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CN-121699108-B - Composite foaming polyurethane material and application thereof

CN121699108BCN 121699108 BCN121699108 BCN 121699108BCN-121699108-B

Abstract

The invention relates to the technical field of polyurethane materials, and provides a composite foaming polyurethane material and application thereof. The composite foaming polyurethane material consists of a component A and a component B, wherein the component A contains di (hydroxyalkyl) anthraquinone, the component B is a polyisocyanate compound, and the chemical bonding weight ratio of the anthraquinone in the polyisocyanate compound is not less than 5 percent. According to the invention, an anthraquinone structure is introduced into the foaming polyurethane material by two methods, and simultaneously, a carbon-based material is added, so that the effect of anthraquinone serving as a redox mediator for promoting denitrification of nitrogen-containing sewage can be fully exerted, and the foaming polyurethane material has high mechanical strength and durability.

Inventors

  • SHI YU
  • JIANG QILONG
  • Yan Bingxuan
  • HONG JIANGBIN
  • HUANG WEIMING
  • XU ZAN
  • YE QIAN
  • YAN BIN

Assignees

  • 厦门理工学院
  • 厦门凯纳石墨烯技术股份有限公司

Dates

Publication Date
20260505
Application Date
20260224

Claims (9)

  1. 1. The composite foaming polyurethane material is characterized by comprising a component A and a component B; the raw material components of the component A comprise 100 parts of polymer dihydric alcohol, 0.5-3 parts of di (hydroxyalkyl) anthraquinone, 1-8 parts of chain extender, 1-3 parts of catalyst, 0-5 parts of cross-linking agent, 0.1-2 parts of carbon-based material and 0.5-2 parts of water; the di (hydroxyalkyl) anthraquinone is selected from one or two or more of 1, 4-bis [ (hydroxyethyl) amino ] anthraquinone, 1- [ (2-hydroxyethyl) amino ] -4- [ (3-hydroxypropyl) amino ] anthraquinone, 1, 4-bis [ (hydroxypropyl) amino ] anthraquinone, 2, 5-bis [ (hydroxypropyl) amino ] anthraquinone, 1, 8-bis [ (hydroxypropyl) amino ] anthraquinone, 2, 5-bis [ (hydroxyethyl) amino ] anthraquinone, 2, 6-bis [ (hydroxyethyl) amino ] anthraquinone and 2, 6-bis [ (hydroxypropyl) amino ] anthraquinone; The component B is a polyisocyanate compound; Anthraquinone with the weight ratio of 5-15% of chemical bonding in the polyisocyanate compound; the polyisocyanate compound is obtained by reacting reaction raw materials comprising diaminoanthraquinone and diisocyanate monomers.
  2. 2. The composite foamed polyurethane material according to claim 1, wherein the NCO content of the polyisocyanate compound is not less than 10wt%.
  3. 3. The composite foaming polyurethane material according to claim 1, wherein the diaminoanthraquinone is selected from one or a combination of two or more of 1, 2-diaminoanthraquinone, 1, 4-diaminoanthraquinone, 1, 8-diaminoanthraquinone, 2, 5-diaminoanthraquinone and 2, 6-diaminoanthraquinone.
  4. 4. The composite foamed polyurethane material according to claim 1, wherein the diisocyanate monomer is selected from one or a combination of two or more of HDI, HMDI, XDI, MDI, TMXDI, IPDI, NDI and TDI.
  5. 5. The composite foamed polyurethane material of claim 1, wherein the reaction raw materials further comprise a polyether polyol; the molar ratio of the polyether polyol to the diaminoanthraquinone is 0.5-3:1.
  6. 6. The composite foamed polyurethane material of claim 1, wherein the catalyst is selected from the group consisting of dihydroxyalkylamines; The cross-linking agent is selected from triethanolamine or triisopropanolamine; the carbon-based material is selected from one or a combination of two or more of carbon nanotubes, graphene and graphene oxide.
  7. 7. The composite foamed polyurethane material according to claim 6, wherein one or a combination of two or more of a primary amino group, a secondary amino group and a hydroxyl group is chemically bonded to the surface of the carbon-based material.
  8. 8. The composite foamed polyurethane material according to claim 1, wherein the molar ratio of active hydrogen in the a component to NCO groups in the B component is 1:1.08-1.2.
  9. 9. Use of a composite foamed polyurethane material according to any one of claims 1 to 8 for the treatment of nitrogen-containing sewage.

Description

Composite foaming polyurethane material and application thereof Technical Field The invention belongs to the technical field of polyurethane materials, and relates to a composite foaming polyurethane material and application thereof. Background Industrial and agricultural activities and daily living bring about a large amount of nitrogen-containing sewage. The nitrogen-containing sewage contains inorganic nitrogen and organic nitrogen, which can bring great negative influence to the ecological system and human life. The microbial anaerobic denitrification method is an effective method for treating nitrogen-containing sewage. The addition of redox mediators can improve the denitrification treatment effect, and anthraquinone compounds are common redox mediators. However, most anthraquinone compounds are water-soluble and easily lost with water, and meanwhile, bring about secondary pollution, and various methods for dispersing anthraquinone compounds into a carrier or grafting anthraquinone compounds onto the surface of the carrier are reported in the prior art. Common polymeric carriers include polyethylene, polypropylene, polyurethane, and the like. In view of practical application, it is desirable that the carrier be suspended in sewage, and for polyurethane-type carriers, the density is greater than the sewage density, and it is generally necessary to make foamed polyurethane. The carrier is required to have better loading effect on anthraquinone compounds, higher mechanical strength, better stability and other performances so as to realize lasting denitrification promotion effect. One prior art method of loading anthraquinones onto polyurethanes has been to use aminoanthraquinone or hydroxyanthraquinone to react with NCO groups and act as an isocyanate curing agent. However, since the reactivity of amino groups or hydroxyl groups on the anthraquinone is relatively low and the large volume of the anthraquinone produces a remarkable steric hindrance, the effect of dispersing the anthraquinone on the polyurethane through chemical bonding is affected, for example, the content of the anthraquinone in the polyurethane is low, and a good denitrification promoting effect cannot be achieved. Therefore, there is a need for further improvement and optimization of existing foamed polyurethanes as carriers for anthraquinone compounds. Disclosure of Invention In order to solve the technical problems, the invention provides a composite foaming polyurethane material and application thereof. The technical scheme of the invention is as follows: A composite foaming polyurethane material consists of a component A and a component B; the raw material components of the component A comprise 100 parts of polymer dihydric alcohol, 0.5-3 parts of di (hydroxyalkyl) anthraquinone, 1-8 parts of chain extender, 1-3 parts of catalyst, 0-5 parts of cross-linking agent, 0.1-2 parts of carbon-based material and 0.5-2 parts of water; the di (hydroxyalkyl) anthraquinone is selected from one or two or more of 1, 4-bis [ (hydroxyethyl) amino ] anthraquinone, 1- [ (2-hydroxyethyl) amino ] -4- [ (3-hydroxypropyl) amino ] anthraquinone, 1, 4-bis [ (hydroxypropyl) amino ] anthraquinone, 2, 5-bis [ (hydroxypropyl) amino ] anthraquinone, 1, 8-bis [ (hydroxypropyl) amino ] anthraquinone, 2, 5-bis [ (hydroxyethyl) amino ] anthraquinone, 2, 6-bis [ (hydroxyethyl) amino ] anthraquinone and 2, 6-bis [ (hydroxypropyl) amino ] anthraquinone; The component B is a polyisocyanate compound; anthraquinone with the weight ratio of 5-15% of the chemical bonding weight in the polyisocyanate compound. Preferably, the NCO content of the polyisocyanate compound is not less than 10% by weight. Preferably, the polyisocyanate compound is obtained by reacting reaction raw materials comprising diaminoanthraquinone and diisocyanate monomers. More preferably, the diaminoanthraquinone is selected from one or a combination of two or more of 1, 2-diaminoanthraquinone, 1, 4-diaminoanthraquinone, 1, 8-diaminoanthraquinone, 2, 5-diaminoanthraquinone and 2, 6-diaminoanthraquinone. More preferably, the diisocyanate monomer is selected from one or a combination of two or more of HDI, HMDI, XDI, MDI, TMXDI, IPDI, NDI and TDI. More preferably, the reaction raw material further comprises polyether polyol; the molar ratio of the polyether polyol to the diaminoanthraquinone is 0.5-3:1. Preferably, the catalyst is selected from dihydroxyalkylamines; The cross-linking agent is selected from triethanolamine or triisopropanolamine; the carbon-based material is selected from one or a combination of two or more of carbon nanotubes, graphene and graphene oxide. More preferably, the carbon-based material surface is chemically bonded with one or a combination of two or more of a primary amino group, a secondary amino group and a hydroxyl group. Preferably, the molar ratio of active hydrogen in the A component to NCO groups in the B component is 1:1.08-1.2. The application of the composite foaming