WO2016003167A1 - Précurseur de polybenzoxazine et son procédé de préparation - Google Patents

Précurseur de polybenzoxazine et son procédé de préparation Download PDF

Info

Publication number
WO2016003167A1
WO2016003167A1 PCT/KR2015/006715 KR2015006715W WO2016003167A1 WO 2016003167 A1 WO2016003167 A1 WO 2016003167A1 KR 2015006715 W KR2015006715 W KR 2015006715W WO 2016003167 A1 WO2016003167 A1 WO 2016003167A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
compound
polybenzoxazine
precursor
mol
Prior art date
Application number
PCT/KR2015/006715
Other languages
English (en)
Korean (ko)
Inventor
조희진
성도경
박기현
박상훈
강현수
Original Assignee
코오롱인더스트리 주식회사
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 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to US15/322,946 priority Critical patent/US10266504B2/en
Priority to CN201580036014.1A priority patent/CN106661208B/zh
Priority claimed from KR1020150092996A external-priority patent/KR101782807B1/ko
Publication of WO2016003167A1 publication Critical patent/WO2016003167A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polybenzoxazine precursor and a method for producing the same.
  • thermosetting resins such as phenol resins, melamine resins, epoxy resins, unsaturated polyester resins, and bismaleimide resins are based on the properties of thermosetting, and are excellent in water resistance, chemical resistance, heat resistance, mechanical strength, reliability, and the like. It is used in various fields.
  • phenol resins and melamine resins have disadvantages such as volatile by-products upon curing, epoxy resins and unsaturated polyester resins are poor in flame retardancy, and bismaleimide resins are very expensive.
  • polybenzoxazine has been studied in which the Benzoxazine ring is ring-opening-polymerized and thermally cured without the occurrence of problematic volatiles.
  • Thermosetting resins having a benzoxazine ring in the molecular structure are subject to encapsulation, impregnation, laminates, adhesives, paints, coatings, friction materials, FRP, and molding materials since the oxazine ring is opened by heating and polymerization proceeds without generation of byproducts. It is attracting attention as a thermosetting resin used for etc.
  • the benzoxazine ring has a complex structure of a benzene ring and an oxazine ring.
  • Such polybenzoxazines are well-balanced cured polymers, including mechanical, electrical and chemical properties, including high glass transition temperature (Tg), low dielectric properties, high tension, low coefficient of thermal expansion, excellent elasticity, low hygroscopicity, and the like.
  • Korean Unexamined Patent Publication No. 10-2012-0058566 relates to a "polybenzoxazine composition," wherein a curable composition comprising a benzoxazine compound and a pentafluoroantimonic acid catalyst is heated for a sufficient temperature and time to polymerize.
  • a method for producing a polybenzoxazine having good thermal stability is disclosed.
  • Republic of Korea Patent Publication No. 10-0818254 relates to "polybenzoxazine-based compound, an electrolyte membrane including the same and a fuel cell employing the same", the acid trapping ability, mechanical and chemical stability, the ability to retain phosphoric acid at high temperature
  • the improved novel polybenzoxazine compound, an electrolyte membrane using the same, and a method of manufacturing the same are disclosed.
  • Epoxy resins are commonly used in coatings, insulation, building materials and adhesives for easy processing, high stability and good mechanical and chemical properties.
  • the epoxy resin composition requires heat resistance and flame retardancy for lead-free application, and in particular, in the case of a copper clad laminate sheet (CCLS) epoxy resin composition, V-0 certification of the UL-94 standard is essential.
  • CCLS copper clad laminate sheet
  • halogenated resins such as brominated epoxy resins, antimony oxide, and the like have been used to impart such flame retardancy.
  • halogen-based flame retardants have adverse effects on the environment, such as gas generation during injection and dioxin generation during incineration.
  • the electrical and electronics and semiconductor industries are the major industries in Korea, and they account for a large portion of the industry in Korea.
  • technologies for flame retardancy of semiconductor encapsulants and adhesive parts related to the semiconductor industry and interest in technology development of raw materials to replace flame retardants harmful to the conventional environment is increasing.
  • polybenzoxazine is a thermosetting polymer in which a benzoxazine-based monomer is polymerized by opening a ring in a molecule by heat, and is capable of self-curing without a by-product, and does not generate a volatile substance upon curing and does not have a volume change. Excellent dimensional stability.
  • it is a high heat resistant polymer having a high glass transition temperature and having a decomposition property of pyrolysis temperature of less than 1% up to 350 ° C. It also serves as a flame retardant in that it is a nitrogen-containing compound suitable for non-halogen products.
  • polybenzoxazines also do not exhibit sufficient flame retardant effects, and additives such as bromine, phosphorus, or chlorine compounds are added to the polybenzoxazine-containing flame retardants. Since these additives do not dissolve in the solvent, they may cause problems during processing, and provide a cured resin having poor oxidation stability and often poor physical properties at high temperatures.
  • Copper Clad Laminate refers to a laminated plate coated with a thin copper foil on an insulating material.
  • PCBs printed circuit boards
  • Heat resistance and low dielectric properties are required.
  • Resin is used as the base material of copper foil laminated board and plays the role of an insulator in the printed circuit board. To be a good insulator, the permittivity must be low.
  • Dielectric constant refers to the degree of polarization of molecules in an insulator against external electrical signals. The smaller the value, the better the insulation. In the operation of a printed circuit board, the smaller the dielectric constant of the insulator, the faster the signal processing speed and the lower the transmission loss.
  • polybenzoxazine As an alternative for satisfying the heat resistance and low dielectric properties of the copper-clad laminate, the use of polybenzoxazine, a phenol-based curing agent, has been highlighted.
  • polybenzoxazine is a thermosetting polymer in which a benzoxazine-based monomer is polymerized by opening a ring in a molecule by heat, and is capable of self-curing without a by-product, and does not generate a volatile substance upon curing and does not have a volume change. Excellent dimensional stability.
  • Patent Document 1 Korean Unexamined Patent Publication No. 10-2012-0058566
  • Patent Document 2 Republic of Korea Patent Publication No. 10-0818254
  • Another object of the present invention is to provide a polybenzoxazine precursor capable of preparing a cured product having significantly improved thermal and flame retardant properties while maintaining electrical properties as compared to conventional polybenzoxazine precursors.
  • the present invention also provides a polybenzoxazine precursor capable of producing a cured product having significantly improved thermal and electrical properties as compared to existing polybenzoxazine precursors.
  • the present invention also provides a method for preparing such polybenzoxazine precursor.
  • the present invention also seeks to provide a cured product of such a polybenzoxazine precursor.
  • the present invention includes a benzoxazine compound represented by the following formula (1),
  • n 0 to 2
  • R 1 is or to be.
  • the precursor according to the embodiment may include a hardened product polymerized while the oxazine ring of the benzoxazine compound represented by Formula 1 is opened.
  • the hardened product of the benzoxazine compound may include a compound represented by the following formula (2).
  • R is And R 1 is or N is an integer of 0-2, n2 is an integer of 1-5.
  • the precursor according to the embodiment may have a weight average molecular weight of 500 to 5000g / mol.
  • n is an integer of 0 to 2.
  • the step (1) is used with respect to 1mol of the phenolic compound, the aldehyde compound is 0.05 to 0.3mol, the step (2) with respect to 1mol of the phenol novolak resin, 1 to 3mol amine compound And 1 to 5 mol of an aldehyde compound.
  • the cured product is R 1 in the benzoxazine-based compound represented by Formula 1 It includes a hardened product of the polybenzoxazine precursor containing the benzoxazine compound, the glass transition temperature may be 190 °C or more.
  • the cured product is R 1 in the benzoxazine-based compound represented by Formula 1 It includes a hardened product of the polybenzoxazine precursor containing the benzoxazine compound, the glass transition temperature may be 250 °C or more.
  • Polybenzoxazine precursor according to the present invention can provide a cured product with improved thermal properties compared to the existing polybenzoxazine precursor,
  • a cured product exhibiting high thermal and electrical properties, and ultimately, it may be usefully used for copper clad laminates, semiconductor encapsulants, printed circuit boards, adhesives, paints, and mold applications.
  • Figure 1a is a 1 H-NMR spectrum of the phenol novolak resin prepared in Example 1 of the present invention.
  • 1B is a 1 H-NMR spectrum of the polybenzoxazine precursor prepared in Example 1 of the present invention.
  • Figure 1c is a result of GPC analysis of the polybenzoxazine precursor prepared in Example 1 of the present invention.
  • Figure 2 shows the infrared spectroscopy (IR) spectrum of the polybenzoxazine precursor prepared in Example 2 of the present invention, compared with the phenol novolak resin as a raw material.
  • IR infrared spectroscopy
  • Example 3 is a 1 H-NMR spectrum of the polybenzoxazine precursor prepared in Example 3 of the present invention.
  • Figure 4 shows the infrared spectroscopy (IR) spectrum of the polybenzoxazine precursor prepared in Example 4 of the present invention as compared to the phenol novolak resin as a raw material.
  • IR infrared spectroscopy
  • the present invention includes a benzoxazine compound represented by the following formula (1),
  • n 0 to 2
  • R 1 is or to be.
  • polybenzoxazine precursor refers to a compound or a group of compounds in which an oxazine ring plays a precursor role of forming a thermosetting resin called a polybenzoxazine by ring-opening reaction. It includes a benzoxazine-based monomer of only, including an oligomer having the same repeating unit structure as the monomer in the main chain, or a combination of a group containing a part of a polymerized autocuring product when the oxazine ring of such monomer or oligomer is ring-opened. define.
  • the self-curing product is produced by the polymerization of the benzoxazine monomer or oligomer while the oxazine ring is ring-opened in the formula (1).
  • the hardened product included in the polybenzoxazine precursor satisfying the above conditions may include a compound represented by the following Formula 2.
  • R is And R 1 is or N is an integer of 0-2, n2 is an integer of 1-5.
  • Representative examples of the compound according to R 1 which is a functional group derived from the amine compound in Formula 1 and its self-curing compound may be represented by the following Formulas 4 and 5, and 6 and 7, respectively.
  • n is an integer of 0 to 2.
  • R is N is an integer of 0-2, n2 is an integer of 1-5.
  • n is an integer of 0 to 2.
  • R is N is an integer of 0-2, n2 is an integer of 1-5.
  • the polybenzoxazine precursor has a weight average molecular weight of 500 to 5000 g / mol, more preferably 900 to 1800 g / mol can prevent the delay of curing or crystallization during curing, the viscosity of the precursor It may be preferable in view of being raised or gelled to prevent deterioration in workability and deterioration in compatibility with other resins.
  • the weight average molecular weight may be defined in terms of polystyrene equivalents determined by gel permeation chromatography (GPC).
  • the polybenzoxazine precursor according to the present invention may provide a cured product having improved thermal properties as compared to the existing polybenzoxazine precursor.
  • R 1 The polybenzoxazine precursor including when (Formula 4) can significantly improve thermal and flame retardant properties while maintaining excellent electrical properties.
  • R 1 is The polybenzoxazine precursor including the case of Formula 6 may provide a cured product having greatly improved thermal and electrical properties.
  • Polybenzoxazine precursor of the present invention may be prepared by using a phenol novolak resin represented by the following formula (3) as a raw material.
  • n is an integer of 0 to 2.
  • the phenol novolak resin may be condensed with an aldehyde compound and an amine compound in the presence of a solvent to prepare a polybenzoxazine precursor maximizing the aromatic content of benzoxazine.
  • the water and the solvent generated in the reaction process can be removed by a known method such as distillation.
  • the phenolic compound may be phenol or cresol.
  • aldehyde compounds are not particularly limited, but specific examples thereof include benzaldehyde, anisaldehyde, 4-methylbenzaldehyde, 2-methoxybenzaldehyde and 2-Methoxybenzaldehyde.
  • 4-methoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxy-benzaldehyde and 3-isopro Foxy-benzaldehyde (3-Isopropoxybenzaldehyde) may be one or more selected from the group consisting of.
  • the acid catalyst used in step (1) is para-toluene solfonic acid, methyl sulfonic acid, boron trifluorid, aluminum chloride and sulfo Nickel acid (Sulfuric acid) may be one or more selected from the group consisting of.
  • the amine compound may be added in an amount of 1 to 3 mol, preferably 1.5 to 2.5 mol, with respect to 1 mol of the phenol novolak resin, and the aldehyde compound is 1 to 5 mol, preferably 1 mol relative to 1 mol of the phenol novolak resin. Preferably from 2.5 to 4.5 mol .
  • the amount of the amine is aniline
  • the ring close reaction does not occur and the benzoxazine reaction cannot be sufficiently formed (the benzoxazine ring cannot be formed sufficiently).
  • the amount of mind bridges may be excessively generated, resulting in deterioration of heat resistance and flame retardant properties, gelation by secondary amines in the molecule, or increase in molecular weight, thereby lowering resin compatibility.
  • the amine is allylamine and the addition amount is less than 1 mol with respect to 1 mol of the phenol novolak resin, the ring close reaction does not occur and the benzoxazine reaction cannot be sufficiently satisfied (benzoxazine ring). If not more than 3 mol), the amount of the mind bridge is excessively generated, the heat resistance and electrical properties are reduced, the gelation by the secondary amine in the molecule or the molecular weight is increased to decrease the compatibility with the resin Can be generated.
  • the aldehyde compound when added to less than 1 mol with respect to 1 mol of the phenol novolak resin, it does not induce a sufficient reaction with the amine compound so that no oxazine ring is formed, and the heat resistance is lowered. Excess unreacted raw material may remain in the product.
  • the solvent used in the reaction is an aromatic hydrocarbon solvent such as toluene, xylene, trimethylbenzene; Halogen solvents such as chloroform, dichloroform and dichloromethane; Ether solvents such as THF, dioxane and the like can be used.
  • the solvent is preferably used in an amount of 25 to 100 parts by weight and aniline as an amine based on 100 parts by weight of the phenol novolak resin, the aldehyde compound and the amine compound, and preferably 50 to 80 parts by weight.
  • the content of the solvent when the content of the solvent is too small, the viscosity of the reactant becomes high, the stirring stress increases, and the workability decreases. When the content is excessively high, the cost of removing the solvent after the reaction increases. It can be economical. In addition, when the selection of the appropriate solvent and the mixing reaction is not made properly, the raw materials do not participate in the reaction, the yield may be lowered.
  • such a cured product can be improved in thermal properties compared with the cured product derived from the existing benzoxazine compound.
  • cured product does not mean only a hardened product of the polybenzoxazine precursor alone, but also encompasses a cured product that is mixed with another resin-based composition in addition to the polybenzoxazine precursor resin. Can be.
  • the obtained phenol novolak resin was confirmed by the structure of nuclear magnetic resonance analysis ( 1 H-NMR) as a result of Figure 1a, which has a -OH peak in the vicinity of 8.0ppm.
  • the NMR apparatus used in the NMR analysis is a Bruance Avance 500 product.
  • the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) is 99%.
  • the percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).
  • Example 1-1 The polybenzoxazine precursor obtained in Example 1-1 was introduced into an aluminum dish having a diameter of 30 mm, and hardened at 220 ° C. for 2 hours to prepare a cured product having a sheet thickness of 1.5 mm.
  • the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) is 99%.
  • the percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).
  • the hydrogen atom peak of the oxazine ring (CH out of plane bending) was confirmed.
  • the infrared spectroscopy instrument is a spectrum 100 product of Perkin Elmer.
  • the raw material is a phenol novolak resin of Formula 3, in contrast to the polybenzoxazine precursor represented by Benzoxazine, -OH stretching peak due to -OH group disappears and a characteristic peak of Benzoxazine can be confirmed.
  • the molecular weight data of the polybenzoxazine precursor obtained by using GPC was analyzed (not shown), which also showed broad peaks of high molecular weight near retention time 30min. As a result, it was determined that the hardened product of the compound of Formula 4, that is, the compound of Formula 5, was produced.
  • the polybenzoxazine precursor obtained in Example 2-1 was introduced into an aluminum dish having a diameter of 30 mm, and cured for 2 hours at 1220 ° C. for 2 hours to prepare a cured product having a sheet thickness of 1.5 mm.
  • the obtained benzoxazine-based compound is 54.26% (GPC Area%) of the benzoxazine monomer, and the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) is 92%.
  • the percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).
  • the polybenzoxazine precursor obtained in Comparative Example 11 was put in an aluminum dish having a diameter of 30 mm, and hardened at 220 ° C. for 3 hours to prepare a cured product having a sheet thickness of 1.5 mm.
  • the obtained polybenzoxazine precursor is 22.58% (GPC Area%) of the benzoxazine monomer, and the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) is 93%.
  • the percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).
  • the polybenzoxazine precursor obtained in Comparative Example 2-1 was put in an aluminum dish having a diameter of 30 mm, and hardened at 220 ° C. for 2 hours to prepare a cured product having a sheet thickness of 1.5 mm.
  • the polybenzoxazine obtained in Comparative Example 1-1 was put in an aluminum dish having a diameter of 30 mm, and hardened at 220 ° C. for 3 hours to prepare a cured product having a sheet thickness of 1.5 mm.
  • Polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (Waters: Waters707).
  • the sample to be measured was dissolved in tetrahydrofuran to have a concentration of 4000 ppm, and 100 ⁇ l was injected into GPC.
  • the mobile phase of GPC used tetrahydrofuran and was introduced at a flow rate of 1.0 mL / min, and the analysis was performed at 35 ° C.
  • the column connected four Waters HR-05,1,2,4E in series. The detector was measured at 35 ° C using RI and PAD Detecter.
  • Agilent's impedance analyzer (Agilent E4991A 1 MHz to 3 GHz) was used to measure the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product under the following conditions.
  • Measurement sample Thickness 1.5 mm (1.3 to 1.7 mm)
  • the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) is 99%.
  • the percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).
  • the obtained benzoxazine was confirmed by the structure of nuclear magnetic resonance analysis ( 1 H-NMR). The results are shown in FIG. 3. When compared with NMR of the phenol novolak resin of FIG. The peak disappears and it can be confirmed that the peak is generated due to the oxazine around 4.0 ⁇ 6.0ppm.
  • the NMR apparatus used in the NMR analysis is a Bruance Avance 500 product.
  • the molecular weight data of the polybenzoxazine precursor obtained by using GPC was analyzed (not shown), which also showed broad peaks of high molecular weight near retention time 30min. As a result, it was determined that the hardened product of the compound of Formula 5, that is, the compound of Formula 7 was produced.
  • the polybenzoxazine precursor obtained in Example 3-1 was put into an aluminum dish having a diameter of 30 mm, and cured at 220 ° C. for 2 hours to prepare a cured product having a thickness of 1.5 mm.
  • Phenol Novolac is a phenol novolak resin of Formula 3
  • Benzoxazine is a polybenzoxazine precursor obtained.
  • characteristic peaks of Benzoxazine can be confirmed (926 cm-1 (the out-of-plane bending vibration of CH) and 1234 cm-1 (COC asymmetric stretching modes) ).
  • the infrared spectroscopy instrument is a spectrum 100 product of Perkin Elmer.
  • the molecular weight data of the polybenzoxazine precursor obtained by using GPC was analyzed (not shown), which also showed broad peaks of high molecular weight near retention time 30min. As a result, it was determined that the hardened product of the compound of Formula 5, that is, the compound of Formula 7 was produced.
  • Example 4-1 The polybenzoxazine obtained in Example 4-1 was put in an aluminum dish having a diameter of 30 mm, and hardened at 1220 ° C. for 2 hours to prepare a cured product having a sheet thickness of 1.5 mm.
  • the cured products prepared in Examples 3 and 4 were difficult to identify Tg by DSC in structure and were measured by DMA (Dynamic Mechanical Analysis; Dynamic Mechanical Analysis).
  • the cured products prepared in Examples 3 and 4 and Comparative Examples 1 and 2 were measured at a temperature increase rate of 3 ° C. per minute from 30 ° C. to 350 ° C. using TA Instruments DMA Q800.
  • Examples 3 and 4 when compared with Comparative Examples 1 and 2, exhibits excellent thermal properties by showing high Tg and Td values, in particular dielectric constant (Dk) and dielectric loss tangent (Df). This low measurement indicates that the electrical properties are quite good.
  • Dk dielectric constant
  • Df dielectric loss tangent

Landscapes

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

Abstract

La présente invention concerne un précurseur de polybenzoxazine et un procédé pour sa préparation et, plus particulièrement, concerne un précurseur de polybenzoxazine et son procédé de préparation, le précurseur de polybenzoxazine permettant de préparer un matériau durci qui présente des caractéristiques thermiques améliorées ; qui, d'une part, présente des caractéristiques thermiques élevées et des caractéristiques ignifuges élevées tout en maintenant d'excellentes caractéristiques électriques intactes ; et qui, d'autre part, présente des caractéristiques thermiques élevées et des caractéristiques électriques élevées et, enfin, le précurseur de polybenzoxazine peut être avantageusement utilisé pour un stratifié plaqué de cuivre, un agent d'encapsulation semi-conducteur, une carte de circuit imprimé, un adhésif, une peinture et un moule.
PCT/KR2015/006715 2014-06-30 2015-06-30 Précurseur de polybenzoxazine et son procédé de préparation WO2016003167A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US15/322,946 US10266504B2 (en) 2014-06-30 2015-06-30 Polybenzoxazine precursor and method for preparing same
CN201580036014.1A CN106661208B (zh) 2014-06-30 2015-06-30 聚苯并噁嗪前体及其制备方法

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
KR20140081402 2014-06-30
KR10-2014-0081402 2014-06-30
KR20140094203 2014-07-24
KR10-2014-0094203 2014-07-24
KR20140174117 2014-12-05
KR10-2014-0174117 2014-12-05
KR10-2015-0092996 2015-06-30
KR1020150092996A KR101782807B1 (ko) 2014-06-30 2015-06-30 폴리벤족사진 전구체 및 그 제조방법

Publications (1)

Publication Number Publication Date
WO2016003167A1 true WO2016003167A1 (fr) 2016-01-07

Family

ID=55019622

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/006715 WO2016003167A1 (fr) 2014-06-30 2015-06-30 Précurseur de polybenzoxazine et son procédé de préparation

Country Status (1)

Country Link
WO (1) WO2016003167A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5543516A (en) * 1994-05-18 1996-08-06 Edison Polymer Innovation Corporation Process for preparation of benzoxazine compounds in solventless systems
JP2003064155A (ja) * 2001-08-23 2003-03-05 Nippon Steel Chem Co Ltd 熱硬化性樹脂組成物
JP2003286320A (ja) * 2002-03-28 2003-10-10 Nippon Steel Chem Co Ltd アリル基含有熱硬化性樹脂及び硬化物
KR20140007856A (ko) * 2011-01-25 2014-01-20 사이텍 테크놀러지 코포레이션 벤즈옥사진 수지
KR20140067006A (ko) * 2011-10-18 2014-06-03 셍기 테크놀로지 코. 엘티디. 벤족사진 중간체 및 이를 제조하는 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5543516A (en) * 1994-05-18 1996-08-06 Edison Polymer Innovation Corporation Process for preparation of benzoxazine compounds in solventless systems
JP2003064155A (ja) * 2001-08-23 2003-03-05 Nippon Steel Chem Co Ltd 熱硬化性樹脂組成物
JP2003286320A (ja) * 2002-03-28 2003-10-10 Nippon Steel Chem Co Ltd アリル基含有熱硬化性樹脂及び硬化物
KR20140007856A (ko) * 2011-01-25 2014-01-20 사이텍 테크놀러지 코포레이션 벤즈옥사진 수지
KR20140067006A (ko) * 2011-10-18 2014-06-03 셍기 테크놀로지 코. 엘티디. 벤족사진 중간체 및 이를 제조하는 방법

Similar Documents

Publication Publication Date Title
Tao et al. Synthesis and properties of novel fluorinated epoxy resins based on 1, 1-bis (4-glycidylesterphenyl)-1-(3′-trifluoromethylphenyl)-2, 2, 2-trifluoroethane
WO2017095174A1 (fr) Composition polymère
WO2017209413A1 (fr) Polyamide-imide transparent haute résistance et son procédé de préparation
WO2017188630A1 (fr) Polyamide-imide transparent de haute résistance et son procédé de fabrication
WO2017209414A1 (fr) Polyamidimide transparent à haute résistance et son procédé de préparation
WO2018004273A1 (fr) Composition de résine thermodurcissable, et préimprégné et substrat l'utilisant
KR101766427B1 (ko) 폴리벤족사진 전구체 및 그 제조방법
KR20090025156A (ko) 열경화성 폴리이미드 실리콘 수지 조성물 및 그 경화 피막
Hwang et al. Low dielectric epoxy resins from dicyclopentadiene-containing poly (phenylene oxide) novolac cured with dicyclopentadiene containing epoxy
WO2018030552A1 (fr) Composition polymerisable
WO2016140459A1 (fr) Composé époxy à base de phosphore, son procédé de préparation, et composition époxy le contenant
WO2016167449A1 (fr) Composé à base de phosphonium, composition de résine époxyde le contenant, et dispositif à semi-conducteur fabriqué à l'aide de celui-ci
WO2016003167A1 (fr) Précurseur de polybenzoxazine et son procédé de préparation
WO2022239955A1 (fr) Composition d'agent durcissant ignifuge pour époxy, et agent durcissant ignifuge pour époxy la comprenant
KR101782807B1 (ko) 폴리벤족사진 전구체 및 그 제조방법
WO2016089182A2 (fr) Précurseur de polybenzoxazine et procédé pour le préparer
CN117836346A (zh) 烯丙基醚化合物、树脂组合物及其固化物
WO2018004289A2 (fr) Mélange à base de benzoxazine et son utilisation
JP6844850B2 (ja) ポリイミド化合物、ポリアミド酸および該ポリイミド化合物を含む成形物
WO2024049140A1 (fr) Résine époxy a cristaux liquides durcie retransformable ou recyclable, produit re-durci de celle-ci, et son procédé de production
WO2022145749A1 (fr) Résine contenant un groupe insaturé, son procédé de préparation et composition la comprenant
WO2015076626A1 (fr) Résine novolaque, agent de durcissement la contenant, et composition de résine époxy, et résine époxy novolaque, leur procédé de préparation, et composition de résine époxy contenant la résine époxy novolaque
WO2019132176A1 (fr) Composition de résine thermoplastique destinée à étanchéifier un dispositif à semi-conducteurs et dispositif à semi-conducteurs étanchéifié à l'aide de celle-ci
WO2020045897A1 (fr) Résine à base de phtalonitrile présentant une résistance aux chocs améliorée
WO2023167513A1 (fr) Composition de résine époxy dérivée d'une composition d'alcool non glucosé et son procédé de préparation, et composition de résine époxy durcissable la comprenant et produit durci de celle-ci

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: 15815914

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15322946

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15815914

Country of ref document: EP

Kind code of ref document: A1