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CN114380938B - Special formaldehyde-free setting agent for improving water resistance of mineral wool - Google Patents

Special formaldehyde-free setting agent for improving water resistance of mineral wool Download PDF

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Publication number
CN114380938B
CN114380938B CN202111654376.0A CN202111654376A CN114380938B CN 114380938 B CN114380938 B CN 114380938B CN 202111654376 A CN202111654376 A CN 202111654376A CN 114380938 B CN114380938 B CN 114380938B
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parts
monomer
acrylate
mineral wool
ethylenically unsaturated
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CN114380938A (en
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朱玉国
李炳泉
董春生
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Jiangsu Aquaset New Material Co ltd
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Jiangsu Aquaset New Material Co ltd
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Priority to CN202111654376.0A priority Critical patent/CN114380938B/en
Priority to KR1020247003510A priority patent/KR20240028465A/en
Priority to JP2022554462A priority patent/JP7269689B2/en
Priority to PCT/CN2022/072535 priority patent/WO2022073527A2/en
Publication of CN114380938A publication Critical patent/CN114380938A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/06—Acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a special formaldehyde-free setting agent for mineral wool, which is capable of improving water resistance and comprises the following components in parts by weight, calculated according to 100% of solid content: water-soluble resin prepolymer: 100 parts of (A); polyol: 10-70 parts; catalyst: 2-15 parts. The water-soluble resin prepolymer is prepared by copolymerization of monomer raw materials, wherein the monomer raw materials comprise the following components in mass: ethylenically unsaturated carboxylic acid monomer: 90.0-99.0%; ethylenically unsaturated hydroxyl functional monomer: 0.5-5.0%; hydrophobic ethylenically unsaturated monomer: 0.5 to 5.0 percent. The sizing agent provided by the invention has no free formaldehyde release, meets the standard requirements of environmental protection, no VOC and no formaldehyde, has good stability, can be stably stored for a long time, is convenient for industrial use, and simultaneously, the hardness of the produced mineral wool board is superior to that of the traditional acrylic acid homopolymer product, and has good water resistance, aging resistance and construction performance.

Description

Special formaldehyde-free setting agent for improving water resistance of mineral wool
Technical Field
The invention belongs to the field of high polymer chemical materials, and particularly relates to a special formaldehyde-free setting agent for mineral wool, which can improve water resistance.
Background
The mineral wool usually comprises rock wool, glass wool and slag wool, has the properties of light capacity, good heat preservation, small heat conductivity, strong heat resistance, sound insulation, water resistance, stable chemical property, acid and alkali resistance, no corrosion and the like, and is a novel light heat preservation material. Mineral wool and products thereof are widely applied to the industrial departments of metallurgy, building, petroleum, chemical industry, light textile, traffic, national defense and the like, particularly, the application of rock wool in the mineral wool in the building field is developed vigorously in recent years, the development in the fields of agriculture and the like has a great rising space, and the outstanding heat preservation, heat insulation, sound absorption, noise reduction and fireproof safety performance of the mineral wool and the products thereof are paid more and more attention in various industries.
In the mineral wool industry, a sizing agent is generally required to be used, the sizing agent is generally an oligomer resin aqueous solution, loose mineral wool is sized into products such as boards, felts, cotton and the like through the curing and bonding effect of resin, the mineral wool heat insulation product is endowed with good physical and mechanical properties, and the function of bonding fibers and increasing the strength of the mineral wool is achieved. In recent years, as the national environmental protection regulation on the heat insulation industry becomes more strict, the traditional phenolic resin rock wool setting agent is strictly regulated and even stops production because of the pollution of a large amount of formaldehyde and phenol sewage, so more and more enterprises are dedicated to research and develop more environment-friendly and safer setting agents to replace the traditional phenolic resin setting agent.
The US5661213 patent discloses a curable aqueous composition comprising a polymeric polyacid polyol and a phosphorous-containing accelerator; the composition can be used as a binder in heat-resistant non-woven fabrics such as non-woven fabrics composed of glass fibers, however, the binder prepared from the composition has unsatisfactory bonding strength when bonding cotton plates with higher performance requirements, especially poor strength under high-temperature and high-humidity environments, so that the cotton plates are easy to droop during use and construction, and have many inconveniences, and the construction efficiency is reduced; patent CN106795247A discloses a binder capable of binding glass fibers, which contains polymer with hydroxyl, however, when the binder is used, the molecular weight is increased due to the volatile alkali (ammonia water), the binder has the tendency of instability, and the binder is further volatilized into the air in the production process, and the production has the problem of environmental pollution. In summary, the existing formaldehyde-free polyacrylic acid styling agents still have some technical problems which are difficult to overcome, wherein the problems of insufficient storage stability and adhesive strength, especially insufficient wet strength and low strength retention rate are a problem to be solved urgently.
Disclosure of Invention
Aiming at the problem that the performance of the produced mineral wool is easy to attenuate under the conditions of high temperature and high humidity due to insufficient strength, particularly low wet strength, of the existing formaldehyde-free setting agent, the invention provides the special formaldehyde-free setting agent for improving the water resistance of the mineral wool, and the special formaldehyde-free setting agent comprises the following components in parts by weight, calculated according to 100% of solid content:
water-soluble resin prepolymer: 100 parts of (A);
polyol (b): 10-70 parts;
catalyst: 2-15 parts.
The water-soluble resin prepolymer is prepared by copolymerization of monomer raw materials, wherein the monomer raw materials comprise the following components in mass:
a, ethylenically unsaturated carboxylic acid monomer: 90.0-99.0%;
b, ethylenically unsaturated hydroxyl functional monomer: 0.5-5.0%;
c, hydrophobic ethylenically unsaturated monomer: 0.5 to 5.0 percent.
Preferably, the special formaldehyde-free setting agent for mineral wool comprises the following components in parts by weight, calculated by 100% of solid content:
water-soluble resin prepolymer: 100 parts of (A);
polyol: 12-50 parts;
catalyst: 5-10 parts.
The water-soluble resin prepolymer is prepared by copolymerization of monomer raw materials, wherein the monomer raw materials comprise the following components in mass:
a, ethylenically unsaturated carboxylic acid monomer: 92.5-96.0%;
b, ethylenically unsaturated hydroxyl functional monomer: 3.0-4.5%;
c, hydrophobic ethylenically unsaturated monomer: 1.0-3.0%.
Preferably, the number average molecular weight of the water-soluble resin prepolymer is 500-30000, preferably 800-10000, more preferably 1000-5000, and the number average molecular weight is measured by using Gel Permeation Chromatography (GPC) technology. The solid content of the composite material can be 1-99%, preferably 20-60%, and the pH value is 1.0-4.0.
The ethylenically unsaturated carboxylic acid monomer can be one or more of Acrylic Acid (AA), Methacrylic Acid (MA), crotonic acid, fumaric acid, maleic acid (MLA), 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, alpha-beta-methylene glutaric acid, monoalkyl maleate, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctyl acrylic anhydride, crotonic anhydride or fumaric anhydride, and preferably one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid or maleic acid.
The ethylenically unsaturated hydroxyl functional monomer, including but not limited to hydroxyalkyl (meth) acrylate monomer, may be one or more of 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate (HPMA), 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate or 2-hydroxybutyl acrylate, and preferably one or more of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
The ethylenically unsaturated hydroxyl functional monomer can effectively improve the adhesive strength of the sizing agent, particularly the dry adhesive strength. The research of the application shows that when the addition amount of the ethylenically unsaturated hydroxyl functional monomer is less than 0.5 mol%, the effect of obviously improving the strength cannot be achieved, and if the addition amount is more than 5 mol%, the viscosity of the setting agent becomes unstable and tends to be gradually improved along with the prolonging of time.
The hydrophobic ethylenic unsaturated monomer in the invention refers to a hydrophobic ethylenic unsaturated monomer containing no carboxyl or hydroxyl functional group, and can further effectively improve the water resistance of the sizing agent, and has a certain shielding effect on the hydrophilic functional group of the sizing agent, thereby effectively improving the wet strength and strength retention rate of the sizing agent. The hydrophobic unsaturated monomer according to the present invention includes, but is not limited to, for example, an acrylate monomer, and may be a (meth) acrylate monomer including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate, or lauryl methacrylate; but also vinyl aromatic monomers such as styrene, alpha-methylstyrene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylene or vinyltoluene; vinyl acetate-based monomers such as vinyl acetate or vinyl butyrate; vinyl monomers such as vinyl alcohol, vinyl chloride, vinyl toluene, vinyl benzophenone, or vinylidene chloride; other monomers which can participate in the polymerization reaction, such as acrylonitrile or glycidyl (meth) acrylate, are also possible.
Furthermore, the hydrophobic unsaturated monomer preferably has a water solubility of 0-1.5 g/100g, and may be ethyl acrylate, n-Butyl Acrylate (BA), isobutyl acrylate (i-BA), sec-butyl acrylate, tert-butyl acrylate, n-Propyl Acrylate (PA), cyclohexyl acrylate (CHA), lauryl acrylate, 2-ethylhexyl acrylate (2-EHMA), methyl methacrylate, ethyl methacrylate, n-butyl methacrylate (n-BMA), Lauryl Methacrylate (LMA), 2-ethylhexyl methacrylate (2-EHMA), isobornyl methacrylate (LMA) styrene, alpha-methyl styrene, p-methyl styrene, ethyl vinyl benzene, vinyl naphthalene, vinyl xylene, methyl ethyl methacrylate, ethyl acrylate, butyl acrylate, vinyl, butyl acrylate, One or more of vinyl toluene or chloroethenyl toluene.
The applicant further finds that when the hydrophobic monomer is used, if a monomer (so-called soft monomer) with a lower glass transition temperature (Tg) of a homopolymer thereof is used for synthesis, the strength and strength retention rate of the obtained sizing agent are further improved, for short, the Tg of the homopolymer of the monomer is referred to as the Tg of the monomer, and can be measured by GB/T29611-2013 "measurement of glass transition temperature of raw rubber" and Differential Scanning Calorimetry (DSC) "test under the conditions of a temperature rise rate of 10 ℃/min and a nitrogen atmosphere. Without being limited by any theory, the possible reason is that the sizing agent of the invention is a product with higher crosslinking density, and the introduction of a proper amount of hydrophobic soft elastomer can improve the toughness of the sizing agent to a certain extent, thereby finally improving the bonding strength of the sizing agent. The preferable low-Tg monomer low-solubility hydrophobic monomer is a hydrophobic unsaturated monomer with the monomer Tg of-15 to-80 ℃ and the water solubility of 0 to 0.5g/100g, and is preferably one or more of n-Butyl Acrylate (BA), lauryl acrylate, n-propyl acrylate (n-BA), isobutyl acrylate, 2-ethylhexyl acrylate 2-EHA or lauryl methacrylate.
The hydrophobic unsaturated monomer is added in an amount of 0.5 to 5% by mole, preferably 1.5 to 4.5% by mole, and more preferably 3.0 to 4.5% by mole. If the addition amount is less than 0.5 mol%, the added unsaturated hydrophobic monomer cannot play a role in obviously improving the water resistance, and if the addition amount is more than 5 mol%, the crosslinking density and the bonding strength of the sizing agent are greatly reduced.
Further, the applicant finds that when the molar ratio of the ethylenically unsaturated hydroxyl functional monomer b to the hydrophobic ethylenically unsaturated monomer c is 1: 1.5-1.5: 1 and the content of the monomer b is 3.0-4.5 mol%, the setting agent has the dry strength of more than 5.0MPa, the wet strength of more than 3.5MPa, the strength retention rate of more than 70%, and the viscosity increase rate of not more than 20%, and has the best performance.
The polyhydric alcohol of the invention is a compound with at least two hydroxyl groups, and can be 1, 2-ethanediol, 1, 3-propanediol, diethylene glycol, 1, 4-butanediol, 1,2, 3-cyclohexanetriol, 1,2, 4-butanetriol, 1,2, 3-butanetriol, 1,2, 5-pentanetriol, glycerol polyether polyol, 2-dimethyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2-methyl-2, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, 2-ethyl-1, 3-hexanediol, 2-hydroxymethyl-2-methyl-1, 3-propanediol, 2-ethyl-2-hydroxymethyl-2-methyl-1, 3-propanediol, 1,2, 6-hexanetriol, 2-dihydroxymethyl-2, 3-propanediol, pentaerythritol, trimethylolpropane, glucose, fructose, sorbitol, sucrose, mannitol, maltose, maltitol, glucose, resorcinol, catechol, pyrogallol, 1, 2-ethylene glycol dimer, 1, 2-ethylene glycol trimer, 1, 2-propylene glycol dimer, or 1, 2-propylene glycol trimer. It may also be an alkanolamine polyol such as ethanolamine, isopropanolamine, diethanolamine, diisopropanolamine or triethanolamine; or addition polymers containing at least two hydroxyl groups, such as polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, homopolymers or copolymers of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; further, the preferable polyhydric alcohol in the invention is one or more of ethylene glycol, propylene glycol, glycerin, trimethylolpropane, diethanolamine, isopropanolamine, triethanolamine or polyvinyl alcohol.
The catalyst described in the present invention means a catalyst which can promote the reaction of carboxylic acid with hydroxyl group, such as a phosphorus-containing catalyst, for example, hypophosphorous acid, hypophosphite, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkylphosphinic acid or Lewis acid; hypophosphites such as sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite, or magnesium hypophosphite; but also metal salts of inorganic acids, such as sodium (pyro) bisulfite or sulfite; the lewis acid catalyst may be a sulfate, nitrate, halide, citrate, lactate, or gluconate salt of zinc, aluminum, zirconium, iron, magnesium, tin, titanium, or boron. The preferred catalyst of the invention is hypophosphite, and the preferred hypophosphite is one or more of sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite or magnesium hypophosphite.
For the invention, one or a combination of a plurality of coupling agents, water repellent and dustproof oil can also be added. The coupling agent can support a 'molecular bridge' between the interfaces of inorganic substances and organic substances, so that two materials with different properties are firmly combined together, the wetting and moisture resistance strength of the sizing agent is improved, the bonding performance of the interfaces is increased, the internal stress is eliminated, and the service life is prolonged; the water repellent can effectively prevent water molecules from being adsorbed on the surface of the glass fiber, and the hydrophobic performance of the mineral wool is improved; the dust-proof oil is used in mineral wool, and can effectively reduce a large amount of flying dust generated in the processes of production, cutting, processing and carrying. The special formaldehyde-free setting agent, the coupling agent, the water repellent and the dustproof oil for the mineral wool are calculated according to 100 percent of solid content, and the coupling agent, the water repellent and the dustproof oil are added according to the following weight ratio:
the special formaldehyde-free setting agent for mineral wool comprises: 100 parts of (A);
coupling agent: 0.1-5 parts; more preferably 0.2 to 1.0 parts;
water repellent: 0-5 parts;
dust-proof oil: 0 to 10 parts.
Furthermore, on the basis of the components, the setting agent can be properly added with water according to the needs, the viscosity can be reduced by adding a proper amount of water, the transportation and the use of the setting agent are facilitated, and generally, purified water, tap water or other circulating water which does not influence the performance of the setting agent can be selected as the water. Preferably, the special formaldehyde-free setting agent for mineral wool is calculated according to 100% solid content, and the addition amount of water in every 100 parts by mass of the special formaldehyde-free setting agent for mineral wool is 0-200 parts by mass.
The styling agent composition of the present invention is preferably an formaldehyde-free copolymer composition. By "formaldehyde-free" is meant that the composition is formaldehyde-free and does not release formaldehyde during curing, that the additives used, such as polyols and other adjuvants, are themselves formaldehyde-free, that no formaldehyde is generated during polymerization, and that no formaldehyde is generated or released during treatment of the substrate.
In order to examine the storage stability of the sizing agent, the stability of the sizing agent is characterized by the viscosity increase (%) of a test sample before and after high-temperature curing in a high-temperature oven at 60 ℃/4 weeks, and the method can effectively observe the stability of the sizing agent, wherein the sizing agent is preferably characterized in that the viscosity increase is not higher than 20%, more preferably not higher than 15%, and still more preferably not higher than 10% under the curing condition at 60 ℃/4 weeks.
The method for testing the bonding strength of the setting agent is tested according to appendix C of GB/T34181 and 2017, and is characterized in that the setting agent and other solid contents replace the premixed phenolic resin in appendix C, the drying time is changed from 180 ℃/20min to 180 ℃/30min, other steps are unchanged, the resin content is uniformly tested according to 5 percent in the test, the dry bonding strength is tested according to the requirement of annex C of the standard at the normal temperature of 23 ℃/50 percent, meanwhile, in order to further examine the water resistance of the sizing agent, the concept of wet strength and strength retention is used, namely the wet strength is defined as the curing time of the prepared sample at 90% of humidity and 40 ℃ for 24h and then the test is carried out, and the water resistance and moisture resistance of the sizing agent are further observed by the concept of strength retention, namely wet strength/dry strength after the test is finished.
The applicant finds that the sizing agent dedicated to mineral wool described in the present application cannot be fully evaluated using the performance standards of matrix binders in the traditional composite or adhesive industry, in which the dry-wet bond strength is the important consideration, whereas the use process of the sizing agent described in the present invention is to coat the fiber surface as uniformly as possible in the form of liquid spray and to achieve the sizing and performance of the mineral wool mainly by means of a weak bond in the form of point contact between the fibers, the effect maintained by the force of this weak bond during the continuous use of the mineral wool having a large relationship with the dry strength, wet strength and strength retention of the sizing agent, so from this point of view, several indicators of dry strength, wet strength and strength retention of the sizing agent are equally important, and a major innovation of the present invention is to comprehensively balance the dry strength, wet strength and strength retention, Three indexes of wet strength and strength retention rate are required, wherein the dry strength of the sizing agent is more than 4.0MPa, the wet strength is more than 3.0MPa, and the strength retention rate is more than 60%; the dry strength of the setting agent is preferably greater than 5.0MPa, the wet strength is greater than 3.5MPa, and the strength retention rate is greater than 70%, through optimization of the three indexes, the performance of the prepared mineral wool product is greatly superior to that of the traditional acrylic acid homopolymer product, and the mineral wool product has good effects of high-temperature and high-humidity environment resistance and construction performance.
Has the advantages that:
1. the formaldehyde-free mineral wool setting agent prepared by the invention has no free formaldehyde release, and no volatile alkali is added, so that the standard requirements of environmental protection, no VOC and no formaldehyde are met;
2. the mineral wool sizing agent has good stability, the viscosity is not obviously changed under the high-temperature environment, the viscosity increase rate is within 10 percent, the long-term stable storage can be realized, and the industrial use is convenient;
3. the formaldehyde-free mineral wool sizing agent prepared by the invention has good dry and wet strength and water resistance, and the optimal comprehensive performance of the mineral wool sizing agent prepared by the scheme of the invention can reach the dry strength of more than 5.0MPa, the wet strength of more than 3.5MPa and the strength retention rate of more than 70 percent, so that the formaldehyde-free mineral wool sizing agent is greatly superior to the traditional acrylic acid homopolymer product;
4. finally, the hardness of the mineral wool board produced by the setting agent product provided by the invention is superior to that of the traditional acrylic acid homopolymer product, and the mineral wool board has good water resistance, aging resistance and construction performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The relevant experimental references listed in this application are given by the following national current standards and specifications:
the test method of the formaldehyde content of the sizing agent is carried out according to the standard GB/T34181 appendix D of 2017 sizing agent for mineral wool heat insulation products, and the test method of the performance of the mineral wool refers to the following standards:
GB/T13350-2017 glass wool for heat insulation and products thereof
GB/T19686-containing 2015 rock wool heat insulation product for buildings
Firstly, stability test and bonding strength test of setting agent
Example 1
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio of 98.0: 1.0: 1.0; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 2
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 97.5: 1.0: 1.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 3
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 96.0: 1.0: 3.0; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 4
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 94.5: 1.0: 4.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 5
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 97.5: 1.5: 1.0; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 6
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 97.0: 1.5: 1.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 7
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 95.5: 1.5: 3.0; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 8
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 94.0: 1.5: 4.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 9
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 96.0: 3.0: 1.0; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 10
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 95.5: 3.0: 1.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, the other part of samples are mixed together by adding 0.3 part of KH560 coupling agent, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the sizing agent are respectively tested according to national standards.
Example 11
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 94.0: 3.0: 3.0; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 12
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 92.5: 3.0: 4.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 13
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 94.5: 4.5: 1.0; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 14
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 94.0: 4.5: 1.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 15
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 92.5: 4.5: 3.0 of the total weight of the mixture; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Example 16
Composition of the resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio 91.0: 4.5: 4.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Comparative example 1
Composition of the resin prepolymer: acrylic acid: butyl acrylate molar ratio 95.5: 4.5; the number average molecular weight Mn of the resin prepolymer is 2500, and hydroxyethyl acrylate is not contained; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine, 5 parts of catalyst sodium hypophosphite and 0.3 part of KH560 coupling agent are mixed together, an appropriate amount of water is added for uniform mixing, the solid content is uniformly prepared to be 50 percent, then the mixture is maintained for 4 weeks at a high temperature of 60 ℃ for testing the viscosity change, and simultaneously, the dry-wet bonding strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Comparative example 2
Composition of the resin prepolymer: acrylic acid: the hydroxyethyl acrylate molar ratio is 95.5: 4.5; the number average molecular weight Mn of the resin prepolymer is 2500, and butyl acrylate is not contained; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Comparative example 3
Composition of resin prepolymer: acrylic acid: the hydroxyethyl acrylate molar ratio is 95.5: 5.5; the number average molecular weight Mn of the resin prepolymer is 2500, and butyl acrylate is not contained; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Comparative example 4
Composition of resin prepolymer: acrylic acid: hydroxyethyl acrylate: butyl acrylate molar ratio of 99.0: 0.5: 0.5; the number average molecular weight Mn of the resin prepolymer is 2500; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Comparative example 5
Composition of resin prepolymer: the monomers are all acrylic acid; the number average molecular weight Mn of the polymer is 2500, and butyl acrylate and hydroxyethyl acrylate are not contained; based on the solid content, 100 parts of the resin prepolymer, 34.5 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a uniform solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the setting agent are respectively tested according to the national standard.
Comparative example 6
Composition of the resin prepolymer: the monomers are all acrylic acid; the number average molecular weight Mn of the polymer is 2500, and butyl acrylate and hydroxyethyl acrylate are not contained; based on the solid content, 100 parts of the resin prepolymer, 38.8 parts of triethanolamine and 5 parts of catalyst sodium hypophosphite are uniformly mixed by adding a proper amount of water to obtain a solid content of 50%, then a part of samples are cured for 4 weeks at a high temperature of 60 ℃ to test the viscosity change of the samples, and the other part of samples are added with 0.3 part of KH560 coupling agent to be mixed together, and the dry-wet adhesive strength, the strength retention rate and the formaldehyde content of the sizing agent are respectively tested according to the national standard; the addition amount of triethanolamine in comparative example 6 was increased in consideration of the fact that the content of carboxyl group in comparative example 5 was about 12% higher than that in comparative example 3 in comparison with comparative example 3, and thus, in order to compare the effect on the adhesive strength at the same carboxyl/hydroxyl group content as in comparative example 3, the ratio of triethanolamine was increased by 12% in this comparative example, which is convenient for comparison with comparative example 3.
The formulation ratios of the styling agents prepared in the above examples and comparative examples are shown in table 1.
TABLE 1 composition of the setting agent
Figure GDA0003668772510000091
The results of the performance tests of the styling agents prepared in the above examples and comparative examples are shown in table 2.
TABLE 2 Performance test results for the styling agents
Figure GDA0003668772510000101
As can be seen from the results in tables 1 and 2 above, when the amount of HEA and BA added is 0.5 to 4.5 mol%, the setting agent has a viscosity increase of not more than 20%, a dry strength of >4.0MPa, a wet strength of >3.0MPa, and a strength retention of > 60%. Further statistics of the data of example 11, example 12, example 15 and example 16 show that when the molar ratio of the ethylenically unsaturated hydroxyl functional monomer b to the hydrophobic ethylenically unsaturated monomer c is 1: 1.5-1.5: 1 and the content of b is 3.0-4.5% by mole, the setting agent has a dry strength >5.0MPa, a wet strength >3.5MPa, a strength retention > 70% and a viscosity increase rate not higher than 20%, with optimal performance.
Effect of two, different solubility and Tg monomers on the Properties of styling Agents
Example 17, based on example 11, with the difference that lauryl acrylate was used instead of BA, the other conditions were unchanged.
Example 18, based on example 11, differs in that 2-EHA is used instead of BA, the other conditions being unchanged.
Comparative example 7, based on example 11, with the difference that MA is used instead of BA, the other conditions being unchanged.
Comparative example 8, based on example 11, with the difference that MMA is used instead of BA, the other conditions being unchanged.
The properties of the monomers used in the above examples and comparative examples are shown in Table 3.
TABLE 3 basic Properties of the monomers
Figure GDA0003668772510000111
The results of the performance tests of the styling agents prepared in the above examples and comparative examples are shown in table 4.
TABLE 4 Performance test results for styling agents
Figure GDA0003668772510000112
As can be seen from the results in tables 3 and 4, the use of monomers with different properties has a great influence on the performance of the styling agent, and when the Tg of the monomer is too low and the water solubility is high, it is not favorable for improving the strength and water resistance of the styling agent.
Influence of different monomer species on the performance of the styling agent
Example 19 is based on example 6 with the difference that different raw materials and ratios are used, the specific raw materials and ratios are shown in table 5.
Example 20 is based on example 6 with the difference that different raw materials and ratios are used, and the specific raw materials and ratios are shown in table 5.
Example 21 is based on example 6 with the difference that different raw materials and ratios are used, the specific raw materials and ratios are shown in table 5.
Example 22 is based on example 6, except that different raw materials and ratios are used, and the specific raw materials and ratios are shown in table 5.
TABLE 5 composition of the setting agent
Figure GDA0003668772510000113
The results of the performance test of the fixing agents prepared in the above examples and comparative examples are shown in table 6.
TABLE 6 Performance test results for styling agents
Figure GDA0003668772510000121
It can be seen from the results in tables 5 and 6 above that, within the scope supported by the present specification, the use of other monomer materials and ratios provided in the solution of the present invention also has better performance, and the overall performance of the setting agent can reach the performance indexes of viscosity increase rate not higher than 20%, dry strength >4.0MPa, wet strength >3.0MPa, and strength retention > 60%.
Fourthly, comparing and testing the water resistance of the mineral wool board by using different formulas
In the experimental examples of the application, the fixing agent formulas of the example 11 and the comparative example 6 in the application are respectively used for preparing the mineral cotton board, and 3 parts of water repellent is further added into 100 parts of the formaldehyde-free fixing agent according to the 100 percent of the solid content of the formaldehyde-free fixing agent special for the mineral cotton; 6 parts of dustproof oil; according to the process requirements, a proper amount of water is added, and in the process aspect, the test example 1 and the comparative example 1 are used for testing rock wool boards; test example 2 the same as comparative example 2, all used for testing slag wool boards; test example 3 was used for testing glass wool boards, as in comparative example 3, with the following specific parameters:
TABLE 7 Water resistance test parameters for mineral wool panels
Test example No. 2 Setting agent formula Organic matter content Test products
Test example 1 Example 11 4％ Rock wool board with density of 120K and thickness of 50mm
Comparative test example 1 Comparative example 6 4％ Rock wool board with density of 120K and thickness of 50mm
Test example 3 Example 11 10％ Glass wool board with density of 90K and thickness of 25mm
Comparative test example 3 Comparative example 6 10％ Glass wool board with density of 90K and thickness of 25mm
Test example 2 Example 11 3％ Slag wool board with density of 100K and thickness of 50mm
Comparative test example 2 Comparative example 6 3％ Slag wool board with density of 100K and thickness of 50mm
The mineral wool samples prepared in the above table 7 were cut into two groups according to the national standard requirements, one group was used as the sample before aging and curing, the strength was measured according to the national standard, the other group was used as the sample after aging and curing, the sample was placed in a constant temperature and humidity chamber, aging and curing was carried out for 7 days under the temperature and humidity conditions of 50 ± 2 ℃ and 95 ± 3%, the strength was measured according to the national standard requirements, and then the strength and strength retention before and after aging were recorded, respectively, and the data are shown in tables 8 and 9.
TABLE 8 compression Strength test results for mineral wool boards
Figure GDA0003668772510000131
TABLE 9 mineral wool Panel flexural failure load test results
Figure GDA0003668772510000132
As can be seen from tables 8 and 9, the mineral wool boards prepared by using the setting agent of the present invention are superior to the conventional acrylic homopolymer setting agent in terms of strength before and after aging, strength retention rate, and the like, and particularly, when the organic content is low, the difference of the comparative test results is particularly significant.

Claims (9)

1. The special formaldehyde-free setting agent for improving the water resistance of mineral wool is characterized by comprising the following components in parts by weight based on 100% of solid content:
water-soluble resin prepolymer: 100 parts of (A);
polyol: 10-70 parts;
catalyst: 2-15 parts of a solvent;
the water-soluble resin prepolymer is prepared by copolymerization of monomer raw materials, wherein the monomer raw materials comprise the following components in mass:
a, ethylenically unsaturated carboxylic acid monomer: 90.0-98.0%;
b, ethylenically unsaturated hydroxyl functional monomer: 1.0-5.0%;
c, hydrophobic ethylenically unsaturated monomer: 1.0-5.0%;
wherein the hydrophobic ethylenically unsaturated monomer is selected from one or more of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate, cyclohexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate or isobornyl methacrylate;
the ethylenically unsaturated carboxylic acid monomer is one or more selected from acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, alpha-beta-methylene glutaric acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctyl acrylic anhydride, crotonic anhydride and fumaric anhydride;
the ethylenically unsaturated hydroxyl functional monomer is selected from 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 1-methyl-2-hydroxyethyl acrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate;
the polyalcohol is one or more selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, diethanolamine, isopropanolamine, triethanolamine or polyvinyl alcohol.
2. The special formaldehyde-free setting agent for mineral wool, which is used for improving water resistance, as claimed in claim 1, wherein the number average molecular weight of the water-soluble resin prepolymer is 500-30000.
3. The special formaldehyde-free fixative for mineral wool for improving water resistance of claim 1, wherein the hydrophobic ethylenic unsaturated monomer has a water solubility of 0-1.5 g/100g, and a glass transition temperature of a homopolymer thereof is-15 ℃ to-80 ℃.
4. The special formaldehyde-free sizing agent for mineral wool for improving water resistance as claimed in claim 3, wherein the hydrophobic ethylenically unsaturated monomer is one or more selected from n-butyl acrylate, lauryl acrylate, n-propyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and lauryl methacrylate.
5. The special formaldehyde-free fixative for mineral wool for improving water resistance as claimed in claim 1, wherein the catalyst is selected from one or more of sodium hypophosphite, zinc hypophosphite, potassium hypophosphite, calcium hypophosphite or magnesium hypophosphite.
6. The special formaldehyde-free setting agent for mineral wool, which is used for improving the water resistance, as recited in any one of claims 1-5, is characterized by comprising the following components in parts by weight, calculated on the basis of 100% of solid content:
water-soluble resin prepolymer: 100 parts of (A);
polyol: 12-50 parts;
catalyst: 5-10 parts;
the water-soluble resin prepolymer is prepared by copolymerization of monomer raw materials, wherein the monomer raw materials comprise the following components in mass:
a, ethylenically unsaturated carboxylic acid monomer: 92.5-96.0%;
b, ethylenically unsaturated hydroxyl functional monomer: 3.0-4.5%;
c, hydrophobic ethylenically unsaturated monomer: 1.0-3.0%.
7. The special formaldehyde-free sizing agent for mineral wool, which is used for improving water resistance, according to claim 6, is characterized in that the molar ratio of the ethylenically unsaturated hydroxyl functional monomer to the hydrophobic ethylenically unsaturated monomer is 1: 1.5-1.5: 1.
8. The special formaldehyde-free setting agent for mineral wool, which is used for improving the water resistance, as claimed in claim 1, further comprises the following components in parts by weight, based on 100 parts by weight of the special formaldehyde-free setting agent for mineral wool, calculated on the basis of 100% of solid content:
coupling agent: 0.1-5 parts;
water repellent: 0-5 parts;
dust-proof oil: 0-10 parts;
water: 0-200 parts of a solvent;
wherein the coupling agent 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.
9. The special formaldehyde-free sizing agent for mineral wool, which is used for improving the water resistance, as claimed in claim 1, wherein the sizing agent has a dry strength of >4.0MPa, a wet strength of >3.0MPa and a strength retention of > 60%.
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