WO2021118233A1 - Composé époxy dérivé de bismaléimide contenant une structure polycyclique et son procédé de préparation - Google Patents

Composé époxy dérivé de bismaléimide contenant une structure polycyclique et son procédé de préparation Download PDF

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Publication number
WO2021118233A1
WO2021118233A1 PCT/KR2020/017980 KR2020017980W WO2021118233A1 WO 2021118233 A1 WO2021118233 A1 WO 2021118233A1 KR 2020017980 W KR2020017980 W KR 2020017980W WO 2021118233 A1 WO2021118233 A1 WO 2021118233A1
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Prior art keywords
epoxy
bismaleimide
formula
epoxy compound
furan
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PCT/KR2020/017980
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English (en)
Korean (ko)
Inventor
이신엽
이혜승
이유미
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국도화학 주식회사
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Publication of WO2021118233A1 publication Critical patent/WO2021118233A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/18—Bridged systems

Definitions

  • the present invention relates to a bismaleimide-derived epoxy compound having a multicyclic structure and a method for preparing the same. Specifically, the present invention relates to an epoxy compound having a novel structure prepared through Diels-Alder reaction of bismaleimide and furan epoxy, and a method for preparing the same.
  • Bismaleimide resin has excellent physical properties such as excellent long-term thermal oxidation stability, hot-wet strength, dimensional stability, flame retardancy and low water absorption. It is an excellent heat-resisting resin that is not only in the spotlight as a matrix resin for Advanced Composite Material, but is also used as a base material for composite materials in all industries that require heat resistance, such as the electronics industry, automobile industry, and general industry.
  • a resin made by copolymerization with only bismaleimide itself has a high cross-linking density, so its heat resistance is very high (Tg is 300°C or higher), but on the other hand, it is very brittle and has a high boiling point.
  • Polar solvents N-methyl-2-pyrrolidone (NMP, N-methyl-2-pyrrolidone, BP 202°C) and N,N'-dimethylformamide (DMF, N,N'-dimethylformamide, BP 153°C)
  • NMP N-methyl-2-pyrrolidone
  • DMF N,N'-dimethylformamide
  • the present inventors completed a reactive epoxy derived from bismaleimide by the Diels-Alder reaction.
  • furan materials have been mainly used in the casting industry in the form of polymers because they have high-temperature stability after curing, but recently, research on high value-added materials in the form of various monomers and oligomers utilizing the characteristics of the furan structure is being conducted.
  • Furan Epoxy can be applied to various reactions using an aromatic ring with diene properties, and can have flexible structural features including a methylene bridge.
  • the present inventors have completed a novel structure of bismaleimide-derived epoxy, focusing on the fact that bismaleimide and Furan ring can be structurally bonded by Diels-Alder reaction.
  • a method for preparing a novel epoxy compound according to an embodiment of the present invention comprises the steps of preparing a furan epoxy having a structure of the following Chemical Formula 1; and reacting bismaleimide with the furan epoxy to obtain an epoxy compound of Formula 2 below.
  • a method for preparing a novel epoxy compound according to an embodiment of the present invention comprises the steps of preparing a furan epoxy having a structure of the following Chemical Formula 3; and reacting bismaleimide with the furan epoxy to obtain an epoxy compound of Formula 4 below.
  • a novel epoxy compound according to an embodiment of the present invention has a structure of the following formula (4).
  • a novel epoxy compound according to an embodiment of the present invention has a structure of the following formula (5).
  • R is a structure containing an aromatic
  • G represents a direct binding, O, S, SO 2 , C(CH 3 ) 2 , CH 2 , CHPh, and Ph is a phenyl group.
  • an epoxy compound of the present invention Through the novel method of preparing an epoxy compound of the present invention, it is possible to prepare an epoxy compound in a short time by only stirring at a specific temperature without a catalyst. In the present invention, it is possible to prepare an epoxy compound having a novel structure through the Diels-Alder reaction of bismaleimide and furan epoxy.
  • the epoxy compound prepared by the production method of the present invention can compensate for the disadvantages of bismaleimide, which has a high melting point and poor solubility. That is, the novel epoxy compound of the present invention not only lowers the melting point of bismaleimide due to the introduction of furan epoxy having low viscosity and flexibility, but also removes structural rigidity and improves solvent solubility and usability due to the epoxy functional group. .
  • the epoxy compound of the present invention can be applied to various curing systems due to its high reactivity. In particular, it can be introduced into a curing system that utilizes one or more double bonds and epoxy functional groups. For example, it is applicable to a dual curing system utilizing epoxy curing and radical curing of double bonds.
  • Example 3 is a GPC data of the novel epoxy compound according to Example 1.
  • Example 5 is a GPC data of the novel epoxy compound according to Example 2.
  • the present invention relates to a bismaleimide-derived epoxy compound having a multicyclic structure and a method for preparing the same. Specifically, the present invention relates to an epoxy compound having a novel structure prepared through Diels-Alder reaction of bismaleimide and furan epoxy, and a method for preparing the same.
  • a method for preparing a novel epoxy compound according to various embodiments of the present invention comprises the steps of preparing a furan epoxy having a structure of the following Chemical Formula 1; and reacting bismaleimide with the furan epoxy to obtain an epoxy compound of Formula 2 below.
  • novel epoxy compound of the present invention can be prepared through the following reaction.
  • the step of obtaining the epoxy compound heating the furan epoxy and the solvent while stirring; adding bismaleimide; and performing an aging reaction.
  • the furan epoxy having the structure of Formula 1 and the solvent may be heated to 70 to 90 °C.
  • the temperature can be raised to 80°C.
  • the furan epoxy and the solvent may be added in a weight ratio of 1:1.
  • the solvent is, for example, MIBK (Methyl Isoboutyl Ketone), MEK (Methyl Ethyl Ketone), n-butanol (n-Butanol), isopropanol (isopropanol), n-propanol (n-propanol) and ethanol (ethanol) It may be any one selected from the group consisting of.
  • the solvent may be n-butanol.
  • the bismaleimide may be added in divided portions at predetermined time intervals while maintaining stirring. For example, bismaleimide may be added in 3 to 9 portions at intervals of 20 to 40 minutes. In this case, the bismaleimide may be added in a molar ratio of 0.1 to 0.5 relative to the furan epoxy. Through this molar ratio, a novel epoxy compound having the structure of Formula 2 can be obtained in high yield.
  • the temperature of the composition to which the bismaleimide is added may be raised to 90°C to 110°C to proceed the aging reaction.
  • the method may further include the step of removing the solvent under reduced pressure and cooling.
  • the pressure may be gradually reduced to 50 torr or less.
  • the epoxy compound of Formula 2 can be prepared through the Diels-Alder reaction of bismaleimide and furan epoxy.
  • the Diels-Alder reaction is an organic chemical reaction between a conjugated diene and an alkene.
  • energy such as heat is applied to a mixture of a conjugated diene and a dienophile, a ring-shaped cyclohexene It is a reaction in which strigs are formed. It is a special kind of conjugation addition reaction and cycloaddition reaction.
  • the epoxy compound prepared by the production method of the present invention can compensate for the disadvantages of bismaleimide, which has a high melting point and poor solubility. That is, the novel epoxy compound of the present invention not only lowers the melting point of bismaleimide due to the introduction of furan epoxy having low viscosity and flexibility, but also removes structural rigidity and improves solvent solubility and usability due to the epoxy functional group. .
  • the epoxy compound of the present invention can be applied to various curing systems due to its high reactivity. In particular, it can be introduced into a curing system that utilizes one or more double bonds and epoxy functional groups. For example, it is applicable to a dual curing system utilizing epoxy curing and radical curing of double bonds.
  • a method for preparing a novel epoxy compound according to various embodiments of the present invention comprises the steps of preparing a furan epoxy having a structure of the following Chemical Formula 3; and reacting bismaleimide with the furan epoxy to obtain an epoxy compound of Formula 4 below.
  • novel epoxy compound of the present invention can be prepared through the following reaction.
  • the step of obtaining the epoxy compound heating the furan epoxy while stirring; adding bismaleimide; and performing an aging reaction.
  • the temperature of the furan epoxy having the structure of Chemical Formula 3 may be raised to 70 °C to 90 °C.
  • the temperature can be raised to 80°C. In this case, it may proceed without a solvent.
  • the bismaleimide may be added in divided portions at predetermined time intervals while maintaining stirring. For example, bismaleimide may be added in 3 to 9 portions at intervals of 20 to 40 minutes. In this case, the bismaleimide may be added in a molar ratio of 0.1 to 0.5 relative to the furan epoxy. Through this molar ratio, a novel epoxy compound having the structure of Formula 4 can be obtained in high yield.
  • the temperature of the composition to which the bismaleimide is added may be raised to 90°C to 110°C to proceed the aging reaction.
  • the step of cooling may be further included.
  • the epoxy compound of Formula 4 can be prepared through the Diels-Alder reaction of bismaleimide and furan epoxy.
  • the epoxy compound prepared by the production method of the present invention can compensate for the disadvantages of bismaleimide, which has a high melting point and poor solubility. That is, the novel epoxy compound of the present invention not only lowers the melting point of bismaleimide due to the introduction of furan epoxy having low viscosity and flexibility, but also removes structural rigidity and improves solvent solubility and usability due to the epoxy functional group. .
  • the epoxy compound of the present invention can be applied to various curing systems due to its high reactivity. In particular, it can be introduced into a curing system that utilizes one or more double bonds and epoxy functional groups. For example, it is applicable to a dual curing system utilizing epoxy curing and radical curing of double bonds.
  • a method for preparing a novel epoxy compound according to various embodiments of the present invention comprises the steps of preparing a furan epoxy having a structure of the following Chemical Formula 3; and reacting bismaleimide having a structure of the following formula (6) with the furan epoxy to obtain an epoxy compound of the following formula (5).
  • R is a structure containing an aromatic
  • G represents a direct binding, O, S, SO 2 , C(CH 3 ) 2 , CH 2 , CHPh, and Ph is a phenyl group.
  • R is , , , , or can be
  • R is a structure containing an aromatic
  • G represents a direct binding, O, S, SO 2 , C(CH 3 ) 2 , CH 2 , CHPh, and Ph is a phenyl group.
  • R is , , , , or can be
  • novel epoxy compound of the present invention can be prepared through the following reaction.
  • the step of obtaining the epoxy compound comprises: raising the temperature while stirring the furan epoxy; adding a compound having the structure of Formula 6; and performing an aging reaction.
  • the temperature of the furan epoxy having the structure of Chemical Formula 3 may be raised to 70 °C to 90 °C.
  • the temperature can be raised to 80°C. In this case, it may proceed without a solvent.
  • the bismaleimide may be divided and added at predetermined time intervals while maintaining stirring. For example, bismaleimide may be added in 3 to 9 portions at intervals of 20 to 40 minutes. In this case, the bismaleimide may be added in a molar ratio of 0.1 to 0.5 relative to the furan epoxy. Through this molar ratio, a novel epoxy compound having the structure of Formula 5 can be obtained in high yield.
  • the temperature of the composition to which the bismaleimide is added may be raised to 90°C to 110°C to proceed the aging reaction.
  • the step of cooling may be further included.
  • the epoxy compound of Formula 5 can be prepared through the Diels-Alder reaction of bismaleimide and furan epoxy.
  • the epoxy compound prepared by the production method of the present invention can compensate for the disadvantages of bismaleimide, which has a high melting point and poor solubility. That is, the novel epoxy compound of the present invention not only lowers the melting point of bismaleimide due to the introduction of furan epoxy having low viscosity and flexibility, but also removes structural rigidity and improves solvent solubility and usability due to the epoxy functional group. .
  • the epoxy compound of the present invention can be applied to various curing systems due to its high reactivity. In particular, it can be introduced into a curing system that utilizes one or more double bonds and epoxy functional groups. For example, it is applicable to a dual curing system utilizing epoxy curing and radical curing of double bonds.
  • the epoxy compound of the novel structure of the present invention is an epoxy compound prepared by the above preparation method and has a structure of Chemical Formula 2, Chemical Formula 4 or Chemical Formula 5, and is an epoxy compound of a multicyclic structure derived from bismaleimide.
  • Example 1 is GPC data of Furfuryl alcohol epoxy used in Example 1.
  • 2 is GPC data of Bismaleimide.
  • 3 is a GPC data of the novel epoxy compound according to Example 1.
  • the epoxy compound obtained according to Example 1 was dissolved in THF at 2.5wt% and analyzed by GPC (Shimadzu, Gel Permeation Chromatography Systems; Shodex, KF-801, 802, 803, 805 Columns). The analysis temperature was 40 o C and the mobile phase was Tetrahydrofuran (HPLC grade) at 1 ml/min.
  • Example 4 is GPC data of BHMF Epoxy.
  • 5 is a GPC data of the novel epoxy compound according to Example 2.
  • the epoxy compound obtained according to Example 2 was dissolved in THF at 2.5wt% and analyzed by GPC (Shimadzu, Gel Permeation Chromatography Systems; Shodex, KF-801, 802, 803, 805 Columns).
  • the analysis temperature was 40 o C and the mobile phase was Tetrahydrofuran (HPLC grade) at 1 ml/min.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Epoxy Resins (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un composé époxy dérivé de bismaléimide contenant une structure polycyclique et son procédé de préparation. Plus particulièrement, la présente invention concerne un nouveau composé époxy structuré préparé par la réaction de Diels-Alder de bismaléimide et d'époxy furannique, et son procédé de préparation.
PCT/KR2020/017980 2019-12-12 2020-12-09 Composé époxy dérivé de bismaléimide contenant une structure polycyclique et son procédé de préparation WO2021118233A1 (fr)

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KR10-2019-0165865 2019-12-12
KR1020190165865A KR20210074800A (ko) 2019-12-12 2019-12-12 다중고리 구조를 포함하는 비스말레이미드 유래 에폭시 화합물 및 이의 제조방법

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023223927A1 (fr) * 2022-05-17 2023-11-23 Dic株式会社 Composé contenant un groupe éther glycidylique, composition de résine durcissable, produit durci, et corps stratifié

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN109679103A (zh) * 2017-10-18 2019-04-26 天津大学 一种动态热可逆可重塑的聚硅氧烷弹性体材料及其制备方法
CN110092911A (zh) * 2018-01-31 2019-08-06 天津大学 基于Diels-Alder反应的聚硅氧烷弹性体材料在自修复材料中的应用
CN110092912A (zh) * 2018-01-31 2019-08-06 天津大学 基于Diels-Alder反应的聚硅氧烷弹性体材料在可重塑材料中的应用

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Publication number Priority date Publication date Assignee Title
CN109679103A (zh) * 2017-10-18 2019-04-26 天津大学 一种动态热可逆可重塑的聚硅氧烷弹性体材料及其制备方法
CN110092911A (zh) * 2018-01-31 2019-08-06 天津大学 基于Diels-Alder反应的聚硅氧烷弹性体材料在自修复材料中的应用
CN110092912A (zh) * 2018-01-31 2019-08-06 天津大学 基于Diels-Alder反应的聚硅氧烷弹性体材料在可重塑材料中的应用

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Title
JAMES H. AUBERT: "Note: Thermally removable epoxy adhesives incorporating thermally reversible diels-alder adducts", THE JOURNAL OF ADHESION, TAYLOR & FRANCIS INC., US, vol. 79, no. 6, 1 June 2003 (2003-06-01), US, pages 609 - 616, XP055252649, ISSN: 0021-8464, DOI: 10.1080/00218460309540 *
SHEN XIAOBIN, LIU XIAOQING, WANG JINGGANG, DAI JINYUE, ZHU JIN: "Synthesis of an Epoxy Monomer from Bio-Based 2,5-Furandimethanol and Its Toughening via Diels–Alder Reaction", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, AMERICAN CHEMICAL SOCIETY, vol. 56, no. 30, 2 August 2017 (2017-08-02), pages 8508 - 8516, XP055820710, ISSN: 0888-5885, DOI: 10.1021/acs.iecr.7b01624 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023223927A1 (fr) * 2022-05-17 2023-11-23 Dic株式会社 Composé contenant un groupe éther glycidylique, composition de résine durcissable, produit durci, et corps stratifié

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