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CN-122011973-A - Low-loss bio-based formaldehyde-free mineral wool sizing agent

CN122011973ACN 122011973 ACN122011973 ACN 122011973ACN-122011973-A

Abstract

The invention belongs to the field of high polymer chemical materials, and particularly relates to a low-loss bio-based formaldehyde-free mineral wool sizing agent which comprises, by weight, 100 parts of water-soluble lignin and 100-200 parts of water-soluble resin cross-linking agents, wherein the water-soluble resin cross-linking agents are prepared from monomer raw materials through copolymerization, the monomer raw materials comprise 70-90% of ethylenically unsaturated carboxylic acid monomers and 10-30% of hydrophobic ethylenically unsaturated monomers in terms of mole percentage, and the water-soluble lignin is lignin sulfonate. The low-loss bio-based formaldehyde-free mineral wool sizing agent provided by the invention is based on lignin generated by waste materials in pulping and papermaking and biorefinery industries as a main raw material, has the advantage of very low cost performance, has no formaldehyde in production and products, meets the standard requirements of environmental protection, no VOC and no formaldehyde, and has good dry and wet strength and water resistance, and in addition, the loss of the sizing agent prepared by the invention is less than 2%, which means that the curing temperature can be further reduced, the curing time is shortened, and the process convenience and stability are improved.

Inventors

  • ZHU YUGUO
  • LI BINGQUAN
  • XIE BING

Assignees

  • 江苏艾科赛特新材料有限公司

Dates

Publication Date
20260512
Application Date
20241108

Claims (12)

  1. 1. The low-loss biobased formaldehyde-free mineral wool sizing agent is characterized by comprising the following components, by weight, 100 parts of water-soluble lignin and 100-200 parts of water-soluble resin cross-linking agent, wherein the water-soluble resin cross-linking agent is prepared from monomer raw materials through copolymerization, the monomer raw materials comprise 70-90% of ethylenically unsaturated carboxylic acid monomers and 10-30% of hydrophobic ethylenically unsaturated monomers according to mole percentage, and the water-soluble lignin is lignin sulfonate.
  2. 2. The low-loss biobased formaldehyde-free mineral wool sizing agent according to claim 1 is characterized by comprising the following components in parts by weight, calculated by 100% of solid content, of 100 parts of water-soluble lignin, 120-150 parts of water-soluble resin cross-linking agent, and the monomer raw materials comprise 70% -85% of ethylenically unsaturated carboxylic acid monomers and 15% -30% of hydrophobic ethylenically unsaturated monomers in mole percent.
  3. 3. The low-loss bio-based formaldehyde-free mineral wool sizing agent of claim 2, wherein the water-soluble resin cross-linking agent has a number average molecular weight of 5000-28000.
  4. 4. The low-loss biobased formaldehyde-free mineral wool sizing agent of claim 2, wherein the water-soluble lignin is one or more of sodium lignin sulfonate, potassium lignin sulfonate, magnesium lignin sulfonate, zinc lignin sulfonate, calcium lignin sulfonate or ammonium lignin sulfonate.
  5. 5. The low-loss, biobased formaldehyde-free mineral wool sizing agent of claim 2, wherein the water-soluble lignin is one or more of zinc lignosulfonate, calcium lignosulfonate, or ammonium lignosulfonate.
  6. 6. The low-loss biobased formaldehyde-free mineral wool sizing agent of claim 2, wherein the ethylenically unsaturated carboxylic acid monomer is one or more of acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, α - β -methyleneglutaric acid, monoalkyl maleate, monoalkyl fumarate, maleic anhydride, acrylic anhydride, methacrylic anhydride, isooctyl acrylic anhydride, crotonic anhydride, or fumaric anhydride; the hydrophobic unsaturated monomer is one or more of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 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, alpha-methylstyrene, p-methylstyrene, ethyl vinyl styrene, 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.
  7. 7. The low-loss bio-based formaldehyde-free mineral wool sizing agent according to claim 6, further comprising a catalyst, wherein the additive amount of the catalyst is 2-15 parts by 100% of solid content, and the catalyst is one or more of hypophosphorous acid, alkali metal hypophosphite, alkali metal phosphite, alkali metal polyphosphate, alkali metal dihydrogen phosphate, polyphosphoric acid, alkylphosphinic acid, lewis acid, (sodium metabisulfite, sulfite, and sulfate, nitrate, halide, citrate, lactate or gluconate of zinc/aluminum/zirconium/iron/magnesium/tin/titanium/boron.
  8. 8. The low-loss bio-based formaldehyde-free mineral wool sizing agent according to claim 7, further comprising one or more of a coupling agent, a water repellent and a dust oil, wherein the coupling agent is one or more of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3-aminopropyl triethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane or 3- (2, 3-glycidoxy) propyldimethoxysilane.
  9. 9. The low-loss bio-based formaldehyde-free mineral wool sizing agent according to claim 8 is characterized by comprising the following components, by weight, 100 parts of water-soluble lignin and water-soluble resin cross-linking agent, 2-15 parts of catalyst, 0.1-5 parts of coupling agent, 0-5 parts of water repellent and 0-10 parts of dust-proof oil, wherein the weight ratio of the components is calculated according to 100% of solid content.
  10. 10. The low-loss bio-based formaldehyde-free mineral wool sizing agent according to claim 1, further comprising water in an amount of 0 to 200 parts by mass per 100 parts by mass of the bio-based formaldehyde-free mineral wool sizing agent, calculated as 100% solids content of the bio-based formaldehyde-free mineral wool sizing agent.
  11. 11. The low-loss, bio-based formaldehyde-free mineral wool sizing agent of claim 8, wherein the loss of the low-loss, bio-based formaldehyde-free mineral wool sizing agent is 2% or less.
  12. 12. Mineral wool prepared using the low-loss, biobased formaldehyde-free mineral wool sizing agent of any one of claims 1-11.

Description

Low-loss bio-based formaldehyde-free mineral wool sizing agent Technical Field The invention belongs to the field of high polymer chemical materials, and particularly relates to a low-loss bio-based formaldehyde-free mineral wool sizing agent. Background Mineral wool is a novel light heat-insulating material, is widely applied to the industrial fields of metallurgy, construction, petroleum, chemical industry, light spinning, traffic, national defense and the like, and particularly the mineral wool in the mineral wool is getting more and more attention in the fields of construction, agriculture and the like because of the superior heat insulation, sound absorption, noise reduction, fire prevention safety and the like. The preparation of mineral wool products generally requires the use of a setting agent, which is generally an aqueous solution of an oligomeric resin, which sets loose mineral wool into products such as boards, felts, cottons and the like through the solidification and bonding action of the resin, and plays a role in bonding mineral fibers to increase the strength of the mineral wool. In recent years, as the state further trends in environmental regulations for the heat insulation industry, traditional phenolic resin rock wool setting agents are strictly regulated and even stopped in production due to the large amount of formaldehyde and phenol sewage pollution generated, more and more enterprises are devoted to develop more environmentally safe setting agents for replacing traditional phenolic resin setting agents, such as binder compositions based on polycarboxy polymers and polyols or polyamines, as disclosed in US5661213, CN106232699a and WO 2013/014399. Another class of non-phenolic resin setting agents are the addition/elimination reaction products of aliphatic and/or aromatic anhydrides with alkanolamines, as disclosed for example in WO 2006/061249. However, the resins used in these patents are chemical substances synthesized from petrochemical technology routes, which are non-renewable resources and have relatively high prices, and at the same time, petrochemical products are also high-carbon-emission products. With the exhaustion of the earth resources, people pay attention to the shortage problem of the resources, and the continuous development of green and environment-friendly bio-based formaldehyde-free sizing agents is imperative. Particularly, the natural renewable biomass resources, particularly the abandoned natural renewable biomass resources, are utilized to be converted into the aldehyde-free, green and environment-friendly mineral cotton sizing agent, and the mineral cotton sizing agent has wide research and development prospects. Currently, syrup-based bio-based styling agents have been widely studied, as disclosed in CN106232699A, CN102438962 a. However, syrup is a costly raw material, and severe dehydration reaction of syrup occurs under high temperature conditions, resulting in a large loss and an increase in the cost of using the final setting agent. Therefore, there is an urgent need to find other natural renewable biomass resources that can replace syrup to prepare the sizing agent, thereby achieving the purpose of economic production. Lignin (an aromatic polymer) is the main component in wood, is the most abundant carbon source next to cellulose on earth, is formaldehyde-free and VOC-free per se, and is an environment-friendly renewable raw material. Common industrial lignin is mainly derived from waste materials of pulp and paper making and biorefinery industries. The pulping and papermaking industry generates 5000 ten thousand tons of lignin every year approximately, and in addition, the biorefinery industry which utilizes plant hydrolysis and conversion to prepare energy alcohol generates a great amount of lignin every year, so the lignin belongs to a renewable biomass resource with very low cost. Although many chemicals and composite materials have been produced using lignin, the overall utilization of lignin is still less than 2%, and a large amount of low-cost lignin is usually used by direct combustion, which is a waste of resources and pollutes the environment, making it not effectively utilized. The lignin itself is used as an environment-friendly formaldehyde-free renewable raw material, and the lignin applied to the mineral wool sizing agent is used as an environment-friendly formaldehyde-free sizing agent to replace the trialdehyde resin, so that the lignin has very good development prospect and economic value. Disclosure of Invention Technical problems: the invention aims to provide a low-loss bio-based formaldehyde-free mineral wool sizing agent, which is prepared from waste industrial lignin mainly from pulping, papermaking and biorefinery industries by adding a proper cross-linking agent and other auxiliary agents. Compared with the technical scheme that syrup is used as a raw material for preparing the sizing agent, the invention has lower loss, high