TWI404747B - Production method of polybenzoxazole type polymer grafted siloxane - Google Patents

Abstract

The invention relates to a method for producing a polybenazole high polymer grafted siloxane. The benzoxazine synthesized in the invention has a specific functional group-silane. The functional group extremely fears water vapor and generates a reaction (hydrolysis condensation) while facing water vapor. Polymer then is formed after performing the reaction. The invention does not only add a dewatering agent or dewatering drug during the synthesis, but also utilizes paraformaldehyde to replace formaldehyde aqueous solution so as to successfully synthesize the monomer of benzoxazine-silane.

Description

Method for producing polybenzoxazole high polymer grafted oxoxane

The present invention relates to a method for producing a thermosetting resin, and more particularly to a method for producing a thermosetting resin grafted siloxane.

In addition, thermosetting resins are used in a large amount in addition to general composite materials for integrated circuit board substrates, semiconductor packaging materials, and aerospace materials. The raw material used for the thermosetting resin is usually a liquid or solid prepolymer having a small molecular weight, and after chemical reaction or heating, a chemical reaction is formed to form an insoluble, infusible three-dimensional network amorphous polymer. In recent years, there have been quite a lot of studies on polybenzoxazine (PBZ) thermosetting resins, because PBZ has a high glass transition temperature (170-350 ° C), high modulus, low water absorption, good dielectric properties, and no hardening. Will shrink or even expand slightly. Precision parts can be manufactured due to the dimensional stability of the products. Furthermore, since the preparation of the PBZ precursor can be selected from a variety of different monomer synthesis, the obtained PBZ can obtain different heat resistance properties and mechanical properties depending on the monomer composition and polymerization conditions, and is expected to be widely used in the packaging of electronic materials. insulation.

According to the Mannich condensation reaction, phenols, formaldehyde, and primary amine are added to the reaction flask, and reflux is performed at an appropriate temperature and time (the temperature and time required for different structures are different). A viscous liquid of yellowish brown (different colors obtained by different structures) is obtained. See Figure 1 for the reaction formula.

By-product water (H2O) is produced in the reaction, and benzoxazine is prepared to contain a small amount of water, and the water does not react with benzoxazine. It is only necessary to remove the water in the purification step. The synthesized benzoxazine has a special functional group, silane, which is extremely afraid of water vapor. When it encounters moisture, it will react (hydrolysis condensation reaction). After this reaction, a polymer is formed, and benzoxazine cannot be prepared. monomer. The hydrolysis condensation reaction is shown in Figure 2.

Further, US Pat. 6, 376, 080, Method for preparing polybenzoxazine, which is disclosed mainly in the addition of a catalyst (heterocyclic dicarboxylic acid) to reduce the hardening temperature and shorten the hardening time to be applied to printed circuit boards, semiconductors, transistors, and diodes. The raw material of the body and other electronic original coating.

The main object of the present invention is to provide a method for producing a polybenzoxazole polymer grafted oxime, which has a high glass transition temperature, high modulus, low water absorption, and a polybenzoxazine-silane. Good dielectric properties.

A secondary object of the present invention is to provide a method for producing a polybenzoxazole-based high polymer grafted methoxyoxane, which is capable of successfully synthesizing benzoxazine-silane by using a water-removing agent in a manufacturing process to avoid hydrolytic condensation reaction. Monomer.

In order to achieve the above object, the present invention provides a method for producing a polybenzoxazole-based high polymer grafted siloxane, which discloses the use of a water-removing agent to produce Polybenzoxazine-silane, which has a high glass due to Polybenzoxazine-silane. Transfer temperature, high modulus, low water absorption, good dielectric properties, and no shrinkage when hardened. Due to the dimensional stability of the products, precision parts can be manufactured, and the design freedom of the products is higher due to lower viscosity. Moreover, since the preparation of the Polybenzoxazine-silane precursor can be selected from a variety of different monomer synthesis, the obtained polybenzoxazine-silane can obtain different heat resistance properties and mechanical properties depending on the monomer composition and polymerization conditions, and can be widely applied to aerospace and automobiles. Packaging and insulation of materials and electronic materials.

The polymerization of the monomer to form polybenzoxazine-silane is a novel thermosetting resin having a high glass transition temperature (Tg) and thermal stability. In addition, the dimensional stability of the material is preferred due to its lower coefficient of thermal expansion.

In order to provide a better understanding and understanding of the structural features and efficacies of the present invention, the preferred embodiments and detailed descriptions are provided as follows:

The present invention is to solve the prior art Mannich condensation reaction, and the benzoxazine synthesized by the invention has a special functional group, silane, which is extremely afraid of moisture and reacts when it encounters moisture ( Hydrolysis condensation reaction), a polymer is formed by this reaction, and a monomer of benzoxazine-silane cannot be prepared. Therefore, in order to improve the above-mentioned deficiency, the present invention can successfully synthesize a monomer of benzoxazine-silane by adding a water removing agent or a water removing drug at the time of synthesis, and using a paraformaldehyde instead of an aqueous formaldehyde solution.

Please refer to FIG. 3, which is a manufacturing flow diagram of a preferred embodiment of the present invention. As shown in the figure, the present invention provides a method for producing a polybenzoxazole-based high polymer grafted oxoxane, the main steps of which include:

Step S100, adding phenols to a solvent to heat (about 60 ° C) until the phenols are completely dissolved in the solvent;

Step S200, adding paraformaldehyde and water removal agent or water removal drug to step S100, maintaining 60 ° C;

Step S300, the primary amine alkane is slowly dropped into the step 200, after the completion of the dropwise, the temperature is raised to 95 ° C reflux 8 hr;

Step S400, the product of step 300 is further added with a water removing agent or a water removing medicine, and stirred;

Step S500, filtering the product of step 400 to obtain a pale yellow or colorless filtrate;

In step S600, the filtrate of step 500 is vacuum-removed to obtain a dark yellow-brown viscous liquid, which is a product.

The invention can successfully synthesize a monomer of benzoxazine-silane by adding a water removing agent or a water removing medicine during synthesis, and replacing the aqueous formaldehyde solution with paraformaldehyde, and according to the Mannich condensation reaction, the phenols and the acetaldehyde. (paraformaldehyde), the primary amine of the primary amine is added to the reaction bottle and then added with water-removing drugs (anhydrous magnesium sulfate, calcium chloride), and refluxed at the appropriate temperature and time (temperature and time required for different structures) Different), a viscous liquid with a yellowish brown color (different colors from different structures) is obtained. The reaction formula is shown in Fig. 4 below.

Among them, phenols: functional groups with -OH attached to the benzene ring, can be called phenols. It is selected from one of the following groups.

Wherein the primary amine of the primary amine is selected from one of the group consisting of the following.

Wherein, the water removing agent is selected from the group consisting of anhydrous magnesium sulfate and calcium chloride.

Among them, the molar ratio:

Monofunctional phenols: trioxane: primary amine azide = 1:2/3:1

Bifunctional phenols: trioxane: primary amine azide = 1:4/3:2

Trifunctional phenols: trioxane: primary amine oxane = 1:2:3

In summary, the present invention is a novelty, progressive and available for industrial use, and should conform to the patent application requirements stipulated in the Patent Law of China, and the invention patent application is filed according to law. Lee, the feeling is a prayer.

However, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the shapes, structures, features, and spirits described in the claims are equivalently changed. Modifications are intended to be included in the scope of the patent application of the present invention.

Figure 1 is a schematic diagram of a reaction scheme of the prior art;

Figure 2 is a schematic diagram of a hydrolysis condensation reaction of the prior art;

Figure 3 is a manufacturing flow diagram of a preferred embodiment of the present invention;

Figure 4 is a schematic representation of the reaction scheme of one preferred embodiment of the invention.

Claims (7)

A method for producing a polybenzoxazole polymer grafted oxoxane, the method comprising the steps of: dissolving a phenol by using a solvent; adding a trioxane and a water removing agent; adding a primary amine oxoxane; Adding a water scavenger and stirring; and filtering to obtain a filtrate, and removing the solvent to obtain a product; wherein the primary amine azide is selected from one of the following groups: The method for producing a polybenzoxazole-based high polymer grafted oxoxane according to claim 1, wherein the phenol is selected from one of the group consisting of the following: The method for producing a polybenzoxazole-based polymer grafted oxoxane according to claim 1, wherein the water-removing agent is selected from the group consisting of anhydrous magnesium sulfate and calcium chloride. One of them. The method for producing a polybenzoxazole polymer grafted oxoxane according to the first aspect of the invention, wherein in the step of dissolving the phenol by using a solvent, heating to 60 ° C is required to completely dissolve the phenol. . The method for producing a polybenzoxazole-based polymer grafted oxoxane according to claim 1, wherein the step of adding the paraformaldehyde and the water-removing agent is maintained at 60 °C. The method for producing a polybenzoxazole polymer grafted oxoxane according to claim 1, wherein the step of further adding a primary amine oxoxane is carried out to raise the temperature to 95 ° C and reflux for 8 hours. . The method for producing a polybenzoxazole-based high polymer grafted oxoxane according to claim 1, wherein in the step of performing filtration to obtain a filtrate and removing the solvent to obtain a product, a vacuum method is used. To remove the solvent.