WO2023092882A1 - Résine thermodurcissable à base biologique pouvant être synthétisée et recyclée dans l'eau, procédé de préparation s'y rapportant et son application - Google Patents

Résine thermodurcissable à base biologique pouvant être synthétisée et recyclée dans l'eau, procédé de préparation s'y rapportant et son application Download PDF

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Publication number
WO2023092882A1
WO2023092882A1 PCT/CN2022/078595 CN2022078595W WO2023092882A1 WO 2023092882 A1 WO2023092882 A1 WO 2023092882A1 CN 2022078595 W CN2022078595 W CN 2022078595W WO 2023092882 A1 WO2023092882 A1 WO 2023092882A1
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parts
bio
water
resin
synthesized
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PCT/CN2022/078595
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English (en)
Chinese (zh)
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东为富
李广龙
黄晶
李婷
张旭辉
汪洋
夏碧华
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江南大学
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Publication of WO2023092882A1 publication Critical patent/WO2023092882A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the invention relates to the technical field of thermosetting resin materials, in particular to a preparation method and application of a bio-based thermosetting resin synthesized and recycled in water.
  • thermosetting polymer materials are widely used in the fields of automobile manufacturing, aerospace, microelectronics, construction and packaging due to their light weight, high strength, good processability, good corrosion resistance and good insulation properties. However, they are composed of stable covalent bonds and are difficult to degrade, causing serious pollution to the environment. Most of the traditional thermosetting polymers are synthesized from non-renewable resources such as petroleum and fossils. Therefore, seeking methods for the synthesis and effective recycling of traditional thermosetting polymers can achieve the dual purposes of saving resources and reducing pollution, which is of great significance to promoting sustainable development, and is in line with the construction of a resource-saving and environment-friendly society in my country. goal of struggle.
  • the present invention provides a bio-based thermosetting polyhydrazone resin that can be synthesized and recycled in water, a preparation method and applications.
  • this application we synthesized a series of bio-based thermosetting polyhydrazone resins that can be recovered in water using small bio-based acid molecules as raw materials and water as a solvent.
  • This application The polymer synthesized in is stable in water and has good water resistance.
  • this bio-based thermosetting polyhydrazone resin has strong mechanical properties and a high glass transition temperature.
  • This application provides new research ideas and directions for the synthesis of ideal bio-based thermosetting polyhydrazone resins.
  • thermosetting resin that can be synthesized and recycled in water.
  • the bio-based thermosetting resin is polyhydrazone resin, which has the following general structural formula:
  • R groups are independently one of phenyl, 2-chloro-propyl or 2-hydroxy-propane; R groups are independently phenyl, methyl, naphthyl, anthracenyl, ethyl, propyl , butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl; R 2 groups are independently phenyl, methyl, furyl , ethyl, 1,2-dichloroethyl, propyl, 2-chloro-2-carboxy-propyl, 2-hydroxy-2-carboxy-propyl, isopropyl, 2-chloro-propyl, butyl one of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
  • thermosetting polyhydrazone resin that can be synthesized and recycled in water.
  • the bio-based thermosetting polyhydrazone resin that can be synthesized and recycled in water has the following components by hydrazide group Click chemistry reaction with aldehyde groups yields:
  • the bio-based thermosetting resin that can be synthesized and recovered in water is prepared by click chemical reaction of hydrazide groups and aldehyde groups in the following parts by weight:
  • the difunctional hydrazide-based monomer or trifunctional hydrazide-based monomer is prepared by reacting the following components in parts by weight: 1-50 parts of carboxyl monomer , 1-300 parts of tetrahydrofuran, 3-50 parts of hydrazine hydrate, 1-50 parts of thionyl chloride, 1-100 parts of methanol, recrystallized in ethanol.
  • the preparation method of the bio-based thermosetting resin that can be synthesized and recycled in water includes:
  • thermosetting polyhydrazone resin (2) Synthesis of bio-based thermosetting polyhydrazone resin in water: Dissolve difunctional hydrazide-based monomers, trifunctional hydrazide-based monomers, and glutaraldehyde in water, mix and stir and pour into molds at 30-100°C After reacting for 1-48h, a bio-based thermosetting polyhydrazone resin is obtained.
  • the preparation method of the bio-based thermosetting resin that can be synthesized and recycled in water may also include:
  • thermosetting polyhydrazone resin (2) Synthesis of bio-based thermosetting polyhydrazone resin in water: Dissolve trifunctional hydrazide-based monomers and glutaraldehyde in water, mix and stir, pour into mold, react at 30-100°C for 1-48h, and obtain bio-based thermosetting polyhydrazone resin Polyhydrazone resin.
  • the present invention provides an application of a bio-based thermosetting resin that can be synthesized and recycled in water or the application of the preparation method, which is applied in aerospace, microelectronics, coatings, water-resistant materials, special engineering plastics, high-performance coatings , Adhesives, anti-aging polymer materials, electronic skin, antibacterial, anti-virus, waterproof materials, water-resistant materials, oil transportation.
  • the present invention provides a method for repairing the bio-based thermosetting resin that can be synthesized and recovered in water.
  • the repair method is as follows: overlap the broken bio-based thermosetting polyhydrazone resin, and drop a drop of bio-based acyl polyhydrazone resin at the overlapping place.
  • the aqueous solution of hydrazine monomer is applied to the overlapping parts of the splines, and heated at 30-80°C for 1-2 hours to obtain the repaired thermosetting polyhydrazone resin.
  • the present invention provides a method for recycling a bio-based thermosetting resin that can be synthesized and recovered in water, adding the bio-based thermosetting polyhydrazone resin to an aqueous solution mixed with a hydrazide-based crosslinking agent, 40- React at 120°C for 12-36 hours to attack the hydrazone group through the hydrazide group to form a new hydrazide anion and carbocation structure, and dissolve the initial thermosetting polyhydrazone resin; The raw material of thermosetting polyhydrazone resin.
  • the preparation method of the near-hydrophobic and repairable bio-based thermosetting resin that can be synthesized and recovered in water can be realized on traditional simple synthesis equipment, and is low in cost, environmentally friendly and easy to realize industrialized production.
  • the repairable bio-based thermosetting polyhydrazone resin obtained by the preparation method provided by the invention has good mechanical properties and heat resistance, is suitable for water-resistant materials, electronic skin, antibacterial and other fields, and can be repaired in water solvents , Recyclable in recycling.
  • the product yield is high, the residue is easy to separate, and has broad application prospects in the recycling of thermosetting polymers.
  • Fig. 1 is the nuclear magnetic spectrum ( 1 H-NMR) of the bifunctional hydrazide-based monomer 1 in Example 1.
  • Fig. 2 is the infrared spectrum of the bio-based thermosetting polyhydrazone resin 1 in Example 6.
  • Fig. 4 is the contact angle test result of the bio-based thermosetting polyhydrazone resin 4 in Example 9.
  • Fig. 5 is the restoration result of the bio-based thermosetting polyhydrazone resin 1 in Example 13.
  • the bio-based thermosetting polyhydrazone resin involved in the present invention refers to a hydrazone-based thermosetting resin synthesized from bio-based small molecules through the reaction of a hydrazide group and an aldehyde group.
  • the primary structure of this polymer is a hydrazone-based molecular chain.
  • succinic acid and citric acid were synthesized from bio-based succinic acid and citric acid, and reacted with aldehyde-based monomers in water to obtain a bio-based thermosetting polyhydrazone resin.
  • the primary structure is the hydrazone molecular chain formed by the reaction of succinic hydrazide and citrin trihydrazide with aldehyde.
  • thermosetting polyhydrazone resin has good mechanical properties and heat resistance, and is suitable for water-resistant materials, electronic skin and other fields.
  • thermosetting polyhydrazone resin is close to hydrophobicity through the contact angle experiment between the polymer and water.
  • Examples 1-5 of the present invention are for preparing hydrazide-based monomers, and Examples 6-10 are for preparing bio-based thermosetting polyhydrazone resins.
  • thermosetting polyhydrazone resin 1 in Example 6 into a spline, cut the spline from the middle, overlap the cut spline by 0.5 cm, add water to the overlapped place, press the overlapping place of the spline with a force of 10 N, and heat the spline at 50°C. Press for 1 hour to obtain the repaired spline, see Figure 5, the crack in the figure refers to the fracture position of the tensile test, indicating that the repaired position is not the weak position of the sample, and the repair effect is very good.
  • Examples 1 to 10 it can be seen from Examples 1 to 10 that the preparation method of the near-hydrophobic and repairable bio-based thermosetting polyhydrazone resin of the present invention, which can be synthesized and recovered in water, can be realized on traditional simple synthesis equipment, which is low in cost, environmentally friendly and easy Realize industrialized production.
  • Examples 11-13, Comparative Example 1, Table 1 and Table 2 it can be seen that the repairable bio-based thermosetting polyhydrazone resin obtained by the preparation method provided by the present invention has good mechanical properties and heat resistance, and can It can be repaired in water solvent, recyclable and recycled, and is suitable for water-resistant materials, electronic skin, antibacterial and other fields.
  • the product yield is high, the residue is easy to separate, and has broad application prospects in the recycling of thermosetting polymers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne le domaine technique des matériaux en résine thermodurcissable et porte sur une résine thermodurcissable à base biologique pouvant être synthétisée et recyclée dans l'eau, un procédé de préparation s'y rapportant et une application de celle-ci. Selon la présente demande, une série de résines de polyhydrazone thermodurcissables à base biologique pouvant être recyclées dans l'eau sont synthétisées à l'aide de petites molécules d'acide à base biologique en tant que matières premières et à l'aide d'eau en tant que solvant. Par comparaison avec des polymères classiques synthétisés dans l'eau, les polymères synthétisés selon la présente invention ont des propriétés stables dans l'eau et ont une bonne résistance à l'eau. De plus, les résines de polyhydrazone thermodurcissables à base biologique ont des propriétés mécaniques robustes et des températures de transition vitreuse élevées. La présente invention fournit une nouvelle orientation et une nouvelle idée pour la recherche sur la synthèse d'une résine de polyhydrazone thermodurcissable à base biologique idéale et est applicable dans les domaines de l'aérospatiale, de la microélectronique, des revêtements, des matériaux résistants à l'eau, des plastiques industriels spéciaux, des revêtements à haute performance, des adhésifs, de l'anti-vieillissement des matériaux polymères, de la peau électronique, de l'antibiose, des antivirus, des matériaux imperméables à l'eau, des matériaux résistants à l'eau et du transport de pétrole.
PCT/CN2022/078595 2021-11-25 2022-03-01 Résine thermodurcissable à base biologique pouvant être synthétisée et recyclée dans l'eau, procédé de préparation s'y rapportant et son application WO2023092882A1 (fr)

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CN202111410104.6A CN114195967B (zh) 2021-11-25 2021-11-25 一种可在水中合成和回收的生物基热固性树脂、制备方法及应用
CN202111410104.6 2021-11-25

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3354122A (en) * 1962-12-21 1967-11-21 Du Pont Polymers of polyacylhydrazones and process of preparation therefor
WO2004003044A2 (fr) * 2002-06-28 2004-01-08 Jean-Marie Lehn Dynameres: materiaux polymeriques a formation reversible et a echange de composants
WO2006003905A1 (fr) * 2004-07-01 2006-01-12 Mitsui Chemicals, Inc. Matériel auto-réparable
CN111718484A (zh) * 2020-07-07 2020-09-29 四川大学 基于乙烯基酰肼键的高性能动态交联聚合物及制备方法
CN112876631A (zh) * 2021-01-19 2021-06-01 江南大学 一种可循环回收、可修复的热固性树脂、制备方法及应用
CN112940283A (zh) * 2021-01-22 2021-06-11 山东师范大学 一种基于酰腙键的自修复聚合物水凝胶及其制备方法
CN113136016A (zh) * 2021-06-08 2021-07-20 江南大学 一种双动态共价键杂化的热固性树脂、制备方法、应用及修复循环回收利用方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3354122A (en) * 1962-12-21 1967-11-21 Du Pont Polymers of polyacylhydrazones and process of preparation therefor
WO2004003044A2 (fr) * 2002-06-28 2004-01-08 Jean-Marie Lehn Dynameres: materiaux polymeriques a formation reversible et a echange de composants
WO2006003905A1 (fr) * 2004-07-01 2006-01-12 Mitsui Chemicals, Inc. Matériel auto-réparable
CN111718484A (zh) * 2020-07-07 2020-09-29 四川大学 基于乙烯基酰肼键的高性能动态交联聚合物及制备方法
CN112876631A (zh) * 2021-01-19 2021-06-01 江南大学 一种可循环回收、可修复的热固性树脂、制备方法及应用
CN112940283A (zh) * 2021-01-22 2021-06-11 山东师范大学 一种基于酰腙键的自修复聚合物水凝胶及其制备方法
CN113136016A (zh) * 2021-06-08 2021-07-20 江南大学 一种双动态共价键杂化的热固性树脂、制备方法、应用及修复循环回收利用方法

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CN114195967A (zh) 2022-03-18
CN114195967B (zh) 2023-04-07

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