Low-loss bio-based formaldehyde-free mineral wool setting agent

Abstract

The invention belongs to the field of polymer chemical materials, and particularly relates to a low-loss bio-based formaldehyde-free mineral wool setting agent which comprises the following components in parts by weight on the basis of 100% of solid content: 100 parts of water-soluble lignin; 100 to 200 parts of a water soluble resin cross-linking agent; wherein the water-soluble resin cross-linking agent is prepared from monomer raw materials through a copolymerization reaction; the monomer raw material contains 70%-90% by mole of an ethylenically unsaturated carboxylic acid monomer and 10%-30% by mole of a hydrophobic ethylenically unsaturated monomer; the water-soluble lignin is lignosulfonate. According to the low-loss bio-based formaldehyde-free mineral wool setting agent provided by the invention, lignin generated from waste materials in pulping, papermaking and biorefinery industries is taken as a main raw material, so that the setting agent has the advantage of very low cost performance, and the produced and produced products are formaldehyde-free and meet the standard requirements of environmental protection, no VOC (Volatile Organic Compounds) and no formaldehyde; the prepared setting agent has good dry and wet strength and water resistance at the same time, and in addition, the prepared setting agent has the loss amount of 2% or below, which means that the curing temperature can be further reduced and the curing time can be further shortened in the actual production process, so that the process convenience and stability are improved.

Description

Technical Field

[0001] This invention belongs to the field of polymer chemical materials, specifically relating to a low-loss bio-based formaldehyde-free mineral wool sizing agent. Background Technology

[0002] Mineral wool is a new type of lightweight thermal insulation material, widely used in metallurgy, construction, petroleum, chemical, light textile, transportation and national defense industries. In particular, rock wool, a type of mineral wool, is receiving increasing attention in the construction and agricultural fields due to its outstanding thermal insulation, sound absorption and noise reduction, and fire safety properties.

[0003] The preparation of mineral wool products usually requires the use of a setting agent, which is generally an aqueous solution of oligomeric resin. Through the curing and bonding effect of the resin, the loose mineral wool is shaped into products such as boards, felts, and cotton, which plays the role of binding mineral fibers and increasing the strength of mineral wool.

[0004] In recent years, with increasingly stringent environmental regulations on the thermal insulation industry, traditional phenolic resin rock wool sizing agents have been subject to strict controls and even production shutdowns due to the large amounts of formaldehyde and phenol wastewater pollution they generate. Therefore, more and more companies are dedicated to developing more environmentally friendly and safer sizing agents to replace traditional phenolic resin sizing agents, such as binder compositions based on polycarboxylic polymers and polyols or polyamines, as disclosed in US5661213, CN106232699A, and WO2013 / 014399. Another type of non-phenolic resin sizing agent is the product of the addition / elimination reaction of aliphatic and / or aromatic anhydrides with alkanolamines, as disclosed in WO2006 / 061249. However, the resins used in these patents are chemical substances synthesized via petrochemical routes, which are non-renewable resources and relatively expensive; at the same time, petrochemical products are also high-carbon emission products. With the depletion of Earth's resources, people are paying increasing attention to resource scarcity, making the continuous development of green and environmentally friendly bio-based formaldehyde-free sizing agents imperative. In particular, the utilization of natural renewable biomass resources, especially waste natural renewable biomass resources, to transform them into formaldehyde-free, green, and environmentally friendly mineral wool fixatives has broad research and development prospects. Currently, syrup-based bio-based fixatives have been extensively studied, as disclosed in CN106232699A and CN102438962A. However, syrup is a high-cost raw material, and it undergoes a violent dehydration reaction at high temperatures, resulting in significant losses and increased final fixative usage costs. Therefore, there is an urgent need to find other natural renewable biomass resources that can replace syrup in the preparation of fixatives to achieve economical production.

[0005] Lignin (an aromatic polymer) is the main component of wood and the second most abundant carbon source on Earth after cellulose. It is formaldehyde-free and VOC-free, making it an environmentally friendly and renewable raw material. Common industrial lignin mainly comes from waste materials in the pulp and paper and biorefining industries. The pulp and paper industry produces approximately 50 million tons of lignin annually. In addition, the biorefining industry, which uses plant hydrolysis to produce energy ethanol, also generates a large amount of lignin each year. Therefore, lignin is a very low-cost renewable biomass resource.

[0006] Although lignin has been used to produce many chemicals and composite materials, its overall utilization rate is still less than 2%. Large quantities of low-cost lignin are typically used through direct combustion, a method that wastes resources and pollutes the environment, preventing its effective utilization. As an environmentally friendly, formaldehyde-free, and renewable raw material, lignin has excellent development prospects and economic value in its application in mineral wool styling agents as an environmentally friendly, formaldehyde-free alternative to trialdehyde resins. Summary of the Invention

[0007] Technical issues:

[0008] The purpose of this invention is to provide a low-loss, bio-based, formaldehyde-free mineral wool setting agent. Using industrial lignin, primarily derived from waste materials in the pulp and paper and biorefining industries, as raw material, and by adding suitable crosslinking agents and other additives, an environmentally friendly, high-bonding-strength, and economical mineral wool setting agent is prepared. Compared to techniques using syrup as a raw material for setting agents, this invention offers lower loss, higher curing efficiency, and higher utilization efficiency, further reducing the cost of formaldehyde-free setting agents. Furthermore, the crosslinking agent synthesized from olefinically unsaturated carboxylic acid monomers and hydrophobic olefinically unsaturated monomers in this invention significantly enhances the mechanical properties of the setting agent, achieving a balance between cost and performance.

[0009] Technical solution:

[0010] The first aspect of this invention provides a low-loss bio-based formaldehyde-free mineral wool setting agent, which, based on 100% solid content, contains the following components in the following weight ratios: water-soluble lignin: 100 parts; water-soluble resin crosslinking agent: 100-200 parts; wherein the water-soluble resin crosslinking agent is obtained by copolymerization of monomer raw materials; wherein the monomer raw materials contain 70%-90% olefinic unsaturated carboxylic acid monomers and 10%-30% hydrophobic olefinic unsaturated monomers by molar percentage.

[0011] In some embodiments, the low-loss bio-based formaldehyde-free mineral wool styling agent, calculated at 100% solid content, contains the following components in the following weight ratios: water-soluble lignin: 100 parts; water-soluble resin crosslinking agent: 120-150 parts; the monomer raw material contains 70%-85% olefinic unsaturated carboxylic acid monomers and 15%-30% hydrophobic olefinic unsaturated monomers by molar percentage.

[0012] The present invention limits the amount of water-soluble resin crosslinking agent added, taking into account both the bonding performance and cost of the setting agent. If the amount of water-soluble resin crosslinking agent added is too low, the bonding strength of the setting agent, especially the wet strength, will be low; if the amount added is too high, the improvement in bonding strength is limited. At the same time, since the water-soluble resin crosslinking agent is a petrochemical product, the cost of the setting agent is too high, resulting in a low cost-performance ratio.

[0013] In some embodiments, the water-soluble lignin is a lignin sulfonate.

[0014] Furthermore, the lignin sulfonate is one or more of sodium lignin sulfonate, potassium lignin sulfonate, magnesium lignin sulfonate, zinc lignin sulfonate, calcium lignin sulfonate, or ammonium lignin sulfonate.

[0015] Furthermore, the lignin sulfonate is one or more of zinc lignin sulfonate, calcium lignin sulfonate, and ammonium lignin sulfonate.

[0016] In some embodiments, the number average molecular weight of the water-soluble resin crosslinking agent is 2,000 to 30,000, preferably 5,000 to 28,000, and more preferably 8,000 to 28,000.

[0017] In some embodiments, the olefinic unsaturated carboxylic acid monomer is one or more of acrylic acid (AA), methacrylic acid (MAA), crotonic acid, fumaric acid, maleic acid (MLA), 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, α-β-methyleneglutaric acid, monoalkyl maleate, monoalkyl fumaric acid, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctylacrylic anhydride, crotonic anhydride, or fumaric anhydride.

[0018] Furthermore, the olefinic unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, or maleic anhydride.

[0019] Furthermore, the olefinically unsaturated carboxylic acid monomer is one or more of acrylic acid or maleic anhydride.

[0020] In some embodiments, the hydrophobic unsaturated monomer is one or more of the following: methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BA), isobutyl acrylate (i-BA), sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate (PA), cyclohexyl acrylate (CHA), 2-ethylhexyl acrylate (2-EHA), decyl acrylate, lauryl acrylate, methyl methacrylate (MMA), ethyl methacrylate, n-butyl methacrylate (n-BMA), isodecyl methacrylate, lauryl methacrylate (LMA), 2-ethylhexyl methacrylate (2-EHMA), isobornyl methacrylate, styrene (ST), α-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinyl xylene, vinyl toluene, vinyl acetate (VAC), vinyl butyrate, vinyl alcohol, vinyl chloride, vinyl toluene, vinyl benzophenone, vinylidene chloride, acrylonitrile, or glycidyl acrylate.

[0021] Further, the hydrophobic unsaturated monomer is one or more of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, styrene, α-methylstyrene, p-methylstyrene, vinyl acetate, and vinyl butyrate.

[0022] Furthermore, the hydrophobic unsaturated monomer is one or more of ethyl acrylate, methyl acrylate, n-butyl acrylate, methyl methacrylate, and styrene.

[0023] In some embodiments, the low-loss bio-based formaldehyde-free mineral wool styling agent also contains a catalyst.

[0024] In some embodiments, the amount of catalyst added is 2 to 15 parts based on 100% solid content.

[0025] In some embodiments, the catalyst is one or more of the following: hypophosphoric acid, alkali metal hypophosphorus, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkyl phosphonic acid, or Lewis acid; sodium (pyro)bisulfite, sulfite; sulfate, nitrate, halide, citrate, lactate, or gluconate of zinc / aluminum / zirconium / iron / magnesium / tin / titanium / boron.

[0026] Furthermore, the catalyst is a hypophosphite.

[0027] Furthermore, the hypophosphite is selected from one or more of sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite, or magnesium hypophosphite.

[0028] In some embodiments, the low-loss bio-based formaldehyde-free mineral wool styling agent further contains one or more of a coupling agent, a water-repellent agent, and a dust-proofing oil.

[0029] Coupling agents can build "molecular bridges" between inorganic and organic substances, firmly binding two materials with vastly different properties together. This improves the wetting and moisture resistance of the setting agent, increases interfacial adhesion, eliminates internal stress, and extends service life. Water-repellent agents effectively prevent water molecules from adsorbing onto the glass fiber surface, improving the water-repellent properties of mineral wool. Dust-proofing oils used in mineral wool can effectively reduce the large amounts of airborne dust generated during production, cutting, processing, and handling.

[0030] In some embodiments, the coupling agent is one or more of 3-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560), 3-aminopropyltriethoxysilane (KH550), 3-(2,3-epoxypropoxy)propyltriethoxysilane (KH561), or 3-(2,3-epoxypropoxy)propyldimethoxysilane.

[0031] Furthermore, the coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560).

[0032] In some embodiments, the low-loss formaldehyde-free mineral wool sizing agent, calculated based on 100% solid content, comprises the following components in the following weight ratios: water-soluble lignin + water-soluble resin crosslinking agent: 100 parts; catalyst: 2-15 parts; coupling agent: 0.1-5 parts; water-repellent agent: 0-5 parts; dust-proof oil: 0-10 parts.

[0033] In some embodiments, the low-loss bio-based formaldehyde-free mineral wool styling agent further includes water, and the amount of water added per 100 parts by weight of the bio-based formaldehyde-free mineral wool styling agent is 0 to 200 parts by weight, calculated based on 100% solid content bio-based formaldehyde-free mineral wool styling agent.

[0034] Furthermore, the water used is selected from purified water, tap water, or other recycled water that does not affect the performance of the setting agent.

[0035] In some embodiments, the loss of the low-loss bio-based formaldehyde-free mineral wool styling agent is less than or equal to 2%.

[0036] A second aspect of the present invention provides a mineral wool prepared using the low-loss bio-based formaldehyde-free mineral wool setting agent described in any one of the above claims.

[0037] Technical effects:

[0038] The purpose of this invention is to provide a low-loss, bio-based, formaldehyde-free mineral wool sizing agent. Using industrial lignin, primarily derived from waste materials in the pulp and paper and biorefining industries, as raw material, and by adding suitable crosslinking agents and other additives, an environmentally friendly, high-bonding-strength, and economical mineral wool sizing agent is prepared. Compared to techniques using syrup as a raw material for sizing agents, syrup undergoes a violent dehydration reaction at high temperatures, resulting in significant energy loss and increased sizing agent costs due to water evaporation. Furthermore, dehydration is an endothermic reaction; more dehydration means more energy consumption, requiring higher curing temperatures, longer curing times, and larger air volumes for curing. However, using the water-soluble lignin described in this invention as a raw material instead of syrup results in less dehydration, leading to higher efficiency and lower losses. In addition, the mineral wool sizing agent prepared by this invention recycles production waste, saving resources and further reducing costs. Moreover, the production process of this lignin-based mineral wool sizing agent is completely formaldehyde-free, and the use of a high-performance crosslinking agent overcomes the shortcomings of previous lignin-based sizing agents in terms of insufficient bonding strength. Furthermore, the bio-based formaldehyde-free mineral wool setting agent prepared by this invention also exhibits good dry and wet strength and water resistance. The setting agent has a dry strength > 2.5 MPa, a wet strength > 1.3 MPa, and a strength retention rate > 50%. Preferably, the setting agent has a dry strength > 3.0 MPa, a wet strength > 2.5 MPa, and a strength retention rate > 75%. Detailed Implementation

[0039] To facilitate the explanation of the technical solution of this application, the following is a general explanation and definition of the terms and expressions used in this application.

[0040] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0041] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0042] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight.

[0043] The sizing agent composition of the present invention is preferably a formaldehyde-free copolymer composition. "Formaldehyde-free" means that the composition does not contain formaldehyde, does not release formaldehyde during the curing process, and the additives used, such as crosslinking agents and other auxiliaries, are themselves formaldehyde-free. No formaldehyde is generated during the polymerization process, and no formaldehyde is generated or released during the treatment of the substrate.

[0044] The relevant experiments listed in this application refer to the following current national standards and specifications:

[0045] The test method for formaldehyde content in sizing agents shall be conducted according to Appendix D of standard GB / T 34181-2017 "Sizing Agents for Mineral Wool Insulation Products". The test methods for mineral wool properties shall refer to the following standards:

[0046] 1. GB / T 13350-2017 Glass wool and its products for thermal insulation.

[0047] 2. GB / T 19686-2015 Rock wool insulation products for building.

[0048] The test method for the adhesive strength of the setting agent described in this invention is conducted according to Appendix C of standard GB / T 34181-2017. The difference is that the premixed phenolic resin in Appendix C is replaced with the solid content of the setting agent of this invention, and the drying time is changed from 180℃ / 20min to 180℃ / 30min. Other steps remain unchanged. The resin content is uniformly tested at 5%. The dry adhesive strength is tested according to the requirements of Appendix C of the standard at room temperature of 23℃ / 50%RH. At the same time, in order to further examine the water resistance of the setting agent, this invention uses the concepts of wet strength and strength retention rate. That is, wet strength is defined as the strength of the prepared sample after curing at 90% humidity and 40℃ for 24h and then testing. After the test, the strength retention rate % = wet strength / dry strength is used to further observe the water and moisture resistance of the setting agent.

[0049] Test method for setting agent loss: Take 1g of sample and dry it in a hot air circulating oven at 120℃ / 2h (solid content test method specified in GB / T 34181-2017) and 200℃ / 10min respectively to test the solid content of the product. The solid content at 120℃ / 2h minus the solid content at 200℃ / 10min is the setting agent loss. Since the curing temperature of mineral wool products often reaches around 200℃ during the production curing process, the drying condition of 200℃ / 10min is closer to the actual production process conditions and has more practical reference value. By analyzing the quality differences of different formulations at low and high temperatures, the differences in high-temperature loss of different formulations can be evaluated.

[0050] The following specific embodiments further illustrate a low-loss bio-based formaldehyde-free mineral wool setting agent provided in this application.

[0051] The water-soluble sodium lignosulfonate and calcium lignosulfonate used in Examples 1-6 and Comparative Examples 1-6 were purchased from Xinyi Feihuang Chemical Co., Ltd., and ammonium lignosulfonate was purchased from Jiangsu Puleisi Biotechnology Co., Ltd. Zinc lignosulfonate was prepared by adding an appropriate amount of zinc sulfate to calcium lignosulfonate. The general preparation method is as follows:

[0052] (1) Prepare calcium lignosulfonate into an aqueous solution with a concentration of 20% to 60%;

[0053] (2) Gradually add zinc sulfate to calcium lignosulfonate, with the amount added being 20% ​​to 50% of the mass of calcium lignosulfonate;

[0054] (3) After the addition is complete, stir at room temperature for 20-180 min, then let stand, filter to remove the precipitate and obtain zinc lignosulfonate solution;

[0055] Zinc lignin sulfonate in this embodiment and comparative example was prepared by the following method:

[0056] (1) Prepare a 45% calcium lignosulfonate aqueous solution;

[0057] (2) Gradually add zinc sulfate to calcium lignosulfonate, with the amount added being 30% of the mass of calcium lignosulfonate;

[0058] (3) After the addition is complete, stir at room temperature for 60 minutes, then let stand, filter to remove the precipitate and obtain zinc lignosulfonate solution;

[0059] The solid content of the prepared zinc lignosulfonate was controlled to be 50%.

[0060] Example 1: Preparation of mineral wool sizing agent

[0061] The composition of the water-soluble resin crosslinking agent is as follows: the molar ratio of acrylic acid (AA) to ethyl acrylate (EA) is 75:25; the number-average molecular weight (Mn) of the water-soluble resin crosslinking agent is 8000 (the number-average molecular weight was obtained using gel permeation chromatography (GPC) technology, the same below). Based on solid content, 100 parts of water-soluble sodium lignosulfonate and 120 parts of the above-mentioned water-soluble resin crosslinking agent were mixed evenly with an appropriate amount of water to prepare a 50% solid content. Then, 0.3 parts of KH560 coupling agent were added and mixed together. The dry-wet bond strength, strength retention rate, and formaldehyde content of the setting agent were tested according to national standards.

[0062] Example 2: Preparation of mineral wool sizing agent

[0063] The formulation and process are the same as in Example 1, except that calcium lignosulfonate is used instead of sodium lignosulfonate.

[0064] Example 3: Preparation of mineral wool sizing agent

[0065] The formulation and process are the same as in Example 1, except that zinc lignosulfonate is used instead of sodium lignosulfonate.

[0066] Example 4: Preparation of mineral wool sizing agent

[0067] The formulation and process are the same as in Example 1, except that ammonium lignosulfonate is used instead of sodium lignosulfonate.

[0068] Example 5: Preparation of mineral wool sizing agent

[0069] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): ethyl acrylate (EA) molar ratio is 75:25; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 12000. Based on solid content, 100 parts of water-soluble calcium lignosulfonate and 120 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to achieve a solid content of 50%. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards.

[0070] Example 6: Preparation of mineral wool sizing agent

[0071] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): methyl acrylate (MA) molar ratio is 70:30; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 18000. Based on solid content, 100 parts of water-soluble calcium lignosulfonate and 150 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to achieve a solid content of 50%. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards.

[0072] Example 7: Preparation of mineral wool sizing agent

[0073] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): ethyl acrylate (EA) molar ratio is 75:25; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 25000. Based on solid content, 100 parts of water-soluble calcium lignosulfonate and 200 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to achieve a solid content of 50%. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards.

[0074] Example 8: Preparation of mineral wool sizing agent

[0075] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): maleic anhydride (MLA): styrene (ST) in a molar ratio of 65:25:10; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 28,000. Based on solid content, 100 parts of water-soluble calcium lignosulfonate and 100 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to achieve a solid content of 50%. Then, 3 parts of sodium hypophosphite and 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards.

[0076] Comparative Example 1: Preparation of Mineral Wool Fixing Agent

[0077] The formulation and process are the same as in Example 1, except for the composition of the water-soluble resin crosslinking agent: the monomer is entirely composed of acrylic acid and does not contain ethyl acrylate.

[0078] Comparative Example 2: Preparation of Mineral Wool Fixing Agent

[0079] The formulation and process are the same as in Example 1, except that glucose is used instead of sodium lignosulfonate.

[0080] Comparative Example 3: Preparation of Mineral Wool Fixing Agent

[0081] The formulation and process are the same as in Example 1, except that maltose is used instead of sodium lignin sulfonate.

[0082] Comparative Example 4: Preparation of Mineral Wool Fixing Agent

[0083] The formulation and process are the same as in Example 1, except that the molar ratio of acrylic acid (AA): ethyl acrylate (EA) in the water-soluble resin crosslinking agent is 92:8.

[0084] Comparative Example 5: Preparation of Mineral Wool Fixing Agent

[0085] The formulation and process are the same as in Example 1, except that the molar ratio of acrylic acid (AA): ethyl acrylate (EA) in the water-soluble resin crosslinking agent is 68:32.

[0086] Comparative Example 6: Preparation of Mineral Wool Fixing Agent

[0087] The formulation and process are the same as in Example 1, except that the number average molecular weight Mn of the water-soluble resin crosslinking agent is 1500.

[0088] The formulations of the sizing agents prepared in the above embodiments and comparative examples are shown in Table 1.

[0089] Table 1. Composition of the setting agent

[0090]

[0091] The performance test results of the fixatives prepared in the above examples and comparative examples are shown in Table 2 below.

[0092] Table 2 Results of performance tests for setting agents

[0093]

[0094]

[0095] The test results of the loss of the sizing agent prepared in the above examples and comparative examples are shown in Table 3 below.

[0096] Table 3. Test results of the loss of the setting agent.

[0097]

[0098]

[0099] As can be seen from the results in Tables 1 and 2 above, when the amount of EA added is between 10% and 30% molar, Example 2 to

[0100] The setting agent prepared in Example 8 exhibits a dry strength >3.0 MPa, a wet strength >2.5 MPa, and a strength retention rate >75%, demonstrating good overall performance. Outside these ranges, its dry strength, wet strength, and strength retention rate are all poor, or its water solubility is insufficient, which will limit its application in mineral wool. Furthermore, increasing the amount of water-soluble resin crosslinking agent can improve dry and wet strength within a certain range, but the performance improvement is limited beyond 150 parts. Moreover, because the crosslinking agent is derived from petrochemical routes, its cost is high, which is detrimental to the final cost of the setting agent. Surprisingly, under the same conditions, the wet strength of the setting agent formulations using calcium lignosulfonate, zinc lignosulfonate, and ammonium lignosulfonate was better than that using sodium lignosulfonate. This is not limited to any single theory; a possible reason is that calcium, zinc, or ammonium ions may have formed some form of coupling crosslinking, coordination crosslinking, or other reactions with carboxyl / hydroxyl groups (e.g., the setting agent color after curing with ammonium lignosulfonate in Example 4 was darker than other formulations, indicating a deeper reaction or other crosslinking reaction), which sodium ions do not exhibit. Furthermore, the results in Table 3 show that the loss of syrup used in the examples was significantly reduced compared to Comparative Examples 2 and 3. Compared to syrup, the loss of setting agent in the lignin-based examples was <2%, much lower than the 7% in Comparative Example 2 and 6% in Comparative Example 3. This further implies that the curing temperature can be further reduced and the curing time shortened in actual production processes, thereby improving process convenience and stability and saving production costs.

[0101] In summary, the results in Tables 1-3 above show that, within the scope supported by this specification, the sizing agent prepared using other monomer raw materials and proportions provided in this invention, as well as water-soluble lignin with different raw material compositions, also exhibits good performance: dry strength > 2.5 MPa, wet strength > 1.3 MPa, and strength retention rate > 50%.

[0102] Example 9: Comparative Test of Weather Resistance and Resilience of Glass Wool Felt with Different Formulas

[0103] In the experimental examples of this application, the sizing agent formulations of Example 5 and Comparative Example 2 of this invention were used to prepare glass wool mats, with the glass wool mats having a bulk density of 12 kg / cm³. 3The thickness is 100mm. Simultaneously, based on a 100% solid content of the formaldehyde-free mineral wool setting agent, 5 parts of water-repellent agent (purchased from Wacker Chemie (China) Co., Ltd., 5130) and 10 parts of dust-proof oil (purchased from Shanghai Mufa Industrial Co., Ltd., C307) were further added to 100 parts of the formaldehyde-free setting agent. Test Example 1 is the same as Comparative Test Example 1, both using glass wool felt for testing. All other process parameters were identical, the main difference being the curing temperature of the curing oven. Specific process parameters are shown in Table 4 below.

[0104] Table 4. Experimental parameter data for glass wool felt

[0105]

[0106]

[0107] The glass wool samples prepared in Table 4 were cut into pieces for testing the weather resistance and resilience of glass wool felt. Each sample was cut into 30*30cm pieces, and 6 pieces were cut into each group of samples. After cutting, the thickness was tested according to national standards and the average value was calculated. Then, the samples were placed in a constant temperature and humidity chamber, and each sample was subjected to continuous pressure of 100Pa by a thin metal plate. After aging and curing for 7 days at 50±2℃ and 95±3% humidity, the samples were taken out and the thickness was retested according to national standards and the average value was calculated. The thickness before and after aging was recorded. The thickness retention rate = thickness after curing / thickness before curing. The results are shown in Table 5.

[0108] Table 5. Resilience performance results of glass wool felt

[0109] Serial Number Thickness before curing / mm Thickness after curing / mm Thickness retention rate / % Experimental Example 1 102 92 91％ Experimental Example 2 101 98 97％ Comparative Test Example 1 101 79 78％ Comparative Test Example 2 103 98 95％

[0110] As can be seen from Table 5, the glass wool felt prepared using the sizing agent of the present invention in Experiment 1 still has good resilience and a thickness retention rate of ≥90% even at a lower curing temperature, basically reaching the initial thickness of the glass wool product. This data is better than the 78% of the comparative experiment 1. In contrast, the sizing agent formulation in comparative experiment 2 requires a higher curing temperature to obtain glass wool felt with a thickness retention rate of ≥90%, indicating that the sizing agent formulation of the present invention has better process performance than the formulation of comparative example 2.

[0111] The above specific embodiments further illustrate the purpose, technical solution and beneficial effects of this application. It should be understood that the above are only specific embodiments of this application and are not intended to limit the scope of protection of this application. Any modifications, equivalent substitutions, improvements, etc., made on the basis of the technical solution of this application should be included within the scope of protection of this application.

Claims

1. A low-loss, bio-based, formaldehyde-free mineral wool setting agent, characterized in that, Based on 100% solid content, it contains the following components in the following weight ratios: water-soluble lignin: 100 parts; water-soluble resin crosslinking agent: 100-200 parts; wherein, the water-soluble resin crosslinking agent is obtained from monomer raw materials through copolymerization reaction; the monomer raw materials contain 70%-90% olefinic unsaturated carboxylic acid monomers and 10%-30% hydrophobic olefinic unsaturated monomers by molar percentage; the water-soluble lignin is lignin sulfonate.

2. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 1, characterized in that, Based on 100% solid content, it contains the following components in the following weight ratios: water-soluble lignin: 100 parts; water-soluble resin crosslinking agent: 120-150 parts; the monomer raw material contains 70%-85% olefinic unsaturated carboxylic acid monomers and 15%-30% hydrophobic olefinic unsaturated monomers by molar percentage.

3. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 2, characterized in that, The number average molecular weight of the water-soluble resin crosslinking agent is 5000 to 28000.

4. The low-loss bio-based formaldehyde-free mineral wool styling agent according to claim 2, wherein the water-soluble lignin is one or more of sodium lignin sulfonate, potassium lignin sulfonate, magnesium lignin sulfonate, zinc lignin sulfonate, calcium lignin sulfonate, or ammonium lignin sulfonate.

5. The low-loss bio-based formaldehyde-free mineral wool styling agent according to claim 2, wherein the water-soluble lignin is one or more of zinc lignin sulfonate, calcium lignin sulfonate, or ammonium lignin sulfonate.

6. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 2, wherein the olefinic unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, α-β-methyleneglutaric acid, monoalkyl maleate, monoalkyl fumaric acid, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctylacrylic anhydride, crotonic anhydride, or fumaric anhydride; wherein the hydrophobic unsaturated monomer is methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, etc. Butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, styrene, α-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene, vinyltoluene, vinyl acetate, vinyl butyrate, vinyl alcohol, vinyl chloride, vinyltoluene, vinyl benzophenone, vinylidene chloride, acrylonitrile, or glycidyl (meth)acrylate, one or more of these.

7. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 6, characterized in that, The sizing agent also contains a catalyst; the amount of catalyst added is 2 to 15 parts based on 100% solid content; the catalyst is one or more of the following: hypophosphorous acid, alkali metal hypophosphorus, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkyl phosphinic acid, Lewis acid; sodium (pyro)bisulfite, sulfite; sulfate, nitrate, halide, citrate, lactate or gluconate of zinc / aluminum / zirconium / iron / magnesium / tin / titanium / boron.

8. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 7, characterized in that, The setting agent further comprises one or more of a coupling agent, a water-repellent agent, and a dust-proof oil; wherein the coupling agent is one or more of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, or 3-(2,3-epoxypropoxy)propyldimethoxysilane.

9. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 8, characterized in that, Based on 100% solid content, the components include the following weight ratios: water-soluble lignin + water-soluble resin crosslinking agent: 100 parts; catalyst: 2-15 parts; Coupling agent: 0.1-5 parts; water-repellent agent: 0-5 parts; dust-proof oil: 0-10 parts.

10. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 1, characterized in that, Further containing water, based on a 100% solid content bio-based formaldehyde-free mineral wool styling agent, the amount of water added per 100 parts by weight of bio-based formaldehyde-free mineral wool styling agent is 0 to 200 parts by weight.

11. The low-loss bio-based formaldehyde-free mineral wool setting agent according to claim 8, characterized in that... The loss of the low-loss bio-based formaldehyde-free mineral wool sizing agent is less than or equal to 2%.

12. Mineral wool prepared using the low-loss bio-based formaldehyde-free mineral wool setting agent according to any one of claims 1-11.

Images