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WO2019112460A1 - Composition pour imprégner un matériau de renfort et procédé de production - Google Patents

Composition pour imprégner un matériau de renfort et procédé de production Download PDF

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Publication number
WO2019112460A1
WO2019112460A1 PCT/RU2017/000910 RU2017000910W WO2019112460A1 WO 2019112460 A1 WO2019112460 A1 WO 2019112460A1 RU 2017000910 W RU2017000910 W RU 2017000910W WO 2019112460 A1 WO2019112460 A1 WO 2019112460A1
Authority
WO
WIPO (PCT)
Prior art keywords
melt
composition
composite materials
reinforcing material
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/RU2017/000910
Other languages
English (en)
Russian (ru)
Inventor
Илья Александрович ВИХРОВ
Василий Федорович АРИСТОВ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
"syntez-Project" LLC
Original Assignee
"syntez-Project" LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by "syntez-Project" LLC filed Critical "syntez-Project" LLC
Priority to PCT/RU2017/000910 priority Critical patent/WO2019112460A1/fr
Priority to EA202091132A priority patent/EA202091132A1/ru
Publication of WO2019112460A1 publication Critical patent/WO2019112460A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00

Definitions

  • the group of inventions relates to a binder for polymer composite materials, in particular for materials for space purposes, and to methods for their preparation.
  • thermosetting binders In the manufacture of polymer composite materials for space applications, three types of thermosetting binders are mainly used: epoxy, bismaleimide, and polycyanurate.
  • Polycyanurate binders differ from epoxy and bismaleimide binders, first of all, by increased crack resistance during thermal cycling, reduced moisture absorption, high resistance to cosmic radiation, and better dielectric characteristics; therefore, they are most suitable for manufacturing dimensionally stable structures for space purposes.
  • compositions based on aromatic or perfluoroaliphatic dicyanates and metal chelates make it possible to obtain polymers with different physicomechanical properties and at different curing temperatures, depending on the amount and type of metal chelate used.
  • the disadvantage of these compositions is that organic solvents, such as methylene chloride or chloroform, are used to obtain them, which leads to residual solvents in the binder and, as a consequence, the formation of pores in the molding process, which reduces the physicomechanical characteristics of composite materials.
  • compositions based on aromatic dicyanates and liquid solutions of metal acetylacetonates in high-boiling alkyl phenols (patent US 4847233A). These compositions also allow to obtain polymers with different physicomechanical properties and at different curing temperatures, depending on the amount and type of metal chelate used, moreover, the absence of a low-boiling solvent solves the problem of increased pore formation during the molding of products.
  • the disadvantage of these compositions is that a large amount of alkylphenol is used to obtain them (10 or more times the amount of metal acetylacetonate), which is partially chemically bound to the polymer, forming thermally unstable hydrophilic imidocarbonate structures that promote increased moisture absorption and gas evolution at elevated temperatures .
  • compositions based on aromatic dicyanates with nanoscale (average particle size from 1 to 100 nm) filler - zinc oxide in the amount of 0.001-1 weight fractions without the use of solvents and diluents (patent JP 2006-328177). These compositions have a low dependence of catalyst activity on temperature and slightly increase the viscosity of the binder after the introduction of the catalyst.
  • a common task addressed by the group of inventions, and a common technical result achieved using a group of inventions, is the development of a polycyanurate binder with a minimum curing temperature not higher than 125 ° C, which eliminates the use of solvents and / or diluents and reduces the gas evolution of composite materials in products space destination.
  • the task and the required technical result is achieved due to the new method of obtaining the composition of melt binders based on metal chelates and oligocyanurate resins with active cyanate groups for impregnation of reinforcing material in polymer composite materials for space purposes, in which the resin is heated to melt state, the catalyst is introduced into the resulting melt in the form of a dry powder of metal chelates with a particle size of 40-125 microns in an amount of 50- 600 ppm in the ratio of the mass of metal ions to the mass of the composition and mix the melt to a visually homogeneous state.
  • the task and the required technical result is also achieved due to the new composition for impregnating reinforcing material in polymer composite materials for space, obtained by the proposed method, in the form of a solution or melt 50-600 ppm of complex compounds or their mixtures of aluminum ions, transition metals and rare earth elements, with various organic ligands in resins with active cyanate groups, without using any solvents or diluents.
  • the composition is a solution or melt of complex compounds or their mixtures of aluminum ions, transition metals and rare earth elements, with various organic ligands in resins with active cyanate groups, without using any solvents or diluents.
  • the proposed composition (binder) includes monomers with active cyanate groups or oligomers with active cyanate groups or their mixtures, contains 50-600 million parts (in terms of the mass of metal ions to the composition) of the dissolved catalyst and does not contain solvents or active diluents.
  • coordination-saturated complex compounds or their mixtures can be used, in which metal ions are used as complexing agents, and acetylacetonate ions and / or neutral molecules capable of binding to complexing agent, for example, 1, 10 are used as ligand.
  • metal ions are used as complexing agents
  • acetylacetonate ions and / or neutral molecules capable of binding to complexing agent for example, 1, 10 are used as ligand.
  • 1, 10 are used as ligand.
  • -fenantrolin, 2,2 '-bipiridin or triphenylphosphine oxide triphenylphosphine oxide.
  • the binder may also contain various additional components: various polymers, resins, fillers, dyes, pigments, thickeners, lubricants or flame retardants acting as modifiers a binder, and not being solvents or diluents of the metal complex catalyst.
  • the method of obtaining the composition (binder) consists in the fact that at first the catalyst is crushed to a particle size of preferably 40-125 ⁇ m and only after that is introduced into the resin.
  • This method allows to obtain a homogeneous solution (melt) of the catalyst in the resin (as opposed to the patent US 4847233A) without using any solvents or diluents.
  • the particle size may be somewhat outside the specified range, however, the use of particles smaller than 40 microns leads to a significant electrification of particles and makes sowing difficult, and the use of particles larger than 125 microns increases the mixing time or does not allow to achieve homogeneity of the melt.
  • a resin (3 samples of 20 g each) based on bisphenol A dicyanate oligomerized at 170–200 ° C (viscosity of 1.5 Pa * s at 80 ° C) is taken and heated to melt state at 80 ° C.
  • the catalyst is introduced into the melt.
  • the first case in the form of a dry powder of copper acetylacetonate with a particle size of not more than 100 microns in an amount of 300 ppm - 0.0247 g.
  • the second case in the form of a solution 200 ppm - 0.0655 g of acetylacetonate copper in 0,400 g of nonylphenol.
  • Part of the prepared compositions 10 g each, is poured into molds and cured at 125 ° C for 10 hours, the glass transition temperature of the obtained samples is measured. The remaining parts of the prepared compositions are maintained at 80 ° C, periodically measuring the viscosity. The results of viscosity measurements are shown in the table.
  • the oligocyanurate resin (30 g) based on bisphenol M dicyanate is heated to 50 ° C (melt viscosity at a given temperature of 0.5 Pa * s).
  • a catalyst 300 ppm Zn
  • the resulting composition is poured into a mold and cured at 125 ° C for 10 hours.
  • the obtained plastic sample after cooling has a glass transition temperature in the region of 103-108 ° C (according to DSC data).
  • the gelation time of this composition is more than 20 hours at 50 ° C.
  • the oligocyanurate resin (30 g) based on bisphenol A dicyanate is heated to 80 ° C (the melt viscosity at this temperature is 1, 5 Pa * s).
  • a catalyst is injected into the melt (50 ppm Fe) - 0.0094 g of iron acetylacetonate powder (Fe (ac) h) with a particle size of not more than 40 ⁇ m and the melt is well mixed at 80 ° C to a homogeneous state (a transparent mass of dark red is formed colors).
  • the resulting composition is poured into a mold and cured at 125 ° C for 10 hours.
  • the obtained plastic sample after cooling has a glass transition temperature of 133-138 ° C (according to DSC).
  • the gelation time of this composition is about 3 hours at 80 ° C.
  • the oligocyanurate resin (30 g) based on bisphenol A dicyanate is heated to 80 ° C (the melt viscosity at this temperature is 1, 5 Pa * s).
  • a catalyst 300 ppm Zr) —0.0636 g of zirconium acetylacetonate powder (Zr (acac) 4) with a particle size of not more than 125 ⁇ m is introduced into the melt and the melt is well mixed at 80 ° C to a homogeneous state (a transparent yellow mass is formed) .
  • the resulting composition is poured into a mold and cured at 125 ° C for 10 hours.
  • the obtained plastic sample after cooling has a glass transition temperature of 125-130 ° C (according to DSC).
  • the gelation time of this composition is about 8 hours at 80 ° C.
  • the oligocyanurate resin (30 g) based on bisphenol E dicyanate is heated to 40 ° C (melt viscosity at a given temperature of 0.3 Pa * s). Then, a catalyst (600 ppm Tm) —0.0690 g of thulium acetylacetonate phenanthrolinate powder (Tm (acac) 3phen) with a particle size of not more than 100 ⁇ m is introduced into the melt and the melt is well mixed at 40 ° C until homogeneous yellow color). The resulting composition is poured into a mold and cured at 125 ° C for 10 hours. The obtained plastic sample after cooling has a glass transition temperature in the region of 150-155 ° C (according to DSC data). The gelation time of this composition is more than 20 hours at 40 ° C.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Ce groupe d'invention concerne des liants pour des matériaux composites polymères, notamment des matériaux à vocation spatiale, ainsi que des procédés de production. L'invention concerne un procédé de production d'une composition de liants fusibles à base de chélates de métaux et de résines d'oligocyanurates avec des groupes cyanates actifs pour imprégner un matériau de renfort dans des matériaux composites polymères à vocation spatiale, dans lequel on chauffe la résine jusqu'à l'état fondu, on introduit dans le bain de fusion obtenu un catalyseur sous forme d'une poudre sèche de chélates de métaux ayant un diamètre des particules de 40-125 microns et dans une quantité de 50 à -600 millions de parts pour ce qui est de la masse des ions de métal par rapport à la masse de la composition, et on mélange le bain de fusion jusqu'à obtenir un état visuellement homogène. L'invention concerne une composition pour imprégner un matériau de renfort dans des matériaux composites polymères à vocation spatiale, obtenue selon ce procédé et se présentant sous forme d'une solution ou d'un bain de fusion de 50 à 600 millions de parts de composés complexes ou de leurs mélanges comprenant des ions d'alumine, des métaux de transition et des éléments des terres rares, avec divers ligands organiques dans des résines comprenant des groupes cyanates actifs sans utiliser de quelconque solvant ou dissolvant.
PCT/RU2017/000910 2017-12-06 2017-12-06 Composition pour imprégner un matériau de renfort et procédé de production Ceased WO2019112460A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/RU2017/000910 WO2019112460A1 (fr) 2017-12-06 2017-12-06 Composition pour imprégner un matériau de renfort et procédé de production
EA202091132A EA202091132A1 (ru) 2017-12-06 2017-12-06 Композиция для пропитки армирующего материала и способ ее получения

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/RU2017/000910 WO2019112460A1 (fr) 2017-12-06 2017-12-06 Composition pour imprégner un matériau de renfort et procédé de production

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WO2019112460A1 true WO2019112460A1 (fr) 2019-06-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114106688A (zh) * 2021-12-22 2022-03-01 华中科技大学 防静电涂层材料及其配置方法、防静电涂层及其形成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3694410A (en) * 1969-03-05 1972-09-26 Minnesota Mining & Mfg Use of chelates in preparing polycyanurates
US4785075A (en) * 1987-07-27 1988-11-15 Interez, Inc. Metal acetylacetonate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
US4931496A (en) * 1987-07-08 1990-06-05 Amoco Corporation Damage tolerant fiber-reinforced composites based on cyanate ester/urea thermosetting composition
RU2630929C1 (ru) * 2016-06-07 2017-09-14 Общество с ограниченной ответственностью "СИНТЕЗ-ПРОЕКТ" (ООО "СИНТЕЗ-ПРОЕКТ") Способ получения композиции расплавных связующих на основе хелатов металлов и олигоциануратных смол с активными цианатными группами для пропитки армирующего материала в полимерных композиционных материалах и композиция, полученная предложенным способом

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3694410A (en) * 1969-03-05 1972-09-26 Minnesota Mining & Mfg Use of chelates in preparing polycyanurates
US4931496A (en) * 1987-07-08 1990-06-05 Amoco Corporation Damage tolerant fiber-reinforced composites based on cyanate ester/urea thermosetting composition
US4785075A (en) * 1987-07-27 1988-11-15 Interez, Inc. Metal acetylacetonate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
RU2630929C1 (ru) * 2016-06-07 2017-09-14 Общество с ограниченной ответственностью "СИНТЕЗ-ПРОЕКТ" (ООО "СИНТЕЗ-ПРОЕКТ") Способ получения композиции расплавных связующих на основе хелатов металлов и олигоциануратных смол с активными цианатными группами для пропитки армирующего материала в полимерных композиционных материалах и композиция, полученная предложенным способом

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114106688A (zh) * 2021-12-22 2022-03-01 华中科技大学 防静电涂层材料及其配置方法、防静电涂层及其形成方法

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