WO2024094961A1 - Procédé de fabrication d'une composition de résine durcissant à l'humidité - Google Patents

Procédé de fabrication d'une composition de résine durcissant à l'humidité Download PDF

Info

Publication number
WO2024094961A1
WO2024094961A1 PCT/GB2023/052700 GB2023052700W WO2024094961A1 WO 2024094961 A1 WO2024094961 A1 WO 2024094961A1 GB 2023052700 W GB2023052700 W GB 2023052700W WO 2024094961 A1 WO2024094961 A1 WO 2024094961A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
moisture
hydroxy alkyl
cure resin
terminated polyether
Prior art date
Application number
PCT/GB2023/052700
Other languages
English (en)
Inventor
Bernard Barthel
Original Assignee
Spider Resin Limited
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
Priority claimed from GBGB2216037.8A external-priority patent/GB202216037D0/en
Application filed by Spider Resin Limited filed Critical Spider Resin Limited
Publication of WO2024094961A1 publication Critical patent/WO2024094961A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides

Definitions

  • the present invention relates to a method of manufacturing a moisture-cure resin composition, to a moisture-cure resin composition preferably but not necessarily exclusively formed in accordance with the method, and to a paint, coating, composite, potting compound, or adhesive product comprising the moisture-cure resin composition.
  • accelerators have a number of disadvantages.
  • Trisdimethylaminomethylphenol Arcamine K- 54 from Evonik (RTM)
  • AEP Accelelerator 399 from Huntsman (RTM)
  • Acids such as salicylic acid, paratoluene sulfonic acid, or boron trifluoride are also accelerators, but have a poor toxicological and environmental profile.
  • a method of producing a moisture-cure resin composition comprising the steps of: preparing a hydroxy alkyl urethane modifier having the formula: where:
  • R 1 is an amine residue
  • R 2 and R 3 are the same or different and are selected from the group consisting of H, alkyl, and hydroxyalkyl; reacting the hydroxy alkyl urethane modifier with an epoxy silane to form a silane- modified hydroxy alkyl urethane; and reacting the silane-modified hydroxy alkyl urethane with a silyl terminated polyether to form a moisture-cure resin composition.
  • a moisture-cure resin composition of the type outlined here has many favourable attributes.
  • the composition has a high refractive index, close to that of glass, and can therefore be used without creating deleterious aesthetics issues.
  • the composition has improved adhesion properties when compared with existing resins, particularly for adhesion to steel, glass, and ceramics.
  • the composition is more flexible than traditional cured resins and has an improved chemical and mechanical resistances. There is good solvent resistance to xylene, MIBK, acetone, and white spirit. It is also able to be cured at thicknesses in excess of 100pm, which has been difficult to achieve for urethane-based resin compositions in the past.
  • the epoxy silane may be selected from the group comprising: (3-glycidoxypropyl)trimethoxysilane; (3-glycidoxypropyl)triethoxysilane; (3- glycidoxypropyl)methyldiethoxyilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.
  • the epoxy silane may be reacted with the hydroxy alkyl urethane modifier in an equivalent weight ratio of 1 :1.
  • the silyl terminated polyether may be a low-viscosity silyl terminated polyether.
  • the silyl terminated polyether may be selected from the group comprising: dimethoxy(methyl)silylmethylcarbamate-terminated polyether; and trimethoxy(methyl)silylmethylcarbamate-terminated polyether.
  • the modified hydroxy alkyl urethane may be reacted with the silyl terminated polyether in an equivalent weight ratio of at least 1 :1.5.
  • a catalyst may be used.
  • the catalyst may comprise an amino silane, such as N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane.
  • the hydroxy alkyl urethane may be prepared by reaction of a primary amine with a monocyclocarbonate.
  • the monocyclocarbonate may be selected from the group comprising: ethylene carbonate; 1 ,2-propylene carbonate; 1 ,2-butylene carbonate; 2,3-butylene carbonate, 1 ,2-pentylene carbonate; and 1 ,2-glycerol carbonate.
  • the primary amine and monocyclocarbonate may be mixed in an equivalent weight ratio of between 1 : 1 and 1 :1.1.
  • the primary amine may be selected from the group comprising: 2, 2, -(2 ,2 ,4)-trimethyl- 1 ,6 hexanediamine; 1 ,6-hexanediamine; 2-methyl-1 ,5 pentanediamine; meta-xylene diamine; 1 ,3-bis(aminomethyl) cyclohexane; isophorone diamine; cyclohexane diamine; 4,4’-diaminodicyclohexyl-methane; polyoxypropylene diamines; polypropoxypropylene triamines; and phenalkamines with a ratio of between 1 :3 and 1 :4.
  • the modified hydroxy alkyl urethane modifier may be formed without any isocyanates or isocyanate-containing intermediates.
  • the hydroxy alkyl urethane modifier may be provided in a ratio of between 20 parts to 40 parts by weight of the moisture-cure resin composition.
  • the epoxy silane may be provided in a ratio of between 20 parts to 40 parts by weight of the moisture-cure resin composition.
  • the silyl terminated polyether may be provided in a ratio of between 20 parts to 60 parts by weight of the moisture-cure resin composition.
  • a moisture-cure resin composition comprising a modified hydroxy alkyl urethane with a silyl terminated polyether, the modified hydroxy alkyl urethane with a silyl terminated polyether being formed by reaction of a hydroxy alkyl urethane modifier having the formula: where:
  • R 1 is an amine residue
  • R 2 and R 3 are the same or different and are selected from the group consisting of H, alkyl, and hydroxyalkyl; with an epoxy silane and a silyl terminated polyether.
  • the moisture-cure resin composition may preferably further comprise a diluent silane composition. Additionally, or alternatively, the composition may further comprise a UV absorber.
  • the moisture-cure resin composition may further comprise a water scavenger, such as vinyltrimithoxysilane.
  • a paint, coating, composite, potting compound, or adhesive product comprising the moisture-cure resin composition in accordance with the second aspect of the invention.
  • This may be suitable for use on any of the following substrates: wood; plastics; concrete; composites; metal; ceramic; and glass.
  • hydroxy alkyl urethane modifier having the formula: where R1 is an amine residue, and R2 and R3 are the same or different and are selected from the group consisting of H, alkyl, and hydroxyalkyl.
  • the composition is formed by reacting an epoxy acrylate resin on a hydroxyalkyl urethane via a Michael addition.
  • HUM-1 hydroxy alkyl urethane modifier
  • HUM-1 Preparation 142 parts of 1 ,3-bis(aminomethyl) cyclohexane (1 ,3 BAC) are introduced into a reactor equipped with a stirring and a cooling system. Then, 224 parts of polypropylene carbonates are gradually introduced over 2 hours. The reaction is exothermic and requires cooling, with the reaction mixture being maintained at a temperature of 90°C. After 8 hours at 90°C, the amine index (MEQ I gram: 0.3) is checked. The reaction temperature is maintained at 100 to 120°C until an amine index value of 0.15 is obtained. The final product has a dry extract of 96.4% (60 minutes at 100°C) and the viscosity at room temperature is high. The viscosity at 50°C is measured as 14 Pa.s. The consumption of the carbonate function is also measured by infra-red analysis (wavelength 1800cm -1 ) replaced by the urethane function.
  • a broad carbonyl absorption was detected at ⁇ 1727cm -1 which is within the region expected for a carbonyl group as part of a urethane structure. It is also similar to than expected of an acrylate. A broad absorption was measured at -1100 cm -1 which is indicative of the C-0 bond in an aliphatic ether.
  • HUM-2 hydroxy alkyl urethane modifier
  • the hydroxy alkyl urethane modifier is prepared by reaction of a primary amine with a monocyclocarbonate.
  • the monocyclocarbonate may be selected from the group comprising: ethylene carbonate; 1 ,2-propylene carbonate; 1 ,2-butylene carbonate; 2,3- butylene carbonate, 1 ,2-pentylene carbonate; and 1 ,2-glycerol carbonate.
  • the primary amine and monocyclocarbonate are mixed in an equivalent weight ratio of between 1 :1 and 1 :1.1.
  • the primary amine is selected from the group comprising: 2,2,-(2,2,4)-trimethyl-1 ,6 hexanediamine; 1 ,6-hexanediamine; 2-methyl-1 ,5 pentanediamine; meta-xylene diamine; 1 ,3-bis(aminomethyl) cyclohexane; isophorone diamine; cyclohexane diamine; 4,4’-diaminodicyclohexyl-methane; polyoxypropylene diamines; polypropoxypropylene triamines; and phenalkamines with a ratio of between 1 :3 and 1 :4.
  • the modified hydroxy alkyl urethane modifier is formed without any isocyanates or isocyanate-containing intermediates.
  • an epoxy silane can be introduced. This acts as a coupling agent.
  • an epoxy silane may be Glymo or (3-glycidoxypropyl)trimethoxysilane.
  • other epoxy silanes could be considered, such as 3-glycidoxypropyl)triethoxysilane; (3- glycidoxypropyhmethyldiethoxyilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and
  • the hydroxy alkyl urethane modifier is mixed with the epoxy silane in a 1 :1 by weight ratio.
  • propylene carbonate is mixed with isophorone diamine in a ratio of 114 parts to 86 parts respectively to form the hydroxy alkyl urethane modifier HUM-2. This is then reacted with 200 parts Glymo. The Glymo reacts with the residual hydroxy group of the hydroxy alkyl urethane modifier, thereby creating a silane-modified hydroxy alkyl urethane.
  • the epoxy silane increases the reactivity of the hydroxy alkyl urethane modifier with silyl terminated polyethers (STPE).
  • STPE silyl terminated polyethers
  • Examples of STPE known in the art include SILRES (RTM) 6290, Geniosil (RTM) XB-502, Geniosil (RTM) E-10, and Geniosil (RTM) E-30, all from Wacker Chemie AG, Hanss-Seidel-Platz 4, 81737, Kunststoff, Germany.
  • a low- viscosity STPE is preferred, however, such as SILRES (RTM) 6290.
  • HUM product based on propylene carbonate and isophorone diamine.
  • an epoxy silane is added, such as Geniosil (RTM) XL 80. This is added in a 1 :1 ratio with the HUM product, at approximately 20°C. This is treated as being 20 parts HUM to 20 parts epoxy silane.
  • silyl terminated polyether such as SILRES (RTM) 6920 is added.
  • viable moisture-cure resin compositions can be formed where the hydroxy alkyl urethane modifier is provided in a ratio of between 20 parts to 40 parts by weight of the final composition, where the epoxy silane is provided in a ratio of between 20 parts and 40 parts of the final composition, and where the silyl terminated polyether is provided in a ratio of between 20 parts and 60 parts.
  • hydroxy alkyl urethane modifier is provided in a ratio of between 10 parts to 70 parts by weight of the final composition
  • the epoxy silane is provided in a ratio of between 10 parts and 70 parts of the final composition
  • the silyl terminated polyether is provided in a ratio of between 10 parts and 80 parts.
  • the moisture-cure resin composition has many uses.
  • a clear coating can be made. This can be created by mixing the moisture-cure resin composition as described above, with a catalyst, such as Geniosil (RTM) GF9. This may be in a ratio of 95 parts to 5 parts, typically after 24 hours.
  • RTM Geniosil
  • the coating will be applicable in this form; however, a reactive diluent can also be added, such as SILRES (RTM) 1316 5, here added in 15 parts to adjust the viscosity of the resin composition, typically after a further 24 hours.
  • the final product is then clear, like water, and has a low viscosity.
  • UV absorber (1 part)
  • water scavenger (1 part)
  • vinyltrimithoxysilane can also be included to improve the properties of the coating.
  • Pigmentation could also be added.
  • a pigmented coating has been prepared by mixing 85 parts of the clear coating outlined above with 15 parts of a pigment concentrate RAL 7040 Holcolzac CC. This is merely one exemplary test for the incorporation of pigmentation, and it will be apparent that a wide range of pigments could be introduced to produce different types of coatings.
  • compositions might include paints, varnishes, floor coatings, electricals, composites, adhesives, potting, and industrial coating.

Landscapes

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

Abstract

La présente invention concerne un procédé de production d'une composition de résine durcissant à l'humidité, le procédé comprenant les étapes consistant à : préparer un modificateur d'hydroxyalkyl-uréthane ayant la formule : (I) ; dans laquelle : R1 est un résidu amine ; et R2 et R3 sont identiques ou différents et sont choisis dans le groupe constitué par H, alkyle et hydroxyalkyle ; la réaction du modificateur hydroxy alkyle uréthane avec un époxy silane pour former un hydroxy alkyle uréthane modifié par silane ; et la réaction de l'hydroxyalkyl uréthane modifié par silane avec un polyéther à extrémité silyle pour former une composition de résine durcissant à l'humidité.
PCT/GB2023/052700 2022-10-30 2023-10-18 Procédé de fabrication d'une composition de résine durcissant à l'humidité WO2024094961A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB2216037.8 2022-10-30
GBGB2216037.8A GB202216037D0 (en) 2022-10-30 2022-10-30 Modified hydroxyl alkyl urethane with an silanated terminated polyether
GB2218620.9A GB2624050A (en) 2022-10-30 2022-12-12 Method of Manufacturing Moisture-Cure Resin Composition
GB2218620.9 2022-12-12

Publications (1)

Publication Number Publication Date
WO2024094961A1 true WO2024094961A1 (fr) 2024-05-10

Family

ID=88839797

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2023/052700 WO2024094961A1 (fr) 2022-10-30 2023-10-18 Procédé de fabrication d'une composition de résine durcissant à l'humidité

Country Status (1)

Country Link
WO (1) WO2024094961A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180244828A1 (en) * 2015-09-10 2018-08-30 Dow Global Technologies Llc Moisture curable systems based on polysilylated polyethers and titanium (iv) catalysts and/or zinc/cyclic amidine catalyst mixtures

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180244828A1 (en) * 2015-09-10 2018-08-30 Dow Global Technologies Llc Moisture curable systems based on polysilylated polyethers and titanium (iv) catalysts and/or zinc/cyclic amidine catalyst mixtures

Similar Documents

Publication Publication Date Title
EP3416996B1 (fr) Composition durcissable
US20110263753A1 (en) Water dispersible epoxy urethane compounds and coating compositions
EP3110870B2 (fr) Amines furanes en tant que durcisseurs pour résines époxy dans des applications à faible teneur en cov
EP2776489B1 (fr) Durcisseur comprenant des groupes aminés aromatiques pour résines époxydes
AU2017220532A1 (en) Curing agent for low-emission epoxy resin compositions
Gupta et al. Development of siliconized epoxy resins and their application as anticorrosive coatings
KR20090029192A (ko) 코팅 시스템
US5847027A (en) Hardeners for elastic epoxy resin systems
CN110914329B (zh) 组合物
US9469721B2 (en) Low emission epoxy curing agents
EP0786481B1 (fr) Accélérateurs réactifs pour des résines époxydes durcies par des amines
EP0783010B1 (fr) Produit d'addition de méthylamine pour le durcissement de résines époxydes
WO2024094961A1 (fr) Procédé de fabrication d'une composition de résine durcissant à l'humidité
GB2624050A (en) Method of Manufacturing Moisture-Cure Resin Composition
WO2023131655A1 (fr) Composition de durcissement à l'humidité à un composant
EP4202002A1 (fr) Composition de revêtement exempte de solvant
KR20230092035A (ko) 콘크리트 구조물용 친환경, 저온 경화성, 고내구성, 무용제형 에폭시 수지계 방수방식재 조성물
CN114854089B (zh) 芳基醇胺类作为环氧树脂稀释剂的应用以及环氧树脂组合物
US10752803B2 (en) 1K high hardness, high impact resistance coating
CN114874417B (zh) 一种环氧树脂稀释剂及其制备方法与应用
EP4223824A1 (fr) Nouveaux composés époxy-uréthane contenant de l'uretdione et leurs polymères thermodurcissables
CN111511795B (zh) 苄基化的三氨基壬烷及其用途
KR100709071B1 (ko) 도막 방수용 친환경 무용제형 에폭시 도료 조성물
EP4223820A1 (fr) Composés d'urée glycidylique et leurs polymères thermodurcissables
CN117946404A (zh) 一种具有耐盐雾性能的水性环氧固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: 23808851

Country of ref document: EP

Kind code of ref document: A1