WO2016003167A1

WO2016003167A1 - Polybenzoxazine precursor and method for preparing same

Info

Publication number: WO2016003167A1
Application number: PCT/KR2015/006715
Authority: WO
Inventors: 조희진; 성도경; 박기현; 박상훈; 강현수
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2014-06-30
Filing date: 2015-06-30
Publication date: 2016-01-07

Abstract

The present invention relates to a polybenzoxazine precursor and a method for preparing the same and, more specifically, provides a polybenzoxazine precursor and a method for preparing the same, wherein the polybenzoxazine precursor makes it possible to prepare a hardened material which exhibits improved thermal characteristics; on the other hand, exhibits high thermal characteristics and flame retardant characteristics while maintaining excellent electrical characteristics intact; and, on the other other hand, exhibits high thermal characteristics and electrical characteristics, and ultimately, the polybenzoxazine precursor can be favorably used for a copper-clad laminate, a semiconductor encapsulant, a printed circuit board, an adhesive, a paint, and a mold.

Description

Polybenzoxazine Precursor and Manufacturing Method Thereof

The present invention relates to a polybenzoxazine precursor and a method for producing the same.

Conventionally, 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.

However, 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.

In order to eliminate these drawbacks, 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.

Techniques for further enhancing the characteristics of these polybenzoxazines are constantly being developed. For example, 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. By this, a method for producing a polybenzoxazine having good thermal stability is disclosed.

In addition, the 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.

On the other hand, with the recent focus on the environment at home and abroad, environmental issues have begun to emerge in the electronic materials industry. Due to RoHS, a restriction on the use of hazardous substances in the European Union and developed countries, the domestic electronic circuit board industry is also increasing the application of eco-friendly PCB technology to lead-free. Environmentally friendly lead-free processes do not use lead, and as the working temperature rises in the process, it is necessary to develop both a material capable of withstanding high temperatures and a suitable equipment.

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. Conventionally, halogenated resins such as brominated epoxy resins, antimony oxide, and the like have been used to impart such flame retardancy.

Currently, 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. In particular, there is a great demand for 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.

As an alternative, the use of polybenzoxazine, a phenol-based curing agent, has emerged. As described above, 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. In addition, 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.

However, conventionally developed 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.

Therefore, it is required to produce a high flame retardant polybenzoxazine that can be used in a high temperature environment without revealing these disadvantages.

Meanwhile, Copper Clad Laminate (CCL) refers to a laminated plate coated with a thin copper foil on an insulating material. Recently, copper clad laminates used in printed circuit boards (PCBs) are excellent due to high performance and high integration of smart devices. 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.

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. As described above, 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

It is an object of the present invention to provide a polybenzoxazine precursor capable of producing a cured product having improved thermal properties as compared to a conventional polybenzoxazine precursor.

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),

The following formula provides a polybenzoxazine precursor comprising 20 to 100% of a benzoxazine compound having n = 0.

[Formula 1]

In Chemical Formula 1, n = 0 to 2, and 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.

In one embodiment, the hardened product of the benzoxazine compound may include a compound represented by the following formula (2).

[Formula 2]

In 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.

In another embodiment of the present invention, (1) reacting a phenolic compound and an aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin; And

(2) It provides a method for producing a polybenzoxazine precursor comprising the step of reacting the phenol novolak resin obtained above with allylamine or aniline as an aldehyde compound and an amine compound.

In one embodiment, the phenol novolak resin is represented by the formula (3), it may be one containing at least 65% n = 0 in the formula (3).

[Formula 3]

In Formula 3, n is an integer of 0 to 2.

In one embodiment, 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.

In another embodiment of the present invention provides a cured product of the polybenzoxazine precursor according to the above embodiments.

In the above embodiment, 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 ℃ or more.

It includes a hardened product of the polybenzoxazine precursor containing the benzoxazine compound, the glass transition temperature may be 250 ℃ or more.

Polybenzoxazine precursor according to the present invention can provide a cured product with improved thermal properties compared to the existing polybenzoxazine precursor,

In particular, according to one embodiment, it is possible to provide a cured product that exhibits high thermal and flame retardant properties while maintaining electrical properties.

According to another embodiment, it is possible to provide 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.

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.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

[Formula 1]

In Chemical Formula 1, n = 0 to 2, and R ₁ is

or

to be.

In the above and the following description, the term "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.

At least 20% of the total composition of the polybenzoxazine precursor according to one embodiment of the present invention, in which n = 0 in Chemical Formula 1, may be preferable in terms of improving electrical properties, thermal properties, and flame retardant properties. Can be.

% Is based on the peak area ratio of gel permeation chromatography (GPC) (Waters: Waters707), and strictly refers to the peak area ratio between the monomer and the polymer component when the precursor contains a polymer such as a hardened substance. Same as below.

The polybenzoxazine precursor according to an embodiment of the present invention includes a compound having n = 1 to 2 in Formula 1 in addition to the compound having n = 0 in Formula 1, and may include a hardened product as described above.

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.

[Formula 2]

In 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.

[Formula 4]

In Formula 4, n is an integer of 0 to 2.

[Formula 5]

In Formula 5, R is

N is an integer of 0-2, n2 is an integer of 1-5.

[Formula 6]

In Chemical Formula 6, n is an integer of 0 to 2.

[Formula 7]

In Formula 7, 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.

In particular, in Formula 1, R ₁

The polybenzoxazine precursor including when (Formula 4) can significantly improve thermal and flame retardant properties while maintaining excellent electrical properties.

Meanwhile, in Formula 1, 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.

[Formula 3]

In Formula 3 n is an integer of 0 to 2.

Specifically, in Formula 3, the compound may be prepared by using a phenol novolak resin containing 65% or more of a compound having n = 0.

More specifically, (1) reacting a phenolic compound and an aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin; And (2) reacting the obtained phenol novolak resin with aniline or allylamine as an aldehyde compound and an amine compound.

More specifically, in the presence of an acid catalyst, a phenolic compound and an aldehyde compound are reacted to obtain a phenol novolak resin containing 65% or more (GPC Area%) of n = 0 components of the compound represented by Formula 3, and then obtaining the above. 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.

As described above, the phenolic compound and the aldehyde compound may be reacted in the presence of an acid catalyst to obtain a phenol novolak resin containing 65% or more (GPC Area%) of a compound having n = 0 in Chemical Formula 3. When the amount of the compound of n = 0 in the case of less than 65%, the viscosity is due to the rapid reactivity in the subsequent benzoxazine production reaction and the large molecular weight of the raw material There may be a problem of elevated or gelling.

At this time, the water and the solvent generated in the reaction process can be removed by a known method such as distillation.

In the step (1), the aldehyde compound may be added at 0.05 to 0.3 mol, preferably 0.1 to 0.2 mol with respect to 1 mol of the phenolic compound. If the aldehyde compound is added to less than 0.05 mol with respect to 1 mole of the phenolic compound, the yield may be drastically reduced. If the aldehyde compound exceeds 0.3 mol, the phenol having a component of n = 0 in Formula 3 is less than 65%. Novolak resin can be synthesized

The phenolic compound may be phenol or cresol.

In addition, the above and below 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.

In step (2), 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 .

When the amount of the amine is aniline, when the added 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 formed (the benzoxazine ring cannot be formed sufficiently). In case of exceeding 3 mol, 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.

On the other hand, when 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.

In addition, when the aldehyde compound is 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. At this time, 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.

In the preparation of the polybenzoxazine precursor, 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.

The polybenzoxazine precursor prepared as described above may include 20% to 100% of n = 0 component in Chemical Formula 1.

In one embodiment of the present invention to provide a cured product of such a polybenzoxazine precursor, such a cured product can be improved in thermal properties compared with the cured product derived from the existing benzoxazine compound.

Particularly, in the compound represented by Formula 4, the cured product obtained from the polybenzoxazine precursor containing 20% or more of the compound having n = 0 exhibits high thermal and flame retardant properties while maintaining excellent electrical properties. It can be usefully used for semiconductor encapsulants, printed circuit boards, adhesives, paints, molding applications and the like.

On the other hand, in the compound represented by the formula (6), the cured product obtained from the polybenzoxazine precursor containing 20% or more of the compound having n = 0 exhibits high thermal characteristics and electrical properties, thereby showing a copper-clad laminate, a semiconductor encapsulant, and a printed circuit. It can be usefully used for substrates, adhesives, paints, molds and the like.

In the above and the following description, the term "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.

Hereinafter, the content of the present invention will be described in detail through examples. However, these are intended to explain the present invention in more detail, and the scope of the present invention is not limited thereto.

<실시예 1><Example 1>

1-1: Preparation of Polybenzoxazine Precursor

202.97 g of benzaldehyde and 1200.0 g of phenol were added at 40 ° C., and the reaction was carried out at 130 ° C. for 5 hours under an acid catalyst, para-toluenesolfonic acid catalyst, containing 75.02% (GPC Area%) of 4,4- (phenylmethylene) diphenol. The remaining 24.98% obtained a phenol novolak resin consisting of a compound of n = 1 to 2 in the following compound (Formula 3).

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.

In this case, the NMR apparatus used in the NMR analysis is a Bruance Avance 500 product.

[Formula 3]

Next, 500 g (1.8094 mol) and 222.8 g of the phenol novolac resin synthesized above and 222.8 g of toluene were added to a 3 L three-neck flask purged with nitrogen, and 168.51 g (1.8094 mol) of aniline and an aqueous solution of formaldehyde (40%) 271.69 g (3.6189 mol) was added. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Then, after heating up to 120 ℃, the solvent was completely removed for 60 minutes under a pressure of 10 torr 708g of polybenzoxazine precursor having a weight average molecular weight of 652g / mol (including 45.9% of n = 0 component of Formula 4, n = 0-2) were prepared. In this case, 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 result of confirming the structure of the obtained polybenzoxazine precursor by nuclear magnetic resonance analysis ( ¹ H-NMR) is the same as in Figure 1b, disappears -OH Peak in the vicinity of 8.0-9.0ppm shown in Figure 1a 4.0 to 6.0ppm It can be seen that the peak generated from the oxazine was generated.

On the other hand, the molecular weight data of the polybenzoxazine precursor obtained by using GPC (Gel Permeation Chromatography, Waters: Waters707) was analyzed and the results are shown in Figure 1c.

From the results of FIG. 1C, a broad peak was observed for the high molecular weight material near retention time 30min, which translates to the result of the formation of a hardened product of the compound of Formula 4, that is, the compound of Formula 5.

1-2: hardened material manufacturing

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.

<실시예 2><Example 2>

2-1: Preparation of Polybenzoxazine Precursor

197.33 g of benzaldehyde and 1250 g of phenol were added at 40 ° C., and reacted at 130 ° C. for 4 hours under an acid catalyst, para-toluenesolfonic acid catalyst, containing 75.27% (GPC Area%) of 4,4- (phenylmethylene) diphenol. 24.73% obtained the phenol novolak resin which consists of a compound of n = 1-2 of General formula (3).

Next, 500 g (3.5262 mol) of the phenol novolac resin and 276.1 g of toluene synthesized above were added to a 3 L three-neck flask purged with nitrogen, and 328.39 g (3.5262 mol) of aniline and an aqueous formaldehyde solution (40%) 529.46 g (7.0524 mol) was added. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Then, after heating up to 130 ℃, the solvent was completely removed for 60 minutes under a pressure of 10 torr 905g of polybenzoxazine precursor having a weight average molecular weight of 889g / mol (34.57% of n = 0 component of Formula 4, n = 0-2) were prepared. In this case, 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).

As a result of confirming the structure of the obtained polybenzoxazine precursor by using infrared spectroscopy, the hydrogen atom peak of the oxazine ring (CH out of plane bending) was confirmed. At this time, the infrared spectroscopy instrument is a spectrum 100 product of Perkin Elmer.

In the base material of FIG. 2, 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 out-of-plane bending vibration of CH) and 1234 cm-1 (COC asymmetric stretching modes)

On the other hand, the molecular weight data of the polybenzoxazine precursor obtained by using GPC (Gel Permeation Chromatography, Waters: Waters707) 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.

2-2: hardened product manufacture

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.

<비교예 1>Comparative Example 1

1-1: Preparation of Polybenzoxazine Precursor

484.2 g of toluene was added to a 3 L three-necked flask purged with nitrogen, and 652.71 g (2.0 mol) of aniline and 800 g (1 mol) of bisphenol A were added thereto. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Then, after heating up to 120 ℃, the solvent was completely removed for 60 minutes under a pressure of 10torr to prepare a 1500g polybenzoxazine precursor having a weight average molecular weight of 698g / mol. 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).

1-2: hardened material manufacturing

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.

<비교예 2>Comparative Example 2

2- 1: Preparation of polybenzoxazine precursor

514.7 g of toluene was added to a 3 L three-necked flask purged with nitrogen, and 744.18 g (2.0 mol) (2.0 mol) of aniline and 800 g (1 mol) of bisphenol F were added thereto. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Thereafter, after heating up to 120 ° C., the solvent was completely removed under a pressure of 10 torr for 60 minutes to prepare 945 g of a polybenzoxazine precursor having a weight average molecular weight of 1240 g / mol. 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).

2-2: hardened product manufacture

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.

1-2: hardened material manufacturing

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.

The molecular weights of the polybenzoxazine precursors prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the following method, and the results are shown in Table 1 below.

<분자량 측정><Molecular weight measurement>

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 µl 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.

On the other hand, the glass transition temperature, thermal decomposition temperature (Td), flame retardancy and dielectric constant of the cured product prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the following method and the results are shown in Table 1 below.

<유리전이온도(Tg) 측정><Glass Transition Temperature (Tg) Measurement>

10 mg of the cured product prepared in Examples 1 and 2 and Comparative Examples 1 and 2 was measured at a temperature rising rate of 20 ° C. per minute from 30 ° C. to 350 ° C. using a TA Instruments DSC Q2000. It was.

<난연성 측정><Flame Retardant Measurement>

The hardened | cured material manufactured in Examples 1 and 2 and Comparative Examples 1 and 2 was evaluated for flame retardancy by the UL-94 method.

<유전율 측정>Dielectric constant measurement

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.

Measuring frequency: 1 GHz

Measuring temperature: 25-27 ℃

Measuring Humidity: 45-55%

Measurement sample: Thickness 1.5 mm (1.3 to 1.7 mm)

Table 1

division	Mn / Mw (g / mol)	Tg (℃)	Flame retardant (UL94-V0)	Dielectric constant (Dk) / dielectric loss tangent (Df)
Example 1	514/652	203	V0	3.28 / 0.01
Example 2	757/889	205	V0	3.22 / 0.01
Comparative Example 1	520/698	170.48	Burns	3 / 0.01
Comparative Example 2	571/1240	173.7	V1	3.45 / 0.015

As shown in Table 1, the dielectric constant values of Examples 1 and 2 and Comparative Examples 1 and 2 are similar, but Examples 1 and 2 show higher glass transition temperature and flame retardancy than Comparative Examples 1 and 2, It was found that the thermal and flame retardant properties were excellent, and in particular, in Comparative Example 1, it could not be measured by burning during the measurement process.

<실시예 3><Example 3>

3-1: Preparation of Polybenzoxazine Precursor

202.97 g of benzaldehyde and 1200.0 g of phenol were added at 40 ° C., and the reaction was carried out at 130 ° C. for 5 hours under a catalyst of para-toluene solfonic acid as an acid catalyst. (GPC Area%) and the remaining 22.86% of the formula (3) to obtain a phenol novolak resin consisting of a compound of n = 1 ~ 2.

Next, 500 g (1.7665 mol) of the synthesized phenol novolak resin and 609.3 g of toluene were added to a 3 L three-neck flask purged with nitrogen, and 201.70 g (3.533 1 mol) of allylamine and an aqueous formaldehyde solution ( 40%) 530.49 g (7.0661 mol) was added. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Then, after heating up to 120 ℃, the solvent was completely removed for 60 minutes under a pressure of 10 torr 787g of polybenzoxazine precursor having a weight average molecular weight of 1420g / mol (including 30.7% of n = 0 component of Formula 6, n = 0-2) were prepared. In this case, 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. In this case, the NMR apparatus used in the NMR analysis is a Bruance Avance 500 product.

On the other hand, the molecular weight data of the polybenzoxazine precursor obtained by using GPC (Gel Permeation Chromatography, Waters: Waters707) 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.

3-2: Cured Product Preparation

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.

<실시예 4><Example 4>

4-1: Preparation of Polybenzoxazine Precursor

197.33 g of benzaldehyde and 1250 g of phenol were added at 40 ° C., and the reaction was carried out at 130 ° C. for 4 hours under an acid catalyst, Para-toluene solfonic acid, to give 75.27% of a component of n = 0 in Chemical Formula 3 (GPC). Area%) and the remaining 24.73% in the formula (3) to obtain a phenol novolak resin consisting of a compound of n = 1 ~ 2.

Next, 500 g (1.7665 mol) of the synthesized phenol novolak resin and 609.3 g of toluene were added to a 3 L three-neck flask purged with nitrogen, and 201.70 g (3.533 1 mol) of allylamine and an aqueous formaldehyde solution ( 40%) 530.49 g (7.0661 mol) was added. When the addition was completed, the reaction solution was heated up to 100 ° C. at a rate 1.3 ° C./min and stirred for 5 hours. Then, after heating up to 120 ℃, the solvent was completely removed for 60 minutes under a pressure of 10 torr 781 g of a polybenzoxazine precursor having a weight average molecular weight of 1264 g / mol (containing 32.7% of n = 0 in the formula 6, n = 0-2) were prepared. In this case, 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).

As a result of confirming the structure of the obtained benzoxazine monomer using infrared spectroscopy, as shown in FIG. 4, in FIG. 4, Phenol Novolac is a phenol novolak resin of Formula 3, and Benzoxazine is a polybenzoxazine precursor obtained. In the case of -OH stretching peak due to -OH group disappears, and 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) ). At this time, the infrared spectroscopy instrument is a spectrum 100 product of Perkin Elmer.

4-2: hardened product manufacture

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 molecular weights of the polybenzoxazine precursors of Examples 3 and 4 were measured by the above-described method, and the results are shown in Table 2 below in comparison with Comparative Examples 1 and 2.

On the other hand, the flame retardancy and dielectric constant of the cured product prepared in Examples 3 and 4 was measured by the above-described method and the results are shown in Table 2 below in comparison with Comparative Examples 1 and 2.

However, the glass transition temperature was measured by the following method and the results are shown in Table 2 below.

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).

Therefore, 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.

TABLE 2

division	Mn / Mw (g / mol)	Tg (℃)	Td 5 (℃)	Permittivity (Dk)	Dielectric loss factor (Df)
Example 3	668/1420	302	351.7	2.95	0.0020
Example 4	638/1264	298	349.4	2.98	0.0025
Comparative Example 1	520/698	198.7	314.6	3.00	0.0100
Comparative Example 2	571/1240	195.9	318.2	3.45	0.0150

As shown in Table 2, 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.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims

To include a benzoxazine compound represented by the formula (1),

A polybenzoxazine precursor comprising 20 to 100% of a benzoxazine compound having n = 0 in Formula 1 below.

[Formula 1]

In Chemical Formula 1, n = 0 to 2, and R 1 is
or
to be.
The polybenzoxazine precursor of claim 1, wherein the precursor comprises a hardened product polymerized while the oxazine ring of the benzoxazine compound represented by Chemical Formula 1 is ring-opened.
3. The polybenzoxazine precursor of claim 2, wherein the hardened product of the benzoxazine compound comprises a compound represented by the following Chemical Formula 2.

[Formula 2]

In Formula 2, R is
And R 1 is
or
N is an integer of 0-2, n2 is an integer of 1-5.
The polybenzoxazine precursor according to claim 1, wherein the precursor has a weight average molecular weight of 500 to 5000 g / mol.
(1) reacting a phenolic compound with an aldehyde compound in the presence of an acid catalyst to obtain a phenol novolak resin; And

(2) a method for producing a polybenzoxazine precursor, comprising the step of reacting the obtained phenol novolak resin with allylamine or aniline as an aldehyde compound and an amine compound.
6. The method according to claim 5, wherein the phenol novolak resin is represented by the formula (3), wherein the phenol novolac resin contains at least 65% of n = 0 components in the formula (3).

[Formula 3]

In Formula 3, n is an integer of 0 to 2.
The method of claim 5, wherein step (1) uses an aldehyde compound in an amount of 0.05 to 0.3 mol with respect to 1 mol of the phenolic compound, and step (2) comprises 1 to 3 mol and an amine compound for 1 mol of a phenol novolak resin; Method for producing a polybenzoxazine precursor, characterized in that used as an aldehyde compound 1 to 5mol.
Hardened | cured material of the polybenzoxazine precursor of any one of Claims 1-4.
According to claim 8, wherein the cured product is R 1 in the benzoxazine-based compound represented by the formula (1)
Hardened | cured material containing the hardened | cured material of the polybenzoxazine precursor containing an benzoxazine compound, and whose glass transition temperature is 190 degreeC or more.
According to claim 8, wherein the cured product is R 1 in the benzoxazine-based compound represented by the formula (1)
Hardened | cured material containing the hardened | cured material of the polybenzoxazine precursor containing a phosphorus benzoxazine compound, and whose glass transition temperature is 250 degreeC or more.