low molecular weight lignin, that is, the lignin molecules of 1 to 10 units of lignin. lignin, are used in step (ia) to form a lignin dispersion.
    [089] A dispersion in step ia) can be formed, for example, by combining water, sodium hydroxide and the lignin fractions under heating at a temperature, for example, from 25 to 60 ° C.
    [090] Alternatively, if the lignin must be alkylated in order to make the lignin even more reactive during the binder cooking step, step (ia) can be carried out by first mixing water and sodium hydroxide and heating the mixture to a temperature of approximately 60 ° C. Then, the high molecular weight lignin can be dispersed in the composition after which the low molecular weight lignin is dispersed. Then, the dispersion formed is allowed to cook at a temperature of approximately 75 ° C for about an hour in order to form the alkylated lignin. Then, the temperature of the dispersion is lowered to approximately 50 ° C for later use.
    [091] Having formed the lignin dispersion in step (ia), the polymerizable substance, the cross-linking agent and the catalyst are added in a predetermined order with simultaneous control of the temperature of the aqueous composition formed (step (ib)). The selected components can be added one after the other or at least partially simultaneously.
    [092] After step (i) of forming the aqueous composition, step (ii) is carried out. Step (ii) comprises cooking the aqueous composition at a temperature of 50 to 95 ° C until a predetermined viscosity of the composition is achieved.
    [093] As a result of step (ia), step (ib) and step (ii), a binder composition that has desired properties 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.
    [094] Figure 2 illustrates a method according to another embodiment of the present invention for producing a binder composition.
    [095] The method according to the embodiment of Figure 2 begins in a similar manner to the embodiment of Figure 1. That is, a dispersion of alkylated lignin or a dispersion of non-alkylated lignin is formed as explained above in relation to Figure 1. However, in the embodiment of Figure 2, only high molecular weight lignin is used to form the dispersion in step (ia).
    [096] After the formation of the dispersion in step (ia), step (ib) is carried out. Step (ib) comprises adding the polymerizable substance, the crosslinking agent and the catalyst to form an aqueous composition. After mixing these components, the composition is baked in step (ic) until the viscosity of the composition is 15 to 70% of a predetermined viscosity value of the final binder composition. The composition can be cooked at a temperature of 20 to 95 ° C.
    [097] Then, the step (id) of adding low molecular weight lignin to the composition is performed. The temperature of the formed aqueous composition is raised to 80 to 90 ° C and the composition is baked at that temperature until a predetermined viscosity of the composition is reached or until a desired polymerization length is reached (step (ii) of Figure 2).
    [098] As a result of step (ia), step (ib), step (ic), step (id) and step (ii), a binder composition that has desired properties 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. EXAMPLE 1 - PREPARATION OF A BINDING COMPOSITION
    [099] In this example, a binder composition was produced. The following components and quantities were used:

    [100] First, water, the first part of NaOH (NaOH-I) and high molecular weight lignin (HMW lignin), that is, lignin which has an average molecular weight of 7,000 g / mol., Were mixed so that a dispersion is formed. At the same time, the temperature increased from room temperature to about 60 ° C. Then, part of the low molecular weight lignin (LMW lignin), that is, lignin which has an average molecular weight of 1,700 g / mol, was added to the dispersion while maintaining the temperature at 25 to 50 ° C.
    [101] Then, all of the phenol was added following the addition of the formaldehyde in steps to form an aqueous composition. The temperature was maintained under 75 ° C. After the addition of formaldehyde, the composition was allowed to react for 10 minutes after which the rest of the low molecular weight lignin was added. After also adding the second part of NaOH (NaOH-II) to the composition, the composition was baked at 85 ° C until the viscosity of the composition formed was about 305 cp. Then, the composition was cooled and the final viscosity was 315 cP. Viscosity was measured at a temperature of 25 ° C.
    [102] In this example, first a dispersion of water, NaOH and lignin was formed, after which the addition of phenol was initiated. However, the dispersion could also have undergone an alkylation treatment in order to make the used lignin even more reactive. Alkylation can be carried out, first, by mixing water and NaOH, after which heating of the mixture is initiated. When the temperature has reached 60 ° C, high molecular weight lignin is added followed by low molecular weight lignin. Then, the temperature can reach 75 ° C and the dispersion is allowed to react for about an hour at that temperature to alkylate the lignin. The dispersion is then cooled to 50 ° C before the addition of phenol begins.
    [103] The procedure of example 1 results in the possibility of replacing 50% of the synthetic phenol normally used in the production method of lignin binder. EXAMPLE 2 - PREPARE A BINDING COMPOSITION
    [104] In this example, a binder composition was produced. The following components and quantities were used:


    [105] First, water and the first part of NaOH (NaOH-I) were mixed and heated to a temperature of 75 ° C. Then, HMW lignin, that is, lignin that has an average molecular weight of 3,000 g / mol, was added followed by the addition of LMW lignin, that is, lignin that has an average molecular weight of 1,300 g / mol. When LMW lignin was also added to the dispersion, the dispersion was heated to a temperature of 75 ° C for about an hour in order to form alkylated lignin.
    [106] After the dispersion was cooled to 50 ° C, phenol was added followed by the addition of the first part of formaldehyde (formaldehyde-I) in steps to form the aqueous composition. Then, the temperature was increased to 75 ° C, after which the other part of formaldehyde (formaldehyde-II) and the second part of NaOH (NaOH-II) were added. Then, the composition was baked at 85 ° C until the viscosity of the composition formed was about 380 cp. Then, the composition was cooled and the final viscosity was 430 cP. Viscosity was measured at a temperature of 25 ° C.
    [107] The procedure in Example 2 results in the possibility of replacing 50% of the synthetic phenol normally used in the binder production method with lignin. EXAMPLE 3 - PREPARATION OF A BINDING COMPOSITION
    [108] In this example, a binder composition was produced. The following components and quantities have been used:

    [109] First, the water, the first part of NaOH (NaOH-I) and the lignin HMW, that is, the lignin which has an average molecular weight of 8,000 g / mol, were mixed under heating so that a dispersion was formed. Then, the temperature was adjusted to 50 ° C, the phenol was added and then the formaldehyde was added in stages over a period of one hour. The temperature was maintained under 75 ° C. After formaldehyde was added, the second part of NaOH (NaOH-II) was added. After the addition of NaOH-II, the composition was baked at 75 ° C until the viscosity of the composition was 100 cP. Then, LMW lignin, that is, lignin which has an average molecular weight of 350 g / mol, was added to the composition. Cooking was continued at a temperature of 75 ° C until the viscosity of the composition formed was about 305 cP. Then, the composition was cooled resulting in a final viscosity of 350 cP. Viscosity was measured at a temperature of 25 ° C.
    [110] The procedure of example 3 results in the possibility of replacing 66% of the synthetic phenol normally used in the binder production method with lignin. EXAMPLE 4 - PREPARATION OF A BINDING COMPOSITION
    [111] In this example, a binder composition was produced. The following components and quantities were used:

    [112] First, the water, the first part of NaOH (NaOH-I) and the lignin HMW, that is, the lignin which has an average molecular weight of 10,000 g / mol, were mixed so that a dispersion was formed . At the same time, the temperature increased from room temperature to about 60 ° C. Then, LMW lignin, that is, lignin which has an average molecular weight of 1,900 g / mol, was added to the dispersion while maintaining the temperature at 25 to 50 ° C.
    [113] Then all of the phenol was added following the addition of formaldehyde in stages to form an aqueous composition. The temperature was maintained under 75 ° C. After the addition of formaldehyde, the composition was allowed to react for 10 minutes, after which the second part of NaOH (NaOH-II) was added to the composition. Then, the composition was baked at 70 to 80 ° C until the viscosity of the composition formed was about 375 cp. Then, the composition was cooled and the final viscosity was 390 cP. Viscosity was measured at a temperature of 25 ° C.
    [114] In this example, first a dispersion of water, NaOH and the two fractions of lignin was formed, after which the addition of phenol was initiated. However, the dispersion could also have been subjected to an alkylation treatment in accordance with the procedure presented in example 1 in order to make the used lignin even more reactive.
    [115] The procedure of example 4 results in the possibility of replacing 80% of the synthetic phenol normally used in the binder production method with lignin. EXAMPLE 5 - PREPARATION OF AN ADHESIVE COMPOSITION
    [116] In this example, the binder composition produced in Example 1 was used to produce an adhesive composition. The binder composition was mixed with extenders, fillers, catalysts, additives, among which, for example, starch, wood flour and hardener (for example, tannins or carbonates) can be mentioned, thus forming the adhesive composition. EXAMPLE 6 - APPLICATION OF THE BINDING COMPOSITION TO PRODUCE A PLYWOOD PRODUCT
    [117] Wood veneers having a thickness below 3 mm were glued together with the binder composition produced in Example 2 to produce a plywood 7. The results showed that the gluing effect was sufficiently satisfactory for gluing of wood veneers. EXAMPLE 7 - APPLICATION OF THE ADHESIVE COMPOSITION TO PRODUCE A PLYWOOD PRODUCT
    [118] In this example, the adhesive composition of Example 5 was applied to wood veneers. The veneers were joined together by the adhesive composition to form a plywood. The dry matter content of the adhesive composition was between 45 and 55%. The wood veneers with the adhesive composition were pressed by the hot press technique at a temperature between 120 to 170 ° C. The adhesive composition was cured simultaneously. The adhesive composition of the present invention has been found to be suitable for bonding veneers to each other and consequently for the manufacture of plywood. EXAMPLE 8 - APPLICATION OF THE BINDING COMPOSITION TO PRODUCE LAMINATES
    [119] In this example, the binder composition as produced in Example 3 was used in an impregnation application. During the production of laminates, the paper was impregnated with an alcohol 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 one above the other and baked by a hot press technique in order to form uniform laminates or thick plates.
    [120] In the binder production method presented in the examples above, phenol and formaldehyde are used as examples of polymerizable substance and crosslinking agent, respectively. However, any other polymerizable substance or crosslinking agent disclosed in this specification can be used equally well in the method of producing binder composition as will be obvious to the individual versed on the basis of this specification.
    权利要求:
    Claims (22)
    [0001]
    1. Method for producing a binder composition characterized by comprising the following steps: (i) forming an aqueous composition comprising reagent components that include lignin molecules from 11 to 60 lignin units, lignin molecules from 1 to 10 lignin units, polymerizable substance and crosslinking agent in the presence of a catalyst, where the lignin molecule weight ratio of 11 to 60 lignin units to lignin molecules from 1 to 10 lignin units is 0.1 to 20, and in which the polymerizable substance is selected from the group consisting of phenol, cresol, resorcinol and combinations thereof, and the crosslinking agent is an aldehyde; and (ii) cooking the aqueous composition at a temperature of 45 to 95 ° C to polymerize the reagent components until a binder composition with a predetermined viscosity value is formed.
    [0002]
    Method according to claim 1, characterized in that the weight ratio of lignin molecules from 11 to 60 lignin units to lignin molecules from 1 to 10 lignin units is 0.2 to 10.
    [0003]
    Method according to claim 1, characterized in that step (i) of forming the aqueous composition comprises the following steps: (ia) forming a dispersion comprising lignin molecules of 11 to 60 units of lignin; and (ib) combining the polymerizable substance and the crosslinking agent with the dispersion to form the aqueous composition in the presence of a catalyst.
    [0004]
    Method according to claim 3, characterized in that the step (i) of forming the aqueous composition comprises, after step (ib), the following steps: (ic) baking the formed aqueous composition until the composition has a viscosity, which corresponds to 15 to 70% of a predetermined viscosity value of the final binder composition; and (id) adding the lignin molecules from 1 to 10 units of lignin as a reagent component to the aqueous composition.
    [0005]
    Method according to any one of claims 3 to 4, characterized in that step (ia) and / or step (ib) comprises adding lignin molecules of 1 to 10 units of lignin as a reagent component.
    [0006]
    Method according to any one of claims 1 to 5, characterized in that step (i) comprises maintaining the aqueous composition at a maximum temperature of 75 ° C.
    [0007]
    Method according to any one of claims 4 to 6, characterized in that step (ic) comprises maintaining the temperature of the aqueous composition between 45 to 95 ° C.
    [0008]
    Method according to any one of claims 4 to 7, characterized in that the temperature of the aqueous composition is lowered below 85 ° C before step (id).
    [0009]
    Method according to any one of claims 1 to 8, characterized in that step (ii) comprises cooking the aqueous composition at a temperature of 50 to 85 ° C.
    [0010]
    Method according to any one of claims 4 to 9, characterized in that the temperature of the aqueous composition is raised to 45 to 95 ° C, before, during or after step (id).
    [0011]
    Method according to any one of claims 1 to 10, characterized in that the weight ratio of lignin molecules from 11 to 60 lignin units and lignin molecules from 1 to 10 lignin units for the polymerizable substance is at least minus 0.2.
    [0012]
    Method according to any one of claims 1 to 11, characterized in that the catalyst is sodium hydroxide.
    [0013]
    Method according to any one of claims 1 to 11, characterized in that the weight ratio of lignin molecules from 11 to 60 units of lignin to lignin molecules from 1 to 10 units of lignin is 0.5 to 5.
    [0014]
    Method according to claim 4, characterized in that step (ic) comprises maintaining the temperature of the aqueous composition between 50 to 85 ° C.
    [0015]
    Method according to claim 4, characterized in that step (ic) comprises maintaining the temperature of the aqueous composition between 60 to 80 ° C.
    [0016]
    16. Method according to claim 4, characterized in that the temperature of the aqueous composition is lowered below 65 ° C before step (id).
    [0017]
    17. Method according to claim 1, characterized in that step (ii) comprises boiling the aqueous composition at a temperature of 60 to 80 ° C.
    [0018]
    Method according to claim 4, characterized in that the temperature of the aqueous composition is increased to 50 to 85 ° C, before, during or after step (id).
    [0019]
    19. Method according to claim 4, characterized in that the temperature of the aqueous composition is increased to 60 to 80 ° C, before, during and after step (id).
    [0020]
    20. Method according to claim 1, characterized in that the weight ratio of the molecules from 11 to 60 units of lignin and the molecules from 1 to 10 units of lignin for the polymerizable substance is at least 1.
    [0021]
    21. Method according to claim 1, characterized in that the weight ratio of the lignin molecules from 11 to 60 lignin units and the lignin molecules from 11 to 60 lignins for the polymerizable substance is at least 5.
    [0022]
    22. Method according to claim 1, characterized in that the cross-linking agent is formaldehyde.
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    同族专利:
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    PT2831150T|2019-07-30|
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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]|
    2020-02-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-20| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-12-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-02| 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. |
    2021-08-10| B17A| Notification of administrative nullity (patentee has 60 days time to reply to this notification)|Free format text: REQUERENTE DA NULIDADE: OTTO BANHO LICKS - 870210070422 - 2/08/2021 |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20125357|2012-03-29|
    FI20125357A|FI123934B|2012-03-29|2012-03-29|Use of low molecular weight lignin for the preparation of a binder composition|
    PCT/FI2013/050352|WO2013144453A1|2012-03-29|2013-03-28|Use of low molecular weight lignin together with lignin for the production of a phenol - formaldehyde binder composition|
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