WO2021037273A1 - Ignifugeant à cadre organique covalent comportant un groupe vanilline contenant une base de schiff, et son procédé de préparation - Google Patents

Ignifugeant à cadre organique covalent comportant un groupe vanilline contenant une base de schiff, et son procédé de préparation Download PDF

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Publication number
WO2021037273A1
WO2021037273A1 PCT/CN2020/112714 CN2020112714W WO2021037273A1 WO 2021037273 A1 WO2021037273 A1 WO 2021037273A1 CN 2020112714 W CN2020112714 W CN 2020112714W WO 2021037273 A1 WO2021037273 A1 WO 2021037273A1
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WO
WIPO (PCT)
Prior art keywords
preparation
flame retardant
tridentate
compound
covalent organic
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PCT/CN2020/112714
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English (en)
Chinese (zh)
Inventor
戴李宗
彭超华
陈婷
陈国荣
袁丛辉
许一婷
曾碧榕
申应军
罗伟昂
Original Assignee
厦门大学
金旸（厦门）新材料科技有限公司
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Application filed by 厦门大学, 金旸（厦门）新材料科技有限公司 filed Critical 厦门大学
Publication of WO2021037273A1 publication Critical patent/WO2021037273A1/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
    • C08G12/06—Amines
    • C08G12/08—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the invention belongs to the technical field of polymer flame retardants, and specifically relates to a vanillin-based covalent organic frame flame retardant containing Schiff base and a preparation method thereof.
  • halogen-free flame retardants containing phosphorus and nitrogen are more environmentally friendly than halogen-containing flame retardants.
  • the current phosphorus-containing small molecules or linear polymers have a low decomposition temperature that does not meet the processing requirements of some high-molecular materials, and at the same time, there is a phenomenon that the flame retardant fails due to migration during long-term use.
  • bio-based raw materials can not only alleviate the pressure of dependence on petroleum, but also alleviate the pollution in the production of petroleum raw materials.
  • Vanillin as a compound produced on a platform of aromatic radicals derived from lignin, has shown good potential in the field of polymers.
  • the purpose of the present invention is to overcome the defects of the prior art and provide a vanillin-based covalent organic frame flame retardant containing Schiff base.
  • Another object of the present invention is to provide a method for preparing the above-mentioned covalent organic frame flame retardant.
  • a vanillin-based covalent organic frame flame retardant containing Schiff base its structural formula is:
  • Method for preparing the flame retardant covalent organic frameworks comprising: a compound containing an aldehyde R 2 tridentate and bidentate amine compound containing as R 1 amine-aldehyde Schiff base via condensation reaction of;
  • step (3) Under a nitrogen atmosphere, add the material obtained in step (2) to the material obtained in step (1), then add an appropriate amount of acetic acid, and stir for 2-4 hours at 75-85°C;
  • step (3) Filter the material obtained in step (3) to obtain a solid, wash the solid with a third solvent, and dry in vacuum to obtain the covalent organic frame flame retardant.
  • the first organic solvent is at least one of acetonitrile, tetrahydrofuran, N,N-dimethylformamide, methanol, dimethyl sulfoxide, trimethylbenzene and dioxane.
  • the second organic solvent is at least one of acetonitrile, tetrahydrofuran, N,N-dimethylformamide, methanol, dimethyl sulfoxide, trimethylbenzene and dioxane.
  • the third organic solvent is at least one of tetrahydrofuran, N,N-dimethylformamide and acetone.
  • the molar ratio of the bidentate amine compound to the tridentate aldehyde compound is 3-4:2.
  • the ratio of the bidentate amine compound to the first organic solvent is 1 g: 10-25 mL.
  • the ratio of the tridentate aldehyde compound to the second organic solvent is 1 g: 10-25 mL.
  • the added amount of the acetic acid is 0.25-1% of the total volume of the material obtained in step (1) and the material obtained in step (2).
  • the synthesis steps of the bidentate amine compound are as follows:
  • the precipitating agent is tetrahydrofuran, ethyl acetate or a mixture of both;
  • the phosphorus-containing compound is
  • the method for synthesizing the tridentate aldehyde compound is: weighing vanillin, sodium hydroxide and trichloride containing R 2 in a molar ratio of 3-3.5:3-3.5:1, First dissolve vanillin in the mixed solution, add hydroxide under ice bath conditions, and magnetically stir for 30min-60min. Slowly add the trichloride solution dissolved in an organic solvent dropwise, continue to stir for 1-3h, and then reflux for 2-4h at 60°C-100°C, and cool naturally. Pour the reacted solution into an appropriate amount of distilled water to form a large amount of white solid. After filtering, the solid powder is washed 2-3 times with 10% sodium carbonate solution and dried in vacuum.
  • the above-mentioned mixed solution may be a mixed solution composed of acetone/tetrahydrofuran and water in a volume ratio of 1-2:1-2; the above-mentioned organic solvent may be acetone or tetrahydrofuran or any mixed solvent of the two.
  • the above-mentioned trichloride is cyanuric chloride or 1,3,5-trichloro-1,3,5-triazine-2,4,6-trione.
  • the present invention is inexpensive, simple and easy to obtain, and at the same time uses green and environmentally friendly vanillin.
  • a high molecular weight flame retardant is prepared through mild amine-aldehyde condensation reaction, which avoids the migration and failure of the flame retardant, and can significantly increase the amount of residual carbon.
  • the introduction of the Schiff base structure can give the material potential
  • the optical and chemical properties, and the six-membered nitrogen heterocyclic structure eventually formed by heating, can significantly improve the thermal stability of the carbon residue.
  • the covalent organic frame flame retardant prepared by the present invention has high molecular weight and is rich in benzene rings, which can exhibit good thermal stability, making it suitable for processing and using various polymers.
  • Figure 1 is an infrared image of the bidentate amine compound, tridentate aldehyde compound and covalent organic frame flame retardant obtained in Example 1 of the present invention.
  • Example 2 is a thermogravimetric diagram of the covalent organic frame flame retardant obtained in Example 1 of the present invention under a nitrogen atmosphere.
  • Fig. 3 is a test heat release curve of the epoxy nanocomposite micro-calorimeter prepared in Example 5 of the present invention.
  • Figure 4 is the thermogravimetric curve of the epoxy resin nanocomposite prepared in Example 5 of the present invention in a nitrogen atmosphere.
  • the application of the covalent organic frame flame retardant prepared in Example 1 as the flame retardant additive of epoxy resin is as follows: Weigh 2g of covalent organic frame flame retardant, 38.4g epoxy resin, stir at 90°C for 3h, and vacuum Remove the water, then cool down to 80°C, add 9.6g of diaminodiphenylmethane, cure at 120°C for two hours, and cure at 180°C for 2 hours.
  • the prepared epoxy resin nanocomposite was subjected to micro-calorimeter test and thermogravimetric test to study its flame-retardant behavior.
  • Figure 3 shows the heat release curve of the epoxy nanocomposite micro-calorimeter test. Compared with pure epoxy, 4% organic frame flame retardant is added, and the peak heat release rate drops significantly.
  • Figure 4 shows the thermogravimetric curve of the prepared epoxy nanocomposite under nitrogen atmosphere. At 750°C, the carbon residue rate has increased from 12wt% of pure epoxy to 21wt%.
  • the application of the covalent organic frame flame retardant prepared in Example 3 as a flame retardant additive of polylactic acid is as follows: weigh 48 g of polylactic acid, weigh 2 g of the covalent organic frame flame retardant prepared in Example 3, and use a mixer Mix at 180°C for 5 minutes with a rotor speed of 60 rpm to obtain a composite material. Then, the obtained composite material was hot pressed at 180° C. under a pressure of 10 MPa for 5 minutes to form a sheet, and then quickly cooled to room temperature.
  • the prepared polylactic acid nanocomposite was tested by a miniature calorimeter, and it was found that compared with the pure polylactic acid prepared under the same conditions, the peak heat release rate of the polylactic acid nanocomposite decreased by nearly 21%.
  • the present invention discloses a frame retardant covalent organic herbs and a preparation method of the aldehyde-containing Schiff bases, according to the present invention is a compound containing an aldehyde R 2 tridentate and bidentate amine-containing compound R 1 through Schiff base Amine-aldehyde condensation reaction system.
  • the invention uses bio-based raw materials to be green and environmentally friendly.
  • the Schiff base structure contained in the molecular structure has high thermal stability and uses amine-aldehyde condensation reaction to make the reaction conditions mild.
  • the formation of covalent organic structures rich in benzene ring structures can be significantly improved
  • the thermal stability and carbon content of flame retardants have industrial applicability.

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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)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un ignifugeant à cadre organique covalent comportant un groupe vanilline contenant une base de Schiff, et un procédé de préparation de celui-ci. Dans la présente invention, l'ignifugeant à cadre organique covalent est préparé par conduite d'une réaction de condensation aldéhyde-amine à base de Schiff sur un composé aldéhyde tridenté contenant R2 et un composé aminé bidenté contenant R1. Une matière première d'origine biologique utilisée dans la présente invention est respectueuse de l'environnement, une structure de base de Schiff contenue dans une structure moléculaire présente une stabilité thermique élevée et utilise une réaction de condensation aldéhyde-amine pour rendre les conditions de réaction douces, et la formation d'une structure organique covalente qui est riche en une structure de cycle benzénique peut améliorer significativement la stabilité thermique de l'ignifugeant et augmenter la quantité de carbone formé.
PCT/CN2020/112714 2019-08-30 2020-08-31 Ignifugeant à cadre organique covalent comportant un groupe vanilline contenant une base de schiff, et son procédé de préparation WO2021037273A1 (fr)

Applications Claiming Priority (2)

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CN201910820925.3 2019-08-30
CN201910820925.3A CN110698620B (zh) 2019-08-30 2019-08-30 一种香草醛基含席夫碱的共价有机框架阻燃剂及其制备方法

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CN113004477B (zh) * 2021-02-25 2022-03-04 中国林业科学研究院林产化学工业研究所 一种基于席夫碱的植物油基自修复聚合物及其制备方法和应用
CN113527313B (zh) * 2021-08-03 2022-07-12 浙江浙能技术研究院有限公司 一种用于检测水中吡啶盐类物质的水溶性超分子有机笼状化合物的制备方法及其应用

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CN107325113A (zh) * 2017-07-06 2017-11-07 福州大学 一种包含Salen单元的笼型共价有机框架化合物的制备方法
CN107501492B (zh) * 2017-08-10 2019-06-07 长春工业大学 席夫碱式磷氮膨胀型阻燃剂及其制备方法和用途

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US20140081014A1 (en) * 2010-09-27 2014-03-20 The Regents Of The University Of California Conductive open frameworks
CN106554484A (zh) * 2015-09-25 2017-04-05 中国科学院大连化学物理研究所 共价有机框架材料的制备及共价有机框架材料和其应用
CN106750528A (zh) * 2016-11-23 2017-05-31 厦门大学 一种磷氮杂环结构阻燃环氧树脂及其合成方法
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