WO2016089182A2 - Précurseur de polybenzoxazine et procédé pour le préparer - Google Patents

Précurseur de polybenzoxazine et procédé pour le préparer Download PDF

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WO2016089182A2
WO2016089182A2 PCT/KR2015/013282 KR2015013282W WO2016089182A2 WO 2016089182 A2 WO2016089182 A2 WO 2016089182A2 KR 2015013282 W KR2015013282 W KR 2015013282W WO 2016089182 A2 WO2016089182 A2 WO 2016089182A2
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formula
polybenzoxazine
mol
precursor
compound
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PCT/KR2015/013282
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English (en)
Korean (ko)
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WO2016089182A9 (fr
WO2016089182A3 (fr
Inventor
조희진
성도경
박기현
박상훈
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코오롱인더스트리 주식회사
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Priority claimed from KR1020150172225A external-priority patent/KR101766427B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to CN201580066189.7A priority Critical patent/CN107001551B/zh
Priority to US15/532,576 priority patent/US10144716B2/en
Publication of WO2016089182A2 publication Critical patent/WO2016089182A2/fr
Publication of WO2016089182A3 publication Critical patent/WO2016089182A3/fr
Publication of WO2016089182A9 publication Critical patent/WO2016089182A9/fr

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  • 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.
  • benzoxazines are well-balanced cured polymers with 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.
  • 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.
  • 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.
  • An object of the present invention is to provide a polybenzoxazine precursor capable of preparing a cured product having improved thermal properties, electrical properties, and dimensional stability as compared to a conventional polybenzoxazine precursor.
  • 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),
  • n1 and n2 are the same as or different from each other, an integer of 0 to 2, and m is an integer of 1 to 6.
  • the precursor according to the embodiment may have a weight average molecular weight of 1500 to 8000 g / mol, the glass transition temperature is 210 °C or more.
  • a method for producing a polybenzoxazine precursor comprising the step of reacting an allylamine and diaminodiphenylmethane as an aldehyde compound and an amine compound to a phenol novolak resin.
  • the method comprises the steps of: (1) reacting a phenolic compound with an aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin;
  • n is an integer of 0 to 2.
  • the step (1) uses an aldehyde compound in 0.05 to 0.3 mol with respect to 1 mol of the phenolic compound
  • the step (2) is based on 1 mol of the phenol novolak resin, 2 to 6 mol of the aldehyde compound
  • Allylamine 0.5 to 1.5 mol and diaminodiphenylmethane (diaminodiphenylmethane) can be used in 0.1 to 0.9 mol.
  • Another embodiment of the present invention provides a method for preparing polybenzoxazine, comprising curing a polybenzoxazine precursor including a benzoxazine compound represented by Chemical Formula 1 at a temperature of 150 to 250 ° C.
  • the polybenzoxazine precursor according to the present invention can provide a cured product having improved electrical properties, thermal properties, and dimensional stability as compared to the existing polybenzoxazine precursor, and ultimately, copper foil laminate, semiconductor encapsulant, printed circuit board, adhesive It can be usefully used for paints, paints, molds and the like.
  • FIG. 1 is a GPC graph (FIG. 1A) and 1 H-NMR spectrum (FIG. 1B) of a polybenzoxazine precursor prepared in Example 1 of the present invention.
  • Figure 2 shows the GPC graph (eh 2a) and infrared spectroscopy (IR) spectrum of the polybenzoxazine precursor prepared in Example 2 of the present invention as compared to the phenol novolak resin as a raw material (Fig. 2b).
  • n1 and n2 are the same as or different from each other, an integer of 0 to 2, and m is an integer of 1 to 6.
  • 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 polybenzoxazine precursor may have a weight average molecular weight of 1500 to 8000 g / mol to prevent the delay of curing or crystallization during curing, and 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, electrical properties, and dimensional stability as compared to the existing polybenzoxazine precursor.
  • Polybenzoxazine precursor of the present invention may be prepared by using a phenol novolak resin represented by the following formula (2) as a raw material.
  • n is an integer of 0 to 2.
  • the phenol novolak resin may be condensed with an aldehyde compound, a monoamine compound, and a diamine compound in the presence of a solvent to prepare a polybenzoxazine precursor in which an aromatic content of benzoxazine is maximized.
  • 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-dimethoxybenzaldehyde and 3-isopropoxy-benzaldehyde It may be one or more selected from the group consisting of (3-Isopropoxy-benzaldehyde).
  • 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 is a combination of a monoamine and a diamine compound, wherein the monoamine is allylamine (diamine), diamine diaminediphenylmethane (diaminodiphenylmethane) may be advantageous in terms of reactivity and ease of production have.
  • the monoamine compound may be used at 0.5 to 1.5 mol, preferably 0.7 to 1.4 mol, with respect to 1 mol of the phenol novolak resin, and the diamine compound may be used at 0.1 to 0.9 mol, preferably 0.2 mol with respect to 1 mol of the phenol novolak resin.
  • the aldehyde compound may be added to 2 to 6 mol, preferably 3 to 5 mol, relative to 1 mol of the phenol novolak resin .
  • the monoamine compound When the monoamine compound is added to less than 0.5 mol with respect to 1 mol of the phenol novolak resin, a ring close reaction does not occur and thus the benzoxazine reaction cannot be sufficiently formed (the benzoxazine ring cannot be sufficiently formed). If it exceeds 1.5 mol, the side reactions lower the thermal, electrical and dimensional stability.
  • the molecular weight is too small to lower the heat resistance characteristics, and when it exceeds 0.9 mol, the molecular weight rises exponentially and the resin compatibility decreases. The problem of an increase in viscosity may occur.
  • the aldehyde compound when added to less than 2 mol with respect to 1 mol of the phenol novolak resin, it does not induce a sufficient reaction with the amine compound does not form oxazine ring, the heat resistance is lowered, if it exceeds 6 mol 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 content of the solvent it is preferable to use 25 to 100 parts by weight based on 100 parts by weight of the total phenol novolak resin, aldehyde compound, monoamine compound and diamine compound.
  • 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.
  • 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 polybenzoxazine may be obtained through a method of curing a polybenzoxazine precursor including the benzoxazine compound represented by Chemical Formula 1 at a temperature of 150 to 250 ° C.
  • the temperature for curing the polybenzoxazine precursor is suitably in the range of 150 to 250 ° C, more preferably 190 to 220 ° C. If the temperature is less than 150 ° C., the curing time may be too long, and if the temperature exceeds 250 ° C., oxidation of impurities may be excessively induced, or too much energy may be consumed during the process. In 190-220 degreeC, it is more preferable from a viewpoint of process time, energy efficiency, etc.
  • the oxazine ring of the benzoxazine compound represented by Chemical Formula 1 is polymerized while ring-opening.
  • the cured product obtained from the polybenzoxazine precursor according to the present invention exhibits excellent thermal properties, electrical properties and dimensional stability, and thus can be usefully used for copper clad laminates, semiconductor encapsulants, printed circuit boards, adhesives, paints, and mold applications.
  • the yield is 99%.
  • the percentage is the peak area ratio (ratio of monomer and polymer component) of gel permeation chromatography (GPC) (Waters: Waters707).
  • the molecular weight data of the polybenzoxazine precursor obtained using GPC was analyzed and the results are shown in FIG. 1A.
  • the obtained polybenzoxazine precursor was confirmed to have a structure by nuclear magnetic resonance analysis ( 1 H-NMR) as shown in FIG. 1B, and -OH near 8.0-9.0 ppm derived from a raw material (Compound 2).
  • the NMR apparatus used in the NMR analysis is a Bruance Avance 500 product.
  • 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 infrared spectroscopy instrument is a spectrum 100 product of Perkin Elmer.
  • the raw material is a phenol novolak resin of Formula 2, 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.
  • Example 2-1 The polybenzoxazine precursor obtained in Example 2-1 was introduced 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.
  • the obtained polybenzoxazine precursor was 54.26% of the benzoxazine monomer, and the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) was 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 1-1 was introduced into an aluminum dish having a diameter of 30 mm, and cured for 3 hours at 220 ° C. for 3 hours to prepare a cured product having a thickness of 1.5 mm.
  • the obtained polybenzoxazine precursor was 22.58% of the benzoxazine monomer, and the yield (relative to the theoretical yield according to the equivalence ratio of the reaction solution) was 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 cured products prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured using a TGA measuring device and measured using a TA Instruments TGA Q500 at a temperature increase rate of 10 ° C. per minute from 30 ° C. to 800 ° C. under a nitrogen atmosphere.
  • 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)
  • Polystyrene reduced weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) (Waters: Waters707).
  • the polymer to be measured was dissolved in tetrahydrofuran to 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.
  • TA Instruments TMA Q400 was used to measure a temperature increase rate of 10 ° C. per minute from 30 ° C. to 300 ° C.
  • ⁇ 1 is the coefficient of thermal expansion from room temperature to Tg and ⁇ 2 is the coefficient of thermal expansion from Tg to 260 ° C.
  • Examples 1 and 2 when compared with Comparative Examples 1 and 2, exhibit high thermal characteristics by showing high Tg and Td values, and in particular, permittivity (Dk) and dielectric loss tangent (Df). This low measurement resulted in an excellent electrical property, and the thermal expansion coefficient was remarkably low, indicating the excellent dimensional stability.

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  • Phenolic Resins Or Amino Resins (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne un précurseur de polybenzoxazine et un procédé le préparer et, plus spécifiquement, un précurseur de polybenzoxazine et un procédé pour le préparer, dans lequel le précurseur de polybenzoxazine peut être préparé en un matériau durci présentant des caractéristiques thermiques, des caractéristiques électriques et des caractéristiques dimensionnelles excellentes car il comprend de la bezoxazine obtenue par réaction d'une résine novolaque phénolique, d'un composé aldéhyde, et, en tant que composés amine, une allylamine et du diamine diphényle méthane, le précurseur de polybenzoxazine pouvant donc, en fin de compte, être avantageusement utilisé pour un stratifié plaqué de cuivre, un agent de scellement de semiconducteur, une carte de circuit imprimé, l'adhésion, une peinture, un moulage et des applications analogues.
PCT/KR2015/013282 2014-12-05 2015-12-07 Précurseur de polybenzoxazine et procédé pour le préparer WO2016089182A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201580066189.7A CN107001551B (zh) 2014-12-05 2015-12-07 聚苯并噁嗪前体及其制备方法
US15/532,576 US10144716B2 (en) 2014-12-05 2015-12-07 Polybenzoxazine precursor and method for preparing same

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2014-0174117 2014-12-05
KR20140174117 2014-12-05
KR20140177622 2014-12-10
KR10-2014-0177622 2014-12-10
KR1020150172225A KR101766427B1 (ko) 2014-12-05 2015-12-04 폴리벤족사진 전구체 및 그 제조방법
KR10-2015-0172225 2015-12-04

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WO2016089182A2 true WO2016089182A2 (fr) 2016-06-09
WO2016089182A3 WO2016089182A3 (fr) 2016-08-25
WO2016089182A9 WO2016089182A9 (fr) 2016-09-29

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031616A (zh) * 2021-12-14 2022-02-11 中北大学 一种高残碳含乙酸乙酯及三唑环结构的苯并噁嗪及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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JP4749625B2 (ja) * 2001-08-23 2011-08-17 新日鐵化学株式会社 熱硬化性樹脂組成物
DE102008032176A1 (de) * 2008-07-09 2010-01-14 Henkel Ag & Co. Kgaa Polymerisierbare Zusammensetzung
KR20120130337A (ko) * 2010-03-19 2012-11-30 케이스 웨스턴 리저브 유니버시티 주쇄 벤족사진 올리고머 조성물 및 이의 제조 방법
EP2742031B1 (fr) * 2011-08-11 2017-02-22 Huntsman Advanced Materials Americas LLC Procédé pour produire des composés de benzoxazine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031616A (zh) * 2021-12-14 2022-02-11 中北大学 一种高残碳含乙酸乙酯及三唑环结构的苯并噁嗪及其制备方法
CN114031616B (zh) * 2021-12-14 2023-05-26 中北大学 一种高残碳含乙酸乙酯及三唑环结构的苯并噁嗪及其制备方法

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WO2016089182A9 (fr) 2016-09-29
WO2016089182A3 (fr) 2016-08-25

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