TWI508971B - Benzene-containing Refractory Benzene Resin - Google Patents

Description

Flame retardant benzo resin containing propyne

The present invention relates to a propyne-containing flame retardant benzo resin, and more particularly to a propargyl-based phospho-based oxo-benzobenzocyclohexane compound to form a propyne-containing flame retardant benzo resin. It can improve the glass transition temperature of the resin and improve its thermal stability, and has better processing performance.

Conventionally, a Phenol formaldehyde resin is obtained by polycondensation of a phenol compound and an aldehyde compound. Among them, phenolic resins obtained by polycondensation of phenol and formaldehyde are the most important. Phenolic resin is widely used in people's livelihood, electronics, military, construction and other related industries because of its easy availability of raw materials, low water absorption, good processability and good performance after resin curing. The benzooxazine resin developed in recent years is also a kind of phenolic resin, which is characterized in that the monomer is ring-hardened after heating, but does not release water or other side reactions during hardening, so Better processability than phenolic resins.

The semiconductor industry is increasingly demanding high temperature and flame resistance requirements for materials. Benzoxazine resins have higher glass transition temperatures (Tg) and higher modulus (Modulus) than conventional phenolic resins. Low moisture absorption rate, good electrical properties, high coke residue (Char Yield), no need to strengthen the acid catalyst during hardening, no by-products and small volume change rate during hardening. The flame-retardant Benzoxazine products currently available on the market must be blended with carbon fiber in their resins, or the introduction of phosphorus-containing materials can improve the flame retardant properties of molecular materials.

With the development of the electronics industry, product requirements are becoming lighter, thinner and more diversified, and polymer materials need to be more varied to develop diversified products. The introduction of different functional groups into the Benzoxazine monomer allows for a relative increase in the original properties. The introduction of a propargyl functional group is a effective and provides a means for more crosslinking points. In addition to increasing the Tg, the thermal stability is improved, but the introduction of a propargyl functional group requires a relatively complicated step. Takeichi et al. introduced a propynyl group into a benzoxazine monomer using a nucleophilic substitution reaction, a reduction of the NO ₂ reaction, and a benzoxazine formation. Yagci, Y et al. have also developed another method to introduce propynyl groups into benzoxazine monomers, but four steps are required to protect the NH ₂ group with acetic acid, carry out nucleophilic substitution reactions, deprotect to form NH ₂ groups and generate Benzoxazine with propynyl.

The present invention synthesizes a benzoxazine bearing a propargyl functional group in a simple form. Benzoxazine by the step of forming the first structure to protect the NH ₂ group, propargyl bromide was added and allowed to hydroxyl group (OH group) comprising reacting benzoxazine propynyl (propargyl) functional group, by this form we do not need complex It is possible to synthesize a benzoxazine with a propynyl group.

In view of the above disadvantages of the prior art, the main object of the present invention is to provide a benzoxazine compound having a propargyl functional group containing phosphorus as a flame resistant material, and a propargyl functional group further providing and increasing cross-linking. Point, to make the thermal stability at high temperature, novel benzoxazine compound containing propargyl functional group, the structure containing phosphorus can be used as a flame resistant material, and the containing propargyl functional group can further provide and increase the crosslinking point, so that Good thermal stability at high temperatures.

One aspect of the present invention is to provide a propyne-containing flame retardant benzo resin (I) having the following formula:

Wherein the R ₁ system may be a hydrogen atom or The R ₂ system may be one of a group consisting of a hydrogen, a methanyl or a phenyl group. According to a specific embodiment of the present invention, when R ₁ and R ₂ of the compound of the above formula (I) are each a hydrogen atom (-H), the structural formula of the compound of the formula (I) may be (A):

According to a specific embodiment of the present invention, when R ₁ of the compound of the above formula (I) is a hydrogen atom (-H) and R ₂ is a methyl group (-CH ₃ ), the structural formula of the compound of the formula (I) may be ( B):

According to a specific embodiment of the present invention, R ₁ of the compound of the above formula (I) is a hydrogen atom (-H), and R ₂ is a phenyl group ( Wherein, the structural formula of the compound of formula (I) may be (C):

According to a particular embodiment of the invention, the R ₁ of the compound of formula (I) is When R ₂ is a hydrogen atom (-H), the structural formula of the compound of the formula (I) may be (D):

According to a particular embodiment of the invention, the R ₁ of the compound of formula (I) is When R ₂ is a methyl group (-CH ₃ ), the structural formula of the compound of the formula (I) may be (E):

One particular embodiment according to the present invention embodiment, (I) R ₁ is a compound of the formula , R ₂ is a phenyl group ( Wherein, the structural formula of the compound of formula (I) may be (F):

According to the preparation of the compound of the invention of the formula (I), wherein, when R ₁ is a hydrogen atom (-H), further polymerization is carried out to produce a polymer of the following formula (II):

The above polymer formula (II), and finally the benzoxazine monomer containing the propargyl functional group is subjected to a stage temperature rise. During heating, the propargyl forms an oxypyrene structure with oxygen first, and then continuously heats the double bond on the benzopyran. Will open for cross-linking to form a polymer of the following formula (II-1):

One of the embodiments according to the present invention, wherein, R the compound of formula (I) as the ₁ At the same time, further polymerization is carried out to produce a polymer of the following formula (III):

The above polymer formula (III), and finally the benzoxazine monomer containing a double propargyl functional group, is subjected to a stage temperature rise. During the heating process, the propargyl first forms an oxypyrene structure with oxygen, and then continuously heats the double on the benzopyran. The bond will open for cross-linking to form a polymer of the following formula (III-1):

The product of the present invention was prepared by the method provided by us to prepare (A) (B) (C) containing a single propargyl functional group, and the reaction scheme is as follows: First, DOPO is reacted with hydroxyacetophenone and aniline in an acidic environment to synthesize a monomer (1-3) having an NH ₂ group structure on the other side of the hydroxyl group (OH group). Then, the monomer (1-3) is reacted with hydroxybenzaldehyde to form an intermediate (1a-3a), and then NaBH ₄ is added for reduction to obtain a monomer (7-9), and the monomer (7-9) is used as a starting material. Paraformaldehyde reacts to form benzoxazines monomer (13-15), and then monomer (13-15) and propargyl bromide are reacted in a basic catalyst potassium carbonate (K ₂ CO ₃ ) to obtain monomer (A) (B). ) (C). Finally, the benzoxazine monomer containing the propargyl functional group is heated at a stage. During the heating process, the propargyl forms an oxypyrano structure with oxygen first, and then the double bond on the benzopyran is continuously heated to open the crosslink (cross- Linking), and the benzoxazines group also self-opening polymerization, thereby increasing the crosslink density.

The product of the present invention was prepared by another method provided by us to prepare (D) (E) (F) containing a double propargyl functional group, and the reaction scheme is as follows: After reacting DOPO with 4-aminoacetophenone and catehol in an acidic environment, a monomer (4-6) having an NH ₂ group structure on the other side having two hydroxyl groups (OH groups) is synthesized. Subsequently the use of monomer (4-6) to form an intermediate (4a-6a) hydroxybenzaldehyde is reacted with, was added NaBH ₄ reduction reacted monomer (10-12), the monomer (10-12) as a starting material and Paraformaldehyde reacts to form benzoxazines monomer (16-18), and then monomer (16-18) is reacted with propargyl bromide in a basic catalyst potassium carbonate (K ₂ CO ₃ ) to obtain monomer (D) (E). ) (F). Finally, the benzoxazine monomer containing the propargyl functional group is heated at a stage. During the heating process, the propargyl forms an oxypyrano structure with oxygen first, and then the double bond on the benzopyran is continuously heated to open the crosslink (cross- Linking), and the benzoxazines group also self-opening polymerization, thereby increasing the crosslink density.

The above summary, the following detailed description and the accompanying drawings are intended to further illustrate the manner, the Other objects and advantages of the present invention will be described in the following description and drawings.

The first figure is a 1H NMR schematic diagram of the compound (B) of the present invention.

The second figure is a schematic diagram of the DSC of the compound (B) of the present invention.

The third figure is a schematic diagram of the temperature-dependent tracking DSC of the compound (B) of the present invention.

The fourth figure is a schematic diagram of the temperature-dependent IR of the compound (B) of the present invention.

The embodiments of the present invention are described below by way of specific examples, and those skilled in the art can readily appreciate the other advantages and advantages of the present invention.

A schematic diagram of the relevant reaction formula of the compound (B) of the specific embodiment of the present invention is as follows:

Synthesis Example: Synthesis of Compound (B): Synthesis of Monomer (1)

DOPO 21.62 g (0.1 mol), 4-hydroxyacetophenone 13.61 g (0.1 mol), aniline 37.2 g (0.276 mol), and pTSA 0.86 g were added and stirred in a 250 mL three-necked round bottom flask. Nitrogen gas was introduced into the reactor at a reaction temperature of 130 ° C, and stirring was stopped after 36 hours of reaction. After the reaction, white powder naturally precipitates out of the bottom of the bottle, and when it is cooled to room temperature, it naturally precipitates. Part of the mixture was poured into methanol to obtain a white powder. The product weighed 23.08 g and the yield was 54%.

Synthesis of monomer (2)

Take monomer (1) 10g (0.012 mol), 2-hydroxybenzaldehyde 3.09g (0.025 mol), ethanol 50mL, react at room temperature for 12 hours, then add NaBH ₄ 1.392g (0.042 mol), reaction 24 hour. After completion of the reaction, it was poured into methanol water to precipitate a white powder. The product weighed 10.94 g and the yield was 82%.

Synthesis of monomer (3)

Take monomer (2) 7.73g (0.014 moles), Paraformaldehyde 0.696g (0.023 moles), tetrahydrofuran 50mL, react for 24 hours, after the reaction, white powder is naturally precipitated, and the natural precipitation part is washed with deionized water. The product weighed 3.97 g and the yield was 52%.

Synthesis of Compound (B)

Take monomer (3) 2.73g (0.005 moles), propargyl bromide 0.892g (0.006 moles), K ₂ CO ₃ 0.829g (0.006 moles), acetone 30mL, react for 24 hours, there is salt precipitation after the reaction After suction filtration, the filtrate was taken out and precipitated in water to obtain a white powder. The product weighed 1.75 g and the yield was 60%. The correlation analysis chart of the compound (B) is as shown in the first FIG. 1H NMR diagram, the second diagram DSC diagram, the third diagram temperature change tracking DSC diagram, and the fourth diagram temperature change IR diagram.

The heat curing procedure mixes monomer (B) with DDM-Bz with 1,4-Dioxane when the solvent is formulated to a phosphorus content (P wt%) of 0.5, 0.75, 1.0, 1.25, 1.5 wt%, etc. It was placed in a circulating oven and dried at 70 ° C for 12 hours to remove most of the solvent, and then baked at a temperature of 180, 200, and 220 ° C for two hours, and then baked at 240 ° C for one hour. The thermal properties of the hardened polyoxynitazobenzocyclohexane are shown in the following table.

In summary, the novel propyne-containing flammable benzoic resin provided by the present invention, further containing a propargyl functional group, can further provide and increase the crosslinking point, so that the thermal stability at high temperature is novel. The propargyl functional benzoxazine compound, which contains phosphorus as a flame resistant material, and the propargyl functional group further provides, increases the cross-linking point, provides better thermal stability at high temperatures, and provides a back-end product. More choices.

The above-described embodiments are merely illustrative of the features and functions of the present invention and are not intended to limit the scope of the technical scope of the present invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention should be as set forth in the scope of the claims described below.

Claims (1)

A non-flammable benzo resin containing propyne having a compound of the formula (I): Wherein the R ₁ system may be a hydrogen atom or (propargyl), the R ₂ system may be one of a group consisting of a hydrogen, a methanyl or a phenyl group.