CN-122029210-A - Formulation and glass-like polymer resin based on epoxide containing dynamic bond

Abstract

Formulations intended to be cured for the manufacture of glass-like polymeric resins of the epoxy type. The first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties, and one or more dynamic covalent bonds, wherein at least one epoxy moiety is separated from at least one other epoxy moiety by at least one dynamic covalent bond, and the second component is or comprises one or more curing agents, and wherein at least one of the first component and the second component is a liquid at a temperature less than or equal to 65 ℃, and wherein the first component is compatible with the second component as determined by compatibility test a at a temperature less than or equal to 65 ℃, and wherein the formulation cures at a temperature less than or equal to 65 ℃ to form an epoxy-based glass polymer.

Inventors

• D. SCHMIDT
• A. Shapulov
• S. Zubukevich
• C. Z'an Nei

Assignees

• 卢森堡科学技术研究院

Dates

Publication Date

20260512

Application Date

20241010

Priority Date

20231016

Claims (20)

1. 1. A formulation consisting of at least a first component and a second component and optionally a third component, said third component being one or more kinetic modifiers, wherein the formulation is intended to be cured to make an epoxy-type glass-like polymeric resin, the formulation characterized in that: The first component comprises one or more epoxy components, wherein at least one epoxy component comprises at least one aromatic ring, two or more epoxy moieties, and one or more dynamic covalent bonds, wherein at least one epoxy moiety is separated from at least one other epoxy moiety by at least one dynamic covalent bond; the second component is or comprises one or more curing agents selected from compounds comprising at least two active hydrogens in the form of at least two aliphatic amine hydrogens and/or at least two aliphatic thiols; wherein at least one of the first component, the second component, and the third component, if present, is a liquid at a temperature of less than or equal to 65 ℃, and Wherein the first component is compatible with the second component and the third component if present, as determined by compatibility test a at a temperature of less than or equal to 65 ℃.
2. 2. The formulation according to claim 1, characterized in that each of the first component, the second component and the third component, if present, is a liquid at a temperature lower than or equal to 65 ℃.
3. 3. The formulation according to claim 1 or 2, characterized in that it has a viscosity of less than 10,000mpa.s measured by Brookfield viscometer with a suitable spindle according to ASTM D2196-20 at a temperature lower than or equal to 65 ℃.
4. 4. A formulation according to any one of claims 1 to 3, wherein the molar ratio of the number of epoxide moieties in the first component to the number of active hydrogens in the second component is between 0.80:1 and 1.20:1.
5. 5. Formulation according to any one of claims 1 to 4, characterized in that the kinetic modulator or modulators are free of hydroxyl groups.
6. 6. Formulation according to any one of claims 1 to 5, characterized in that the one or more kinetic modulators are selected from one or more non-nucleophilic amine bases, one or more lewis acids, one or more bronsted bases, one or more bronsted acids, one or more ionic liquids or any combination thereof.
7. 7. Formulation according to any one of claims 1 to 6, characterized in that the content of each of the one or more kinetic modulators is less than 15mol.% relative to the dynamic covalent bond molar content.
8. 8. Formulation according to any one of claims 1 to 7, characterized in that the first component has the following chemical structure Wherein R comprises at least one aromatic ring; wherein X comprises the at least one dynamic covalent bond; Wherein n, m and k are integers and n+m+k is not less than 2; Wherein n+k is greater than or equal to 1; And wherein R 'is an optional group, R' is one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more phenyl groups substituted at the ortho position, one or more phenyl groups substituted at the meta position, one or more phenyl groups substituted at the para position, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more ketoheteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof; And wherein R '' is an optional group, R '' is one or more selected from one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more heteroatoms selected from N, S, O or any combination thereof, the presence or absence of one or more-CH 2 -groups connecting the optional R '' group to the remainder of the chemical structure and/or to adjacent epoxy moieties.
9. 9. The formulation of claim 8, wherein R comprises one or more aromatic rings functionalized with one or more groups selected from the group consisting of one or more linear aliphatic groups, one or more branched aliphatic groups, one or more cycloaliphatic groups, one or more aromatic groups, one or more heterocyclic (C3-C6 alkyl) groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more phenyl groups substituted at the ortho position, one or more phenyl groups substituted at the meta position, one or more phenyl groups substituted at the para position, one or more polycyclic aromatic groups, one or more heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof, one or more keto heteroaromatic hydrocarbon groups having one or more heteroatoms selected from N, S, O or any combination thereof.
10. 10. The formulation of claim 8 or 9, wherein X comprises the at least one dynamic covalent bond selected from one or more carboxylic acid ester linkages, one or more siloxane linkages, one or more silyl ether linkages, one or more disulfide linkages, one or more boric acid ester linkages, one or more phosphonate linkages, one or more phosphate ester linkages, one or more triazine ether linkages, one or more amide linkages, or a combination thereof, and in any orientation and with or without one or more-CH 2 -groups connecting the dynamic bond to the remainder of the chemical structure.
11. 11. The formulation according to claim 10, wherein X comprises a dynamic covalent bond, which is a carboxylic ester bond in any orientation and with or without one or more-CH 2 -groups connecting the carboxylic ester bond to the rest of the chemical structure, preferably X comprises a dynamic covalent bond, which is a carboxylic ester bond in any orientation and with one-CH 2 -group connecting the carboxylic ester bond to the rest of the chemical structure.
12. 12. Formulation according to any one of claims 1 to 11, characterized in that the first component is selected from the group consisting of Or a mixture thereof.
13. 13. Formulation according to any one of claims 1 to 12, characterized in that the first component is selected from the diglycidyl family of phthalic acids.
14. 14. Formulation according to any one of claims 1 to 13, characterized in that the first component is selected from the triglycidyl family of trimellitic acids.
15. 15. Formulation according to any one of claims 1 to 14, characterized in that the first component is selected from the family of epoxidized hydroxybenzoic acids containing one glycidyl ether and one glycidyl ester.
16. 16. The formulation according to any one of claims 1 to 15, wherein the first component is selected from the diglycidyl ether family of bisphenols comprising two phenolic substituents separated by a dynamic bond.
17. 17. Formulation according to any one of claims 1 to 16, characterized in that the family of epoxidized aminobenzoic acids contains two glycidylamines and one glycidylester.
18. 18. Formulation according to any one of claims 1 to 17, characterized in that the at least one curing agent is selected from one or more oligomers of poly (alkylene oxide), one or more oligomers of poly (siloxane), one or more oligomers of poly (diene), one or more oligomers of poly (olefin), one or more oligomers of poly (amide), one or more oligomers of poly (alkylene sulfide), one or more oligomers of poly (alkylene disulfide) or any combination thereof, the one or more oligomers being one or more amine-terminated oligomers and/or one or more thiol-terminated oligomers.
19. 19. The formulation according to any one of claims 1 to 18, wherein the second component is or comprises at least one curing agent selected from the group consisting of: or a mixture thereof.
20. 20. A method for producing an epoxy-type glass-like polymer resin, the method characterized by comprising the steps of: a) Providing a first component and a second component of the formulation of any one of claims 1 to 19, and optionally a third component, the third component being one or more kinetic modulators; b) Mixing together said first component, said second component and, if present, said third component to obtain said formulation, wherein said formulation is a homogeneous liquid at a temperature of less than or equal to 65 ℃; c) Curing the formulation to obtain an epoxy-type glass-like polymeric resin; wherein the curing in step (C) is initiated at a temperature of less than 65 ℃.

Description

Formulation and glass-like polymer resin based on epoxide containing dynamic bond Technical Field The present disclosure relates to a formulation intended to cure to make an epoxy-type glass-like polymeric (vitrimer) resin, and the use of the formulation for making one or more epoxy-type glass-like polymeric resins. The present disclosure also relates to a method of manufacturing the one or more epoxy-type glass-like polymeric resins, and an epoxy-type glass-like polymeric resin containing a composition prepared by combining all formulation components. Background Thermosetting resins (or thermoset materials) have the advantage of high mechanical strength and high heat and chemical resistance and can therefore replace metals in certain applications. They have the advantage of being lighter than metals. They can also be used as substrates in composite materials, as adhesives and as coatings. For example, they are widely used in the automotive industry or in the field of wind turbine engineering. However, the main problem with thermosets is that they are not repairable or recyclable. This leads to problems with end-of-life management of industrial thermosets. For example, it is predicted that in 2050, only epoxy-based composite waste from the wind energy field will accumulate around 6500 ten thousand tons. To address these difficulties associated with end-of-life management, new polymer families have emerged. These are glass-like polymers (vitrimer) that provide the typical properties of thermosets, such as chemical and creep resistance, and good thermal and mechanical properties, combined with reworkability similar to thermoplastics, including weldability, repairability, and chemical and mechanical recyclability. Glass-like macromolecules are permanent networks of polymer chains connected by dynamic covalent bonds (e.g., carboxylate linkages) that allow the network to change its topology while maintaining a nearly constant number of chemical bonds at temperatures below its degradation temperature. In a study entitled "Thermo-healing and recyclable epoxy thermosets based on dynamic phenol-carbamate bonds"(Reactive and Functional Polymers,2022,180,105411) by Qin j. Et al, a dynamic reversible epoxy thermoset based on a phenol-urethane linkage was obtained. Low relaxation times are reported, as well as high glass transition temperatures and high storage moduli (E'). However, this thermoset is obtained by heating the components under vacuum at high temperature (80 ℃). The need for heating during curing has hampered industrial development in the field of composite manufacturing. In the study of Zhang S. Et al, entitled "Hempseed oil-based covalent adaptable epoxy-amine network and its potential use for room temperature curable coatings"(ACS Sustainable Chem.Eng.,2020,8,14964-14974), a room temperature curable biobased epoxy-based glass polymer was designed. The glass transition temperature of the pure hemp seed oil-based network is reported to be 40 ℃ to about 50 ℃ and the relaxation time is about 1900 seconds. The storage modulus (E') measured at 25 ℃ is lower than 2,000MPa. The addition of DER 331 epoxy (bisphenol a diglycidyl ether, DGEBA) allows for an increase in glass transition temperature and storage modulus (E'), but can significantly increase relaxation times, compromising recyclability and repairability. In a study by Wang h. Et al, entitled "Insight into the structure-property relationships of intramolecularly-catalyzed epoxy vitrimers"(Materials&Design,2022,221,110924), epoxy-based glass polymers with intramolecular catalyzed transesterification were prepared by curing an ester-containing epoxy resin with diethylenetriamine and monoamine. Curing was started at room temperature. A glass-like polymer having a high Tg, i.e., 99 ℃ as measured from the tan delta peak using DMTA, can be obtained with a medium relaxation time of 712 s measured at 180 ℃. These studies indicate that the prior art epoxy formulations currently known for preparing glass-like polymeric resins lack the combination of properties required for industrial processing and use in structural applications. In particular, existing glass-like polymeric materials produced from epoxy formulations typically have at least one of the following problems: 1) They exhibit low glass transition temperatures Tg, typically between-30 ℃ and 50 ℃, as determined by differential scanning calorimetry, which means that they cannot be used as a load carrying capacity due to softening and loss of mechanical properties at temperatures associated with structural applications. 2) They exhibit a combination of low room temperature stiffness as determined by dynamic mechanical analysis (DMA storage modulus, E') or quasi-static mechanical testing (e.g. tensile modulus, flexural modulus, etc.) and fast reworkability (short relaxation time at temperatures well below degradation temperature) as determined by e.g. isothermal stress relaxation experiments, facilitating mai