WO2025240102A1 - Formulation de résine d'imprégnation - Google Patents

Formulation de résine d'imprégnation

Info

Publication number
WO2025240102A1
WO2025240102A1 PCT/US2025/026491 US2025026491W WO2025240102A1 WO 2025240102 A1 WO2025240102 A1 WO 2025240102A1 US 2025026491 W US2025026491 W US 2025026491W WO 2025240102 A1 WO2025240102 A1 WO 2025240102A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin formulation
resin
formulation
volume
liquid epoxy
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.)
Pending
Application number
PCT/US2025/026491
Other languages
English (en)
Inventor
Felix Koch
Cathy Grossnickel
Andrea GMÜER-THOMA
Werner Hollstein
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.)
DDP Specialty Electronic Materials US LLC
Original Assignee
DDP Specialty Electronic Materials US 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 DDP Specialty Electronic Materials US LLC filed Critical DDP Specialty Electronic Materials US LLC
Publication of WO2025240102A1 publication Critical patent/WO2025240102A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/54—Amino amides>
    • 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

Definitions

  • the voltage levels for electrical traction motors in vehicles have increased from 400 to 800V to enable fast charging but still require reliable electrical insulation to avoid partial discharges which could lead to breakdowns and failure of the e-motor over time.
  • Magnet-free e-motors represent a sustainable solution to avoid using rare earth elements as permanent magnets
  • the external excitation through copper wound rotors requires sufficient mechanical fixation over the whole range of operational conditions from low to high temperatures of 150°C and rotational speed of 15,000 rpm.
  • the present invention provides an un-cured impregnation resin formulation that comprises: a) 70% to 96% of a liquid epoxy resin by volume of the resin formulation; and b) 2% to 8% of a solid dicyandiamide curing agent by volume of the resin formulation, the solid dicyandiamide curing agent being dispersed in the liquid epoxy resin.
  • the present invention also provides methods of using the impregnation formulation, e.g., as an insulating coating on a suitable substrate, as well as products prepared by applying the resin formulation to a substrate and allowing the formulation to cure.
  • Liquid epoxy resins are thermoplastic materials which can be cured to a thermoset polymer.
  • Major resin types include diglycidyl ethers of bisphenol A and bisphenol F, novolacs, peracid resins, and hydantoin resins, among others.
  • a variety of epoxy resins are suitable for the formulation. Suitable resin types include glycidyl ether based resins, glycidyl ester based resins, and glycidylamine based resins, among others.
  • Suitable glycidyl ether type epoxy resins include bisphenol A type, bisphenol F type, halogenated bisphenol A or F type, hydrogenated bisphenol A of F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolac type, cresol novolac type, DPP novolac type, trifunctional type, tris(hydroxyphenyl)methane type, and tetraphenylolethane type epoxy resins.
  • Hydroxy compounds that are suitable for the preparation of glycidyl ethers are novolaks, obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols or bisphenols, any of which can be substituted or unsubstituted.
  • suitable glycidyl ester type epoxy resins include hexahydrophthalate type and phthalate type epoxy resins.
  • suitable glycidylamine type epoxy resins include tetraglycidyldiaminodiphenylmethane, triglycidyl isocyanurate, hydantoin type, 1 ,3-bis(N,N diglycidylaminomethyl)cyclohexane, aminophenol type, aniline type, and toluidine type epoxy resins.
  • the epoxy resin comprises a glycidyl ether having the following structure: wherein R 1 and R 2 are independently hydrogen or C1-C4 alkyl, including C1-C4 substituted or unsubstituted alkyl, and each instance of n is independently an integer ranging 1-4. In a specific embodiment, each R 1 and R 2 is hydrogen, and each n is 1 . In a further specific embodiment, each R 1 and R 2 is methyl, and each n is 1 .
  • a combination of glycidyl ethers having the above structure can be used, e.g., one glycidyl ether in which each R 1 and R 2 is hydrogen, and each n is 1 , and a second glycidyl ether in which each R 1 and R 2 is methyl, and each n is 1 , i.e. , a combination of bisphenol A and bisphenol F type glycidyl ethers.
  • the liquid epoxy resin can be present in the impregnation resin formulation in any suitable amount.
  • the formulation comprises 70% to 96% of the liquid epoxy resin by volume of the resin formulation.
  • the formulation comprises 75% to 96% of the liquid epoxy resin by volume of the resin formulation.
  • the formulation comprises 80% to 96% of the liquid epoxy resin by volume of the resin formulation.
  • the formulation comprises 85% to 96% of the liquid epoxy resin by volume of the resin formulation.
  • the formulation comprises 90% to 95% of the liquid epoxy resin by volume of the resin formulation.
  • the formulation comprises 90% to 93% of the liquid epoxy resin by volume of the resin formulation.
  • the impregnation resin formulation can comprise a suitable dicyandiamide curing agent.
  • Dicyandiamide is also known as 2-cyanoguanidine, a nitrile derived from guanidine and a dimer of cyanamide.
  • the dicyandiamide curing agent will react with the liquid epoxy resin under suitable reaction conditions to cure the impregnation resin formulation.
  • the dicyandiamide curing agent is a solid, which is dispersed in the liquid epoxy resin.
  • the resin formulation exhibits superior characteristics when the dicyandiamide curing agent is a solid dispersed in the epoxy resin, i.e., the resin formulation remains stable and performs well with a curing agent that remains solidified and dispersed in the epoxy resin.
  • the solid dicyandiamide curing agent is a powder having a D90 particle size distribution of 5 microns or less. That is, 90% of a sample of the powder will have a particle size of 5 microns or less. Particle size can be measured by methods known in the art, such as dynamic light scattering among other methods.
  • the solid dicyandiamide curing agent is a powder having an average particle size ranging from 1-5 microns, e.g., 1-3 microns, or 1-2 microns.
  • the resin formulation can comprise 2% to 8% of the dicyandiamide curing agent by volume of the resin formulation. In a further embodiment, the resin formulation comprises 4% to 8% of the solid dicyandiamide curing agent by volume of the resin formulation. In a further embodiment, the resin formulation comprises 5% to 7% of the solid dicyandiamide curing agent by volume of the resin formulation.
  • the resin formulation can include a variety of other ingredients, including accelerators, reactive and non-reactive diluents, fillers, tougheners, wetting agents, coloring agents, fluorescent agents, among others. i. Accelerators
  • the resin formulation comprises an accelerator.
  • the accelerator comprises at least one dialkyl amino group, e.g., at least one dimethyl amino group. Suitable examples of such include benzyldimethylamine, a-methylbenzyldimethylamine, N, N-diethyl-N ', N'-dimethyl- 1 ,3-propanediamine, N, N-dimethylethanolamine, 3- (N, N-dimethylamino) propane-1 -ol, 2- or 4-(dimethylaminomethyl) phenol, 2,4- or 2,6-bis-(N, N- dimethylaminomethyl) phenol, 2,4,6-tris-(N, N-dimethylaminomethyl) phenol, or 2,4,5-Tris (N, N-dimethyl-4-amino-2-azabutyl) phenol.
  • the accelerator is 2 ,4,6-tris-(N , N-dimethylaminomethyl) phenol.
  • the accelerator can be microencapsulated by a suitable carrier, e.g., poly(p-vinyl)phenol.
  • a suitable carrier e.g., poly(p-vinyl)phenol.
  • the accelerator is a dialkyl amino based accelerator, e g., dimethyl amino based accelerator, incorporated into a suitable polymeric carrier such as poly(p- vinyl)phenol.
  • the accelerator is 2,4,6-tris-(N, N- dimethylaminomethyl) phenol incorporated into a suitable carrier such as poly(p- vinyl)phenol.
  • urea-based accelerators can also be present in the formulation. These include substituted urea-based accelerators.
  • Non-limiting examples include 3- (3-Trifluoromethylphenyl)-1 ,1 -dimethylurea (known as UR700), N, N"-(4-methyl-1 ,3- phenylene)bis [N',N - dimethylurea], N, N"-(methyl-m-phenylene)bis [N 1 , N'- dimethylurea], or a mixture of N, N"-(4-methyl-1 ,3-phenylene)bis [N',N'- dimethylurea] and N, N"-(methyl-m-phenylene)bis [N 1 , N'-dimethylurea], A mixture of 80% N, N"-(4-methyl-1,3-phenylene)bis [N',N'- dimethylurea] and 20% N, N"-(methyl- m-phenylene)bis [N', N'-dimethylure
  • the accelerator can be present in the formulation in any suitable amount.
  • the resin comprises 0.2% to 3% of the accelerator by volume of the resin formulation.
  • the resin comprises 0.2% to 2% of the accelerator by volume of the resin formulation.
  • the resin comprises 0.2% to 1 .5% of the accelerator by volume of the resin formulation.
  • the resin comprises 0.5% to 1 .5% of the accelerator by volume of the resin formulation.
  • the accelerator can be present in the formulation as a solid or liquid but in some embodiments is present as a solid, which is dispersed in the liquid epoxy resin. ii. Reactive Diluent
  • the resin formulation can comprise a suitable reactive diluent.
  • suitable reactive diluents include mono- and diglycidyl ethers of aliphatic alcohols and polyether glycols such as C2-C24 alkylene glycols and polyethylene oxide) or polypropylene oxide) glycols, and mixtures thereof.
  • Commercially available diglycidyl ethers of alcohols that are useful include for example 1 ,6-Hexanediol diglycidylether, 1 ,4-butanediol diglycidylether, and mixtures thereof.
  • the resin formulation can comprise a first glycidyl ether type epoxy compound and a second glycidyl ether type reactive diluent.
  • the reactive diluent is 1 ,4-butanediol diglycidylether.
  • the reactive diluent can be present in any suitable amount.
  • the resin formulation comprises 0.5% to 10% of the reactive diluent by volume of the resin formulation.
  • the resin formulation comprises 0.5% to 5% of the reactive diluent by volume of the resin formulation. In a further embodiment, the resin formulation comprises 1 % to 5% of the reactive diluent by volume of the resin formulation. In a further embodiment, the resin formulation comprises 1 % to 3% of the reactive diluent by volume of the resin formulation. In a further embodiment, the resin formulation comprises 1 % to 2% of the reactive diluent by volume of the resin formulation.
  • resin formulation in any suitable amount.
  • examples include polyglycidyl epoxy (0-20% by volume of the resin formulation), fillers (0-30% by volume of the resin formulation), tougheners (0-10% by volume of the resin formulation), wetting agents (0-0.99% by volume of the resin formulation), coloring agents (0-0.5% by volume of the resin formulation), and fluorescent agents (0-0.1% by volume of the resin formulation).
  • the impregnation resin formulations are generally stable when stored yet also cure very quickly when applied to a suitable substrate.
  • the formulation can be applied to a suitable substrate, such as a winding on an electrical traction motor (e.g., a copper winding) or other component of an electrical vehicle motor, and cured through polymerization.
  • the impregnation method can comprise any suitable method such as bath impregnation (roll dipping) or trickle impregnation, among others.
  • a suitable substrate comprising the impregnation resin formulation can be heated, e.g., in an oven, to cure the formulation, In some embodiments, the substrate can be heated to a temperature ranging from 60-220°C In a further embodiment, the substrate comprising the impregnation resin can be heated at a temperature ranging from 80-200°C. In a further embodiment, the substrate comprising the impregnation resin can be heated at a temperature ranging from 100- 190°C, e.g., 150°C, depending on the material used and the desired curing time.
  • a further embodiment is a cured product which is obtainable by curing a described curable resin formulation.
  • Viscosity was measured with a rotational rheometer Bohlin, 10s-1 , Viscosity after 60s, CP4/20.
  • Impregnation capability was measured by pouring the resin on a stack of 25 filter papers (Macherey Nagel MN 713, grammage 70g/m2, thickness 0.15mm, filtering speed 20s) fixed in a mould, and after gelification (2 hours at 80°C) the net weight was measured.
  • Storage / bath stability was measured as doubling of the initial viscosity vs storage time.
  • Curing time was measured using DSC: a first isothermal run defining the cure temperature and time was conducted. A second run (dynamic from 25°C to 250°C with 10K/minutes) was used to determine the residual enthalpy. The material is considered fully cured if it shows less than 5% residual reaction enthalpy in the described second run compared to the reaction enthalpy in a dynamic DSC run from 25°C to 250°C with 10K/minutes.
  • formulations- Preparation of formulations-.
  • the formulations were mixed on a planetary mixer or on a dual asymmetric centrifuge.
  • the liquid phases were mixed before the solid materials were added to the formulation.
  • the formulation was mixed for about 30 minutes under vacuum before being filled into pails or drums.
  • comparative example 1 has low viscosity, it does not adequately impregnate the copper windings of motors, generators or transformers, it does not cure in less than 60’ ( minutes), and the resin bath is not stable because the viscosity increased to more than double in less than 30d 140°C.
  • Comparative example 2 has low viscosity, cures fast, and is latent enough, but it does not impregnate copper windings of electrical components.
  • Comparative example 3 has low viscosity, high reactivity, and high latency but it has low impregnation capability and mechanical strength on a helical coil at 150°C.
  • Inventive examples 1 to 5 represent solutions for these problems. They have low viscosity and high impregnation capability, are storage stable as one-component systems for more than 30d at 40°C, are fast curing in less than 60’ at 150°C, have high 3 point bending strength on an impregnated helical coil of more than 100 N at 150°C, and are free of components with carcinogenic, mutagenic or reprotoxic classification.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une formulation de résine d'imprégnation et des procédés d'utilisation de celle-ci.
PCT/US2025/026491 2024-05-13 2025-04-25 Formulation de résine d'imprégnation Pending WO2025240102A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202463646734P 2024-05-13 2024-05-13
US63/646,734 2024-05-13

Publications (1)

Publication Number Publication Date
WO2025240102A1 true WO2025240102A1 (fr) 2025-11-20

Family

ID=97720585

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2025/026491 Pending WO2025240102A1 (fr) 2024-05-13 2025-04-25 Formulation de résine d'imprégnation

Country Status (1)

Country Link
WO (1) WO2025240102A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101693A (en) * 1971-08-05 1978-07-18 General Electric Company Method of preparing epoxy-glass prepregs
EP2017296A1 (fr) * 2006-04-25 2009-01-21 The Yokohama Rubber Co., Ltd. Composition de résine époxy destinée à un matériau composite renforcé par fibres
WO2014001537A1 (fr) * 2012-06-29 2014-01-03 Gurit (Uk) Ltd Préimprégnés utilisables en vue de la fabrication de matériaux composites
WO2017030988A1 (fr) * 2015-08-14 2017-02-23 Cytec Industries Inc. Pré-imprégné à durcissement rapide
WO2017066056A1 (fr) * 2015-10-13 2017-04-20 Dow Global Technologies Llc Composition d'époxy à durcissement rapide destinée à être utilisée dans des procédés de fabrication à haut rendement

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101693A (en) * 1971-08-05 1978-07-18 General Electric Company Method of preparing epoxy-glass prepregs
EP2017296A1 (fr) * 2006-04-25 2009-01-21 The Yokohama Rubber Co., Ltd. Composition de résine époxy destinée à un matériau composite renforcé par fibres
WO2014001537A1 (fr) * 2012-06-29 2014-01-03 Gurit (Uk) Ltd Préimprégnés utilisables en vue de la fabrication de matériaux composites
WO2017030988A1 (fr) * 2015-08-14 2017-02-23 Cytec Industries Inc. Pré-imprégné à durcissement rapide
WO2017066056A1 (fr) * 2015-10-13 2017-04-20 Dow Global Technologies Llc Composition d'époxy à durcissement rapide destinée à être utilisée dans des procédés de fabrication à haut rendement

Similar Documents

Publication Publication Date Title
KR100437735B1 (ko) 열경화성수지조성물,전기절연선륜,회전전기및그제조방법
CA3028844A1 (fr) Systeme d'isolation electrique a base de resines epoxy pour generateurs et moteurs
JP5603610B2 (ja) 無溶剤一液型シアン酸エステル−エポキシ複合樹脂組成物
JP2016169314A (ja) オキサゾリドン環含有エポキシ樹脂、その製造方法、エポキシ樹脂組成物及び硬化物
KR101089540B1 (ko) 1액형 열경화성 에폭시 수지 조성물
CN102558508A (zh) 低温可固化环氧组合物
JP5579059B2 (ja) エポキシドの硬化触媒
JP5876414B2 (ja) 潜在性硬化剤組成物及び一液硬化性エポキシ樹脂組成物
JP2004269641A (ja) 高弾性エポキシ樹脂組成物
US5077355A (en) Epoxy resin/imidazole/polyphenol adduct as epoxy curing agent
US4309512A (en) Heat-resistant thermosetting resin composition
AU595593B2 (en) Epoxy resin composition
WO2025240102A1 (fr) Formulation de résine d'imprégnation
ES2790740T3 (es) Sistema de aislamiento eléctrico basado en resinas epoxi para generadores y motores
KR20190038845A (ko) 에폭시/무수물 조성물을 위한 잠재 촉매 혼합물
US3642698A (en) Epoxy resin curing with imidazole alkyl acid phosphate salt catalyst
JPS58219217A (ja) 変性エポキシ樹脂
CN110088165A (zh) 用于发电机和电动机的基于环氧树脂的电绝缘体系
JP2005344112A (ja) 硬化促進剤
JP2004526396A (ja) 粉体コーティングされたロータ
JPWO2016093253A1 (ja) 熱硬化性樹脂組成物
RU2792592C1 (ru) Состав и способ получения связующего на основе эпоксидно-бензоксазиновой композиции
JP6765252B2 (ja) 組成物、半導体封止用組成物、及びこれらの組成物の硬化物
RU2810881C1 (ru) Ускоритель отверждения ленты и его применение, твердый изоляционный материал и безангидридная система изоляции
JP7693334B2 (ja) 熱硬化性樹脂用硬化剤組成物、エポキシ樹脂組成物、および繊維強化複合材

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: 25804078

Country of ref document: EP

Kind code of ref document: A1