KR100688912B1 - Hyperbranch polyimide compound and process for preparing the same - Google Patents

Abstract

Provided is a hyper-branched polyimide, which exhibits an excellent glass transition temperature, thermal stability and gas permeability, and is useful for producing highly heat resistant films for electric and electronic materials, liquid crystal aligning layers, semiconductor components, molding components and adhesives. The hyper-branched polyimide has a structure of an amine-terminated polyimide represented by a formula 1 or an anydride-terminated polyimide represented by a formula 2, and weight average molecular weight of 6,000-20,000. In the formulae 1 and 2, X represents a repeating unit represented by formulae 3 and 4, wherein Xn represents a hyper-branch having n X groups linked radially to each other, and n is an integer of 8-41.

Description

HYPERBRANCH POLYIMIDE COMPOUND AND PROCESS FOR PREPARING THE SAME}

1 is a result of FT-IR analysis of the hyperbranched polyimide prepared in Examples 1 and 2,

2 is a ¹ H NMR analysis of the hyperbranched polyimide prepared in Examples 1 and 2,

3 is a TGA thermal analysis of the hyperbranched polyimide prepared in Examples 1 and 2. FIG.

The present invention relates to a hyperbranched polyimide having excellent glass transition temperature, thermal stability, gas permeability, and the like, and a method of manufacturing the same.

Polyimides exhibit not only good mechanical properties and chemical resistance but also thermal stability at high temperatures of 300 ° C., and have low hygroscopicity, thermal expansion and dielectric constant. Therefore, various kinds of polyimide polymers have been developed using the characteristics of the polyimide, and are usefully used in various industries such as high heat-resistant films for electric and electronic materials, affection alignment films, semiconductor materials, materials for molded parts, and adhesives. have.

Existing linear polyimide polymers have mainly been studied to improve the mechanical and chemical properties by changing the chemical structure of the main chain (WO01 / 068742; and M. Barikani et al. , J. Appl. Polym. Sci. , 77 , 1102, 2000).

Recently, studies on hyperbranched polymers synthesized through polymerization from ABx-type monomers have been actively conducted. These hyperbranched polymers have lower solution viscosity, higher solubility in organic solvents, and easier mass production than linear polymers. One advantage is that it attracts much attention, especially in the fields of chemistry, biology and biomedical science. For example, after the synthesis of polyesters having hyperbranched structures (Kricheldorf, Polymer, 23, 1821, 1982), many kinds of hyperbranched polymers have been synthesized, specifically, polyamides and polyethers. ), Polymethacrylate, polyphenylene and poly (ether ketone) were synthesized in the form of hyperbranched polymers.

As part of this study, the present inventors have diligently studied to synthesize hyperbranched polyimide polymers with improved physical and chemical properties over existing linear polyimide polymers, and have shown that amine-terminated with excellent glass transition temperature, thermal stability and gas permeability. To provide hyperbranched polyimide (amine-terminated) or anhydride-terminated (hyminated).

Disclosure of Invention An object of the present invention is to provide a hyperbranched polyimide polymer having improved physical and chemical properties than a conventional linear polyimide polymer and a method of manufacturing the same.

In accordance with the above object, the present invention provides an amine-terminated or anhydride-terminated, hyperbranched polyimide polymer of the general formula (1).

의 구조를 가진 반복 단위로서, X_n은 n개의 X가 방사형으로 연결되어 있는 하이퍼브랜치를 나타내며, n은 8 내지 41의 정수이다.In Formulas 1 and 2, X is

As a repeating unit having a structure of, X _n represents a hyperbranch in which n pieces of X are connected radially, and n is an integer of 8 to 41.

According to the above another object, in the present invention, after the triamine (dianhydride) is reacted in a nitrogen atmosphere to obtain a polyamic acid, the dehydrating agent is added thereto to perform the imidization reaction, It provides a method for producing a hyperbranched polyimide polymer of the present invention.

Hereinafter, the present invention will be described in detail.

을 반복단위로 방사형으로 연결되어 하이퍼브랜치 고분자를 이루면서, 상기 화학식 1에 나타낸 바와 같이, 아민-말단화되거나, 상기 화학식 2에 나타낸 바와 같이, 안하이드라이드-말단화됨을 특징으로 한다.The hyperbranched polyimide of the present invention is X =

To form a hyperbranched polymer is radially connected in a repeating unit, as shown in the formula (1), amine-terminated, or as shown in the formula (2), characterized in that the anhydride-terminated.

Hyperbranched polyimide of the present invention is a polymer having a weight average molecular weight of 4,000 to 20,000, characterized in that the degree of branching (DB) is 0.3 to 0.8 range, the glass transition temperature is 250 to 280 ℃ range, The thermal stability factors T _5% (5% weight loss temperature) and T _10% (10% weight loss temperature) are high at 390 to 470 ° C. and 400 to 500 ° C., respectively, so that the linear linear polyimide polymer (glass transition temperature: 240-270 ° C., thermal stability factors T _5% and T _10% : 370-440 ° C. and 390-470 ° C., respectively, are superior in physical properties.

The hyperbranched polyimide polymer is a mixture of triamine and dianhydride under a nitrogen atmosphere to obtain a hyperbranched polyamic acid, and then, an imidization reaction is performed by adding a dehydrating agent thereto. It can be obtained by the manufacturing method of.

In the preparation method of the present invention, the starting material triamine is 2,4,6-triaminopyrrimidine (TAP) of the formula (3), 3,4,4 'of the formula (4) -Triaminodiphenyl ether (3,4,4'-triaminodiphenyl ether, TADE) or triamterene (TAT) of the formula (5) may be used, and dianhydride 4,4 -4,4-biphthalic anhydride (BPAD), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (3,3', 4,4) '-diphenylsulfone tetracarboxylic dianhydride (DSDA), 3,3', 4,4'-benzophenonetetracarboxylic dianhydride (3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) of Formula 8) 9,4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride (GFDA), 4,4'- oxydiphthal of formula 10 No or the like can be used hydride (4,4'-oxydiphthalic anhydride, ODPA) or a pyromellitic dianhydride (pyromellitic dianhydride, PMDA) of formula (11).

In addition, in the preparation method of the present invention, by controlling the reaction molar ratio of the reacted triamine and dianhydride, the terminal of the final hyperbranched polyimide can be determined, wherein the target branch is amine-terminated hyperbranched. In the case of polyimide, the reaction molar ratio of triamine and dianhydride is in the range of 1: 0.7 to 1.3, preferably 1: 0.9 to 1.1, respectively, and the hyper-anhydride-terminated compound In the case of branched polyimides, the reaction molar ratio of triamine and dianhydride is suitably in the range of 1: 1.5 to 2.5, preferably 1: 1.8 to 2.2, respectively.

The reaction of the two compounds may be carried out for 10 to 30 hours, preferably 15 to 20 hours at 0 to 40 ℃, preferably 20 to 40 ℃. In addition, the solvent used for the reaction of the two compounds is a polar organic solvent such as N, N-dimethyl acetamide, N-methylpyrrolidone, N, N-dimethylformamide and dimethyl sulfoxide, preferably N, N-dimethyl acetamide, which may be used in an amount of 5 to 20 weight times, preferably 8 to 12 weight times, relative to the total weight of triamine and dianhydride.

The imidation reaction may be performed at 140 to 170 ° C. for 5 to 15 hours. As the dehydrating agent, m-xylene, p-xylene and toluene may be used in an amount ranging from 3 to 15 times by weight with respect to the weight of the polyamic acid obtained in the previous process.

The amine-terminated or anhydride-terminated hyperbranched polyimide of the present invention thus prepared exhibits excellent glass transition temperature, thermal stability and gas permeability. It can be usefully used in various industries such as high heat resistant film for materials, love alignment film, semiconductor material, molded part material and adhesive.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

In the following examples, 2,4,6-triaminopyrimidine (content> 98%), 3,4,4'-triaminodiphenyl ether (content> 98%), triamterene (content> 98) %), 4,4'-biphthalic anhydride (content> 97%), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (content> 96%), 3,3 ', 4,4'-bentophenonetetracarboxylic dianhydride (content> 95%), 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (content> 98%), 4,4 '-Oxydiphthalic anhydride (content> 96%) and pyromellitic dianhydride (content> 95%) were used as is without purification of the first-class reagents of Tokyo Kasei Kogyo Co., Ltd. (Japan), reaction solvent and dehydration. As zero, respectively, N, N-dimethylacetamide (DMAc) and m-xylene, which are also the first-class reagents of Tokyo Kasei Kogyo Co., Ltd., were used.

Example 1

0.375 g (3 mmol) of 2,4,6-triaminopyrimidine (TAP), 0.883 g (3 mmol) of 4,4'-biphthalic anhydride (BPAD) and 15 ml of DMAc were placed in a 500 ml reactor. After heating to 30 ° C., the mixture was stirred for 15 hours under a nitrogen atmosphere. 10 ml of m-xylene was added thereto and reacted at 160 ° C. for 7 hours. The reaction mixture was cooled to room temperature and added to methanol to obtain a yellow precipitate. The precipitate obtained was filtered with a filter and then dried under vacuum at 80 ° C. for 24 hours to prepare an amine-terminated BPAD-TAP hyperbranched polyimide (yield: 83%).

Example 2

Anhydride-terminated BPAD-TAP hyperbranched polyimide was prepared in the same manner as in Example 1, except that 0.188 g (1.5 mmol) of 2,4,6-triaminopyrimidine (TAP) was used ( Yield: 87%).

Example 3

Example 1, except that 1.075 g (3 mmol) of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA) was used instead of 4,4'-biphthalic anhydride. An amine-terminated DSDA-TAP hyperbranched polyimide was prepared in the same manner as (yield: 82%).

Example 4

Anhydride-terminated DSDA-TAP hyperbranched polyimide was prepared in the same manner as in Example 3, except that 0.188 g (1.5 mmol) of 2,4,6-triaminopyrimidine (TAP) was used ( Yield: 88%).

Example 5

Amine-terminated DMDA-TAP hyperbranch in the same manner as in Example 1, except that 0.654 g (3 mmol) of pyromellitic dianhydride (DMDA) was used instead of 4,4'-biphthalic anhydride. Polyimide was prepared (yield: 82%).

Example 6

Anhydride-terminated DMDA-TAP hyperbranched polyimide was prepared in the same manner as in Example 5, except that 0.188 g (1.5 mmol) of 2,4,6-triaminopyrimidine (TAP) was used ( Yield: 86%).

Measurement of physical properties of hyperbranched polyimide

FT-IR and ¹ H NMR analysis results of the hyperbranched polyimide prepared in Examples 1 and 2 are shown in FIGS. 1 and 2, respectively.

Number average molecular weight, weight average molecular weight, degree of branching, glass transition temperature and thermal characteristics (thermal stability factor T _{5 %} (temperature at 5% weight reduction)) according to the following method for the compounds prepared in Examples 1 to 6 And T _{10 %} (temperature at 10% weight loss).

- Molecular Weight

The number average molecular weight and the weight average molecular weight of the target compound were measured by using GPC (Waters 2690 gel permeation chromatography), at this time was used as a diluent DMF (dimethylfuran).

Degree of branching (DB)

In the hyperbranched polymer, there are three types of repeating unit structures of dendritic, linear, or terminal depending on the number of unreacted monomer functional groups. Accordingly, the degree of branching of each target compound was calculated according to the following formula.

Branch degree (BD) = 2D / (2D + L)

Where D and L are the number of dendritic and linear unit structures, respectively.

-Glass transition temperature

The glass transition temperature of the target compound was measured under nitrogen crisis by using a differential scanning calorimetry (Perkin Elmer, DSC 6) at a temperature increase rate of 10 ° C / min in the range of 30-300 ° C.

Thermal properties

The thermal properties of the compounds were analyzed by TGA (du Pont TGA-2950) analyzer in a nitrogen atmosphere at a temperature increase rate of 10 ℃ / min in the range 30-800 ℃.

The test results of the compounds of Examples 1 to 6 are shown in Table 1 below, and in particular, the results of FT-IR, ¹ H NMR and TGA analysis for the compounds of Examples 1 and 2 are shown in FIGS. 1 to 3, respectively.

As a result, as shown in Table 1, the amine-terminated or anhydride-terminated hyperbranched polyimide according to the present invention has excellent glass transition temperature and thermal stability. It confirmed that it was shown.

Amine-terminated or anhydride-terminated hyperbranched polyimide according to the present invention exhibits excellent glass transition temperature, thermal stability and gas permeability. It can be usefully used in various industries such as a high heat resistant film, an affection alignment film, a material for semiconductors, a material for molding parts and an adhesive.

Claims (14)

A hyperbranched polyimide having an amine-terminated structure of Formula 1 or an anhydride-terminated structure of Formula 2 having a weight average molecular weight ranging from 6,000 to 20,000: Formula 1

Formula 2

In Formulas 1 and 2, X is

or

As a repeating unit having a structure of, X _n represents a hyperbranch in which n pieces of X are connected radially, and n is an integer of 8 to 41. delete The method of claim 1, Hyperbranched polyimide, characterized in that the degree of branching (DB) ranges from 0.3 to 0.8. The method of claim 1, Hyperbranched polyimide, characterized in that the glass transition temperature ranges from 250 to 280 ℃. The method of claim 1, Hyperbranched polyimide, characterized in that the thermal stability factors T _5% and T _{10% range} from 390 to 470 ° C, and 400 to 500 ° C, respectively. 2,4,6-triaminopyrimidine and 4,4-biphthalic anhydride or 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride are reacted under a nitrogen atmosphere to obtain a polyamic acid. A method for preparing an amine-terminated or anhydride-terminated hyperbranched polyimide of formula (1), comprising obtaining and then carrying out an imidation reaction by adding a dehydrating agent thereto. delete delete The method of claim 6, Using triaminopyrimidine and dianhydride in molar ratios ranging from 1: 0.7 to 1.3, to obtain an amine-terminated hyperbranched polyimide of formula (I). The method of claim 6, A process for producing an anhydride-terminated hyperbranched polyimide of formula (2) using triaminopyrimidine and dianhydride in molar ratios ranging from 1: 1.5 to 2.5. The method of claim 6, The reaction method of triaminopyrimidine and dianhydride is performed for 10 to 30 hours at 0-40 degreeC. The method of claim 6, The reaction of triaminopyrimidine and dianhydride is carried out in at least one organic solvent selected from N, N-dimethyl acetamide, N-methylpyrrolidone, N, N-dimethylformamide and dimethyl sulfoxide. Manufacturing method. The method of claim 6, The dehydrating agent in the imidization reaction, characterized in that selected from m-xylene (m-xylene), p-xylene (p-xylene) and toluene (toluene). The method of claim 6, The imidation reaction is carried out at 140 to 170 ° C for 5 to 15 hours.

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