Bio-based formaldehyde-free mineral wool setting agent based on molasses

Abstract

The invention belongs to the field of polymer chemical materials, and particularly relates to a molasses-based bio-based formaldehyde-free mineral wool setting agent which comprises the following components in parts by weight based on 100% of solid content: 100 parts of molasses; 80 to 300 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, and the monomer raw materials comprise the following components in percentage by mole: a, 70-90% of an ethylenic bond type unsaturated carboxylic acid monomer; and b, 10 to 30 percent of a hydrophobic ethylenic bond type unsaturated monomer. According to the molasses-based bio-based formaldehyde-free mineral wool setting agent provided by the invention, by-product molasses generated in a modern sugar production process is taken as a main raw material, both production and products are formaldehyde-free, the standard requirements of environmental protection, no VOC (Volatile Organic Compounds) and no formaldehyde are met, and the prepared setting agent has good dry and wet strength and water resistance at the same time.

Description

Technical Field

[0001] The present invention belongs to the field of polymer chemical materials, and particularly relates to a bio-based formaldehyde-free mineral wool sizing agent based on molasses. Background Art

[0002] Mineral wool generally includes rock wool, glass wool and slag wool, and has properties such as light weight, good heat preservation, low thermal conductivity, strong heat resistance, sound insulation, waterproof, stable chemical properties, acid and alkali resistance, and non-corrosion. It is a new type of lightweight heat preservation material. Mineral wool and its products are widely used in industrial sectors such as metallurgy, construction, petroleum, chemical industry, light textile, transportation and national defense. In particular, the application of rock wool in the mineral wool in the construction field has only seen vigorous development in recent years, and there is still great room for growth in the development in agricultural and other fields. Its outstanding heat insulation, sound absorption and noise reduction, and fire safety performance have received more and more attention from all walks of life.

[0003] In the mineral wool industry, a sizing agent is usually required. The sizing agent is generally an aqueous solution of oligomeric resin. Through the curing and bonding action of the resin, the loose mineral wool is shaped into products such as boards, felts, and cotton, endowing the mineral wool insulation products with good physical and mechanical properties, and playing a role in bonding fibers to increase the strength of the mineral wool. In recent years, with the further tightening of environmental protection supervision in the thermal insulation industry by the state, the traditional phenolic resin rock wool sizing agent has been strictly regulated or even shut down due to the production of a large amount of formaldehyde and phenol sewage pollution. Therefore, more and more enterprises are committed to developing more environmentally friendly and safe sizing agents to replace the traditional phenolic resin sizing agent.

[0004] Molasses is a by-product of the sugar industry. During the sugar production process, after the sugar solution is concentrated to precipitate crystalline sugar, the remaining brown viscous liquid has a relatively complex composition, mainly containing sucrose and some reducing sugars, as well as some organic non-sugar substances and inorganic components. Generally speaking, the solid content of molasses ranges from about 40% to 80%. Among the solids of molasses, approximately 40% to 60% are sucrose and reducing sugars, approximately 5% to 15% are organic non-sugar components, and approximately 5% to 15% are inorganic components. The organic non-sugar substances are very complex, and the main components include soluble colloids and other sugars, organic acids such as aconitic acid, citric acid, malic acid, succinic acid, vitamins, and other nitrogen-containing substances such as amino acids, proteins, etc.; the inorganic substances mainly come from elemental components such as sulfate ions, sodium, potassium, calcium, chlorine, phosphorus, etc. Moreover, the main raw material components of molasses vary greatly depending on the sugar raw materials and processing conditions. For example, cane molasses is a by-product of cane sugar factories, and its composition varies with the cane variety, maturity, planting climate, soil conditions, and the processing methods of the sugar factory. The molasses with relatively large yields include cane molasses, beet molasses, glucose molasses, and corn molasses, while the molasses with relatively small yields include invert molasses and refined molasses, etc. Generally, the effective sugar components of cane molasses and beet molasses are expressed by the total sugar content. For example, according to the industry standards of our country, "QB / T2684-2005 Cane Molasses" and "QBT5005-2016 Beet Molasses", the technical indicators of cane molasses are:

[0005] 1. Total sugar content (sucrose content + reducing sugar content) (g / 100g) ≥ 48%;

[0006] 2. Purity (total sugar content / refractive brix) (g / 100g) ≥ 60%;

[0007] 3. Total ash content (sulfated ash) (g / 100g) ≤ 12.0%.

[0008] The technical indicators of beet molasses are:

[0009] 1. Total sugar content (sucrose content + reducing sugar content) (g / 100g) ≥ 45%;

[0010] 2. Purity (total sugar content / refractive brix) (g / 100g) ≥ 56%;

[0011] 3. Total ash content (sulfated ash) (g / 100g) ≤ 12.0%.

[0012] U.S. Patent No. 5,661,213 discloses a curable aqueous composition comprising a polymerized polyacid polyol and a phosphite promoter; this composition can be used as a binder in heat-resistant nonwoven fabrics such as those made of glass fibers. However, the adhesive prepared from this composition has insufficient bonding strength when bonding cotton boards with high performance requirements, especially poor strength in high-temperature and high-humidity environments, which causes the cotton boards to sag easily during construction, resulting in many inconveniences and reducing construction efficiency. At the same time, the polymerized polyacid resin used in this patent is a chemical substance synthesized from a petrochemical technology route. As is well known, petrochemical products are non-renewable resources, their sources are not sustainable, and their prices are relatively high. At the same time, petrochemical products are also high-carbon emission products. It has become a global consensus to use renewable low-carbon emission products as much as possible.

[0013] CN106232699A discloses an aqueous adhesive composition comprising one or more reducing sugars, one or more amino acids, and a polyglycidyl ether compound of one or more polyols. Compared with existing phenolic resin (PFR), it is inexpensive and can exhibit physical properties equivalent to or better than those of PFR, and does not contain or release toxic substances such as formaldehyde or phenol. During processing, it can reduce the odor problem, which is a defect of existing PFR resins, and can significantly improve the mechanical properties such as water resistance, tensile strength, and hardness of the processed product, as well as the dust rate. However, the reducing sugar used in this method is food-grade syrup, and its cost is still relatively high and not economical.

[0014] CN102438962A discloses an aqueous binder composition comprising: (a) a syrup containing a reducing sugar and having a dextrose equivalent DE 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). It mentions that molasses can be used to prepare the aqueous binder composition and its use for bonding mineral fiber products. However, the polycarboxylic acid component described in this patent belongs to monomolecular or small-molecule polycarboxylic acids, and the strength of the composition prepared by this formulation is insufficient. Moreover, among the amine components described, the raw material used in the best example is ammonia water. As is well known, ammonia water is a hazardous chemical with high irritation and environmental harmfulness, and the environmental performance of the technical solution described in this patent is still lacking.

[0015] With the depletion of the earth's resources, people are paying more and more attention to the problem of resource shortage. It is imperative to develop a green and environmentally friendly bio-based formaldehyde-free sizing agent. In particular, converting natural renewable biomass resources, especially waste natural renewable biomass resources, into formaldehyde-free, green, and environmentally friendly mineral wool sizing agents has broad prospects for research and development. Summary of the Invention

[0016] The present invention aims to overcome the shortcomings of the prior art by providing a molasses-based bio-based formaldehyde-free mineral wool setting agent. Molasses, a byproduct or even production waste from modern sugar production, is used as the primary raw material. By adding a suitable crosslinking agent and other additives, an environmentally friendly bio-based formaldehyde-free mineral wool setting agent is produced. The molasses-based bio-based formaldehyde-free mineral wool setting agent prepared by the present invention recycles production waste resources, conserving resources and reducing costs.

[0017] The present invention provides a molasses-based bio-based formaldehyde-free mineral wool setting agent, which comprises the following components in weight ratios calculated based on 100% solid content: molasses: 100 parts; water-soluble resin cross-linking agent: 80-300 parts;

[0018] The water-soluble resin crosslinking agent is prepared from monomer raw materials through copolymerization reaction. The monomer raw materials include the following components by molar percentage: a, ethylenically unsaturated carboxylic acid monomer: 70-90%; b, hydrophobic ethylenically unsaturated monomer: 10-30%.

[0019] The composition of molasses' main raw materials can have significant quality variation depending on the variety and origin. The molasses industry standard stipulates a purity of ≥60% and a total ash content of ≤12.0%, indicating that molasses contains a high concentration of soluble inorganic and organic non-sugar components. These components are difficult to remove through simple methods, and complex technical means would incur significant costs, making them uneconomical. Furthermore, from a formulation design perspective, these complex components are expected to significantly negatively impact the adhesive strength of the setting agent. This is a technical difficulty that the present invention aims to overcome. The molasses described in this invention may cause significant fluctuations in the quality of the setting agent due to inherent quality variations. To minimize the quality of waste molasses, the waste molasses described in this invention refers to molasses with the following parameters: total sugar content (sucrose + reducing sugars ≥45%); purity (total sugars / refractive brix ≥56%); and total ash content (sulfated ash ≤12%).

[0020] In some embodiments, the components and contents of the molasses are as follows by weight: 40-60% sucrose and reducing sugars, 5-15% organic non-sugar components, 5-15% total ash, and 20-50% water; the soluble solid components of the molasses are sucrose and reducing sugars, organic non-sugar components, and total ash; and the soluble solid content accounts for 50-80% of the molasses components.

[0021] In some embodiments, the number-average molecular weight of the water-soluble resin crosslinking agent is 500 to 30,000, the solid content is 1 to 99%, and the pH value is 1 to 3; the addition amount of the water-soluble resin crosslinking agent is 90 to 200 parts.

[0022] In some embodiments, the number-average molecular weight of the water-soluble resin crosslinking agent is 1,000 to 5,000, the solid content is 20 to 60%, and the addition amount is 100 to 150 parts. The addition amount of the water-soluble resin crosslinking agent defined in the present invention is comprehensively considered in terms of the bonding performance and cost of the setting agent. If the addition amount of the water-soluble resin crosslinking agent is too low, the bonding strength of the setting agent, especially the wet strength, is low; if the addition amount is too large, not only the improvement of the bonding strength performance is limited, but also since the water-soluble resin crosslinking agent belongs to petrochemical products, the cost of the setting agent is too high and the cost performance is low.

[0023] The ethylenically unsaturated carboxylic acid monomer described in the present invention may be one or more of acrylic acid (AA), methacrylic acid (MAA), crotonic acid, fumaric acid, maleic acid (MLA), 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, α-β-methylene glutaric acid, monoalkyl maleate, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctyl acrylic anhydride, crotonic anhydride or fumaric anhydride, and is preferably one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid or maleic acid.

[0024] The hydrophobic ethylenically unsaturated monomer described in the present invention refers to a hydrophobic ethylenically unsaturated monomer that does not contain carboxyl or hydroxyl functional groups. It can significantly and effectively improve the water resistance of the sizing agent, and has a good shielding effect on the hydrophilic functional groups of the sizing agent, especially the large number of hydrophilic groups in molasses waste, thereby effectively improving the wet strength and strength retention rate of the sizing agent. The hydrophobic unsaturated monomers described in the present invention include, but are not limited to, acrylate monomers, which can be (meth)acrylate monomers, including 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, etc.; it can also be vinyl aromatic monomers, such as styrene (ST), α-methylstyrene, p-methylstyrene, ethyl vinylbenzene, vinylnaphthalene, vinylxylene or vinyltoluene; vinyl acetate monomers, such as vinyl acetate (VAC) or vinyl butyrate; vinyl monomers, such as vinyl alcohol, vinyl chloride, vinyltoluene, vinyl benzophenone or vinylidene chloride; it can also be other monomers that can participate in the polymerization reaction, such as acrylonitrile or glycidyl (meth)acrylate.

[0025] The addition amount of the hydrophobic unsaturated monomer described in the present invention is 10 to 30% molar parts, preferably 15 to 25% molar parts. If the addition amount is less than 10% molar parts, the added unsaturated hydrophobic monomer cannot play an obvious role in improving water resistance. If the addition amount is greater than 30% molar parts, the water solubility of the crosslinking agent will become very low, and even lose water solubility, making it inapplicable to the continuous production process of mineral wool.

[0026] In some embodiments, the molasses-based bio-based formaldehyde-free mineral wool sizing agent can also be added with a catalyst as needed. Calculated based on 100% solid content, the addition amount of the catalyst is 2 to 15 parts.

[0027] The catalyst described in the present invention refers to a catalyst that can promote the reaction between carboxylic acid and hydroxyl group, such as phosphorus-containing catalysts, for example, hypophosphorous acid, hypophosphite, alkali metal hypophosphite, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkyl phosphinic acid or Lewis acid; hypophosphites such as sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite or magnesium hypophosphite; it can also be a metal salt of inorganic acid, such as (pyro) sodium bisulfite or sulfite; the Lewis acid catalyst can be sulfate, nitrate, halide, citrate, lactate or gluconate of zinc, aluminum, zirconium, iron, magnesium, tin, titanium or boron. 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.

[0028] For the present invention, one or several combinations of coupling agents, water repellents and dust-proof oils can also be added. The coupling agent can build a "molecular bridge" between the interfaces of inorganic and organic substances, firmly combine two materials with very different properties, improve the wetting and wet strength resistance of the sizing agent, increase the bonding performance of the interface, eliminate internal stress, improve the service life. The preferred coupling agents of the present invention are epoxy silane coupling agents and amino silane coupling agents. Further, the preferred amino coupling agent or epoxy coupling agent in the present invention is selected from 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; the water repellent can effectively prevent water molecules from adsorbing on the surface of glass fiber and improve the water repellent performance of mineral wool; the dust-proof oil can effectively reduce a large amount of flying dust generated during the production, cutting, processing and handling of mineral wool. The molasses-based bio-based formaldehyde-free mineral wool sizing agent includes molasses, water-soluble resin crosslinking agent, coupling agent, water repellent and dust-proof oil, and is added according to the following weight ratio based on 100% solid content:

[0029] Molasses, water-soluble resin crosslinking agent: 100 parts; coupling agent: 0.1 - 5 parts; water repellent: 0 - 5 parts; dust-proof oil: 0 - 10 parts.

[0030] Further, on the basis of the above components, the sizing agent of the present invention can also appropriately add water as needed. Adding an appropriate amount of water can reduce the viscosity and is beneficial to the transportation and use of the sizing agent. Usually, water can be selected as pure water, tap water or other circulating water that does not affect the performance of the sizing agent. Calculated based on 100% solid content of the formaldehyde-free sizing agent for mineral wool, the addition amount of water per 100 mass parts of the formaldehyde-free sizing agent for mineral wool is 0 - 200 mass parts.

[0031] 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, the additives used, such as crosslinking agents and other auxiliaries, etc. do not contain formaldehyde themselves, formaldehyde is not generated during the polymerization process, and formaldehyde is not generated or released during the process of treating the substrate.

[0032] Advantages:

[0033] The present invention provides a molasses-based bio-based formaldehyde-free mineral wool sizing agent, which uses molasses, a by-product generated during modern sugar production, as the main raw material. Both the production and the product are formaldehyde-free, meeting the standard requirements of green environmental protection without VOC and formaldehyde. The prepared bio-based formaldehyde-free mineral wool sizing agent has good dry and wet strength and water resistance at the same time. The dry strength of the sizing agent is >3 MPa, the wet strength is >2 MPa, and the strength retention rate is >62%. Detailed implementation manners

[0034] To enable those skilled in the art to understand the characteristics and effects of the present invention, the following provides a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meaning understood by those skilled in the art regarding the present invention. In case of conflict, the definition in this specification shall prevail.

[0035] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0036] In this article, all features defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are only for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be regarded as having covered and specifically disclosed all possible sub-ranges and individual numerical values within the range (including integers and fractions).

[0037] In this article, for the sake of concise description, all possible combinations of all technical features in each embodiment or example are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered to be within the scope described in this specification.

[0038] The following further elaborates the present invention in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0039] In the following examples, conventional instruments and equipment in the art are used. For the experimental methods without specific conditions noted in the following examples, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer. In the following examples, various raw materials are used. Unless otherwise specified, conventional commercially available products are used, and their specifications are conventional specifications in the art. In the specification of the present invention and the following examples, unless otherwise specified, "%" represents weight percentage, "parts" represents weight parts, and the ratios represent weights.

[0040] The following further describes a molasses-based bio-based formaldehyde-free mineral wool sizing agent provided by the present application in combination with specific examples.

[0041] The current national standards and specifications referred to in the relevant experiments listed in the present application are as follows:

[0042] For the test method of the formaldehyde content of the sizing agent, it is tested according to Appendix D of the standard GB / T 34181-2017 "Sizing Agent for Mineral Wool Thermal Insulation Products". For the test method of the properties of mineral wool, refer to the following standards:

[0043] 1. GB / T 13350-2017 "Glass Wool and Its Products for Thermal Insulation".

[0044] 2. GB / T 19686-2015 "Rock Wool Thermal Insulation Products for Buildings".

[0045] For the test method of the bonding strength of the sizing agent described in the present invention, it is tested according to Appendix C of the standard GB / T 34181-2017. The difference is that the sizing agent with the same solid content of the present invention is used to replace the premixed phenolic resin in Appendix C, and the drying time is changed from the original 180°C / 20 min to 180°C / 30 min, and other steps remain unchanged. In the test, the resin content is uniformly tested at 5%. The dry bonding strength is tested under the conditions of 23°C / 50% at normal temperature according to the requirements of Appendix C of the standard. At the same time, in order to further investigate the water resistance of the sizing agent, the concepts of wet strength and strength retention rate are used in the present invention. That is, the wet strength is defined as the sample prepared and tested after curing for 24 h at a humidity of 90% and a temperature of 40°C, and after the test, the concept of strength retention rate % = wet strength / dry strength is used to further observe the water and humidity resistance of the sizing agent.

[0046] I. Influence of the composition of the crosslinking agent on the performance

[0047] In the following Examples 1 to 6 and Comparative Examples 1 to 6, the molasses type is cane molasses, and its raw material composition is:

[0048] 1. Total sugar content (sucrose + reducing sugar) (g / 100 g): 50.2%;

[0049] 2. Purity (total sugar content / refractive brix) (g / 100g): 67.6%;

[0050] 3. Total ash content (sulfated ash) (g / 100g): 11.8%.

[0051] Example 1

[0052] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid (AA) to ethyl acrylate (EA) is 90:10; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2130. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed evenly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the sizing agent are tested according to national standards.

[0053] Example 2

[0054] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid to ethyl acrylate is 85:15; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2172. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed evenly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the sizing agent are tested according to national standards.

[0055] Example 3

[0056] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid to ethyl acrylate is 82:18; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2097. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed evenly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the sizing agent are tested according to national standards.

[0057] Example 4

[0058] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid to ethyl acrylate is 77:23; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2231. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed evenly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the sizing agent are tested according to national standards.

[0059] Example 5

[0060] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid to ethyl acrylate is 70:30; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2305. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed uniformly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards respectively.

[0061] Comparative Example 1

[0062] Composition of the water-soluble resin crosslinking agent: The composition of the monomer is all acrylic acid, without ethyl acrylate, and the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2218. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed uniformly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards respectively.

[0063] Comparative Example 2

[0064] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid to ethyl acrylate is 95:5; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2140. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed uniformly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards respectively.

[0065] Comparative Example 3

[0066] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid to ethyl acrylate is 92:8; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2169. Based on the solid content, 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent are mixed uniformly by adding an appropriate amount of water, and a solid content of 50% is uniformly configured. Then, 0.3 parts of KH560 coupling agent are added and mixed together. The dry-wet bonding strength, strength retention rate, and formaldehyde content of the setting agent are tested according to national standards respectively.

[0067] Comparative Example 4

[0068] Composition of the water-soluble resin crosslinking agent: The molar ratio of acrylic acid to ethyl acrylate is 68:32; the number-average molecular weight Mn of the water-soluble resin crosslinking agent is 2580 (soluble part). After the product is synthesized, there is a milky white precipitate, and its water solubility has been lost, so subsequent tests cannot be carried out.

[0069] Comparative Example 5

[0070] Composition of the water-soluble resin crosslinking agent: Use anhydrous citric acid to replace the water-soluble resin crosslinking agent; based on the solid content, mix 100 parts of molasses, 100 parts of the above water-soluble resin crosslinking agent evenly by adding an appropriate amount of water, and uniformly prepare a solid content of 50%, then add 0.3 parts of KH560 coupling agent and mix them together. According to national standards, test the dry-wet bonding strength, strength retention rate, and formaldehyde content of the setting agent respectively.

[0071] Comparative Example 6

[0072] Composition of the water-soluble resin crosslinking agent (the ratio refers to Example 2 of CN102438962A): Use anhydrous citric acid and 27% ammonia water to replace the water-soluble resin crosslinking agent; based on the solid content, mix 100 parts of molasses, 27.4 parts of the above water-soluble resin crosslinking agent evenly by adding an appropriate amount of water, and uniformly prepare a solid content of 50%, then add 0.3 parts of KH560 coupling agent and mix them together. According to national standards, test the dry-wet bonding strength, strength retention rate, and formaldehyde content of the setting agent respectively.

[0073] The formulations of the setting agents prepared in the above examples and comparative examples are shown in Table 1.

[0074] Table 1 Formulation Composition of the Setting Agent

[0075]

[0076] The performance test results of the setting agents prepared in the above examples and comparative examples are shown in Table 2 below.

[0077] Table 2 Performance Test Results of the Setting Agent

[0078]

[0079] The molasses of Examples 1 to 6 and Comparative Examples 1 to 6 can be purchased from Liuzhou Jinqianwan Molasses Co., Ltd. The number-average molecular weight of the water-soluble resin crosslinking agent is obtained by testing using gel permeation chromatography (GPC) technology. It can be seen from the results of Table 1 and Table 2 above that when the addition amount of EA is 10 - 30% mole parts, the dry strength of the prepared setting agent > 3 MPa, the wet strength > 2 MPa, and the strength retention rate > 62%, having good comprehensive performance. Outside this range, its dry strength, wet strength, and strength retention rate are poor, or its water solubility is insufficient, which will limit the application of mineral wool in the next step.

[0080] II. Influence of monomer type composition, molasses composition, crosslinking agent ratio, and addition of other components on the performance of the setting agent

[0081] Example 6

[0082] Based on Example 1, the difference lies in using styrene (ST) to replace EA, changing the coupling agent to KH550, and keeping other conditions unchanged.

[0083] Example 7

[0084] Based on Example 2, the difference lies in using methyl methacrylate (MMA) to replace EA, changing the dosage of the water-soluble resin crosslinking agent to 90 parts, changing the coupling agent to KH550, adding 2 parts of the catalyst sodium hypophosphite, and keeping other conditions unchanged.

[0085] Example 8

[0086] Based on Example 3, the difference lies in using vinyl acetate (VAC) to replace EA, changing the dosage of the water-soluble resin crosslinking agent to 80 parts, changing the coupling agent to KH550, and keeping other conditions unchanged.

[0087] Example 9

[0088] Based on Example 4, the difference lies in using 2-ethylhexyl acrylate (2-EHA) to replace EA, changing the dosage of the water-soluble resin crosslinking agent to 80 parts, changing the coupling agent to KH550, and keeping other conditions unchanged.

[0089] Example 10

[0090] Based on Example 5, the difference lies in the composition of the water-soluble resin crosslinking agent: the molar ratio of AA: methacrylic acid (MAA): EA is 40:30:30, changing the dosage of the water-soluble resin crosslinking agent to 120 parts, changing the coupling agent to KH550, and keeping other conditions unchanged.

[0091] Example 11

[0092] Based on Example 5, the difference lies in the composition of the water-soluble resin crosslinking agent: the molar ratio of AA: maleic anhydride (MLA): EA is 50:20:30, changing the dosage of the water-soluble resin crosslinking agent to 150 parts, changing the coupling agent to KH550, and keeping other conditions unchanged.

[0093] Example 12

[0094] Based on Example 5, the difference lies in the type of molasses being beet molasses, and its composition is as follows:

[0095] 1) Total sugar content (sucrose + reducing sugar) (g / 100g): 48.8%;

[0096] 2) Purity (total sugar / refractive brix) (g / 100g): 61.1%;

[0097] 3) Total ash content (sulfated ash) (g / 100g): 10.4%;

[0098] The dosage of the water-soluble resin crosslinking agent is changed to 150 parts, the coupling agent is changed to KH550, and other conditions remain unchanged.

[0099] Example 13

[0100] Based on Example 5, the difference is that the type of molasses is beet molasses, and its composition is:

[0101] 1) Total sugar content (sucrose + reducing sugar) (g / 100g): 55.2%;

[0102] 2) Purity (total sugar / refractive brix) (g / 100g): 56.7%;

[0103] 3) Total ash content (sulfated ash) (g / 100g): 5.9%;

[0104] The dosage of the water-soluble resin crosslinking agent is changed to 180 parts, the coupling agent is changed to KH550, 15 parts of catalyst potassium hypophosphite are added, and other conditions remain unchanged.

[0105] Example 14

[0106] Based on Example 5, the difference is that the type of molasses is cane molasses, and its composition is:

[0107] 1) Total sugar content (sucrose + reducing sugar) (g / 100g): 48.5%;

[0108] 2) Purity (total sugar / refractive brix) (g / 100g): 57.6%;

[0109] 3) Total ash content (sulfated ash) (g / 100g): 9.8%;

[0110] The dosage of the water-soluble resin crosslinking agent is changed to 230 parts, the coupling agent is changed to KH550, and other conditions remain unchanged.

[0111] Example 15

[0112] Based on Example 5, the difference is that the type of molasses is cane molasses, and its composition is:

[0113] 1) Total sugar content (sucrose + reducing sugar) (g / 100g): 60.9%;

[0114] 2) Purity (total sugar / refractive brix) (g / 100g): 65.4%;

[0115] 3) Total ash content (sulfated ash) (g / 100g): 5.2%;

[0116] The dosage of the water-soluble resin crosslinking agent was changed to 280 parts, and the coupling agent was changed to KH550, with other conditions remaining unchanged. The performance of the monomers used in the above examples and comparative examples is shown in Table 3.

[0117] Table 3 Composition ratio of the setting agent

[0118]

[0119] The performance test results of the setting agents prepared in the above examples and comparative examples are shown in Table 4.

[0120] Table 4 Performance test results of the setting agent

[0121]

[0122]

[0123] It can be seen from the results of Table 3 and Table 4 above that within the scope supported by this specification, by using other monomer raw materials and their ratios provided in the solution of the present invention and using molasses with different raw material compositions, the setting agent also has good performance. The performance of the setting agent can fully meet the requirements that the dry strength > 3 MPa, the wet strength > 2 MPa, and the strength retention rate > 62%. Among them, increasing the dosage of the water-soluble resin crosslinking agent within a certain range can improve the dry strength and wet strength. However, when it exceeds 150 parts, the performance improvement is limited, and since the crosslinking agent is sourced from the petrochemical route, the cost is relatively high, which is not conducive to the final cost of the setting agent.

[0124] III. Weather resistance and resilience performance of glass wool mats in different formulation comparison tests

[0125] In the test examples of this application, the setting agent formulations of Example 5 and Comparative Example 6 in the present invention were respectively used to prepare glass wool mats. The specifications of the glass wool mats were a bulk density of 16 kg / cm 3 , and a thickness of 75 mm. At the same time, based on the mineral wool special formaldehyde-free setting agent with a 100% solid content, 5 parts of a water repellent and 10 parts of a dustproof oil were further added to 100 parts of the formaldehyde-free setting agent; Test Example 1 was the same as Comparative Example 1, both were used for testing glass wool mats, and the specific parameters are shown in Table 5 below:

[0126] Table 5 Test parameters of glass wool mats

[0127] Test Example Serial Number Finishing Agent Formula Organic Matter Content Test Product Test Example 1 Example 5 4.5％ Glass Wool Mat, Density 16K, Thickness 75mm Comparative Test Example 1 Comparative Example 6 4.5％ Glass Wool Mat, Density 16K, Thickness 75mm

[0128] The glass wool samples prepared in Table 5 above were cut separately for the weathering resilience performance test of the glass wool felt. The cutting size of each sample was 30*30cm, and the number of cut samples in each group was 6. After cutting, the thickness was first tested according to the national standard and the average value was calculated. Then, they were placed in a constant temperature and humidity chamber, and each sample was continuously pressurized with a thin metal plate applying a pressure of 100Pa. After aging and curing for 7 days under the temperature and humidity conditions of 50±2℃ and 95±3%, they were taken out and re-measured according to the national standard requirements and the average value was calculated. Then, the thickness before and after aging was recorded respectively. The thickness retention rate = thickness after curing / thickness before curing. The data are shown in Table 6.

[0129] Table 6 Rebound performance of glass wool felt

[0130] Test Example Serial Number Thickness before Curing / mm Thickness after Curing / mm Thickness Retention Rate / % Test Example 1 76 70 92％ Comparative Test Example 1 73 58 79％

[0131] As can be seen from Table 6, the glass wool felt prepared using the setting agent of the present invention has good resilience and a thickness retention rate of ≥90%, which basically reaches the initial thickness of the glass wool product. This data is much better than 75% of the comparative example, indicating that the setting agent formula of the present invention has better comprehensive performance than the formula of comparative example 6.

[0132] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A molasses-based bio-based formaldehyde-free mineral wool sizing agent, characterized in that, Calculated on a 100% solids content basis, it includes components with the following weight ratios: molasses: 100 parts; water-soluble resin crosslinking agent: 80 - 300 parts; Among them, the water-soluble resin crosslinking agent is prepared by copolymerization from monomer raw materials. The monomer raw materials include the following components in mole percentages: a, ethylenically unsaturated carboxylic acid monomers: 70 - 90%; b, hydrophobic ethylenically unsaturated monomers: 10 - 30%.

2. The bio-based formaldehyde-free mineral wool sizing agent based on molasses according to claim 1, wherein Calculated by mass percentage, the molasses refers to molasses with the following indicators: total sugar: sucrose + reducing sugar ≥ 45%; purity: total sugar / refractive brix ≥ 56%; total ash: sulfuric acid ash ≤ 12%.

3. The bio-based formaldehyde-free mineral wool sizing agent based on molasses according to claim 2, wherein The components and contents of the molasses are as follows by weight percentage: 40 - 60% sucrose and reducing sugar, 5 - 15% organic non-sugar components, 5 - 15% total ash, 20 - 50% water; the components of the soluble solids in the molasses are sucrose and reducing sugar, organic non-sugar components, total ash; the content of the soluble solids accounts for 50 - 80% of the molasses components.

4. A molasses-based bio-based formaldehyde-free mineral wool sizing agent according to claim 1, characterized in that, The number-average molecular weight of the water-soluble resin crosslinking agent is 500 - 30000, the solids content is 1 - 99%, and the pH value is 1 - 3; the addition amount of the water-soluble resin crosslinking agent is 90 - 200 parts.

5. A molasses-based bio-based formaldehyde-free mineral wool sizing agent according to claim 4, characterized in that, The number-average molecular weight of the water-soluble resin crosslinking agent is 1000 - 5000, the solids content is 20 - 60%, and the addition amount is 100 - 150 parts.

6. The bio-based formaldehyde-free mineral wool sizing agent based on molasses according to claim 1, characterized in that, The ethylenically unsaturated carboxylic acid monomers are one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, α-β-methylene glutaric acid, monoalkyl maleate, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctyl acrylic anhydride, crotonic anhydride or fumaric anhydride.

7. A molasses-based bio-based formaldehyde-free mineral wool sizing agent according to claim 1, characterized in that, The hydrophobic ethylenically unsaturated monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl 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, ethyl vinylbenzene, vinyl naphthalene, vinyl xylene, vinyl toluene, vinyl acetate, vinyl butyrate, vinyl alcohol, vinyl chloride, vinyl toluene, vinyl benzophenone, vinylidene chloride, acrylonitrile or glycidyl (meth)acrylate.

8. A molasses-based bio-based formaldehyde-free mineral wool sizing agent according to claim 1, characterized in that, The molasses-based bio-based formaldehyde-free mineral wool setting agent further includes a catalyst. Calculated on a 100% solids content basis, the addition amount of the catalyst is 2 - 15 parts.

9. The bio-based formaldehyde-free mineral wool sizing agent based on molasses according to claim 8, characterized in that, The catalyst is hypophosphorous acid, hypophosphite, alkali metal hypophosphite, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkyl phosphinic acid, Lewis acid, sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite, magnesium hypophosphite, (pyro) sodium bisulfite, sulfite, sulfate, nitrate, halide, citrate, lactate or gluconate of zinc / aluminum / zirconium / iron / magnesium / tin / titanium / boron.

10. A molasses-based bio-based formaldehyde-free mineral wool sizing agent according to claim 1, characterized in that, The molasses-based bio-based formaldehyde-free mineral wool sizing agent includes molasses, water-soluble resin crosslinking agent, coupling agent, water repellent and dust-proof oil, and is added in the following weight ratio based on 100% solid content: Molasses, water-soluble resin crosslinking agent: 100 parts; coupling agent: 0.1 - 5 parts; water repellent: 0 - 5 parts; dust-proof oil: 0 - 10 parts.

11. A molasses-based bio-based formaldehyde-free mineral wool sizing agent according to claim 10, characterized in that, 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.

12. The bio-based formaldehyde-free mineral wool sizing agent based on molasses according to claim 1, characterized in that, The bio-based formaldehyde-free mineral wool sizing agent further includes water. Based on 100% solid content of the formaldehyde-free sizing agent for mineral wool, the addition amount of water per 100 mass parts of the formaldehyde-free sizing agent for mineral wool is 0 - 200 mass parts.

13. The bio-based formaldehyde-free mineral wool sizing agent based on molasses according to claim 1, characterized in that, The dry strength of the sizing agent > 3 MPa, the wet strength > 2 MPa, and the strength retention rate > 62%.

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