KR100782932B1 - Method for making polyetherimide precursor - Google Patents

Abstract

A method for preparing a polyetherimide precursor is provided to improve work stability by using a common solvent having no toxicity and to inhibit phase separation by increasing the compatibility with an epoxy resin. A method for preparing a polyetherimide precursor comprises the steps of adding a first monomer containing an aniline group to a solvent represented by RO-(CH2)n-OH to prepare a mixture solution; and adding a second monomer containing an anhydrous group to the obtained mixture solution to react them, wherein R is a substituted or unsubstituted C1-C3 alkyl group; and n is an integer of 2-10. Preferably the solvent is at least one selected from 2-methoxyethanol, 2-methoxypropanol, 2-ethoxyethanol, and 2-ethoxypropanol.

Description

Synthesis method of polyetherimide precursor material {Method for making polyetherimide precursor}

The present invention relates to a method for synthesizing a polyetherimide precursor material, and more particularly, to a method for synthesizing a polyetherimide precursor material added to improve the mechanical and thermal properties of an imprint insulating material.

In general, epoxy resins having a high dielectric constant and low elongation are used as insulating materials for imprints. Various methods have been applied to improve the mechanical strength and thermal properties of such insulating materials, and the addition of double engineering plastics has been an issue.

Among them, polyether imide (PEI) has been in the spotlight as an additive for improving the properties of a polymer because of its high mechanical strength and thermal properties. However, since polyetherimide itself has a very low solubility, a method of adding polyetherimide to improve the mechanical properties of polymer resins has been to treat polyetherimide with NaOH solution and use NMP (N-methyl pyrrolidone), MC. A method of dissolving in a toxic solvent such as (dichloromethane) and adding it was used.

However, such a method is difficult to synthesize the carbonyl functional groups of the polyetherimide, and is limited in solution blending with the epoxy system due to the problem of phase separation and low solubility of the solvent used.

The present invention is to solve the above-mentioned problems of the prior art, an object of the present invention is to synthesize a polyetherimide precursor material is added to improve the mechanical and thermal properties of the imprint insulating material using a stable solvent with low toxicity To provide.

In order to solve the above technical problem, the present invention,

Preparing a mixed solution by adding a first monomer including an aniline group in a solvent represented by Formula 1 below; And

Reacting the mixed solution by adding a second monomer including an anhydride group;

It provides a method for synthesizing a polyetherimide precursor material comprising a.

[Formula 1]

In said formula, R is a substituted or unsubstituted C1-C3 alkyl group, n is an integer of 2-10.

According to one embodiment of the present invention, the solvent of Formula 1 may be at least one selected from the group consisting of 2-methoxy ethanol, 2-methoxy propanol, 2-ethoxy ethanol and 2-ethoxy propanol.

The first monomer including the aniline group may be at least one selected from the group consisting of 4,4-oxydianiline and m-phenylenediamine.

The second monomer comprising the anhydride group is selected from the group consisting of 4,4- (hexafluoro-isopropylidene) diphthalic anhydride and bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride It may be at least one.

Most preferably, 4,4-oxydianiline is used as the first monomer containing the aniline group, and 4,4- (hexafluoro-isopropylidene) diphthalic anhydride is used as the second monomer containing the anhydride group. Can be used.

The total content of the first monomer and the second monomer is 10 to 20% by weight, the content of the solvent is preferably 80 to 90% by weight, the molar ratio of the first monomer and the second monomer is 1: 1. desirable.

The reaction step is preferably performed by slowly adding the first monomer containing the aniline group to the mixed solution for 5 to 30 hours.

In addition, the reaction step is more preferably reacted while cooling the mixture.

The synthesis method according to the invention is more preferably carried out in an inert atmosphere.

Hereinafter, a method for synthesizing the polyetherimide precursor material according to the present invention will be described in more detail.

Epoxy resin, which is one of the insulating materials used for imprinting, is widely used as a matrix resin for coatings, adhesives, electrical and electronic materials, and composite materials due to its excellent thermal stability, corrosion resistance, chemical resistance, insulation, adhesive properties, and mechanical properties. However, epoxy resin is brittle due to its high degree of crosslinking as a representative thermosetting resin whose linear structure is changed into a three-dimensional network through the curing process. Therefore, since the use of the epoxy resin due to the low toughness is limited, much research has been conducted to improve such brittleness. One of them is to add polyetherimide as a toughening agent in curing the epoxy resin. However, this method uses a toxic volatile solvent, which results in poor working stability, and is constrained in solution blending due to the phase separation and low solubility of the solvent. In contrast, the present invention synthesizes a polyetherimide precursor material for adding to an insulating material for imprint using a solvent having excellent compatibility with epoxy resins, which can suppress phase separation and have no toxicity and excellent work stability.

Synthesis method of a polyetherimide precursor material according to the present invention comprises the steps of preparing a mixed solution by adding a first monomer containing an aniline group in a solvent represented by the formula (1); And adding and reacting a second monomer including an anhydride group to the mixed solution.

[Formula 1]

In said formula, R is a substituted or unsubstituted C1-C3 alkyl group, n is an integer of 2-10.

First, the compound used in the present invention will be described.

More specific examples of the solvent of Formula 1 include 2-methoxy ethanol, 2-methoxy propanol, 2-ethoxy ethanol, 2-ethoxy propanol and the like. These solvents include commercially available solvents, and thus have excellent work stability, and can not only prevent phase separation in solution blending with the epoxy resin, but also have a lower boiling point than conventional solvents. Curing can be facilitated.

The unsubstituted alkyl group having 1 to 3 carbon atoms in Chemical Formula 1 may be linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, and isopropyl.

At least one hydrogen atom of the functional group R in Formula 1 may be substituted with a halogen atom, a haloalkyl group, a carbonyl group, a hydroxy group, a nitro group, a cyano group, an amino group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, or the like. Can be.

The first monomer including the aniline group can be used without limitation so long as it is a compound containing an aniline group so as to imidize both ends of the chain. Specific examples include 4,4-oxydianiline, m-phenylenediamine, and the like, but are not limited thereto.

The second monomer including the anhydride group can be used without limitation so long as it is a compound including an anhydride group so as to imidize both ends of the chain. Specific examples include, but are not limited to, 4,4- (hexafluoro-isopropylidene) diphthalic anhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, and the like. .

According to a preferred embodiment, 4,4-oxydianiline is used as the first monomer containing the aniline group, and 4,4- (hexafluoro-isopropylidene) diphthalic acid is used as the second monomer containing the anhydride group. Anhydrides can be used.

In the present invention, the total content of the first monomer and the second monomer is 10 to 20% by weight, the content of the solvent is preferably 80 to 90% by weight. If the total content of the monomer in the total reaction solution is less than 10% by weight, it is not preferable because the functional group for the self-polyimidization reaction and the epoxy group reaction is too small, and if it exceeds 20% by weight, the first monomer and the second monomer are sufficiently dissolved It is not preferable because the viscosity of the compound is too high and uniformity is not achieved. In addition, the molar ratio of the first monomer and the second monomer is 1: 1. This is to prepare a polyetherimide precursor material including amic acid through a 1: 1 reaction in quantitative manner.

In the method for synthesizing a polyetherimide precursor material according to the present invention, first, a mixed solution is prepared by adding a first monomer containing an aniline group in the solvent represented by Formula 1, and then adding a second monomer including anhydride groups to the mixed solution. It proceeds by reaction.

When the second monomer is added to the mixed solution, the second monomer is preferably added slowly to cause a uniform reaction with the first monomer, and the reaction is preferably performed for 5 to 30 hours. If the reaction time is less than 5 hours, the degree of polymerization is too low to inhibit the effect of improving mechanical properties, and if it exceeds 30 hours, the degree of polymerization is too high and the functional groups that can react with the epoxy are not preferable.

In addition, since the synthesis reaction of the polyetherimide precursor is exothermic, it is more preferable to react the mixture while cooling the mixture in order to improve reactivity.

Since the synthesis method according to the present invention is sensitive to moisture, it is more preferable to proceed with the reaction in an inert atmosphere.

As such, the polyetherimide precursor material including amid acid may be synthesized through condensation reaction between monomers through the synthesis process.

The polyetherimide precursor material synthesized by the above method can be added to an epoxy resin system to cause condensation reaction of amic acid groups to form imide domains in the epoxy to improve mechanical and thermal properties. The polyetherimide precursor material according to the present invention may be added at least 30% by weight to the epoxy receiving system.

Hereinafter, the present invention will be illustrated by the following examples, but the protection scope of the present invention is not limited only to the following examples.

<Example>

First, 85% by weight of 2-methoxy ethanol was used as the solvent, and the total content of the monomers was 15% by weight. Here, 4,4-oxydianiline (ODA) was used as the first monomer, and 4,4- (hexafluoro-isopropylidene) diphthalic anhydride (FDA) was used as the second monomer, and 1: It was prepared at a molar ratio of 1. The synthesis was carried out at room temperature in an inert atmosphere. ODA was added to the prepared 2-methoxy ethanol and stirred for 2 hours to dissolve completely. The FDA was slowly added thereto and then reacted for at least 12 hours to synthesize a polyetherimide precursor material.

When the precursor material synthesized according to the present invention was added to an epoxy resin monomer to perform condensation reaction, the modulus was improved by 10% or more compared with the epoxy resin using the conventional phenol novolac epoxy resin.

The present invention is not limited to the above embodiments, and many variations are possible by those skilled in the art within the spirit of the present invention.

As described above, the method for synthesizing the polyetherimide precursor material according to the present invention has excellent work stability by using a non-toxic solvent, and excellent compatibility with epoxy resins, which can inhibit phase separation and have a low boiling point. Resin blending and curing may be easy.

Claims (10)

Preparing a mixed solution by adding a first monomer including an aniline group in a solvent represented by Formula 1 below; And Reacting the mixed solution by adding a second monomer including an anhydride group; Synthesis method of polyetherimide precursor material comprising: [Formula 1]

In said formula, R is a substituted or unsubstituted C1-C3 alkyl group, n is an integer of 2-10. The method of claim 1, The solvent of Formula 1 is at least one selected from the group consisting of 2-methoxy ethanol, 2-methoxy propanol, 2-ethoxy ethanol and 2-ethoxy propanol. The method of claim 1, The first monomer comprising an aniline group is at least one selected from the group consisting of 4,4-oxydianiline and m-phenylenediamine. The method of claim 1, The second monomer comprising the anhydride group is selected from the group consisting of 4,4- (hexafluoro-isopropylidene) diphthalic anhydride and bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride At least one polyetherimide precursor material. The method of claim 1, The first monomer containing the aniline group is 4,4-oxydianiline, and the second monomer including the anhydride group is 4,4- (hexafluoro-isopropylidene) diphthalic anhydride polyether precursor material Method of synthesis. The method of claim 1, The total content of the first monomer and the second monomer is 10 to 20% by weight, the content of the solvent is 80 to 90% by weight of the synthesis method of the polyetherimide precursor material. The method of claim 1, A method of synthesizing a polyetherimide precursor material, wherein the molar ratio of the first monomer and the second monomer is 1: 1. The method of claim 1, The reaction step is a method of synthesizing a polyetherimide precursor material is carried out by slowly adding a first monomer containing an aniline group to the mixture and then proceeding for 5 to 30 hours. The method of claim 1, The reaction step is a method of synthesizing the polyetherimide precursor material while the mixture is cooled. The method of claim 1, The synthesis method is a method for synthesizing a polyetherimide precursor material which is thickened in an inert atmosphere.