Furan-free, low-taste, biobased, formaldehyde-free mineral wool setting agent

Abstract

This invention belongs to the field of polymer chemical materials, specifically relating to a furan-free, low-odor, bio-based, formaldehyde-free mineral wool styling agent. Based on 100% solid content, it contains the following components in the following weight ratio: polydextrose: 100 parts; water-soluble resin crosslinking agent: 100-200 parts; wherein the water-soluble resin crosslinking agent is obtained from monomer raw materials through a copolymerization reaction; the monomer raw materials contain 70%-90% olefinically unsaturated carboxylic acid monomers and 10%-30% hydrophobic olefinically unsaturated monomers by molar percentage. The mineral wool styling agent provided by this invention is free of furan and formaldehyde, environmentally friendly, and has a lower odor; furthermore, the styling agent has a loss rate of less than 2%, and also exhibits good dry and wet strength and water resistance.

Description

Technical Field

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

[0002] Mineral wool is widely used in metallurgy, construction, petroleum, chemical, light textile, transportation and military industries due to its lightweight, good thermal insulation, low thermal conductivity, strong heat resistance, sound insulation, waterproofing, chemical stability, acid and alkali resistance and non-corrosiveness.

[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, giving the mineral wool insulation products good physical and mechanical properties and playing the role of binding fibers to increase the strength of the mineral wool.

[0004] In recent years, as the country has further tightened its environmental regulations on the thermal insulation industry, traditional phenolic resin rock wool sizing agents have been subject to strict control or even production stoppages due to the large amount of formaldehyde and phenol wastewater pollution they generate. As a result, more and more companies are committed to developing more environmentally friendly and safer sizing agents to replace traditional phenolic resin sizing agents.

[0005] Currently, bio-based formaldehyde-free setting agents have attracted widespread attention, and there are already a large number of related published patent applications. For example, CN102363721A discloses a carbohydrate component of one or more monosaccharides or disaccharides and oligosaccharides having at least three sugar groups, a polyacid, and a bleaching agent, wherein the glucose equivalent (DE) value of the carbohydrate component of the composition is preferably ≥4, or the DE value is as high as 75, which can provide a thermosetting material with a light or white color and acceptable physical properties; CN106232699A discloses an aqueous adhesive composition comprising a polyglycidyl ether compound of one or more reducing sugars, one or more amino acids, and one or more polyols; CN102438962A discloses an aqueous adhesive composition comprising: (a) a syrup containing reducing sugars and having a glucose DE value of at least 50 and less than 85; (b) a polycarboxylic acid component; (c) an amine component; and, optionally, (d) a reaction product of the polycarboxylic acid component (b) and the amine component (c). However, all of these patents require bio-based carbohydrates or syrups to have a high DE value, typically between 4 and 100. The DE value is usually defined as the reducing sugar content. However, in practical use, it has been found that excessively high reducing sugar content can lead to several problems. For example, excessive reducing sugar content may cause excessive sugar volatilization in the curing oven, affecting the utilization rate of the setting agent. Furthermore, reducing sugars may easily produce furans and other caramel compounds under high-temperature conditions, ultimately affecting the taste of the mineral wool. This limits the use of mineral wool products in environments and applications where the taste of mineral wool is particularly important, such as ventilation ducts and household appliances.

[0006] Therefore, it is still necessary to develop a furan-free, low-odor, bio-based, formaldehyde-free mineral wool, so that the prepared mineral wool products are furan-free, have a lower odor, and are more suitable for use in environments and occasions where the odor of mineral wool is particularly important, such as ventilation ducts and household appliances; in addition, the prepared sizing agent should have a higher utilization rate, thereby improving its cost performance. Summary of the Invention

[0007] Technical issues

[0008] The purpose of this invention is to provide a furan-free, low-odor, bio-based, formaldehyde-free mineral wool styling agent. Using low-DE-value, water-soluble polydextrose as a raw material, and by adding suitable polyacrylic acid copolymer crosslinking agents and other additives, a furan-free, high-utilization, superior bonding strength, and low-odor, environmentally friendly mineral wool styling agent is prepared. Compared to traditional techniques using high-DE-value syrups as raw materials for styling agents, the styling agent of this invention is free of furan and formaldehyde, is environmentally friendly, and has a lower odor. Furthermore, the styling agent of this invention exhibits lower loss and higher utilization during use, resulting in a higher cost-performance advantage. In addition, the crosslinking agent synthesized by this invention using olefinically unsaturated carboxylic acid monomers and hydrophobic olefinically unsaturated monomers greatly enhances the wet bonding strength of the styling agent, making the product more suitable for use in high-temperature and high-humidity environments.

[0009] Technical solution

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

[0011] Furthermore, based on 100% solid content, the furan-free, low-odor, bio-based, formaldehyde-free mineral wool styling agent contains the following components in the following weight ratios: polydextrose: 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 polydextrose is a randomly cross-linked polymer formed by high-temperature melt polycondensation of more than 90% glucose, sorbitol or other polyols, citric acid and / or phosphoric acid, etc., in a specific ratio. It is primarily bonded by 1,6-glycosidic bonds, and the glucose content is typically >90% based on anhydrous solids content. The raw materials used in the polydextrose, such as glucose, sorbitol, and citric acid, are all renewable raw materials. The polydextrose described in this invention is typically selected from commercially available polydextrose that is soluble in water and has good solubility. The polydextrose described in this invention can be selected from polydextrose conforming to the GB 25541-2010 standard "Polydextrose".

[0014] In some embodiments, the polydextrose has an average number-average molecular weight of 700 to 5000.

[0015] In some embodiments, the glucose content in the polydextrose is less than 4%, preferably less than 3%, more preferably less than 2%, and even more preferably less than 1%.

[0016] In some embodiments, from the perspective of glucose equivalent (DE) value, the DE value of the polydextrose is less than 4, preferably less than or equal to 2.

[0017] As is well known, products such as glucose, fructose, malt syrup, glucose syrup, and corn syrup have high DE values ​​and a high content of reducing sugars. Reducing sugars are chemically reactive and, during high-temperature dehydration reactions with organic acids, easily undergo various complex caramelization reactions, producing various caramel flavors. This can be unacceptable to customers sensitive to caramel tastes. Therefore, the bio-based raw material polydextrose used in this invention contains very little glucose and other reducing sugars, minimizing the caramel flavor and resulting in a low-flavor, formaldehyde-free mineral wool fixative.

[0018] Furthermore, through arduous research, the patent applicant discovered that some existing bio-based formaldehyde-free mineral wool fixatives, when using reducing sugars such as glucose and other monosaccharides, can even produce furans under high temperatures and other specific conditions. For example, research shows that during the heat processing of food, the Maillard reaction occurs when reducing sugars and amino acids coexist, and the product can also form furans. Furans are colorless, volatile (boiling point 31°C), lipophilic organic compounds. The International Agency for Research on Cancer (IARC) discovered in 1995 that furans are carcinogenic and cytotoxic to rodents and classified them as Group 2B, possibly carcinogenic to humans. The U.S. Food and Drug Administration (FDA) reported the detection of furans in many heat-processed foods, especially canned heat-processed foods, including infant formula and milk powder. In addition, the FDA analyzed and tested nearly 340 food samples, finding furan content ranging from 0 to 170 ng / g. The European Food Safety Authority (EFSA) also tested a large number of heat-processed foods, and all results showed the presence of furans. Furans can potentially be generated during high-temperature curing in the presence of reducing sugars, amino acid compounds, organic amines, or ammonium compounds. Therefore, in the formaldehyde-free mineral wool sizing agent of this invention, the polydextrose content limits the reducing sugar content. Furthermore, the formaldehyde-free mineral wool sizing agent of this invention does not contain amino acid compounds, organic amines, or ammonium compounds. Consequently, the prepared formaldehyde-free mineral wool sizing agent does not produce furan during high-temperature curing, and formaldehyde has not been detected in mineral wool products prepared using this formaldehyde-free mineral wool sizing agent.

[0019] In some embodiments, the number average molecular weight of the water-soluble resin crosslinking agent is 500-5000, preferably 800-2000, and more preferably 800-1000.

[0020] 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, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, α-β-methyleneglutaric acid, monoalkyl maleate, monoalkyl fumaric acid, maleic anhydride (MLA), acrylic anhydride, methacrylic anhydride, isooctylacrylic anhydride, crotonic anhydride, or fumaric anhydride.

[0021] 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.

[0022] Furthermore, the olefinically unsaturated carboxylic acid monomer is one or more of acrylic acid or maleic anhydride.

[0023] 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.

[0024] 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.

[0025] Furthermore, the hydrophobic unsaturated monomer is one or more of ethyl acrylate, methyl acrylate, styrene, and n-butyl acrylate.

[0026] In some embodiments, the furan-free, low-odor, bio-based, formaldehyde-free mineral wool styling agent also contains a catalyst.

[0027] In some embodiments, the amount of catalyst added is 2 to 15 parts based on 100% solid content.

[0028] 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 hypophosphoric acid, or Lewis acid; sodium (pyro)bisulfite, sulfite; sulfate, nitrate, halide, citrate, lactate, or gluconate of zinc / aluminum / zirconium / iron / magnesium / tin / titanium / boron.

[0029] Furthermore, the catalyst is a hypophosphite.

[0030] Furthermore, the hypophosphite is selected from one or more of sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite, or magnesium hypophosphite.

[0031] In some embodiments, the furan-free, low-odor, 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.

[0032] 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.

[0033] 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.

[0034] Furthermore, the coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560).

[0035] In some embodiments, the furan-free, low-odor, formaldehyde-free mineral wool styling agent, calculated at 100% solid content, comprises the following components in the following weight ratios: polydextrose + 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.

[0036] In some embodiments, the furan-free, low-odor, 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.

[0037] 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.

[0038] In some embodiments, the loss of the furan-free, low-odor, bio-based, formaldehyde-free mineral wool styling agent is less than or equal to 2%.

[0039] A second aspect of the present invention provides a mineral wool prepared using the furan-free, low-odor, bio-based, formaldehyde-free mineral wool setting agent described in any one of the above-mentioned claims.

[0040] Technical effect

[0041] Compared to traditional high-DE-value, high-reducing-sugar syrups used as raw materials for preparing fixatives, which produce a strong caramel flavor due to the intense caramelization reaction of reducing sugars at high temperatures, the polydextrose used in this invention has a very low reducing sugar content and produces virtually no caramel flavor during the curing process. Therefore, compared to traditional high-DE-value syrups used as raw materials for preparing fixatives, the fixative of this invention does not contain furan and has a lower odor.

[0042] Furthermore, the setting agent of this invention is formaldehyde-free, making it more environmentally friendly.

[0043] Furthermore, the crosslinking agent synthesized by the present invention through olefinic unsaturated carboxylic acid monomers and hydrophobic olefinic unsaturated monomers has a high performance that greatly enhances the wet bonding strength of the setting agent, making the product more suitable for use in high temperature and high humidity environments.

[0044] 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 >3.5 MPa, a wet strength >2.5 MPa, and a strength retention rate >65%. Preferably, the setting agent has a dry strength >4.0 MPa, a wet strength >3.0 MPa, and a strength retention rate >70%.

[0045] Furthermore, the setting agent prepared by this invention has a loss rate of less than 2%, which means that the curing temperature can be further reduced and the curing time shortened in actual production processes, thereby improving process convenience and stability. Detailed Implementation

[0046] To facilitate the explanation of the technical solutions applied for, the terms and expressions used in this invention will first be explained and defined in general terms below.

[0047] The terms “comprising,” “including,” or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase “comprising one…” does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0048] In this invention, "glucose equivalent (DE)" refers to the percentage of reducing sugars in the dry matter of the syrup.

[0049] The "Maillard reaction" in this invention refers to the polymerization and condensation reactions that occur between amino-containing compounds and carbonyl compounds at room temperature or upon heating, ultimately producing brown or even brownish-black macromolecular substances called melanoidins or pseudomelanins, hence it is also known as the carbonylamine reaction. Besides producing melanoidins, the reaction also generates reductones, aldehydes, and heterocyclic compounds. Almost all foods containing carbonyl and amino groups can undergo the Maillard reaction under heating conditions.

[0050] The relevant experiments listed in this invention refer to the following current national standards and specifications:

[0051] 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:

[0052] 1. GB / T 13350-2017 Glass wool and its products for thermal insulation.

[0053] 2. GB / T 19686-2015 Rock wool insulation products for building.

[0054] 3. The odor test standard for formaldehyde-free mineral wool fixative is based on ASTM C3104-23, Standard Test Method for Assessing the Odor Emission of Thermal Insulation Materials. The odor level is classified into three levels: weak, medium, and strong.

[0055] 4. For furan content testing, refer to GB / T 29899-2013 and use high performance liquid chromatography (HPLC) for testing.

[0056] 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.

[0057] 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.

[0058] In the comparative experiments provided by this invention, unless otherwise specified, the experimental conditions and materials are kept consistent in order to ensure comparability.

[0059] Unless otherwise specified, all reagents and instruments used in the embodiments of this invention can be purchased from the market.

[0060] The following is a further description of the furan-free, low-odor, bio-based, formaldehyde-free mineral wool styling agent provided by the present invention.

[0061] Raw material description:

[0062] Polydextrose A, with a polydextrose content of 99.0%, a glucose content of 0.6%, a DE value of 1.1, and a number-average molecular weight of 3200;

[0063] Polydextrose B, with a polydextrose content of 98.2%, a glucose content of 1.1%, a DE value of 1.5, and a number-average molecular weight of 800;

[0064] A glucose syrup with a DE value of 70 is made from 40% glucose and 60% maltose.

[0065] A glucose syrup with a DE value of 25 is obtained by mixing 10% glucose, 10% maltose, and the remaining components are polysaccharide products.

[0066] Glucose with a theoretical DE value of 100.

[0067] Example 1: Preparation of mineral wool sizing agent

[0068] The composition of the water-soluble resin crosslinking agent is as follows: the molar ratio of acrylic acid (AA) to methyl acrylate (MA) is 70:30; the number-average molecular weight (Mn) of the water-soluble resin crosslinking agent is 5000 (the number-average molecular weight was obtained using gel permeation chromatography (GPC) technology, the same below). Based on solid content, 100 parts of polydextrose A 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, odor, furan content, and formaldehyde content of the setting agent were tested according to national standards.

[0069] Example 2: Preparation of mineral wool sizing agent

[0070] 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 3500. Based on solid content, 100 parts of polydextrose B 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, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0071] Example 3: Preparation of mineral wool sizing agent

[0072] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): ethyl acrylate (EA) molar ratio is 85:15; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 1500. Based on solid content, 100 parts of polydextrose A and 120 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to prepare a 50% solid content. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0073] Example 4: Preparation of mineral wool sizing agent

[0074] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): butyl acrylate (BA) molar ratio is 90:10; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 1000. Based on solid content, 100 parts of polydextrose A and 120 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to prepare a 50% solid content. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0075] Example 5: Preparation of mineral wool sizing agent

[0076] 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 600. Based on solid content, 100 parts of polydextrose A 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, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0077] Example 6: Preparation of mineral wool sizing agent

[0078] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): styrene (ST) molar ratio is 90:10; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 2000. Based on solid content, 100 parts of polydextrose A 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, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0079] Example 7: Preparation of mineral wool sizing agent

[0080] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): styrene (ST) molar ratio is 90:10; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 1500. Based on solid content, 100 parts of polydextrose A and 100 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to prepare a 50% solid content. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0081] Example 8: Preparation of mineral wool sizing agent

[0082] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): ethyl acrylate (EA) molar ratio is 70:30; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 4500. Based on solid content, 100 parts of polydextrose A and 200 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to prepare a 50% solid content. Then, 5 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, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0083] Example 9: Preparation of mineral wool sizing agent

[0084] The composition of the water-soluble resin crosslinking agent is as follows: acrylic acid (AA): maleic anhydride: methyl acrylate (MA) molar ratio is 70:20:10; the number average molecular weight (Mn) of the water-soluble resin crosslinking agent is 4500. Based on solid content, 100 parts of polydextrose A and 200 parts of the above-mentioned water-soluble resin crosslinking agent are mixed evenly with an appropriate amount of water to prepare a 50% solid content. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bond strength, strength retention rate, odor, furan content, and formaldehyde content of the setting agent are tested according to national standards.

[0085] Comparative Example 1: Preparation of Mineral Wool Fixing Agent

[0086] 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 composed entirely of acrylic acid and does not contain methyl acrylate.

[0087] Comparative Example 2: Preparation of Mineral Wool Fixing Agent

[0088] The formulation and process were the same as in Example 1, except that glucose (theoretical DE value 100) was used instead of polydextrose. Comparative Example 3: Preparation of mineral wool sizing agent.

[0089] The formulation and process were the same as in Example 1, except that glucose syrup (DE value 70) was used instead of polydextrose. Comparative Example 4: Preparation of mineral wool sizing agent.

[0090] The formulation and process were the same as in Example 1, except that glucose syrup (DE value 25) was used instead of polydextrose. Comparative Example 5: Preparation of mineral wool sizing agent.

[0091] 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.

[0092] Comparative Example 6: Preparation of Mineral Wool Fixing Agent

[0093] The formulation and process are the same as in Example 1, except that the molar ratio of acrylic acid (AA): methyl acrylate (MA) in the water-soluble resin crosslinking agent is 93:7, and the number average molecular weight Mn of the water-soluble resin crosslinking agent is 8000.

[0094] The formulations of the sizing agents prepared in the above embodiments and comparative examples are shown in Table 1.

[0095] Table 1. Composition of the setting agent

[0096]

[0097]

[0098] The performance test results of the fixatives prepared in the above examples and comparative examples are shown in Table 2 below.

[0099] Table 2 Results of performance tests for setting agents

[0100]

[0101] The test results of the loss of the sizing agent prepared in the above examples and comparative examples are shown in Table 3 below.

[0102] Table 3. Test results of the loss of the setting agent.

[0103]

[0104]

[0105] As can be seen from the results in Tables 1-3 above, compared with the traditional high DE value, high reducing sugar syrup used as raw material in Comparative Examples 2-4 for preparing the setting agent, the polydextrose scheme used in Examples 1-8 has a very low reducing sugar content, and the cured product has a very low taste level, i.e., a lower odor, and no furan or formaldehyde was detected, making it more environmentally friendly. Furthermore, the crosslinking agent with good performance synthesized by the present invention through olefinic unsaturated carboxylic acid monomers and hydrophobic olefinic unsaturated monomers greatly enhances the wet bonding strength of the setting agent, making the product more suitable for use in high temperature and high humidity environments, as shown in Examples 1-8. 8. When the amount of hydrophobic olefinic unsaturated monomer added is between 10% and 30% molar, the prepared setting agent has a dry strength > 4.0 MPa, a wet strength > 3.0 MPa, and a strength retention rate > 70%, exhibiting good comprehensive performance. Setting agents prepared outside this range have poor dry strength, wet strength, and strength retention rate, or insufficient water solubility, which will limit the subsequent application of mineral wool. Furthermore, the setting agent prepared by this invention has a loss rate of less than 2%, which means that the curing temperature can be further reduced and the curing time shortened in actual production processes, thereby improving process convenience and stability.

[0106] Mineral wool products were prepared using different formulations of setting agents, and their performance and taste levels were compared, as follows:

[0107] The experimental examples in this application used some of the sizing agent formulations from the embodiments and comparative examples in this application to prepare mineral wool boards. At the same time, based on the mineral wool-specific formaldehyde-free sizing agent with a solid content of 100%, 5 parts of water-repellent agent and 10 parts of dust-proof oil were further added to 100 parts of formaldehyde-free sizing agent. An appropriate amount of water was added according to the process requirements. Experimental Example 1 is the same as Comparative Experiments 1 and 2, and is used to test glass wool boards. The specific parameters are shown in Table 4 below.

[0108] Table 4. Water resistance test parameters for mineral wool boards

[0109]

[0110] The glass wool samples prepared in Table 4 above were cut into two groups according to the national standard requirements. One group was used as the sample before aging and curing, and its strength was tested according to the national standard. The other group was used as the sample after aging and curing. The samples were placed in a constant temperature and humidity chamber and aged for 7 days at 50±2℃ and 95±3% humidity. The strength was then tested according to the national standard (GB / T 13350-2017). The strength and strength retention rate before and after aging were recorded respectively. The data are shown in Table 5.

[0111] Table 5. Bending failure load and odor test results of glass wool board

[0112] Test Case Number Bending failure load, N Bending failure load, N Strength retention rate % Flavor Level Experimental Example 1 75 68 90.1％ weak Comparative Test Example 1 67 57 85.0％ middle Comparative Test Example 2 74 66 89.2％ powerful

[0113] As can be further seen from Tables 4 and 5, the glass wool board prepared using the sizing agent of the formulation of the present invention has better strength values ​​before aging and strength retention rate after aging, and has a lower odor. In contrast, the glass wool board prepared using the formulation of the comparative example requires a higher curing temperature to obtain similar strength and strength retention rate, and has a stronger odor level, making it unsuitable for use in situations requiring low odor.

[0114] Other embodiments of the invention will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention that follow the general principles of the invention and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of the invention are indicated by the following claims.

Claims

1. A furan-free, low-taste, 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: polydextrose: 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; the monomer raw materials contain 70%-90% olefinic unsaturated carboxylic acid monomers and 10%-30% hydrophobic olefinic unsaturated monomers by molar percentage.

2. The furan-free, low-taste, bio-based, no-formaldehyde 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: polydextrose: 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 furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to claim 2, characterized in that, The polydextrose has a number-average molecular weight of 700 to 5000; the water-soluble resin crosslinking agent has a number-average molecular weight of 500 to 5000.

4. The furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to claim 1, characterized in that, The raw materials for the polydextrose include glucose, sorbitol, citric acid and / or phosphoric acid; wherein the glucose equivalent (DE) of the polydextrose is less than 4.

5. The furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to claim 1, characterized in that, The olefinically unsaturated carboxylic acid monomer is one or more of the following: 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; the hydrophobic unsaturated monomer is methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-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.

6. The furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to claim 5, 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: hypophosphoric acid, alkali metal hypophosphorus, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkyl hypophosphoric acid, Lewis acid; sodium (pyro)bisulfite, sulfite; sulfate, nitrate, halide, citrate, lactate or gluconate of zinc / aluminum / zirconium / iron / magnesium / tin / titanium / boron.

7. The furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to claim 6, characterized in that, The setting agent further contains 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.

8. The furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to claim 7, characterized in that, Based on 100% solid content, the components include the following weight ratios: polydextrose + water-soluble resin crosslinking agent: 100 parts; catalyst: 2-15 parts; coupling agent: 0.1-5 parts; water-repellent agent: 0-5 parts; dust-proofing oil: 0-10 parts.

9. The furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to claim 1, characterized in that, The setting agent further contains water; calculated based on a 100% solid content setting agent, the amount of water added per 100 parts by weight is 0 to 200 parts by weight.

10. The furan-free, low-taste, bio-based, no-formaldehyde mineral wool setting agent according to any one of claims 1 to 9, characterized in that The loss of the setting agent is less than or equal to 2%.

11. Mineral wool prepared using the furan-free, low-odor, bio-based, formaldehyde-free mineral wool setting agent according to any one of claims 1-10.

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