AU2022449624A1

AU2022449624A1 - Special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool

Info

Publication number: AU2022449624A1
Application number: AU2022449624A
Authority: AU
Inventors: Chunsheng DONG; Bingquan Li; Yuguo ZHU
Original assignee: Jiangsu Akst New Materials Co Ltd
Current assignee: Jiangsu Akst New Materials Co Ltd
Priority date: 2022-04-02
Filing date: 2022-06-28
Publication date: 2024-01-25
Also published as: CA3228230A1; WO2023184755A1; CN114621709A; CN114621709B

Abstract

The present invention provides a special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool, comprising the following components in parts by weight: 100 parts of a water-soluble resin prepolymer; 30-250 parts of a bio-based carbohydrate; 0-100 parts of monomolecular polycarboxylic acid; 0-5 parts of a wet strength modifier; 2-15 parts of a catalyst; and 0-20 parts of a pH value regulator. In the setting agent of the present invention, the natural renewable resource bio-based carbohydrate is used as a raw material, so that the mode of relying on petroleum resource raw materials is changed, the setting agent is a more environmentally-friendly material, and meanwhile, the costs of the setting agent are greatly reduced. In addition, the setting agent prepared by the present invention does not release free formaldehyde, meets the standard requirements of environmental protection, no VOC, and no formaldehyde, and has good dry and wet strength and water resistance, and the comprehensive performance that the dry strength is greater than 4.0 MPa, the wet strength is greater than 3.0 MPa, and the strength retention rate is greater than 60% can be achieved.

Description

SPECIAL HIGH-WATER-RESISTANCE BIO-BASED FORMALDEHYDE-FREE SETTING AGENT FOR MINERAL WOOL TECHNICAL FIELD

The present invention belongs to the field of polymer chemical materials, and in particular relates to a special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool.

BACKGROUND

Mineral wool insulation products are fluffy short thin fibers made from natural rocks and minerals as raw materials through high-temperature melting followed by fiberization, during which the physical and chemical properties of the mineral wool insulation material are improved and enhanced by utilizing the film-forming property of a setting agent on the surface of the mineral wool fibers and the bonding between the fibers. In mineral wool industry, it is usually necessary to use a setting agent, typically an aqueous oligomeric resin solution. Loose mineral wool is shaped into boards, felts, cotton and other products through curing and bonding of the resin, which imparts good physical and mechanical properties to the mineral wool insulation products and plays the role of bonding fibers to increase the strength of the mineral wool. Conventional mineral wool setting agents often require the use of chemical raw materials, such as phenol, urea, polymerized polyacid, and polyols. Those compounds are synthesized from petrochemical raw materials through a series of reactions. With the gradual depletion of petroleum resources, more and more companies are committed to developing the use of non-petrochemical raw materials in place of existing petrochemical raw materials in production processes. Therefore, it has gradually become an industry trend to find green and environmentally-friendly raw materials in place of the chemicals synthesized from petrochemical raw materials for use in mineral wool setting agents. Patent CN102363721A discloses an aqueous adhesive composition free of nitrogen containing Maillard reactants, which comprises: one or more polymeric polyacids with a weight average molecular weight equal to or greater than 1,000 and up to 500,000; carbohydrate components having a formula weight of up to 5,000, including monosaccharides and/or disaccharides and one or more oligosaccharides comprising three or more sugar groups; and 0.5-30 w% of one or more bleaching agents based on total weight of adhesive solids, wherein the ratio of OH groups in the carbohydrate components to carboxylic acid groups in the polymeric polyacids is equal to or less than 10.0:1 and equal to or greater than 0.2:1. However, compared with conventional phenolic resins, the adhesive prepared using this patent still has the problem of insufficient bonding strength in high-humidity and high-temperature environments; in addition, since the viscosity of the glue obtained in examples of this patent is relatively large, the problem of easy roller sticking during production also needs to be solved urgently.

SUMMARY

In order to solve the problem that the existing bio-based formaldehyde-free setting agents have insufficient strength, especially the low wet strength, which causes the performance of produced mineral wool to be easily degraded under high temperature and high humidity conditions, the present invention provides a special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool, comprising the following components in parts by weight on the basis of 100% solid content: t0 100 parts of a water-soluble resin prepolymer; 30-250 parts of a bio-based carbohydrate; 0-100 parts of monomolecular polycarboxylic acid; 0-5 parts of a wet strength modifier; 2-15 parts of a catalyst; and 0-20 parts of a pH value regulator. Among them, the water-soluble resin prepolymer is prepared from monomer raw materials through copolymerization, the monomer raw materials comprising the following components based on the amount of substance: a. 90 .0- 9 9 .0% of an ethylenically unsaturated carboxylic acid monomer; b. 0.5-5.0% of an ethylenically unsaturated hydroxy functional monomer; and c. 0.5-5.0% of a hydrophobic ethylenically unsaturated monomer. Preferably, the special formaldehyde-free setting agent for mineral wool of the present invention comprises the following components by weight on the basis of 100% solid content: 100 parts of a water-soluble resin prepolymer; 100-150 parts of a bio-based carbohydrate; 0-50 parts of monomolecular polycarboxylic acid; 0.5-3 parts of a wet strength modifier; 5-10 parts of a catalyst; and 0-15 parts of a pH value regulator. Among them, the water-soluble resin prepolymer is prepared from monomer raw materials through copolymerization, the monomer raw materials comprising the following components based on the amount of substance: a. 91.0-96.0% of an ethylenically unsaturated carboxylic acid monomer; b. 2.5-4.5% of an ethylenically unsaturated hydroxy functional monomer; and c. 1.5-4.5% of a hydrophobic ethylenically unsaturated monomer. Preferably, the number average molecular weight of the water-soluble resin prepolymer is 500-30,000, preferably 800-10,000, and most preferably 800-3,000. The number average molecular weight of the present invention is measured using gel permeation chromatography (GPC) technology. It has a solid content of 1-99%, preferably, 20-60%, and a pH value of 1.0-4.0. The ethylenically unsaturated carboxylic acid monomer of the present invention can be one or more of acrylic acid (AA), methacrylic acid (MA), crotonic acid, fumaric acid, maleic acid (MLA), 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, a-p methyleneglutaric acid, monoalkyl maleate, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctyl acrylic anhydride, crotonic anhydride or fumaric anhydride, preferably one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid or maleic acid. t0 The ethylenically unsaturated hydroxy functional monomer of the present invention includes but is not limited to hydroxyalkyl (meth)acrylate monomer, which can be one or more of 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 2 hydroxypropyl methacrylate (HPMA), 1-methyl-2-hydroxyethyl methacrylate, 2 hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate or 2-hydroxybutyl acrylate, preferably one or more of 2-hydroxyethyl acrylate or 2 hydroxyethyl methacrylate. The ethylenically unsaturated hydroxy functional monomer can effectively improve the bonding strength of the setting agent, especially the dry bonding strength. In the present application, it is found through research that when the addition amount of the ethylenically unsaturated hydroxy functional monomer is less than 0.5 mol%, it cannot significantly improve the strength; but if the addition amount is greater than 5 mol%, the viscosity of the setting agent will become unstable and is tend to increase gradually over time. The hydrophobic ethylenically unsaturated monomer of the present invention refers to a hydrophobic ethylenically unsaturated monomer that does not comprise carboxyl or hydroxy functional groups. It can further effectively improve the water resistance of the setting agent and block the hydrophilic functional groups of the setting agent to a certain extent, thereby effectively improving the wet strength and strength retention rate of the setting agent. The hydrophobic unsaturated monomer of the present invention includes but is not limited to acrylate monomers, which can be (meth)acrylate monomers, including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate or lauryl methacrylate; vinyl aromatic monomers, such as styrene, a-methylstyrene, p methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene or vinyltoluene; vinyl acetate monomers, such as vinyl acetate or vinyl butyrate; vinyl monomers, such as vinyl alcohol, vinyl chloride, vinyl toluene, vinyl benzophenone or vinylidene chloride; and other monomers that can participate in the polymerization reaction, such as acrylonitrile or glycidyl (meth)acrylate. Further, the hydrophobic unsaturated monomer of the present invention is preferably a hydrophobic unsaturated monomer with a water solubility of 0-1.5g/100g, which can be one or more of ethyl acrylate, n-butyl acrylate (BA), isobutyl acrylate (i-BA), sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate (PA), cyclohexyl acrylate (CHA), lauryl acrylate, 2-ethylhexyl acrylate (2-EHMA), methyl methacrylate, ethyl methacrylate, n butyl methacrylate (n-BMA), lauryl methacrylate (LMA), 2-ethylhexyl methacrylate (2 EHMA), isobornyl methacrylate (LMA), styrene, a-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene, vinyltoluene or chlorovinyltoluene. The applicant further found that when using the above-mentioned hydrophobic monomers, if a type of monomer (so-called soft monomer) of which homopolymers have a lower glass transition temperature (Tg) is used for the synthesis, the strength and strength retention rate of the obtained setting agent are further improved. For the sake of abbreviation, the Tg of a homopolymer of a monomer of the present invention is referred to as the Tg of the monomer. Meanwhile, the Tg of the present invention can be determined according to GB/T29611-2013 "Determination of Glass Transition Temperature of Raw Rubber, Differential Scanning Calorimetry (DSC)" with test conditions being a heating rate of 10°C/min and a nitrogen atmosphere. Without being constrained by any theory, the possible reason for the improvement is that the setting agent of the present invention itself is a product with high cross-linking density. The introduction of an appropriate amount of hydrophobic soft elastomer can improve the flexibility of the setting agent itself to a certain extent, thereby ultimately improving the bonding strength of the setting agent. Preferred low-Tg and low-solubility hydrophobic monomers of the present invention refers to a hydrophobic unsaturated monomer with a monomer Tg between -15°C and -80°C and a water solubility of 0-0.5g/100g, preferably one or more of n-butyl acrylate (BA), lauryl acrylate, n-propyl acrylate (n-BA), isobutyl acrylate, 2-ethylhexyl acrylate 2-EHA or lauryl methacrylate. The addition amount of the hydrophobic unsaturated monomer of the present invention is 0.5-5 mol%, preferably 1.5-4.5 mol%, and more preferably 3.0-4.5 mol%. If the addition amount is less than 0.5 mol%, the added unsaturated hydrophobic monomer cannot significantly improve the water resistance; but if the addition amount is greater than 5 mol%, the cross-linking density and bonding strength of the setting agent will decrease to a greater extent. Further, the applicant found that when the molar ratio of the ethylenically unsaturated hydroxy functional monomer b to the hydrophobic ethylenically unsaturated monomer c is 1:1.5 to 1.5:1 and the content of the monomer b is between 2.5-4.5 mol%, the setting agent has high dry and wet strength and a viscosity increased no more than 20%, i.e., a better performance. The bio-based carbohydrates of the present invention are monosaccharide, polysaccharide and oligosaccharide products derived from natural renewable resources, which are usually derived from fermentation products of plants such as corn, sugar cane, sorghum, and cassava. The monosaccharides of the present invention may include monosaccharides with 3 to 8 carbon atoms, such as xylose, arabinose, lactose, glucose, fructose, and sorbose, and may also include disaccharides, such as sucrose, lactose and maltose, and may also include oligosaccharides, such as maltotriose and maltodextrin, which comprise three or more sugar groups and have a number average molecular weight of less than or equal to 9,000. Based on the weight ratio of the components, it is preferred that among the bio-based carbohydrates of the present invention, the sum of content of the monosaccharide and disaccharide is greater than or equal to 55% of the total weight of the bio-based carbohydrates and the content of oligosaccharides is less than or equal to 45% of the total weight of the bio-based carbohydrates. The use of the bio-based carbohydrates from natural renewable resources in the setting agent of the present invention can be exempted from the limitations of petrochemical raw material sources, and the raw materials are easier to purchase and the cost is lowered. Without being constrained by any existing theory, the applicant believes that since during the high-temperature heating and curing process, part of the hydroxy groups of the bio-based carbohydrates participate in the reaction with the carboxylic acids of the water-soluble resin prepolymer and the other remaining hydroxy groups can undergo a sugar caramelization reaction at the same time, thereby generating a complex water-resistant cross-linked complex, the amount of the bio based carbohydrates used can be greatly increased compared to ordinary polyol products on the premise of without essentially reducing performance, greatly reducing the cost of the setting agent. The monomolecular polycarboxylic acid of the present invention refers to an organic carboxylic acid containing at least two carboxyl groups, preferably an organic acid containing 3 carboxyl groups. The reason why the present invention uses the monomolecular polycarboxylic acid is that its water-soluble viscosity is very low such that it can partially replace the above-mentioned water-soluble resin prepolymer (carboxylic acid polymer) as the cross-linking agent of the setting agent, thereby further reducing the viscosity of the setting agent, which is advantageous for reducing the problem of roller sticking during the production of mineral wool. As for the setting agent prepared by the solution of the present invention, based on a 50% solid content, the viscosity can reach below 200 cP, and some of the better ones can reach below 100 cP. The test method is to use a rotational viscometer to test at 30 rpm, 25°C with a 2# rotor. The molecular weight of the monomolecular polycarboxylic acid is less than or equal to 1,000, preferably less than or equal to 750, and more preferably less than or equal to 500. The monomolecular polycarboxylic acid can be a dicarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid and derivatives thereof (particularly comprising at least one boron or a chlorine atom), tetrahydrophthalic acid and derivatives thereof (particularly comprising at least one chlorine atom, such as chloromycin), isophthalic acid, terephthalic acid, methylfumaric acid and citraconic acid, or dicarboxylic acid precursors, especially anhydrides, such as maleic anhydride, succinic anhydride and phthalic anhydride; and also a tricarboxylic acid, such as citric acid, propanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, 1,2,3 benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acid; as well as a tetracarboxylic acid, such as 1,2,3,4-butanetetracarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid. Based on the weight of the components, the usage amount of the monomolecular polycarboxylic acid of the present invention is 0 to 100 parts, preferably 0 to 50 parts. t0 The wet strength modifier of the present invention refers to a carbodiimide-based modifier. The carbodiimide is a general term for a class of chemical substances containing a -N=C=N- functional group, including monomeric carbodiimide and polycarbodiimide, etc. Water-soluble polycarbodiimides are preferred in the present invention. Without being constrained by any theory, it is found in the present invention that by using a small amount of the wet strength modifier, the wet strength of the setting agent can be effectively improved. The possible reasons are the chemical reaction between the wet strength modifier and the carboxyl components in the setting agent, better hydrolysis resistance, and inhibition of hygroscopic attenuation of the product. The catalyst of the present invention refers to a catalyst that can promote the reaction between carboxylic acid and hydroxy group, such as a phosphorus-containing catalyst, such as hypophosphorous acid, hypophosphites (such as sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite or magnesium hypophosphite), alkali metal hypophosphites, alkali metal phosphites, alkali metal polyphosphates, alkali metal dihydrogen phosphates, polyphosphoric acids, alkylphosphinic acids or Lewis acids (which is a catalyst and can be sulfates, nitrates, halides, citrates, lactates or gluconates of zinc, aluminum, zirconium, iron, magnesium, tin, titanium or boron); and metal salts of inorganic acids, such as sodium (pyro)bisulfites or sulfites. The preferred catalyst of the present invention is hypophosphite, and the preferred hypophosphite is one or more of sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite or magnesium hypophosphite. Furthermore, in order to adjust the pH value of the setting agent and reduce the acid corrosion of devices caused by the setting agent, the present invention can also add a pH value regulator as needed. The selected pH value regulator can be ammonia, alkaline earth metal oxides, and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide; and organic amines such as alkanolamines, including monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, monoisopropanolamine, N-methyl diethanolamine, and 2-dimethylaminoethanol. The pH value regulator of the setting agent of the present invention is preferably one or more of ammonia, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, isopropanol amine, N methyldiethanolamine, and 2-dimethylaminoethanol. For the present invention, one or a combination of a coupling agent, a hydrophobic agent and a dust-proof oil can also be added. The coupling agent can construct a "molecular bridge" between interfaces of inorganic substances and organic substances, firmly combining the two materials of very different properties, improving the wet and anti-moisture strength of the setting agent, increasing the adhesion of the interfaces, eliminating internal stress and improving service life. The coupling agent of the present invention is preferably an epoxy siloxane coupling agent and an aminosilane coupling agent. Furthermore, the preferred amino coupling agent or epoxy coupling agent of the present invention is one or more selected from 3-(2,3 epoxypropoxy)propyltrimethoxysilane (KH560), 3-aminopropyltriethoxysilane (KH550), 3-(2,3-epoxypropoxy)propyltriethoxysilane (KH561) or 3-(2,3 epoxypropoxy)propyldimethoxysilane. The hydrophobic agent can effectively prevent the adsorption of water molecules on the surface of glass fibers, improving the hydrophobic performance of mineral wool. The dust-proof oil is used in mineral wool to effectively reduce the large amount of flying dust generated during production, cutting, processing, and transportation. Based on 100% solid content of the special formaldehyde-free setting agent for mineral wool, coupling agent, hydrophobic agent and dust-proof oil, the coupling agent, hydrophobic agent and dust-proof oil are added according to the following weight ratio: 100 parts of the special formaldehyde-free setting agent for mineral wool; 0.1-5 parts, more preferably 0.2-1.0 part of the coupling agent; 0-5 parts of the hydrophobic agent; and 0-10 parts of the dust-proof oil. Further, on the basis of the above components, water can be also added appropriately to the setting agent of the present invention as needed. Adding an appropriate amount of water can reduce the viscosity, which is beneficial for the transportation and use of the setting agent. Usually, the water can be pure water, tap water or other circulating water that does not affect the performance of the setting agent. Preferably, based on 100% solid content of the special formaldehyde-free setting agent for mineral wool, the amount of water added to every 100 parts by mass of the special formaldehyde-free setting agent for mineral wool is 0 to 200 parts by mass. The setting agent composition of the present invention is preferably a formaldehyde free copolymer composition. "Formaldehyde-free" means that the composition does not contain formaldehyde and does not release formaldehyde during curing. The additives used, such as the bio-based carbohydrate and other additives, themselves do not contain formaldehyde, and do not produce formaldehyde during polymerization, and no formaldehyde is generated or released during the treatment of the matrix.

In order to examine the storage stability of the setting agent of the present invention, in the present invention, its stability is characterized by testing the viscosity growth rate (%) before and after high-temperature maintaining a sample in a high-temperature oven at 60°C/4 weeks. Through this method, the stability of the setting agent can be effectively observed. In the present invention, the setting agent has preferably a viscosity growth rate (%) not higher than 20%, further preferably a viscosity growth rate not higher than 15%, and furthermore preferably a viscosity growth rate not higher than 10%, under the maintaining condition of 60°C/4 weeks. The test method for the bonding strength of the setting agent of the present invention is performed according to Appendix C of the standard GB/T 34181-2017 with differences in that the solid content of the setting agent of the present invention and the like is used instead of the premixed phenolic resin in Appendix C and the drying time is changed from the original 180°C/20min to 180°C/30min, while other steps remain unchanged. The resin content in the tests is uniformly 5%. The test of dry bonding strength is performed in accordance with the requirements of Appendix C of the standard under 23°C/50% condition. Meanwhile, in order to further examine the water resistance of the setting agent, it uses the concepts of wet strength and strength retention rate in the present invention to further observe the water and moisture resistance of the setting agent, namely, the wet strength is defined by testing the prepared sample after maintaining at a humidity of 90% and a temperature of 40 degrees for 24 hours, after the test is completed with the concept of the strength retention rate % = wet strength/dry strength. The applicant found that the special setting agent for mineral wool of the present application may not be completely evaluated using performance standards of matrix binders in the conventional composite material or adhesive industries which mainly focus on dry and wet bonding strength. In contrast, the application process of the setting agent of the present invention is aim to coating the liquid as evenly as possible on the fiber surface by spraying, and the shaping and performance of the mineral wool are mainly achieved through a kind of weak bonding in the form of point contact between fibers. During the continuous use of the mineral wool, the effect maintained by this weak bonding force is closely related to the dry strength, wet strength and strength retention rate of the setting agent. Thus, from this perspective, the dry strength, wet strength and strength retention rate of the setting agent are equally important indicators. A major innovation of the present invention is to comprehensively balance the three indicators, i.e., dry strength, wet strength and strength retention rate, by demanding that the dry strength of the setting agent is greater than 4.0 MPa, the wet strength is greater than 3.0 MPa, and the strength retention rate is greater than 60%. Through the optimization of these three indicators, the performance of the prepared mineral wool products is much better than conventional products, has good resistance to high-temperature and high-humidity environment, and has good construction performance.

Beneficial effects: 1. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool prepared by the present invention has no free formaldehyde release and meets the standard requirements of green, environmentally friendly, VOC-free and formaldehyde free; 2. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool prepared by the present invention uses a plenty of bio-based carbohydrates, and adds a large amount of carbohydrate raw materials from natural renewable resources, thereby altering the mode of relying on petroleum resource raw materials and greatly reducing the costs of the setting agent; 3. The high-water-resistance bio-based formaldehyde-free setting agent of the present invention has good stability, its viscosity does not change significantly (viscosity growth rate within 10%) under high temperature environment, which may achieve long-term stable storage, and can further reduce the viscosity by adding monomolecular polycarboxylic acid, thereby making it less likely to stick to the roller during production and thus convenient for continuous industrial production; and 4. The high-water-resistance bio-based formaldehyde-free setting agent prepared by the present invention can have good dry and wet strength as well as good water resistance, the comprehensive performance of the setting agent for mineral wool produced by the solution of the present invention can reach a dry strength greater than 4.0 MPa, a wet strength greater than 3.0 MPa and a strength retention rate greater than 60%, and the strength retention rate even greater than 70% if with a further optimized formulation, and thus it has good water resistance and aging resistance.

DETAIL DESCRIPTION OF THE INVENTION

The technical solutions in examples of the present invention will be described clearly and completely below. Apparently, the described examples are only parts, but not all of the examples of the present invention. Based on the examples of the present invention, all other examples obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. The current national standards and specifications referenced by relevant experiments listed in the present application are as follows: the test method for formaldehyde content of the setting agent is performed according to Appendix D of the standard GB/T 34181-2017 "Setting Agent for Mineral Wool Insulation Products"; and the testing method for performance of mineral wool refers to the following standards: GB/T 13350-2017 "Glass Wool and its Products for Thermal Insulation" and GB/T 19686-2015 "Rock Wool Insulation Products for Construction".

I. Stability test and bonding strength test of the setting agent Example 1 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 97.0: 1.5: 1.5; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 80 parts of the above resin prepolymer, 100 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 2 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 96.0: 1.5: 2.5; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 80 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 3 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 95.5: 1.5: 3.0; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 80 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards.

Example 4 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 94.0: 1.5: 4.5; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 80 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 5 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 94.5: 2.5: 3.0; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 40 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 6 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 94.5: 2.5: 3.0; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 80 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 7 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 94.5: 2.5: 3.0; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 120 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. t0 Example 8 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 94.5: 2.5: 3.0; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 160 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 9 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 94.0: 4.5: 1.5; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 100 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 10 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 93.0: 4.5: 2.5; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 100 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 11 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 92.5: 4.5: 3.0; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 100 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Example 12 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 91.0: 4.5: 4.5; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 100 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Comparative example 1 The composition of the resin prepolymer was acrylic acid and butyl acrylate in a molar ratio of 95.5: 4.5 without hydroxyethyl acrylate; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 80 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), 5 parts of catalyst sodium hypophosphite and 0.3 parts of coupling agent KH560 were mix together and then mixed homogeneously by adding an appropriate amount of water, formulated uniformly to have 50% solid content, and then maintained at a high temperature of 60°C for 4 weeks to test its viscosity change; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were also tested according to national standards. Comparative example 2 The composition of the resin prepolymer was acrylic acid and hydroxyethyl acrylate in a molar ratio of 95.5: 4.5 without butyl acrylate; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 100 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Comparative example 3 The composition of the resin prepolymer was acrylic acid and hydroxyethyl acrylate in a molar ratio of 94.5: 5.5 without butyl acrylate; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 100 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Comparative example 4 The composition of the resin prepolymer was acrylic acid, hydroxyethyl acrylate and butyl acrylate in a molar ratio of 99.0: 0.5: 0.5; the number average molecular weight Mn of the resin prepolymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 30 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards.

Comparative example 5 The composition of the resin prepolymer was solely the acrylic acid monomer without butyl acrylate and hydroxyethyl acrylate; the number average molecular weight Mn of the polymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 40 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Comparative example 6 The composition of the resin prepolymer was solely the acrylic acid monomer without butyl acrylate and hydroxyethyl acrylate; the number average molecular weight Mn of the polymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 80 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Comparative example 7 The composition of the resin prepolymer was solely the acrylic acid monomer without butyl acrylate and hydroxyethyl acrylate; the number average molecular weight Mn of the polymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 120 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. Comparative example 8 The composition of the resin prepolymer was only the acrylic acid monomer without butyl acrylate and hydroxyethyl acrylate; the number average molecular weight Mn of the polymer was 800; on a solid content basis, 100 parts of the above resin prepolymer, 160 parts of bio-based carbohydrates (comprising 55% maltose, 10% glucose, and 35% maltodextrin with a DE value of 14), and 5 parts of catalyst sodium hypophosphite were mix homogeneously by adding an appropriate amount of water, and formulated uniformly to have 50% solid content, and then a part of the sample was maintained at a high temperature of 60°C for 4 weeks to test its viscosity change, and another part of the sample was mixed with 0.3 parts of coupling agent KH560; and the dry and wet bonding strength, strength retention rate and formaldehyde content of the setting agent were tested according to national standards. t0 The formulation of the setting agents prepared in the above examples and comparative examples are shown in Table 1. Table 1 The composition of the formulation of the setting agent A B C D Composition of A (Parts by (Parts by (Parts by (Parts by Items weight) weight) weight) weight) AA HEA BA Prepolyme Bio-based Sodium (mol%) (mol%) rA carbohydr hypophosp KH560 (mol%) ate hite Example 1 97.0 1.5 1.5 100.0 80 5 0.3 Example 2 96.0 1.5 2.5 100.0 80 5 0.3 Example 3 95.5 1.5 3.0 100.0 80 5 0.3 Example 4 94.0 1.5 4.5 100.0 80 5 0.3 Example 5 94.5 2.5 3.0 100.0 40 5 0.3 Example 6 94.5 2.5 3.0 100.0 80 5 0.3 Example 7 94.5 2.5 3.0 100.0 120 5 0.3 Example 8 94.5 2.5 3.0 100.0 160 5 0.3 Example 9 94.0 4.5 1.5 100.0 100 5 0.3 Example 93.0 4.5 2.5 100.0 100 5 0.3 10 Example 92.5 4.5 3.0 100.0 100 5 0.3 11 Example 91.0 4.5 4.5 100.0 100 5 0.3 12 Comparati ve 95.5 0.0 4.5 100.0 80 5 0.3 example 1 Comparati ve 95.5 4.5 0.0 100.0 100 5 0.3 example 2 Comparati ve 94.5 5.5 0.0 100.0 100 5 0.3 example 3 Comparati ve 99.0 0.5 0.5 100.0 30 5 0.3 example 4 Comparati ve 100.0 0 0 100.0 40 5 0.3 example 5

A B C D Composition of A (Parts by (Parts by (Parts by (Parts by Items weight) weight) weight) weight) AA HEA BA Prepolyme Bio-based Sodium (mol%) (mol%) rA carbohydr hypophosp KH560 (mol%) ate hite Comparati ve 100.0 0 0 100.0 80 5 0.3 example 6 Comparati ve 100.0 0 0 100.0 120 5 0.3 example 7 Comparati ve 100.0 0 0 100.0 160 5 0.3 example 8

The performance test results of the setting agents prepared in the above examples and comparative examples are shown in Table 2. Table 2 The performance test results of the setting agents Viscosity growth rate Dry Wet Strength retention (%) after bonding bonding rate (dry Formaldehyde Items maintainence strength strength strength/wet content (%) at 600 C/4 (MPa) (MPa) strength, %) weeks Example 1 2 4.9 3.2 65.3% Not detected Example 2 2 4.4 3.2 72.7% Not detected Example 3 3 4.1 3.3 80.5% Not detected Example 4 2 4.0 3.4 85.0% Not detected Example 5 7 4.8 3.6 75.0% Not detected Example 6 6 5.1 3.8 74.5% Not detected Example 7 7 4.7 3.5 74.5% Not detected Example 8 7 4.0 3.0 75.0% Not detected Example 9 13 5.6 3.5 62.5% Not detected Example 10 13 5.2 3.6 69.2% Not detected Example 11 14 4.9 3.7 75.5% Not detected Example 12 13 4.7 3.6 76.6% Not detected Comparative example 1 0 3.6 2.7 75.0% Not detected Comparative example 2 13 5.3 3.1 58.5% Not detected Comparative example 3 26 5.8 3.5 60.3% Not detected Comparative example 4 1 4.3 2.7 62.8% Not detected Comparative example 5 0 4.2 2.8 66.7% Not detected Comparative example 6 0 4.4 2.9 65.9% Not detected Comparative example 7 0 3.9 2.6 66.7% Not detected Comparative example 8 0 3.7 2.4 64.9% Not detected It can be seen from the results in Table 1 and Table 2 above that when the addition amount of HEA and BA is between 0.5 and 4.5 mol%, the viscosity growth rate of the setting agent is not higher than 20%, the dry strength is greater than 4.0 MPa, the wet strength is greater than 3.0 MPa, and the strength retention rate is greater than 60%. On this basis, the addition of bio-based carbohydrates in a wide range of proportions can make the setting agent achieve a desirable performance. As shown in Example 8, even if the addition proportion of the bio-based carbohydrates reaches 160 parts, the viscosity growth rate of the setting agent is still not higher than 20%. Although the dry strength has somewhat decreased, the wet strength has not been significantly reduced, and the dry strength has remained greater than 4.0 MPa, the wet strength has remained greater than 3.0 MPa and the strength retention rate is greater than 60%, and the strength retention rate of some examples is greater than 70%, still showing good water resistance. t0 II. The influence of monomers with different solubility and Tg on the performance of the setting agents Example 13 is based on Example 8, except that lauryl acrylate is used instead of BA, the molecular weight Mn is 2,500, and other conditions remain unchanged. Example 14 is based on Example 8, except that 2-EHA is used instead of BA, the molecular weight Mn is 2,500, and other conditions remain unchanged. Comparative example 9 is based on Example 8, except that MA is used instead of BA, the molecular weight Mn is 2,500, and other conditions remain unchanged. Comparative example 10 is based on Example 8, except that MMA is used instead of BA, the molecular weight Mn is 2,500, and other conditions remain unchanged. The properties of the monomers used in the above examples and comparative examples are shown in Table 3. Table 3 Basic properties of the monomers Water Tgof Items Monomers solubility of Tof monomer, monomer, g/100g Example 13 Lauryl acrylate 0.001 -17 Example 14 2-EHA 0.01 -67 Comparative example 9 MA 5 8 Comparative example 10 MMA 1.59 105 The performance test results of the setting agents prepared in the above examples and comparative examples are shown in Table 4. Table 4 The performance test results of the setting agents Viscosity growth rate Dry Wet Strength (%) (high- bonding bonding retention Formaldehyde Items Itm epeauerate, (dry cotn() temperature strength strength strength/wet content maintainence (MPa) (MPa) strength/wet at 60°C/30 strength, %) days) Example 13 8 4.5 3.4 75.6% Not detected Example 14 9 4.7 3.5 74.5% Not detected

Comparative example 9 8 3.3 2.4 72.7% Not detected Comparative example 10 10 3.6 2.7 75.0% Not detected It can be seen from the results in Table 3 and Table 4 above that the use of monomers with different properties has a great impact on the performance of the setting agent. With an excessive lower monomer Tg and a higher water solubility, it is not conducive to improve the strength and water resistance of the setting agent.

III. The influence of different types of monomer on the performance of the setting agents Example 15 is based on Example 1, except that different raw materials and their proportion are used. Among them, the bio-based carbohydrate is sucrose and other specific raw materials and their proportion are shown in Table 5. Example 16 is based on Example 1, except that different raw materials and their proportion are used. Among them, the bio-based carbohydrate is sucrose and other specific raw materials and their proportion are shown in Table 5. Example 17 is based on Example 1, except that different raw materials and their proportion are used. Among them, the bio-based carbohydrate is sucrose and other specific raw materials and their proportion are shown in Table 5. Example 18 is based on Example 1, except that different raw materials and their proportion are used. Among them, the bio-based carbohydrate is sucrose and other specific raw materials and their proportion are shown in Table 5. Table 5 The composition of the formulation of the setting agent Composition of A A B C D (Parts by (Parts by (Parts by (Parts by a b c weight) weight) weight) weight) 1.5mol 1.5mol Prepolyme Bio-based Sodium 97mol% % % rA carbohydr hypophosp KH550 ate hite Example MA HEMA n-BA 100.0 100 7 0.4 15 AA:MLA Example =0.5:0.5 HEMA n-BA 100.0 100 7 0.4 16 (molar ratio) MA:MLA Example 0.75:0.25 HPMA n-BA 100.0 100 7 0.4 17 (molar ratio) MA:MLA Example 0.75:0.25 HPMA n-BA 100.0 100 7 0.4 18 (molar ratio)

The performance test results of the setting agents prepared in the above examples are shown in Table 6.

Table 6 The performance test results of the setting agents

Viscosity growth rate (%) Dry Wet Strength retention (high- bonding bonding rate, (dry Formaldehyde Items temperature strength strength strength/wet content (%) maintainence at (MPa) (MPa) strength, %) 60°C/30 days) Example 7 4.8 70.8% 15 3.4 Not detected Example 8 4.7 70.2% 16 3.3 Not detected Example 6 4.5 71.1% 17 3.2 Not detected Example 6 4.3 76.7% 18 3.3 Not detected

It can be seen from the results in Table 5 and Table 6 above that, use of the other monomer raw materials and their proportions provided in the solutions of the present invention within the scope supported by this specification also has a good performance. The comprehensive performance of the setting agent can provide the performance indicators of viscosity growth rate not higher than 20%, dry strength greater than 4.0 MPa, wet strength greater than 3.0 MPa, and strength retention rate greater than 60%.

t0 IV. The influence of the formulation of different raw materials on the performance of the setting agent Example 19 is based on Example 6. The composition of the resin prepolymer A is the same as that of Example 6 except for the use of different other raw materials and their proportion. Among them, the bio-based carbohydrates comprise 70% maltose, 5 % glucose, 5% fructose and 20% maltodextrin with a DE value of 17; the wet strength modifier is a water-soluble polycarbodiimide having a solid content of 40% from CA-01 of Shanghai Langyi Functional Materials Co., Ltd.; the pH value regulator is ammonia; and other specific raw materials and their proportion are shown in Table 7. Example 20 is based on Example 6. The composition of the resin prepolymer A is the same as that of Example 6 except for the use of different other raw materials and their proportion. Among them, the bio-based carbohydrates comprise 70% maltose, 5 % glucose, 5% fructose and 20% maltodextrin with a DE value of 17; the wet strength modifier is a water-soluble polycarbodiimide having a solid content of 40% from CA-01 of Shanghai Langyi Functional Materials Co., Ltd.; the pH value regulator is triethanolamine; and other specific raw materials and their proportion are shown in Table 7. Example 21 is based on Example 6. The composition of the resin prepolymer A is the same as that of Example 6 except for the use of different other raw materials and their proportion. Among them, the bio-based carbohydrates comprise 70% maltose, 5 % glucose, 5% fructose and 20% maltodextrin with a DE value of 17; the monomolecular polycarboxylic acid is citric acid; the wet strength modifier is a water-soluble polycarbodiimide having a solid content of 40% from CA-01 of Shanghai Langyi Functional Materials Co., Ltd.; and other specific raw materials and their proportion are shown in Table 7. Example 22 is based on Example 6. The composition of the resin prepolymer A is the same as that of Example 6 except for the use of different other raw materials and their proportion. Among them, the bio-based carbohydrates comprise 70% maltose, 5 % glucose, 5% fructose and 20% maltodextrin with a DE value of 17; the monomolecular polycarboxylic acid is malic acid; the wet strength modifier is a water-soluble polycarbodiimide having a solid content of 40% from CA-01 of Shanghai Langyi Functional Materials Co., Ltd.; and other specific raw materials and their proportion are shown in Table 7. Example 23 is based on Example 6. The composition of the resin prepolymer A is the same as that of Example 6 except for the use of different other raw materials and their proportion. Among them, the bio-based carbohydrates comprise 70% maltose, 5 % glucose, 5% fructose and 20% maltodextrin with a DE value of 17; the monomolecular polycarboxylic acid is citric acid; the wet strength modifier is a water-soluble polycarbodiimide having a solid content of 40% from CA-01 of Shanghai Langyi Functional Materials Co., Ltd.; and other specific raw materials and their proportion are shown in Table 7. Example 24 is based on Example 6. The composition of the resin prepolymer A is the same as that of Example 6 except for the use of different other raw materials and their proportion. Among them, the bio-based carbohydrates comprise 70% maltose, 5 % glucose, 5% fructose and 20% maltodextrin with a DE value of 17; the monomolecular polycarboxylic acid is malic acid; the wet strength modifier is a water-soluble polycarbodiimide having a solid content of 40% from CA-01 of Shanghai Langyi Functional Materials Co., Ltd.; and other specific raw materials and their proportion are shown in Table 7. Comparative example 11is the same as Example 19, except that no wet strength modifier is added. Comparative example 12 is the same as Example 21, except that no wet strength modifier is added. Comparative example 13 is the same as Example 23, except that no wet strength modifier is added. Comparative example 14 is the same as Example 23, except that no wet strength modifier is added, no monomolecular polycarboxylic acid is added, and all bio-based carbohydrates are replaced by maltodextrin with a DE value of 17. Comparative Example 15 is the same as Example 23, except that no wet strength modifier is added and the bio-based carbohydrate is changed to anhydrous glucose. Comparative Example 16 is the same as Example 23, except that no wet strength modifier is added and the bio-based carbohydrate is changed to polyol trimethylolpropane. Comparative example 17 is the same as Example 23, except that no wet strength modifier or the resin prepolymer A is added.

Table 7 The composition of the formulation of the setting agent

A B C D E F G (Parts by (Parts by (Parts by (Parts by (Parts by (Parts by (Parts by weight) weight) weight) weight) weight) weight) weight) Items Bio-based Sodium Monomole Wet Prepolyme carbohydrat hypophosphit KH561 ulcar strength pH value rAe e xoyicacid modifier regulator xylic acid Example 100.0 100 8 0.2 0 3.0 20 19 Example 100.0 100 8 0.2 0 0.5 15 20 Example 100.0 130 12 0.2 15 1.5 0 21 Example 100.0 220 12 0.2 60 2.5 0 22 Example 100.0 245 12 0.2 90 3.0 0 23 Example 100.0 245 12 0.2 95 4.5 0 24 Comparat

example 100.0 100 8 0.2 0 0 20

example 100.0 130 12 0.2 15 0 0 12 13 Comparat Comparat

example 100.0 245 12 0.2 90 0 0 13 example Comparat ive 100.0 245 12 0.2 90 0 0

14 Comparat

example 100.0 245 12 0.2 90 0 0 15 ive 100245 12 0.2 90 0 0 Comparat example 100 (oyl 16 Comparat ive10.241202900

exml 0 245 12 0.2 0 0 0 17 _ _ _ _ _ _ _ _ _ _

The performance test results of the setting agents prepared in the above examples and comparative examples are shown in Table 8. Among them, the pH value was tested with the PHS-3C model pH acidity meter from Shanghai Leici, and the viscosity was tested with the LVDV-2T from Shanghai Fangrui Instrument Co., Ltd.

Table 8 The performance test results of the setting agents

Viscosity growth rate (%) Viscosity, Strength (high- cP Dry Wet retention Items temperatu (50% pH bonding bonding rate,(dry Formaldehyde re solid value strength strength strength/wet content maintaine content,2 (MPa) (MPa) strength, %) nce at #,30 rpm) 60°C/30 days)

Example 6 6 179 3.5 5.1 3.8 74.5% Not detected

Example 19 2 136 6.8 4.7 4 85.1% Not detected

Example 20 2 <10a 5.2 4.8 3.6 75.0% Not detected Example 21 2 <10a < 1 .5b 4.6 3.6 78.3% Not detected

Example 22 2 <10a < 1 .5b 4.4 3.5 79.5% Not detected

Example 23 2 <10a < 1 .5b 4.3 3.7 86.0% Not detected

Example 24 2 <10a < 1 .5b 4.2 3.3 78.6% Not detected

Comparative 2 148 6.9 4.4 2.8 63.6% Not detected example11 Comparative 2 <10a < 1 .5b 4.7 2.6 55.3% Not detected example 12 Comparative 2 <10a < 1 .5b 4.1 2.5 61.0% Not detected example 13 Comparative 2 261 < 1 .5b 4.3 3.5 81.4% Not detected example 14 Comparative 2 <10a < 1 .5b 3.8 1.7 44.7% Not detected example 15 Comparative 2 126 < 1 .5b 2.6 0.8 30.8% Not detected example 16 Comparative 0 153 5.5 3.7 1.6 43.2% Not detected example 17

Note: a indicates that the test results exceed the testing range of the viscometer;

b indicates that the solution with too low pH value cannot be stably tested by the pH acidity meter, and the test result may be beyond the testing accuracy range of the acidity meter. It can be seen from Table 8 that using a pH value regulator together with a wet strength modifier can effectively increase the pH value of the system, thereby reducing the corrosion of the device caused by the setting agent; at the same time, after adding a wet strength modifier, a monomolecular polycarboxylic acid can be added to reduce the viscosity of the setting agent and reduce roller sticking that may occur during production; further, more bio based carbohydrates can be added, and the performance indicators of dry strength greater than 4.0 MPa, wet strength greater than 3.0 MPa, and strength retention rate greater than 60% of the setting agent can be achieved and meet the performance standard for setting agent in the present application; in contrast, it can be seen from Comparative example 14 that if the monomolecular polycarboxylic acid is not used and only oligosaccharides are used as the bio-based carbohydrates, the viscosity will be large (greater than 200cP), which may have adverse effects on later production process; if a monosaccharide such as glucose is used alone, it is found that the dry and wet strength properties of the setting agent are greatly attenuated; nevertheless, in Comparative Example 16, when a large amount of polyol was added to reach 245 parts, the performance was seriously attenuated; without being not constrained by any existing theory, this may be because excess polyols cannot caramelize themselves like biocarbohydrates, resulting in a serious excess of polyols. In conclusion, the proportion of the bio-based carbohydrates and the optimization of component content have an important impact on the performance.

V. Comparative testing of water resistance properties of mineral wool boards using different formulation The test examples of the present application each used the setting agent formulations of some examples and comparative examples in the present application to prepare mineral wool boards. Meanwhile, based on the 100% solid content of the special formaldehyde-free setting agent for mineral wool, 3 parts of hydrophobic agent and 6 parts of dust-proof oil were further added to 100 parts of the formaldehyde-free setting agent; an appropriate amount of water was added according to the demands of process. In terms of process, Test example 1 is the same as Comparative example 1, both are used to test rock wool boards; Test example 2 is the same as Comparative example 2, both are used to test slag wool boards; and Test example 3 is the same as Comparative example 3, both are used to test glass wool boards. The specific parameters are shown in Table 9 below:

Table 9 Parameters of water resistance test of mineral wool boards

#Test example Setting agent Organics Test product formulation content

Test example 1 Example 5 4% Rock wool board, density: 120K, thickness: 50mm

Comparative test Comparative 4% Rock wool board, density: 120K, example 1 example 5 thickness: 50mm

Test example 2 Example 23 3% Slag wool board, density: 100K, thickness: 50mm

Comparative test Comparative 3% Slag wool board, density: 100K, example 2 example 13 thickness: 50mm

Test example 3 Example 8 10% Glass wool board, density: 90K, thickness: 25mm

Comparative test Comparative 10% Glass wool board, density: 90K, example 3 example 8 thickness: 25mm

The mineral wool samples prepared according to above Table 9 were cut into two groups according to the national standard requirements. One group was used as the sample before aging and maintaining, and the strength was tested according to the national standard. The other group was used as the sample after aging and maintaining and was placed in a box with constant temperature and humidity, aging and maintaining for 7 days under the condition of 50±2°C and 95±3%, and then the strength was tested according to the national standard demands. Then, both the strength and strength retention rate before and after aging were recorded and the data are shown in Table 10 and Table 11. Table 10 Compressive strength testing results of mineral wool boards Compressive Compressive Strength #Test strength before strength after retention rate Test standard example maintainence, maintainence, KPa KPa %

Test example 30 25 83.3% 1 Comparative test example 27 16 59.3% GB/T 19686 1 2015 Test example 17 13 76.5% 2 Comparative test example 12 8 66.7% 2

Table 11 Bending failure load testing results of mineral wool boards Bending failure Bending failure Strength #Test example load, N load, N retention rate Test standard

Test example 63 55 87.3% 3 GB/T 13350 Comparative 56 34 60.7%2017 test example 3

It can be seen from Table 10 and Table 11 that various mineral wool boards prepared by using the setting agents having the formulations in the present invention have good post aging strength and post-aging strength retention rate. Other embodiments of the present invention will be readily apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. The present application is intended to contemplate any variations, uses, or adaptations of the present invention that follow the general principles of the present invention and include common knowledge or conventional technical means in the technical field that are not disclosed in the present invention. It is intended that the specification and examples are considered as illustrative only, with a true scope and spirit of the present invention being indicated by the following claims.

Claims

1. A special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool, comprising the following components in parts by weight on the basis of 100% solid content: 100 parts of a water-soluble resin prepolymer; 30-250 parts of a bio-based carbohydrate; 0-100 parts of monomolecular polycarboxylic acid; 0-5 parts of a wet strength modifier; 2-15 parts of a catalyst; and t0 0-20 parts of a pH value regulator; wherein the water-soluble resin prepolymer is prepared from monomer raw materials through copolymerization, the monomer raw materials comprising the following components based on the amount of substance: a. 90 .0- 9 9 .0% of an ethylenically unsaturated carboxylic acid monomer; b. 0.5-5.0% of an ethylenically unsaturated hydroxy functional monomer; and c. 0.5-5.0% of a hydrophobic ethylenically unsaturated monomer.

2. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, wherein the number average molecular weight of the water-soluble resin prepolymer is 500-30,000.

3. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, wherein the bio-based carbohydrate comprises a monosaccharide, a disaccharide and an oligosaccharide, wherein the sum of the content of the monosaccharide and disaccharide is greater than or equal to 55% of the total weight of the bio-based carbohydrate, and the content of the oligosaccharide is less than or equal to 45% of the total weight of the bio-based carbohydrate.

4. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 3, wherein the monosaccharide is one or more selected from xylose, arabinose, lactose, glucose, fructose or sorbose; the disaccharide is one or more selected from sucrose, lactose or maltose; and the oligosaccharide is one or more selected from maltotriose or maltodextrin.

5. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, wherein the molecular weight of the monomolecular polycarboxylic acid is not higher than 1,000.

6. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 5, wherein the monomolecular polycarboxylic acid is one or more selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid, chloromycin, isophthalic acid, terephthalic acid, methylfumaric acid, citraconic acid, maleic anhydride, succinic anhydride, phthalic anhydride, citric acid, propanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5 benzenetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or 1,2,4,5 benzenetetracarboxylic acid.

7. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, wherein the wet strength modifier is polycarbodiimide.

8. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, wherein the pH value regulator is one or more selected from ammonia, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, isopropanolamine, N-methyldiethanolamine or 2-dimethylaminoethanol.

9. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, wherein the ethylenically unsaturated carboxylic acid monomer is one or more selected from acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, a-p methyleneglutaric acid, monoalkyl maleate, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctyl acrylic anhydride, crotonic anhydride or fumaric anhydride; the ethylenically unsaturated hydroxy functional monomer is selected from 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1-methyl 2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate; the hydrophobic ethylenically unsaturated monomer is one or more selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate, cyclohexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate, 2 ethylhexyl methacrylate, isobornyl methacrylate, styrene, a-methylstyrene, p methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene, vinyltoluene or chlorovinyltoluene; and the catalyst is one or more selected from sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite or magnesium hypophosphite.

10. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 9, wherein the water solubility of the hydrophobic ethylenically unsaturated monomer is 0-1.5g/100g, and the glass transition temperature of its homopolymer is -15°C to -80°C.

11. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to any one of claims 1-10, comprising the following components in parts by weight on the basis of 100% solid content: 100 parts of a water-soluble resin prepolymer; 0-50 parts of a bio-based carbohydrate;

0-50 parts of monomolecular polycarboxylic acid; 0.5-3 parts of a wet strength modifier; 5-10 parts of a catalyst; and 0-15 parts of a pH value regulator; wherein the water-soluble resin prepolymer is prepared from monomer raw materials through copolymerization, the monomer raw materials comprising the following components based on the amount of substance: a. 91.0-96.0% of an ethylenically unsaturated carboxylic acid monomer; b. 2.5-4.5% of an ethylenically unsaturated hydroxy functional monomer; and t0 c. 1.5-4.5% of a hydrophobic ethylenically unsaturated monomer.

12. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 11, wherein the molar ratio of the ethylenically unsaturated hydroxy functional monomer to the hydrophobic ethylenically unsaturated monomer is 1:1.5 to 1.5:1.

13. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, comprising the following components in parts by weight on the basis of 100% solid content: 100 parts of the special formaldehyde-free setting agent for mineral wool; 0.1-5 parts of a coupling agent; 0-5 parts of the hydrophobic agent; 0-10 parts of the dust-proof oil; and 0-200 parts of water; wherein the coupling agent is one or more selected from 3-(2,3-epoxypropoxy) propyltrimethoxysilane (KH560), 3-aminopropyltriethoxysilane (KH550), 3-(2,3 epoxypropoxy) propyltriethoxysilane (KH561) or 3-(2,3-epoxypropoxy) propyldimethoxysilane.

14. The special high-water-resistance bio-based formaldehyde-free setting agent for mineral wool according to claim 1, wherein the setting agent has a dry strength greater than 4.0 MPa, a wet strength greater than 3.0 MPa, and a strength retention rate greater than 60%.