WO2021118235A1 - Procédé de préparation de résine novolaque multifonctionnelle, procédé de préparation de résine époxyde, et résine novolaque multifonctionnelle et résine époxyde ainsi préparées - Google Patents

Procédé de préparation de résine novolaque multifonctionnelle, procédé de préparation de résine époxyde, et résine novolaque multifonctionnelle et résine époxyde ainsi préparées Download PDF

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Publication number
WO2021118235A1
WO2021118235A1 PCT/KR2020/017983 KR2020017983W WO2021118235A1 WO 2021118235 A1 WO2021118235 A1 WO 2021118235A1 KR 2020017983 W KR2020017983 W KR 2020017983W WO 2021118235 A1 WO2021118235 A1 WO 2021118235A1
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WIPO (PCT)
Prior art keywords
epoxy resin
formula
resin
producing
novolak resin
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PCT/KR2020/017983
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English (en)
Korean (ko)
Inventor
이신엽
이혜승
이유미
Original Assignee
국도화학 주식회사
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Publication of WO2021118235A1 publication Critical patent/WO2021118235A1/fr

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    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of furfural
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols

Definitions

  • the present invention relates to a method for preparing a polyfunctional novolac resin, a method for preparing an epoxy resin, and a polyfunctional novolak resin and an epoxy resin prepared therethrough. Specifically, the present invention relates to a method for producing a polyfunctional novolak resin based on a bio-material, a method for producing an epoxy resin, and a polyfunctional novolak resin and an epoxy resin produced through the method.
  • Petroleum-based polymer resins are still widely used as materials for various uses such as plastics.
  • petroleum-based bisphenol-based epoxy resins are widely used in various industrial fields such as coatings, adhesives, electrical and electronic devices, civil engineering and construction, due to their excellent adhesion, mechanical properties, and chemical resistance and less shrinkage during curing.
  • These bisphenol-based epoxy resin-based chemicals are derived from petroleum and generate chemicals harmful to the human body, such as environmental hormones, during manufacture and use.
  • such petroleum-based polymer resins have a problem of causing environmental pollution, such as emitting a large amount of carbon dioxide, which is a global warming gas, when discarded.
  • the development of a biomass-based polymer resin production technology is recently dealt with as an important issue in both academia and industry.
  • bio-based materials in the field of epoxy various materials using bio-materials such as Sorbitol, Butanediol, and Soybean have been developed.
  • the present inventors have completed a polyfunctional novolak resin derived from biomass and an epoxy resin based thereon.
  • the method for preparing the polyfunctional novolak resin of Chemical Formula 1 may include reacting Catechol and Furfural under a base catalyst.
  • n 1 to 100.
  • the novel epoxy resin according to various embodiments of the present invention has a structure of the following formula (2).
  • m is 1 to 100.
  • the method for producing a polyfunctional novolak resin according to various embodiments of the present invention is environmentally friendly because it uses catechol, which has more reactive groups than phenol, as a starting material, and uses furfural as a starting material instead of formalin derived from petrochemicals. .
  • the polyfunctional novolak resin of the present invention prepared through this has a large number of functional groups and thus has high reactivity, and can be used as a curing agent, an epoxy raw material, and the like.
  • the novel epoxy resin according to various embodiments of the present invention is prepared based on a bio raw material, and has excellent flame retardancy without using a halogen-based compound.
  • a halogen-based compound is used to impart flame retardancy, but the novel epoxy resin of the present invention can be used as a halogen-free electronic material.
  • the use of a halogen-based flame retardant not only causes environmental problems due to the generation of dioxins, but also causes deterioration of reliability when left at high temperatures, and this problem can be solved through the novel epoxy resin of the present invention.
  • the novel epoxy resin of the present invention has a fast reaction rate and excellent heat resistance and flame retardancy due to the structural characteristics of furfural.
  • Example 1 is a GPC data of the polyfunctional novolac resin according to Example 1.
  • the present invention relates to a method for preparing a polyfunctional novolac resin, a method for preparing an epoxy resin, and a polyfunctional novolac resin and an epoxy resin prepared therethrough. Specifically, the present invention relates to a method for producing a polyfunctional novolak resin based on a bio-material, a method for producing an epoxy resin, and a polyfunctional novolak resin and an epoxy resin produced through the method.
  • the method for preparing a polyfunctional novolak resin according to various embodiments of the present invention may include reacting catechol and furfural under a base catalyst.
  • Catechol is 1,2-dihydroxybenzene in which two hydroxyl groups are located adjacent to each other.
  • Catechol has a structure of the following formula (2).
  • Furfural is an organic compound derived from various agricultural by-products such as corncob, sugar cane bagasse, oats, bran and sawdust, and has a ring structure represented by the following Chemical Formula 3 (C 4 H 3 OCHO) It is an aromatic aldehyde with Furfural is a substance produced when acid hydrolysis of lignocellulosic biomass, mainly through the dehydration reaction of aldopentose, a pentose sugar such as xylose. is created
  • the present invention has the characteristics of having a multifunctional group by using more catechols compared to the above and phenol and being environmentally friendly by using furfural instead of formalin derived from petrochemicals.
  • the polyfunctional novolak resin of the present invention may be prepared through the following reaction.
  • the base catalyst may be at least one selected from the group consisting of NaOH, KOH, NaOCH 3 , KOCH 3 , Ca(OH) 2 , NH 4 OH and Mg(OH) 2 .
  • the base catalyst may be NaOH.
  • the base catalyst may be included in a weight ratio of 2% to 8% at 1000 ppm relative to the catechol. By including the base catalyst in a weight ratio in the corresponding range, the polyfunctional novolak resin can be obtained.
  • the molar ratio of catechol and furfural, which are starting materials may be 0.7:1 to 10:1.
  • the molar ratio of catechol and furfural may be 1.7:1.
  • an acid may be added to neutralize the base catalyst to proceed with the neutralization process.
  • a neutralizing material for the neutralization process for example, phosphoric acid may be used.
  • the neutralizing material may be added in various amounts depending on the amount of the base catalyst.
  • the pressure may be reduced to about 50 torr to remove residual moisture.
  • a high-purity polyfunctional novolak resin can be prepared.
  • the polyfunctional novolak resin according to various embodiments of the present invention prepared through the above preparation method, has a structure of the following Chemical Formula 1.
  • n may be 1 to 100.
  • the polyfunctional novolak resin of the present invention has a large number of functional groups and is highly reactive, and can be used as a curing agent, an epoxy raw material, and the like.
  • the novel epoxy resin according to various embodiments of the present invention has a structure of the following formula (2).
  • the novel epoxy resin of Formula 2 may have physical properties of an epoxy equivalent of 100 to 300 g/eq and a softening point of 20 to 90°C.
  • m may be 1 to 100.
  • the novel epoxy resin according to various embodiments of the present invention has excellent flame retardancy without using a halogen-based compound.
  • a halogen-based compound is used to impart flame retardancy, but the novel epoxy resin of the present invention can be used as a halogen-free electronic material.
  • the use of a halogen-based flame retardant not only causes environmental problems due to the generation of dioxins, but also causes deterioration of reliability when left at high temperatures, and this problem can be solved through the novel epoxy resin of the present invention.
  • the novel epoxy resin of the present invention has high reactivity and excellent heat resistance and flame retardancy due to the structural characteristics of furfural.
  • a method for preparing a novel epoxy resin according to various embodiments of the present invention comprises the steps of reacting catechol and furfural under a base catalyst to prepare a polyfunctional novolak resin; and epoxidizing the polyfunctional novolak resin under a base catalyst.
  • the novel epoxy resin of the present invention may be prepared from a polyfunctional novolak resin having the structure of Formula 1 above. That is, the method for preparing a novel epoxy resin of the present invention includes the steps of preparing a polyfunctional novolak resin of Formula 1 and epoxidizing the polyfunctional novolak resin to obtain an epoxy resin of Formula 2 can do.
  • novel epoxy resin of the present invention can be prepared through the following reaction.
  • n 1 to 100
  • m 1 to 100
  • the step of obtaining the epoxy resin may include the step of proceeding the reaction by introducing the polyfunctional novolak resin, epihalohydrin, a solvent and a base catalyst.
  • the epihalohydrin input may be epichlorohydrin, ⁇ -methylepichlorohydrin, ⁇ -methylepichlorohydrin, epibromohydrin, or the like.
  • it may be bio-derived epichlorohydrin.
  • bio-derived epichlorohydrin may be Crude Glycerol-based glycerine ECH.
  • the molar ratio of the polyfunctional novolak resin and epihalohydrin may be 1:3 to 1:20.
  • it may be 1:5 to 1:7.
  • the solvent is bis(2-methoxy ethyl)ether (Bis(2-methoxy ethyl)ether), ethylene glycol methyl ether, propylene glycol methyl ether (PGME, propylene glycol methyl ether), and butylene. It may include at least one selected from the group consisting of glycol methyl ether (butylene glycol methyl ether). Preferably, the solvent may be bis(2-methoxy ethyl)ether.
  • the base catalyst may be at least one selected from the group consisting of NaOH, KOH, NaOCH 3 , KOCH 3 , Ca(OH) 2 , NH 4 OH and Mg(OH) 2 .
  • the base catalyst may be NaOH.
  • the amount of the base catalyst is preferably 93 to 230 parts by weight, and more preferably 103 to 135 parts by weight is effective.
  • At least one solvent selected from the group consisting of Methyl ethyl ketone (MEK), Methyl isobutyl Ketone (MIBK), Toluene, Xylene, Dimethyl Sulfoxide (DMSO), and Dimethyl Formamide (DMF) and PW (Purified) Water), etc. can be used to proceed.
  • Example One multifunctionality Novolac resin manufacturing
  • n may be 1 to 100.
  • Example 1 is a GPC data of the polyfunctional novolac resin according to Example 1.
  • the polyfunctional novolak resin obtained according to Example 1 was dissolved in THF at 2.5 wt % 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.
  • m may be 1 to 100.
  • Example 2 is a GPC data of the novel epoxy resin according to Example 2.
  • the epoxy resin 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.
  • KDN-1085 is a phenol novolak type resin, and is an oligomer type made from phenol and formalin.
  • An epoxy resin composition was prepared in the same manner as in Example 3, except that o-cresol novolak-type epoxy YDCN-500-4P (Kukdo Chemical Co., Ltd.), which is a commercially available resin for EMC, was used.
  • the gelation time (Varnish Gel time) was measured. 1 g of the epoxy resin composition was placed on a hot plate at 170° C., stirred with a toothpick, and lifted, and the time until the resin did not come drooping like a thread was measured.
  • Tg glass transition temperature
  • the thermal properties of the epoxy resin composition were measured by thermogravimetry analysis (TGA) after curing by holding the epoxy resin composition at 180 ° C. for 2 hours.
  • TGA thermogravimetry analysis
  • the temperature was increased from 50 ° C. to 700 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere, and was heated at 700 ° C. for 60 minutes. It was maintained and the content of carbon powder (Char) was measured at the temperature and 700° C. when it was reduced by 5% by weight.
  • the resin composition according to Example 3 of the present invention had a very fast reactivity as the varnish gel time was greatly shortened compared to the o-cresol novolac epoxy used in the comparative example.
  • the resin composition according to Example 2 exhibited a similar level of heat resistance to the resin composition of Comparative Example.
  • the carbon powder (Char) was as high as 40% or more to have excellent flame retardancy. It is known in the art that flame retardancy improves as the amount of coal residues that can be formed in pyrolysis increases. That is, through the above experiments, it was confirmed that the epoxy resin of the present invention has a faster reaction rate when the same curing agent is applied compared to the conventional epoxy resin, has a similar level of heat resistance, and has excellent flame retardancy.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une résine novolaque multifonctionnelle, un procédé de préparation d'une résine époxyde, et une résine novolaque multifonctionnelle et une résine époxyde ainsi préparées. En particulier, la présente invention concerne un procédé de préparation d'une résine novolaque multifonctionnelle à base d'une matière première biologique, un procédé de préparation d'une résine époxyde, et une résine novolaque multifonctionnelle et une résine époxyde ainsi préparées.
PCT/KR2020/017983 2019-12-12 2020-12-09 Procédé de préparation de résine novolaque multifonctionnelle, procédé de préparation de résine époxyde, et résine novolaque multifonctionnelle et résine époxyde ainsi préparées WO2021118235A1 (fr)

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KR1020190165867A KR20210074802A (ko) 2019-12-12 2019-12-12 다관능성 노볼락 수지를 제조하는 방법, 에폭시 수지를 제조하는 방법, 이를 통해 제조된 다관능성 노볼락 수지 및 에폭시 수지
KR10-2019-0165867 2019-12-12

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WO2021118235A1 true WO2021118235A1 (fr) 2021-06-17

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000007756A (ja) * 1998-06-24 2000-01-11 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
KR20010023189A (ko) * 1998-06-24 2001-03-26 다께다 가즈히꼬 다가 페놀류 화합물, 에폭시 수지, 에폭시 수지 조성물 및그의 경화물
KR20120029326A (ko) * 2010-09-16 2012-03-26 스미또모 베이크라이트 가부시키가이샤 노볼락형 페놀 수지 및 포토 레지스트용 수지 조성물
KR101966878B1 (ko) * 2018-06-22 2019-04-08 국도화학 주식회사 퍼퓨릴 알코올 유래 2 관능성 퓨란 에폭시 및 이의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000007756A (ja) * 1998-06-24 2000-01-11 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
KR20010023189A (ko) * 1998-06-24 2001-03-26 다께다 가즈히꼬 다가 페놀류 화합물, 에폭시 수지, 에폭시 수지 조성물 및그의 경화물
KR20120029326A (ko) * 2010-09-16 2012-03-26 스미또모 베이크라이트 가부시키가이샤 노볼락형 페놀 수지 및 포토 레지스트용 수지 조성물
KR101966878B1 (ko) * 2018-06-22 2019-04-08 국도화학 주식회사 퍼퓨릴 알코올 유래 2 관능성 퓨란 에폭시 및 이의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANG YUAN, DING DUANCHEN, ZHAO SHOU, ZHU HANYU, KENTTÄMAA HILKKA I., ABU-OMAR MAHDI M.: "Renewable thermoset polymers based on lignin and carbohydrate derived monomers", GREEN CHEMISTRY, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 20, no. 5, 1 January 2018 (2018-01-01), GB, pages 1131 - 1138, XP055820707, ISSN: 1463-9262, DOI: 10.1039/C7GC03552G *

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