[go: up one dir, main page]

WO2022211653A1 - Procédé de production d'une dispersion époxyde aqueuse - Google Patents

Procédé de production d'une dispersion époxyde aqueuse Download PDF

Info

Publication number
WO2022211653A1
WO2022211653A1 PCT/RU2020/000756 RU2020000756W WO2022211653A1 WO 2022211653 A1 WO2022211653 A1 WO 2022211653A1 RU 2020000756 W RU2020000756 W RU 2020000756W WO 2022211653 A1 WO2022211653 A1 WO 2022211653A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy
epoxy resin
dispersion
pbw
aqueous
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/RU2020/000756
Other languages
English (en)
Russian (ru)
Inventor
Ирина Анатольевна СТАРОВОЙТОВА
Антон Николаевич СЕМЕНОВ
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.)
Obshchestvo S Ogranichennoi Otvetstvennostiu "nauchno Proizvodstvennaya "recon" Firma
Original Assignee
Obshchestvo S Ogranichennoi Otvetstvennostiu "nauchno Proizvodstvennaya "recon" Firma
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 Obshchestvo S Ogranichennoi Otvetstvennostiu "nauchno Proizvodstvennaya "recon" Firma filed Critical Obshchestvo S Ogranichennoi Otvetstvennostiu "nauchno Proizvodstvennaya "recon" Firma
Priority to PCT/RU2020/000756 priority Critical patent/WO2022211653A1/fr
Publication of WO2022211653A1 publication Critical patent/WO2022211653A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the invention relates to a method for producing an aqueous epoxy dispersion for use as a film-forming component of lubricants for inorganic (glass and basalt) and carbon fibers, a binder for protective-decorative and anti-corrosion paints, primers, water-dispersion coatings, etc.
  • a known method for producing an epoxy emulsion including the combination of epoxy resin with a non-ionic type emulsifier with a hydrophilic-lipophilic balance (HLB) of 14-20 and/or anionic emulsifier at 51-79°C, followed by a batch introduction of water.
  • HLB hydrophilic-lipophilic balance
  • the disadvantages of the proposed method is a rather short period of possible storage (3-6 months) and predominantly large particle size.
  • a known method for producing an aqueous epoxy dispersion (RF patent Ns2365607, C09D 163/00, C09D 5/02, published 08/27/2009), which consists in the fact that the interaction of the epoxy component - A (a mixture of cycloaliphatic or aliphatic resin with aromatic epoxy resin) and aliphatic difunctional compound B, at a temperature of 50-90°C for E5 h in the presence of a catalyst (tertiary amine or dimethylamine) to reduce the content of epoxy groups in component A to 5-70% of the original amount.
  • component A is added to the interaction product, mixed, and then four equal portions of distilled water are added.
  • the result is a stable emulsion that does not contain solvents.
  • a significant disadvantage of this solution is the complexity, complexity and multi-stage process of manufacturing the dispersion.
  • a method for obtaining an aqueous epoxy emulsion (RF patent N°2587091, C09D 5/02, C09D 163/00, C09D 163/02, published on 06/10/2016) was chosen by direct emulsification of low molecular weight epoxy resin (liquid) with epoxy equivalent weight up to 300 g/eq. in an aqueous solution of surfactants containing a polycarboxylate ester and a copolymer of ethylene oxide and propylene oxide, as well as additionally silica sol.
  • the disadvantages of the proposed method are the inability to use the method in the process of dispersion of medium and high molecular weight resins with a higher epoxy weight equivalent - accordingly, there is no possibility of controlling the degree of stickiness of the film of dried dispersions (films are sticky when dried); as well as the impossibility of obtaining aqueous emulsions with an average particle size controlled over a wide range (in particular, more than 0.6 ⁇ m).
  • the objective of the invention is to develop a method for producing a stable aqueous epoxy dispersion with a particle size controlled over a wide range, containing epoxy groups, which, when used, allows interaction with lubricant components (in particular, with some silanes), with epoxy resin hardeners.
  • the technical result consists in optimizing the recipe and technological parameters for the manufacture of aqueous dispersions of epoxy resins, providing: uniformity, high colloidal chemical stability of dispersions, small particle size of the dispersed phase (high dispersion), long shelf life, increased interfacial adhesion strength between the fiber (with applied lubricant based on the developed film formers - aqueous dispersions of nanomodified epoxy resin) and thermosetting binders based on epoxy, polyester and vinyl ester resins in the manufacture of polymer composite materials.
  • the method for producing an aqueous epoxy dispersion includes preparing a suspension of a nanomodifier, which is a multilayer carbon nanotubes, in an epoxy resin with an epoxy equivalent of 180 g/eq. up to 1000 g/eq.
  • Nanomodifier carbon nanotubes 0.001-0.05
  • medium and high molecular weight epoxy resins with an epoxy equivalent molecular weight (EEW) from 180 to 1000 g / eq were used, for example, Russian resins under the trademarks ED-20, ED-16, ED-8 from FKP “Plant named after Ya.M. Sverdlov, imported resins under the trademarks Epikote 1002 from Hexion Inc.
  • EW epoxy equivalent molecular weight
  • NPES-901, NPES-902, NPES-903, NPES-904 from NanYa Plastics Co.
  • nonionic surfactants a block copolymer of ethylene oxide and propylene oxide with a content of polyoxyethylene units from 78 to 85 mass% and HLB above 14.0, as a co-emulsifier - alkyl polyethylene glycol ether with 28 moles of ethylene oxide and HLB about 18.0;
  • the method provides for the production of storage-stable aqueous dispersions of low- and medium-molecular epoxy resins with a wide range of dry residue, fineness and viscosity, which ensure the formation of films of varying degrees of stickiness when applied to the fiber.
  • the use of low- and medium-molecular epoxy resins, nanomodification, optimized modes for obtaining dispersions, the inclusion of an organic solvent and a co-emulsifier in a number of compositions made it possible to obtain film formers with an average particle size of 0.1 to 1.0 ⁇ m.
  • the introduction of multilayer CNTs as a nanomodifier makes it possible to increase interfacial adhesion in the "fiber (with a lubricant based on a nanomodified film former) - epoxy binder" system.
  • the organic solvent allows the epoxy resin to be combined with an aqueous solution of surfactants at lower temperatures (compared to their softening and flow temperature without the introduction of a solvent). It is preferable to use an organic solvent with a boiling point higher than the softening point of the epoxy resin by at least 30-40°C to minimize the harmful effects on production personnel and avoid intense evaporation.
  • the method for obtaining an aqueous epoxy dispersion according to the claimed invention includes: preparation of a nanomodifier suspension
  • multiwalled CNTs in epoxy resin with an epoxy equivalent (from 180 g/eq. to 1000 g/eq.) or a mixture of epoxy resin with an organic solvent (in the case of semi-solid and solid epoxy resins); dosing nanomodified epoxy resin into an aqueous solution of surfactants (block copolymer of ethylene oxide and propylene oxide or its mixture with alkyl polyethylene glycol ether with 28 moles of ethylene oxide); dispersion at a speed of 1000-4500 rpm (peripheral speed of at least 20 m/s) for 5-30 minutes.
  • surfactants block copolymer of ethylene oxide and propylene oxide or its mixture with alkyl polyethylene glycol ether with 28 moles of ethylene oxide
  • an organic solvent makes it possible to: dissolve semi-solid and solid epoxy resins and ensure their processing at lower temperatures (compared to their softening point); obtain more finely dispersed systems (with a smaller average particle size); to ensure an increase in the manufacturability of the process - on average, the time of mixing the components during emulsification is reduced by 20-30%; increase the stability of the dispersion of medium molecular weight epoxy resins.
  • the block copolymer of ethylene oxide and propylene oxide is mixed with water and, in a number of compositions, with alkyl polyethylene glycol ether with 28 moles of ethylene oxide, after which epoxy resin or its mixture is introduced into the prepared aqueous surfactant solution with solvent.
  • distilled water with a temperature of +16 to +35 °C is used (preferably, from +18 to +30 °C).
  • dispersion is carried out at a speed of 1000-4500 rpm (peripheral speed should be at least 20 m/s, preferably from 25 to 40 m/s) for 5-30 minutes.
  • the viscosity of the resin/melt resin/solid resin solution determines the processability of the dispersion process (a product with a higher viscosity is harder to pump and disperse at the specified rate). Reducing the circumferential velocity to 20 m/s or less will not allow obtaining a dispersion with a particle size of less than 1 ⁇ m).
  • a nanomodifier dispersion (multilayer CNTs) is preliminarily prepared in a liquid epoxy resin in the following ratio of components:
  • Nanomodifier multilayer CNTs - 0.001-0.01 m.h.
  • the mixer (dissolver) is loaded with the calculated amount of a pre-prepared aqueous solution of surfactant (block copolymer of ethylene oxide and propylene oxide).
  • Nanomodified epoxy resin is dosed into the surfactant solution with constant stirring. After the end of dosing, the mixture is dispersed at a speed of 2000-4000 rpm (but not less than 20 m/s) for at least 10 minutes until a homogeneous stable dispersion is obtained.
  • the dispersion can be diluted to 50-60% dry residue (mass fraction of non-volatile substances) and homogenized in a dissolver.
  • the speed can be reduced to 1000 rpm.
  • a solution of semi-solid or solid epoxy resin is preliminarily prepared in an organic solvent at a ratio of components:
  • nanomodifier dispersions (multilayer CNTs) are prepared in a solution of epoxy resin or a mixture of epoxy resins in the following ratio of components: Epoxy resin diluted with an organic solvent - 110-130 m.h.
  • Nanomodifier (multilayer CNTs) - 0.005-0.05 m.h.
  • the mixer (dissolver) is loaded with the calculated amount of a pre-prepared aqueous solution of surfactant (a block copolymer of ethylene oxide and propylene oxide or a mixture of a block copolymer of ethylene oxide and propylene oxide with alkyl polyethylene glycol ether).
  • surfactant a block copolymer of ethylene oxide and propylene oxide or a mixture of a block copolymer of ethylene oxide and propylene oxide with alkyl polyethylene glycol ether.
  • Nanomodified epoxy resin is dosed into the surfactant solution with constant stirring. After the end of dosing, the mixture is dispersed at a speed of 1500-4500 rpm (but not less than 20 m/s) for at least 5-7 minutes until a homogeneous stable dispersion is obtained.
  • the ratio of components is shown in table 1.
  • the dispersion can be diluted to 45-50% dry residue (mass fraction of non-volatile substances) and homogenized in a dissolver.
  • the speed can be reduced to 1000 rpm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Nanotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production d'une dispersion époxyde aqueuse. Ce procédé de production d'une dispersion époxyde aqueuse consiste à préparer une suspension d'un nano-modificateur dans une résine époxyde ou un mélange de résine époxyde avec un solvant organique, à doser la résine époxyde nano-modifiée dans une solution aqueuse de substances tension-actives, à effectuer une dispersion à une vitesse de 1000-4500 t/min pendant 5-30 minutes, ceci selon le rapport suivant des composants (parts en poids): Résine époxyde ou un mélange de résines époxyde 100; solvant organique 0-30; copolymère séquencé éthylène oxyde et propylène oxyde 5-22; ester d'alkylpolyéthylène glycol (co-émulsifiant) 0-5; nano-modificateur (nanotubes de carbone) 0,001-0,05; eau 40-80. Le résultat technique consiste en une optimisation des paramètres industriels de formulation pour la production de dispersions aqueuses de résines époxydes.
PCT/RU2020/000756 2021-03-29 2021-03-29 Procédé de production d'une dispersion époxyde aqueuse Ceased WO2022211653A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/RU2020/000756 WO2022211653A1 (fr) 2021-03-29 2021-03-29 Procédé de production d'une dispersion époxyde aqueuse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/RU2020/000756 WO2022211653A1 (fr) 2021-03-29 2021-03-29 Procédé de production d'une dispersion époxyde aqueuse

Publications (1)

Publication Number Publication Date
WO2022211653A1 true WO2022211653A1 (fr) 2022-10-06

Family

ID=83459962

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2020/000756 Ceased WO2022211653A1 (fr) 2021-03-29 2021-03-29 Procédé de production d'une dispersion époxyde aqueuse

Country Status (1)

Country Link
WO (1) WO2022211653A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU740982B2 (en) * 1997-08-14 2001-11-22 Shell Internationale Research Maatschappij B.V. Aqueous dispersions of epoxy resins
BY12535C1 (fr) * 2008-07-14 2009-10-30
US9346925B2 (en) * 2012-06-29 2016-05-24 Dow Global Technologies Llc Epoxy resin blend dispersion and a process for preparing the dispersion
RU2587091C1 (ru) * 2014-12-30 2016-06-10 Общество с ограниченной ответственностью "НАУЧНО-ПРОИЗВОДСТВЕННАЯ ФИРМА "РЕКОН" Способ получения водной эпоксидной эмульсии
RU2699100C1 (ru) * 2019-04-01 2019-09-03 Общество с ограниченной ответственностью "НАУЧНО-ПРОИЗВОДСТВЕННАЯ ФИРМА "РЕКОН" Способ получения водной эпоксидной дисперсии

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU740982B2 (en) * 1997-08-14 2001-11-22 Shell Internationale Research Maatschappij B.V. Aqueous dispersions of epoxy resins
BY12535C1 (fr) * 2008-07-14 2009-10-30
US9346925B2 (en) * 2012-06-29 2016-05-24 Dow Global Technologies Llc Epoxy resin blend dispersion and a process for preparing the dispersion
RU2587091C1 (ru) * 2014-12-30 2016-06-10 Общество с ограниченной ответственностью "НАУЧНО-ПРОИЗВОДСТВЕННАЯ ФИРМА "РЕКОН" Способ получения водной эпоксидной эмульсии
RU2699100C1 (ru) * 2019-04-01 2019-09-03 Общество с ограниченной ответственностью "НАУЧНО-ПРОИЗВОДСТВЕННАЯ ФИРМА "РЕКОН" Способ получения водной эпоксидной дисперсии

Similar Documents

Publication Publication Date Title
US4415682A (en) Stable aqueous epoxide resin dispersion, a process for its preparation, and its use
JP2000504372A (ja) エポキシ樹脂用乳化剤として使用するためのエポキシ・アミン付加化合物；水性ベースのエポキシ樹脂分散系及びその製造のための方法
JPH0120191B2 (fr)
AU605405B2 (en) High polymer content silicone emulsions
CN104558524A (zh) 一种非离子型反应性水性环氧树脂乳液的制备方法
KR101699187B1 (ko) 에폭시 수지와 실란의 수성 공분산액 및 이의 용도
CN107033739B (zh) 涂膜柔韧性可调控的非离子型水性环氧乳液及其制备方法
CN108929423B (zh) 一种用于水性环氧树脂的非离子乳化剂及其制备方法和应用
US5500461A (en) Stable waterborne epoxy resin dispersion containing micronized DICY
US5523336A (en) Aqueous, one-component coating composition and use thereof in processes for repair lacquer coating of plastic substrates
WO2009002671A1 (fr) Résine époxy contenant des nanocharges et leurs dispersions aqueuses stables
EP2107075B1 (fr) Emulsifiants pour résines époxydes
WO2022211653A1 (fr) Procédé de production d'une dispersion époxyde aqueuse
US3514421A (en) Aqueous coating compositions
RU2699100C1 (ru) Способ получения водной эпоксидной дисперсии
RU2587091C1 (ru) Способ получения водной эпоксидной эмульсии
CN108373533A (zh) 一种自乳化水性环氧固化剂的制备方法
KR102391148B1 (ko) 계면활성제 조성물
RU2129582C1 (ru) Двухкомпонентный состав для покрытий и способ изготовления связующих для покрытий
CN119775533A (zh) 一种阴离子型环氧乳化剂及其制备方法、环氧树脂水分散体
CN116694188B (zh) 一种高性能的水性环氧树脂乳液及其制备方法和应用
CN119039615A (zh) 一种水性环氧树脂及其制备方法
JP6368878B1 (ja) 塗料組成物調製用水性シリコーン樹脂エマルションの製造方法
CN118146519A (zh) 一种单组份大分子环氧乳液及其制备方法
CN116854925A (zh) 一种用于制备零voc水性环氧乳液的乳化剂及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20968189

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20968189

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 20968189

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 26/03/2024)

122 Ep: pct application non-entry in european phase

Ref document number: 20968189

Country of ref document: EP

Kind code of ref document: A1