Cellulose-based adhesive as well as preparation method and application thereof

Abstract

The invention provides a cellulose-based adhesive as well as a preparation method and application thereof. The cellulose-based adhesive is a polymerization product of a cellulose-based adhesive precursor solution, the cellulose-based adhesive precursor solution comprises a cellulose suspension, a monomer and a catalyst; the cellulose suspension comprises a cellulose solution and a coagulating bath system. The cellulose-based adhesive disclosed by the invention has relatively high reaction efficiency and relatively good bonding capacity, and has a relatively good application prospect in the fields of plywood, interface bonding and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and in particular relates to a cellulose-based adhesive and a preparation method and application thereof. Background Art

[0002] Formaldehyde-based adhesives are produced from non-renewable fossil resources, and wood materials prepared using these adhesives will release phenol and formaldehyde. These toxic and volatile substances are important pollutants that threaten human and environmental health. With the increasingly stringent relevant regulations and the reduction of petrochemical resource reserves and the increase in prices, the research on degradable and non-toxic adhesives has attracted great attention from researchers from all over the world. Promoting safe and non-toxic biodegradable adhesive materials has become a research hotspot and future development trend in the adhesive industry.

[0003] Bio-based adhesives must be low-cost and have similar or better bonding properties than existing non-sustainable adhesives to effectively compete with fossil-derived adhesives. Cellulose-based adhesives have received increasing attention in the adhesive field due to their renewability, biodegradability and environmental friendliness. As a natural polymer material, cellulose has excellent physical and chemical properties and can form good bonds with a variety of substances. Therefore, it is widely used in industries such as packaging, paper products, textiles and wood. However, cellulose-based adhesives still have shortcomings in terms of bonding properties. For example, the bonding strength of cellulose-based adhesives is generally low, especially in bonding to metal, glass and certain non-polar surfaces, the performance is far inferior to synthetic adhesives (such as epoxy resins or polyurethanes). This is because the cellulose molecular structure itself is relatively loose and its hydrophilicity is strong, which makes it difficult to form a strong and stable bonding interface in some applications. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a cellulose-based adhesive and a preparation method thereof, which solves the problem of insufficient bonding performance in the prior art.

[0005] In one aspect, the present invention provides a cellulose-based adhesive, which is a polymerization product of a cellulose-based adhesive precursor solution; the cellulose-based adhesive precursor solution comprises a cellulose suspension, a monomer and a catalyst; the cellulose suspension comprises a cellulose solution and a coagulation bath system.

[0006] According to an embodiment of the present invention, the cellulose-based adhesive has good bonding ability.

[0007] According to an embodiment of the present invention, the cellulose-based adhesive has enhanced tensile shear strength. In one embodiment of the present invention, the tensile shear strength of the cellulose-based adhesive is 0.8-10 MPa.

[0008] According to an embodiment of the present invention, the polymerization product includes a cellulose graft copolymer generated by the reaction of cellulose and a monomer.

[0009] According to an embodiment of the present invention, in the cellulose solution, the cellulose may be selected from at least one of the following substances: 1) microcrystalline cellulose; 2) bacterial cellulose; 3) at least one of cotton pulp, wood pulp, bamboo pulp, straw pulp, refined cotton, absorbent cotton, and cotton linters; and 4) cellulose or low-quality cellulose extracted from plant tissue (which may be at least one of herbaceous plants and agricultural and forestry wastes, etc.; specifically, for example, at least one of bagasse, wood, and straw, etc.). Preferably, the cellulose may be selected from at least one of microcrystalline cellulose, refined cotton, absorbent cotton, and wood pulp.

[0010] According to an embodiment of the present invention, the low-quality cellulose is a plant tissue containing at least two components, cellulose and lignin. The plant tissue can be at least one of herbaceous plants and agricultural and forestry wastes, such as plant tissues selected from trees, shrubs, vines, leaves, bamboos, etc. For example, the agricultural and forestry wastes are selected from bark, leaves, sawdust, straw (such as crop straw), fruit shells or fruit cores, corn cobs, sugarcane bagasse, etc. Preferably, the crop straw can be selected from at least one of wheat straw, rice straw, corn straw, soybean straw, cotton straw, ginger stalks, and sesame straw.

[0011] According to an embodiment of the present invention, the solvent system of the cellulose solution can be selected from at least one of the following substances or systems: 1) ionic liquid; 2) a mixed solvent of an ionic liquid and an organic co-solvent; 3) an organic co-solvent / salt system; 4) an amine oxide system (NMMO); 5) an alkali / urea system; 6) an organic acid system; or 7) an aqueous metal salt solution.

[0012] According to an embodiment of the present invention, the ionic liquid is selected from organic molten salts formed by cations and anions with a melting point lower than 100° C., preferably molten salts capable of dissolving the cellulose.

[0013] Wherein, the cation is selected from at least one of substituted or unsubstituted imidazole, pyridine, pyrrole, amine, phosphine, choline, diazabicyclic, and amino acid type cations. For example, the substituent can be C 1-12 Alkyl, C 2-12 Alkenyl, C1-C 12 Alkoxy C1-C 12 Alkyl, hydroxyl, hydroxyl C 1-12 Alkyl, C 6-12 Aryl, C 6-12 Aryl C 1-12 Alkyl, C 6-12 Aryl C 1-12 At least one of alkoxy, etc.; preferably C1-6 Alkyl, C 2-6 Alkenyl, Hydroxyl, Hydroxyl C 1-6 Alkyl, phenyl, C 6-10 Aryl C 1-6 Alkyl, C 6-10 Aryl C 1-6 At least one of the alkoxy groups, for example, at least one of methyl, ethyl, butyl, pentyl, allyl, hydroxy, methoxymethyl, hydroxyethyl, phenyl, benzyl, m-methoxyphenyl, and m-methoxybenzyl. Exemplarily, the cation may be selected from: 1-ethyl-3-methylimidazolium cation ([EMIM]), 3-methylimidazolium cation ([MIM]), 1-propyl-3-methylimidazolium cation ([PMIM]), 1-allyl-3-methylimidazolium cation ([AMIM]), 1-butyl-3-methylimidazolium cation ([BMIM]), 1-butyl-2,3-dimethylimidazolium cation ([BMMIM]), 1,3-dimethylimidazolium cation ([MMIM]), 1-methoxyethyl-3-methylimidazolium cation ([MeOEMIM]), 1-methoxymethyl-3-methylimidazolium cation ([MeOMMIM]), 1-hydroxy-3-methyl-imidazolium cation ([HMIM]), 1-(2-hydroxyethyl)-3-methylimidazolium cation ([HOEMIM]), 1-methyl-3-benzylimidazolium cation ([MBzIM]), 1-pentyl-3- At least one of cations selected from the group consisting of methylimidazolium cation ([PeMIM]), 1-benzyl-3-methylimidazolium cation ([BzMIM]), 1-m-methoxybenzyl-3-methylimidazolium cation ([MeOBzMIM]), 1-m-methylbenzyl-3-methylimidazolium cation ([MeBzMIM]), N-methylpyridinium cation ([MPyr]), N-ethylpyridinium cation ([EPyr]), N-butylpyridinium cation ([BPyr]), N-n-hexylpyridinium cation ([HPyr]), 1-butyl-3-methylpyrrolidinium ion ([BMPyrr]), tris(2-hydroxyethyl)methylamine ([THEMA]), tetrabutylamine ([TBA]), tetrabutylphosphine ([PBu4]), glycine cation ([Gly]), choline cation ([Ch]), and 1,5-diazabicyclo[4.3.0]one-5-ene ([DBNH]). More preferably, the cation is selected from at least one of 1-ethyl-3-methylimidazolium cation ([EMIM]), 1-allyl-3-methylimidazolium cation ([AMIM]), 1-butyl-3-methylimidazolium cation ([BMIM]), and choline cation ([Ch]).

[0014] Wherein, the anion is selected from at least one of halogen anions, organic acid radical ions, organic acid ester anions, amino acid type anions, etc. For example, the anion is selected from: chloride ion ([Cl]), bromide ion ([Br]), fluoride ion ([F]), formate ion ([HCOO]), acetate ion ([CH3COO] or [Ac]), glycolate ion ([HOCH2COO]), propionate ion ([CH3CH2COO] or [OPr]), butyrate ion ([CH3CH2CH2COO] or [OBu]), octanoate ([Oct]), benzoate ion ([C6H5COO] or [PhCOO]), lactate ion ([CH3CH(OH)COO] or [Lac]), thioglycolate ion ([HSCH2COO]), hexafluorophosphate ion ion ([PF6]), trifluoroborate ([BF3]), methyl phosphate ion ([(MeO)HPO2] or [MP]), dimethyl phosphate ion ([(MeO)2PO2] or [DMP]), diethyl phosphate ion ([(EtO)2PO2] or [DEP]), methyl sulfonate anion ([MeOSO3]), trifluoromethylsulfonate anion ([CF3SO3]), glycine anion ([Gly]), lysine anion ([Lys]), valine anion ([Val]), dicyanamide anion ([N(CN)2] or [DCA]), bistrifluoromethylsulfonyl imide ([Tf2N]) and the like. More preferably, the anion is selected from at least one of: chloride ion ([Cl]), formate ion ([HCOO]), acetate ion ([Ac]), methyl phosphate ion ([(MeO)HPO2] or [MP]), dimethyl phosphate ion ([(MeO)2PO2] or [DMP]), and dicyanamide anion ([N(CN)2] or [DCA]).

[0015] According to an embodiment of the present invention, the ionic liquid can be selected from: 1-ethyl-3-methylimidazolium chloride ionic liquid ([EMIM][Cl]), 1-ethyl-3-methylimidazolium bromide ionic liquid ([EMIM][Br]), 1-ethyl-3-methylimidazolium formate ionic liquid ([EMIM][HCOO]), 1-ethyl-3-methylimidazolium acetate ionic liquid ([EMIM][Ac]), 1-ethyl-3-methylimidazolium octanoate ionic liquid ([EMIM][Oct]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][MP]), 1-ethyl-3-methylimidazolium dimethyl phosphate ionic liquid ([EMIM][DMP ... methyl phosphate ionic liquid ([EMIM][DMP]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][DMP]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][DMP]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][DMP]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][DMP]), 1-ethyl-3-methylimidazolium methyl phosphate ionic liquid ([EMIM][HCOO]), 1-ethyl-3-methylimidazolium acetate ionic 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid ([EMIM][DEP]), 1-ethyl-3-methylimidazolium propionate ionic liquid ([EMIM][OPr]), 1-ethyl-3-methylimidazolium top ionic liquid ([EMIM][OBu]), 1-ethyl-3-methylimidazolium glycinate ionic liquid ([EMIM][Gly]), 1-ethyl-3-methylimidazolium lysine ionic liquid ([EMIM][Lys]), 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM][Cl]), 1-allyl-3-methylimidazolium bromide ionic liquid ([AMIM][Br]), 1-allyl-3-methylimidazolium formate ionic liquid ([AMIM][Br]), M][HCOO]), 1-allyl-3-methylimidazolium acetate ionic liquid ([AMIM][Ac]), 1-butyl-3-methylimidazolium chloride ionic liquid ([BMIM][Cl]), 1-butyl-3-methylimidazolium bromide ionic liquid ([BMIM][Br]), 1-butyl-3-methylimidazolium formate ionic liquid ([BMIM][HCOO]), 1-butyl-3-methylimidazolium acetate ionic liquid ([BMIM][Ac]), 1-butyl-3-methylimidazolium hydroxyacetate ionic liquid ([BMIM][HOCH2COO]), 1-butyl-3-methylimidazolium propionate ionic liquid ([BMIM][CH3CH2COO]), 1-butyl-3-methylimidazolium acetate ionic liquid ([BMIM][HCOO]), 1-butyl-3-methylimidazolium acetate ionic liquid ([BMIM][Ac]), 1-butyl-3-methylimidazolium propionate ionic liquid ([BMIM][CH3CH2COO]), Methylimidazolium lactate ionic liquid [BMIM][Lac], 1-butyl-3-methylimidazolium butyrate ionic liquid ([BMIM][CH3CH2CH2COO]), 1-butyl-3-methylimidazolium benzoate ionic liquid ([BMIM][C6H5COO]), 1-butyl-3-methylimidazolium glycine salt ionic liquid ([BMIM][H2NCH2COO]), 1-butyl-3-methylimidazolium dicyanamide ionic liquid ([BMIM][N(CN)2]), 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide ionic liquid ([BMIM][Tf2N]), 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid ([BMIM][PF6]),1-Butyl-3-methylimidazolium tetrafluoroborate ionic liquid ([BMIM][BF4]), 1-Butyl-3-methylimidazolium methanesulfonate ionic liquid ([BMIM][MeOSO3]), 1-Butyl-3-methylimidazolium trifluoromethylsulfonate ionic liquid ([BMIM][CF3SO3]), 1-Butyl-2,3-dimethylimidazolium tetrafluoroborate ionic liquid ([BMMIM][BF4]), 3-methylimidazolium formate ionic liquid ([MIM][HCOO]), 1,3-dimethylimidazolium chloride ionic liquid ([MMIM][Cl]), 1,3-dimethylimidazolium methyl phosphate ionic liquid ([MMIM][MP]), 1,3-dimethylimidazolium dimethyl phosphite ionic liquid ([MMIM][MP]), ester ionic liquid ([MMIM][DMP]), 1,3-dimethylimidazolium methylsulfonate ionic liquid ([MMIM][MeOSO3]), 1-hydroxy-3-methyl-imidazolium chloride ionic liquid ([HMIM][Cl]), 1-hydroxy-3-methyl-imidazolium trifluoromethylsulfonate ionic liquid ([HMIM][CF3SO3]), 1-(2-hydroxyethyl)-3-methylimidazolium chloride ionic liquid ([HOEMIM][Cl]), 1-methoxymethyl-3-methylimidazolium bromide ionic liquid ([MeOMMIM][Br]), 1-methoxyethyl-3-methylimidazolium bromide ionic liquid ([MeOEMIM][Br]), N-ethylpyridinium chloride ionic liquid ([E Pyr][Cl]), N-ethylpyridinium bromide ionic liquid ([EPyr][Br]), N-methylpicolinate ionic liquid ([MPyr][HCOO]), tris(2-hydroxyethyl)methylamine acetate ionic liquid ([THEMA][Ac]), tris(2-hydroxyethyl)methylamine methylsulfonate ionic liquid ([THEMA][MeOSO3]), tris(2-hydroxyethyl)methylamine trifluoromethylsulfonate ionic liquid [THEMA][CF3SO3], tetrabutylphosphine valine salt ionic liquid [PBu4][Val], tetrabutylphosphine lysine salt ionic liquid [PBu4][Lys], tetrabutylphosphine glycinate ionic liquid [PBu4][Gly], 1-benzyl- 3-Methylimidazolium chloride ionic liquid ([BzMIM][Cl]), 1-benzyl-3-methylimidazolium dicyanamide ionic liquid ([BzMIM][DCA]), 1-m-methylbenzyl-3-methylimidazolium chloride ionic liquid ([MeBzMIM][Cl]), 1-m-methoxybenzyl-3-methylimidazolium chloride ionic liquid ([MeOBzMIM][Cl]), choline chloride ionic liquid ([Ch][Cl]), choline bromide ionic liquid (Ch][Br]), choline acetate ionic liquid ([Ch][CH3COO]), choline propionate ionic liquid ([Ch][CH3CH2COO]), choline butyrate ionic liquid ([Ch][CH3CH2CH2COO]),At least one of the ionic liquids selected from the group consisting of glycine hydrochloride ionic liquid ([Gly][Cl]), 1,5-diazabicyclo[4.3.0]keto-5-ene acetate ionic liquid ([DBNH][Ac]).

[0016] According to an embodiment of the present invention, the organic co-solvent can be selected from at least one of methanol, ethanol, ethylene glycol, propanol, glycerol, isopropanol, n-butanol, isobutanol, tert-butanol, acetone, N,N-dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methylimidazole, imidazole, pyridine, ethylenediamine, hexafluoroacetone, hexafluoroisopropanol, methyl isobutyl ketone, tetrahydrofuran, dioxane, and γ-valerolactone (GVL).

[0017] According to an embodiment of the present invention, the organic co-solvent / salt system can be selected from at least one of N,N-dimethylacetamide / lithium chloride (DMAc / LiCl) system, N-methyl-2-pyrrolidone / NMP and N,N-dimethyl sulfoxide / tetrabutylammonium fluoride system (DMSO / TBAF).

[0018] According to an embodiment of the present invention, the amine oxide system may be at least one of a NMMO / H2O / DMSO system, a NMMO / H2O / diethyltriamine system, a NMMO / H2O system, and the like.

[0019] According to an embodiment of the present invention, the alkali / urea system may be selected from a strong alkali / urea system, such as NaOH / urea (Urea).

[0020] According to an embodiment of the present invention, the organic acid may be selected from at least one of formic acid, acetic acid, propionic acid, butyric acid, succinic acid, lactic acid, glutamic acid, glycine, dichloroacetic acid, trichloroacetic acid, toluenesulfonic acid, phosphoric acid and the like.

[0021] According to an embodiment of the present invention, the aqueous metal salt solution may be selected from aqueous solutions of CaCl2, ZnCl2, LiClO4, Ca(SCN)2, LiSCN, and the like.

[0022] According to an embodiment of the present invention, the coagulation bath system includes at least one of water, alcohol or alcohol-water mixture, HCl aqueous solution, inorganic salt aqueous solution, organic co-solvent aqueous solution, ionic liquid solution or a mixed solution thereof. For example, the alcohol can be selected from at least one of methanol, ethanol, ethylene glycol, propanol, glycerol, isopropanol, n-butanol, isobutanol, preferably at least one of methanol, ethanol, and ethylene glycol. For example, the inorganic salt aqueous solution can be at least one of Na2SO4 aqueous solution, NaCl aqueous solution, KCl aqueous solution, CaCl2 aqueous solution, MgCl2 aqueous solution, FeCl3 aqueous solution, KNO3 aqueous solution, NaNO3 aqueous solution, etc. For example, the ionic liquid solution can be selected from at least one of ionic liquid / aqueous solution, ionic liquid / alcohol solution, ionic liquid / alcohol / aqueous solution, ionic liquid / organic co-solvent solution, and ionic liquid / organic co-solvent / aqueous solution. Preferably, the coagulation bath system is an alcohol-water mixture, for example, a mixture of at least one of methanol, ethanol, ethylene glycol, propanol, glycerol, isopropanol, n-butanol, isobutanol and water, preferably a mixture of methanol, ethanol or ethylene glycol and water, exemplified by a mixture of ethanol and water. Further, the ratio of alcohol to water in the alcohol-water mixture is not particularly limited.

[0023] According to an embodiment of the present invention, the cellulose morphology in the cellulose suspension is at least one of nanofiber web, dendritic fiber, wrinkled fiber and ribbon fiber.

[0024] According to an embodiment of the present invention, the cellulose concentration in the cellulose suspension is 0.1 to 20 wt%.

[0025] According to an embodiment of the present invention, the monomer is a compound containing a carbon-carbon double bond.

[0026] According to an embodiment of the present invention, the compound containing a carbon-carbon double bond may be selected from at least one of acrylic acid, methacrylic acid, acrylate, acrylamide, acrylamide derivatives, acrylonitrile, vinyl acetate, and styrene.

[0027] According to an embodiment of the present invention, the acrylic acid ester can be selected from at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate, n-butyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, diaminoethyl methacrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and isobornyl acrylate.

[0028] According to an embodiment of the present invention, the acrylamide derivative can be selected from at least one of N-isopropylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, (3-acrylamidopropyl)trimethylammonium chloride, N-(hydroxymethyl)acrylamide, N-phenylacrylamide, and diacetone acrylamide.

[0029] According to an embodiment of the present invention, in the cellulose-based adhesive precursor solution, the monomer accounts for 0.1 to 50 wt % of the mass of the cellulose suspension.

[0030] According to an embodiment of the present invention, the mass ratio of cellulose to monomer is (0.1-20):(0.1-50).

[0031] According to an embodiment of the present invention, in the cellulose-based adhesive precursor solution, the mass percentage of the catalyst to the monomer is 0.01 to 10 wt %.

[0032] The second aspect of the present invention provides a method for preparing the above-mentioned cellulose-based adhesive, comprising subjecting a cellulose-based adhesive precursor solution to a polymerization reaction to obtain the cellulose-based adhesive; wherein the cellulose-based adhesive precursor solution comprises a cellulose suspension, a monomer and a catalyst; and the cellulose suspension comprises a cellulose solution and a coagulation bath system.

[0033] According to an embodiment of the present invention, the preparation method comprises the following steps:

[0034] 1) Preparation of cellulose suspension: adding cellulose solution into a coagulation bath system to obtain cellulose suspension;

[0035] 2) Preparation of cellulose-based adhesive precursor solution: adding monomers and catalysts to a cellulose suspension to obtain a cellulose-based adhesive precursor solution;

[0036] 3) Preparation of cellulose-based adhesive: A cellulose-based adhesive precursor solution is polymerized to obtain a cellulose-based adhesive.

[0037] According to an embodiment of the present invention, in step 1), the cellulose and / or solvent system in the cellulose solution have the above definitions.

[0038] According to an embodiment of the present invention, in step 1), the coagulation bath system has the above definition.

[0039] According to an embodiment of the present invention, the state of the coagulation bath system in step 1) is a laminar flow or turbulent flow state; specifically, the state is obtained by stirring; further specifically, the rotation speed is 1 to 100000 rpm.

[0040] According to an embodiment of the present invention, the monomers in step 2) have the above definition.

[0041] According to an embodiment of the present invention, the catalyst in step 2) is ammonium cerium nitrate.

[0042] According to an embodiment of the present invention, the pH of the cellulose-based adhesive precursor solution in step 2) is 2-12.

[0043] According to an embodiment of the present invention, the monomers and / or catalysts in step 2) have the amounts defined above.

[0044] According to an embodiment of the present invention, the polymerization reaction conditions in step 3) are: reaction temperature 20-90° C., reaction time 10 min-48 h.

[0045] According to an embodiment of the present invention, the polymerization reaction in step 3) is carried out under nitrogen protection.

[0046] The third aspect of the present invention provides a coating comprising the above-mentioned cellulose-based adhesive.

[0047] According to a fourth aspect of the present invention, there is provided a coating comprising the above-mentioned cellulose-based adhesive or the above-mentioned coating.

[0048] In a fifth aspect, the present invention provides the above-mentioned cellulose-based adhesive or the above-mentioned coating for coating or bonding an interface, wherein the interface includes glass, metal, wood or other non-polar surfaces.

[0049] In one embodiment of the present invention, the above-mentioned adhesive or the above-mentioned coating is used to bond wooden boards, and the tensile shear strength of the wooden boards is 3-8.5 MPa.

[0050] In one embodiment of the present invention, the above adhesive or the above coating is used to bond glass, and the tensile shear strength of the glass is 5-10 MPa.

[0051] In one embodiment of the present invention, the above adhesive or the above coating is used to bond iron sheets, and the tensile shear strength of the iron sheets is 0.5-2.5 MPa.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] The cellulose-based adhesive of the present invention has a faster reaction efficiency and better bonding ability, and has good application prospects in the fields of plywood, interface bonding, etc. The rich micro-nano structure in the cellulose of the present invention not only has a reinforcing effect but also has a cross-linking effect, forming an overall cross-linked network structure with stronger shear strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1Photo of wood after stretching for cellulose based adhesive.

[0055] Figure 2 This is a photo of the cellulose-based adhesive prepared in Example 1.

[0056] Figure 3 This is an electron microscopic image of the nanofiber web fibers prepared in Example 1.

[0057] Figure 4 This is an electron microscopic image of the dendritic fiber cellulose prepared in Example 6.

[0058] Figure 5 This is an electron microscopic image of the wrinkled fiber cellulose prepared in Example 11. DETAILED DESCRIPTION

[0059] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0060] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0061] The tensile shear strength in the present invention is measured using the ASTM D1002 standard, and the specific testing process is as follows: a plate of 100 mm × 25 mm × 2.5 mm is used as a substrate, the overlap length is 12.5 mm, 0.5 mL of cellulose-based adhesive is evenly applied to the substrate, and a sample is obtained by hot pressing at 70° C. for 5 min under a pressure of 0.02 MPa. The sample is placed at 25° C. and 30% humidity for 48 hours, and a tensile test is performed on a universal tensile machine at a tensile rate of 0.5 mm / min.

[0062] Example 1

[0063] Weigh 5.0g of wood pulp / NaOH / Urea solution and add it to water at a speed of 10200rpm. After washing, a nanofiber web cellulose suspension is obtained. Take 100g of 2wt% cellulose suspension and add 10.0g of acrylic acid and 0.05g of ammonium cerium nitrate. After dissolution, place it in an 80℃ oil bath for 5h. After testing, the tensile shear strength of the bonded wood board is 8.1MPa. The appearance of the wood after stretching after the cellulose-based adhesive is bonded to the wood board is as follows: Figure 1 The morphology of cellulose-based adhesives is shown in Figure 2 The electron microscopic image of the prepared nanofiber web is shown in Figure 3 shown.

[0064] Example 2

[0065] Weigh 5.0g of wood pulp / NaOH / Urea solution and add it to water at a speed of 10200rpm. After washing, obtain a nanofiber web cellulose suspension. Take 100g of 2wt% cellulose suspension and add 10.0g acrylamide and 0.05g cerium ammonium nitrate. After dissolution, place it in an 80℃ oil bath for 5h. After testing, the tensile shear strength of the bonded wood board is 6.1MPa.

[0066] Example 3

[0067] Weigh 5.0g of wood pulp / NaOH / Urea solution and add it to water at a speed of 10200rpm. After washing, obtain a nanofiber web cellulose suspension. Take 100g of 2wt% cellulose suspension and add 10.0g butyl acrylate and 0.05g ammonium cerium nitrate. After dissolution, place it in an 80℃ oil bath for 5h. After testing, the tensile shear strength of the bonded wood board is 7.3MPa.

[0068] Example 4

[0069] Weigh 5.0g of wood pulp / DMAc / LiCl solution and add it to water at a speed of 20,000rpm. After washing, obtain a nanofiber web cellulose suspension. Take 100g of 2wt% cellulose suspension and add 10.0g ethyl acrylate and 0.05g cerium ammonium nitrate. After dissolution, place it in an 80℃ oil bath for 5h. After testing, the tensile shear strength of the bonded wood board is 3.5MPa.

[0070] Example 5

[0071] Weigh 5.0g of wood pulp / DMAc / LiCl solution and add it to water at a speed of 20000rpm. After washing, obtain a nanofiber web cellulose suspension. Take 100g of 2wt% cellulose suspension and add 10.0g of methacrylamide and 0.05g of ammonium cerium nitrate. After dissolution, place it in an 80℃ oil bath for 5h. After testing, the tensile shear strength of the bonded iron sheet is 1.1MPa.

[0072] Example 6

[0073] 5.0 g of wood pulp / DMAc / LiCl solution was weighed and added into glycerol at a rotation speed of 20000 rpm. After washing, a dendritic fiber cellulose suspension was obtained (electron microscopic image as shown in FIG. Figure 4 As shown, 100g of 2wt% cellulose suspension was added with 10.0g methacrylic acid and 0.05g cerium ammonium nitrate, and after dissolution, it was placed in an 80°C oil bath for 5h. After testing, the tensile shear strength of the bonded iron sheet was 1.2MPa.

[0074] Example 7

[0075] Weigh 5.0g of wood pulp / DMAc / LiCl solution and add it to glycerol at a speed of 20000rpm. After washing, a dendritic fiber cellulose suspension is obtained. Take 100g of 2wt% cellulose suspension and add 10.0g ethyl acrylate and 0.05g cerium ammonium nitrate. After dissolution, place it in a 50℃ oil bath for 10h. After testing, the tensile shear strength of the bonded iron sheet is 0.8MPa.

[0076] Example 8

[0077] Weigh 5.0g of wood pulp / DMAc / LiCl solution and add it to glycerol at a speed of 20000rpm. After washing, a dendritic fiber cellulose suspension is obtained. Take 100g of 2wt% cellulose suspension and add 10.0g ethyl acrylate and 0.05g cerium ammonium nitrate. After dissolution, place it in a 20℃ oil bath for 48h. After testing, the tensile shear strength of the bonded iron sheet is 2.4MPa.

[0078] Example 9

[0079] Weigh 5.0g of wood pulp / DMAc / LiCl solution and add it to glycerol at a speed of 20000rpm. After washing, a dendritic fiber cellulose suspension is obtained. Take 100g of 2wt% cellulose suspension and add 20.0g hydroxyethyl methacrylate and 0.05g cerium ammonium nitrate. After dissolution, place it in a 50℃ oil bath for 10h. After testing, the tensile shear strength of the bonded glass is 8.1MPa.

[0080] Example 10

[0081] Weigh 5.0g of wood pulp / DMAc / LiCl solution and add it to glycerol at a speed of 20000rpm. After washing, a dendritic fiber cellulose suspension is obtained. 100g of 2wt% cellulose suspension is added with 30.0g hydroxyethyl methacrylate and 0.05g cerium ammonium nitrate. After dissolution, place it in a 50℃ oil bath for 10h. After testing, the tensile shear strength of the bonded glass is 9.6MPa.

[0082] Embodiment 11

[0083] 5.0 g of wood pulp / DMAc / LiCl solution was weighed and added into glycerol / water at a rotation speed of 20000 rpm. After washing, a wrinkled fiber cellulose suspension was obtained (electron microscopic image as shown in FIG. Figure 5 As shown, 100g of 2wt% cellulose suspension was added with 5.0g hydroxyethyl methacrylate and 0.05g cerium ammonium nitrate, and after dissolution, it was placed in a 50°C oil bath for reaction for 10h. After testing, the tensile shear strength of the bonded glass was 8.7MPa.

[0084] Example 12

[0085] Weigh 5.0g of wood pulp / DMAc / LiCl solution and add it to glycerol / water at a speed of 20000rpm. After washing, a pleated fiber cellulose suspension is obtained. Take 100g of 2wt% cellulose suspension and add 20.0g of hydroxyethyl methacrylate and 0.05g of ammonium cerium nitrate. After dissolution, place it in a 50℃ oil bath for reaction for 10h. After testing, the tensile shear strength of the bonded glass is 5.1MPa.

[0086] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the purpose and scope of the technical solution of the present invention, which should be included in the scope of the claims of the present invention.

Claims

1. A cellulose-based adhesive, characterized in that: The cellulose-based adhesive is a polymerization product of a cellulose-based adhesive precursor solution; the cellulose-based adhesive precursor solution comprises a cellulose suspension, a monomer and a catalyst; and the cellulose suspension comprises a cellulose solution and a coagulation bath system.

2. The cellulose-based adhesive according to claim 1, characterized in that The polymer product includes a cellulose graft copolymer generated by the reaction of cellulose and a monomer; And / or, the cellulose morphology in the cellulose suspension is at least one of nanofiber web, dendritic fiber, wrinkled fiber and ribbon fiber.

3. The cellulose-based adhesive according to claim 1 or 2, characterized in that: In the cellulose suspension, the cellulose is selected from at least one of the following substances: 1) microcrystalline cellulose; 2) bacterial cellulose; 3) at least one of cotton pulp, wood pulp, bamboo pulp, straw pulp, refined cotton, absorbent cotton, and cotton linters; and 4) cellulose extracted from plant tissues or low-quality cellulose; And / or, the solvent system of the cellulose solution is selected from at least one of the following substances or systems: 1) ionic liquid; 2) a mixed solvent of an ionic liquid and an organic co-solvent; 3) an organic co-solvent / salt system; 4) an amine oxide system (NMMO); 5) an alkali / urea system; 6) an organic acid system; or 7) an aqueous solution of a metal salt; And / or, the coagulation bath system comprises at least one of water, alcohol or alcohol-water mixture, HCl aqueous solution, inorganic salt aqueous solution, organic co-solvent aqueous solution, ionic liquid solution or a mixed solution thereof.

4. The cellulose-based adhesive according to any one of claims 1 to 3, characterized in that: The cellulose concentration in the cellulose suspension is 0.1 to 20 wt %; And / or, the monomer is a compound containing a carbon-carbon double bond; And / or, the compound containing a carbon-carbon double bond may be selected from at least one of acrylic acid, methacrylic acid, acrylate, acrylamide, acrylamide derivatives, acrylonitrile, vinyl acetate, and styrene; and / or, in the cellulose-based adhesive precursor solution, the monomer accounts for 0.1 to 50 wt% of the mass of the cellulose suspension; And / or, the mass ratio of cellulose to monomer is (0.1-20):(0.1-50); And / or, in the cellulose-based adhesive precursor solution, the mass percentage of the catalyst to the monomer is 0.01 to 10 wt %.

5. A method for preparing the cellulose-based adhesive according to any one of claims 1 to 4, characterized in that: The method comprises subjecting a cellulose-based adhesive precursor solution to a polymerization reaction to obtain the cellulose-based adhesive; wherein the cellulose-based adhesive precursor solution comprises a cellulose suspension, a monomer and a catalyst; and the cellulose suspension comprises a cellulose solution and a coagulation bath system.

6. The method according to claim 5, characterized in that The preparation method comprises the following steps: 1) Preparation of cellulose suspension: adding cellulose solution into a coagulation bath system to obtain cellulose suspension; 2) Preparation of cellulose-based adhesive precursor solution: adding monomers and catalysts to a cellulose suspension to obtain a cellulose-based adhesive precursor solution; 3) Preparation of cellulose-based adhesive: A cellulose-based adhesive precursor solution is polymerized to obtain a cellulose-based adhesive.

7. The method according to claim 6, characterized in that The state of the coagulation bath system in step 1) is a laminar flow or turbulent flow state; And / or, the catalyst in step 2) is ammonium cerium nitrate; And / or, the pH of the cellulose-based adhesive precursor solution in step 2) is 2-12.

8. A coating, characterized in that: The coating comprises the cellulose-based adhesive according to any one of claims 1-4.

9. A coating, characterized in that: The coating comprises the cellulose-based adhesive according to any one of claims 1 to 4 or the coating according to claim 8.

10. The cellulose-based adhesive of any one of claims 1 to 4 or the coating of claim 8 is used for coating or bonding an interface, wherein the interface comprises glass, metal, wood or other non-polar surfaces.

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