WO2022267271A1 - Polymère hybride, son procédé de préparation et son utilisation - Google Patents

Polymère hybride, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2022267271A1
WO2022267271A1 PCT/CN2021/124669 CN2021124669W WO2022267271A1 WO 2022267271 A1 WO2022267271 A1 WO 2022267271A1 CN 2021124669 W CN2021124669 W CN 2021124669W WO 2022267271 A1 WO2022267271 A1 WO 2022267271A1
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Prior art keywords
hybrid polymer
compound
preparation
reaction
monomer
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PCT/CN2021/124669
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English (en)
Chinese (zh)
Inventor
尹家福
杨俊升
殷盼超
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华南理工大学
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Publication of WO2022267271A1 publication Critical patent/WO2022267271A1/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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/144—Side-chains containing silicon
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/145—Side-chains containing sulfur
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3342—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms derived from cycloolefins containing heteroatoms
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the invention relates to the technical field of polymer nanocomposite materials, in particular to a hybrid polymer and its preparation method and application.
  • Impact-resistant materials are special materials with high strength and excellent toughness, which can withstand instantaneous severe impacts and quickly dissipate energy, so as to effectively protect internal structures and equipment.
  • the most widely used impact-resistant materials in the industry are polymer materials such as polyethylene (PE), polyurethane (PU), and acrylonitrile-butadiene-styrene copolymer (ABS).
  • PE polyethylene
  • PU polyurethane
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the impact effect requires ultra-high molecular weight, and as the molecular weight increases, the toughness of the system will decrease, and the viscosity coefficient of the system will increase accordingly, which will eventually lead to difficulties in molding and processing the material.
  • the recycling rate of ultra-high molecular weight polymers is low, and the environmental pollution problems caused by them cannot be underestimated.
  • the object of the present invention is to provide a hybrid polymer and its preparation method and application.
  • a hybrid polymer whose repeat unit structure is as follows:
  • the number average molecular weight of the hybrid polymer is 10000g/mol ⁇ 100000g/mol.
  • the preparation method of above-mentioned hybrid polymer comprises the following steps:
  • the preparation method of above-mentioned hybrid polymer comprises the following steps:
  • the molar ratio of trisilanol isooctyl-POSS to vinyltrichlorosilane in step 1) is 1:1.2 ⁇ 1:1.4.
  • the reaction in step 1) is carried out at 0°C to 5°C, and the reaction time is 15h to 25h.
  • the molar ratio of compound 1 and mercaptoethylamine hydrochloride in step 2) is 1:1.8 ⁇ 1:2.2.
  • the photoinitiator of step 2) is photoinitiator Igracure 2959.
  • the reaction in step 2) is carried out under ultraviolet light irradiation, and the reaction time is 10 minutes to 20 minutes.
  • the molar ratio of compound 2 and cis-5-norbornene-exo-2,3-dicarboxylic anhydride in step 3) is 1:1.8 ⁇ 1:2.2.
  • the reaction in step 3) is carried out at 130°C-140°C, and the reaction time is 30h-40h.
  • the catalyst in step 4) is [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]bis(2-bromopyridine)(phenylmethylene ) ruthenium dichloride, 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlorobenzylidene)(tricyclohexylphosphine)ruthenium at least one.
  • the catalyst in step 4) is Grubbs third-generation catalyst ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]bis(2-bromopyridine)( phenylmethylene) ruthenium dichloride).
  • the water and oxygen removal in step 4) adopts a cycle freezing and thawing method.
  • the polymerization reaction in step 4) is carried out at room temperature, and the reaction time is 0.5h-2h.
  • the hybrid polymer of the invention has the advantages of light weight, high strength, easy processing and molding, low cost, and environmental friendliness, and is suitable for large-scale popularization and application.
  • the impact resistance of the hybrid polymer of the present invention does not depend on high molecular weight, has good processability, is convenient for processing and molding, and is conducive to large-scale production and processing;
  • the hybrid polymer of the present invention can be reshaped through simple reprocessing operations when it becomes invalid due to impact, and the recycling rate is extremely high. It is a kind of resource-saving and environment-friendly polymer material.
  • Fig. 1 is the proton nuclear magnetic resonance spectrum figure of the compound 1 in the embodiment.
  • Fig. 2 is the proton nuclear magnetic resonance spectrum of compound 2 in the embodiment.
  • Fig. 3 is the proton nuclear magnetic resonance spectrogram of the monomer in the embodiment.
  • Fig. 4 is a comparison chart of the H NMR spectrum of the monomer and the hybrid polymer in the embodiment.
  • Fig. 5 is a comparison chart of gel permeation chromatograms of monomers and hybrid polymers in the examples.
  • Fig. 6 is a physical photo of the separated Hopkinson compression bar experimental device.
  • Fig. 7 is the stress-strain curve of the hybrid polymer in the embodiment after being impacted at different speeds.
  • Fig. 8 is a physical photo of the hybrid polymer in the embodiment after being impacted at different speeds.
  • Fig. 9 is the stress-strain curve of the hybrid polymer in the embodiment after multiple reprocessing.
  • a kind of hybrid polymer, its preparation method comprises the following steps:
  • the hybrid polymer exhibits excellent impact resistance at different strain rates.
  • the hybrid polymer can withstand a dynamic impact with a strain rate of 1000s -1 , and only the edge part will be damaged, and the middle part will be damaged.
  • the sample can still remain intact.
  • the strain rate reaches 1800s -1 , the specimen can no longer withstand the stress wave with such a high strain rate, so that the hybrid polymer completely fails after the impact .
  • the quantitative recovery of the sample can be achieved after simple reprocessing. Compared with the original sample, the impact resistance of the recovered sample has no obvious change, even after multiple impacts. The recovery situation is still the same.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Un polymère hybride, son procédé de préparation et son utilisation sont divulgués dans la présente invention. La structure du motif répétitif du polymère hybride selon la présente invention est telle que représentée dans la formule (I). Le procédé de préparation du polymère hybride selon la présente invention comprend les étapes suivantes consistant : 1) à faire réagir du trisilanol isooctyle-POSS et du trichlorosilane de vinyle pour obtenir un composé 1 ; 2) à faire réagir le composé 1 et du chlorhydrate de mercaptoéthylamine pour obtenir un composé 2 ; 3) à faire réagir le composé 2 et l'anhydride cis-5-norbornène-exo-2,3-dicarboxylique pour obtenir un monomère ; et 4) à soumettre le monomère à une réaction de polymérisation pour obtenir le polymère hybride. Le polymère hybride selon la présente invention a pour avantages un poids léger, une résistance élevée, une transformation et un moulage faciles, un faible coût, le respect de l'environnement, etc., et est approprié pour une popularisation et une application à grande échelle.
PCT/CN2021/124669 2021-06-24 2021-10-19 Polymère hybride, son procédé de préparation et son utilisation WO2022267271A1 (fr)

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CN202110715841.0A CN113372537B (zh) 2021-06-24 2021-06-24 一种杂化聚合物及其制备方法和应用

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