KR101845148B1

KR101845148B1 - Method for preparing polyamic acid, polyimide prepared using the same and display device comprising the same

Info

Publication number: KR101845148B1
Application number: KR1020160031715A
Authority: KR
Inventors: 조재철
Original assignee: 삼성에스디아이 주식회사
Priority date: 2016-03-16
Filing date: 2016-03-16
Publication date: 2018-04-03
Also published as: KR20170107855A

Abstract

A step of adding diamine and dianhydride and polymerizing the diamine and dianhydride, wherein at least one of the dianhydride and the diamine is charged in the form of granules, and a process for producing And a display element comprising the same.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for producing polyamic acid, a polyimide prepared from the same, and a display device comprising the polyimide,

The present invention relates to a process for producing polyamic acid, a polyimide prepared from the process, and a display device including the polyimide.

The polyamic acid may be prepared by polymerizing a diamine and a dianhydride. The polyamic acid can be thermally imidized or chemically imidized into a polyamide.

The diamine and dianhydride are each in the form of a fine powder, and are usually prepared by putting the powder form into the polymerization reactor during polymerization. Particularly, the powdered dianhydride is slowly added to the diamine completely dissolved in the polar solvent. However, since powdered dianhydride is not smoothly controlled in injection amount, it is difficult to produce a homogeneous polymerized product, and since a powdered dianhydride is inevitably attached to a polymerization reactor, a production loss of the polyamic acid may be generated, There is a problem of dust generation of dianhydride. In addition, the powdered dianhydride is not adsorbed to each other, and can be adsorbed to each other by water or the like, but in such a case, the acid anhydride group of the dianhydride is damaged and can not react with the diamine. However, the powdery dianhydride has a high reaction rate, which makes it possible to produce a polyamic acid having a high viscosity and a high production yield of polyamic acid. Accordingly, there is a need for a method for producing polyamic acid which can produce a polyamic acid having a high production yield of polyamic acid and a desired viscosity by minimizing a difference in contrast reaction rate when using powdery dianhydride while solving the above problems do.

The background art of the present invention is disclosed in Korean Patent Publication No. 2013-0075423.

A problem to be solved by the present invention is to provide a method for producing a polyamic acid which can facilitate the reaction between a diamine and a dianhydride in a predetermined amount.

Another problem to be solved by the present invention is to provide a method for producing polyamic acid which can solve the problem of generation of dust due to the input of powdered diamine or dianhydride.

Another object to be solved by the present invention is to provide a polyamic acid capable of producing a polyamic acid having a high production yield of polyamic acid and having a desired viscosity by minimizing the difference in the rate of contrast reaction when powdered dianhydride is used Method.

The method for producing a polyamic acid according to the present invention comprises the steps of charging a diamine and a dianhydride and polymerizing the diamine and a dianhydride, and the dianhydride may be introduced into a granular form.

The polyimide of the present invention can be prepared from a polyamic acid prepared by the process for producing a polyamic acid of the present invention.

The display element of the present invention may include the polyimide of the present invention.

The present invention provides a process for preparing polyamic acid which can facilitate the reaction between a predetermined amount of diamine and dianhydride.

The present invention provides a method for producing polyamic acid which can solve the problem of generation of dust due to the input of powdered diamine or dianhydride.

The present invention provides a method for producing a polyamic acid which can produce a polyamic acid having a high production yield of polyamic acid and a desired viscosity by minimizing a difference in the rate of contrast reaction when a dianhydride powder is used.

The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

As used herein, unless specifically stated otherwise, at least one hydrogen atom of the functional group may be replaced by a hydroxyl group, an unsubstituted C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C3 to C10 cycloalkyl group, C20 aryl group, C7-C20 arylalkyl group, C6-C20 aryl group substituted with C1-C10 alkyl group, or C1-C10 alkoxy group, Quot; and "alkyl group" may be linear or branched.

Hereinafter, a method for producing polyamic acid according to an embodiment of the present invention includes a step of adding a diamine and a dianhydride to polymerize the diamine and a dianhydride, The hydride may be injected in the form of a granule. The method of producing polyamic acid in this embodiment can prevent the generation of dust due to the conventional powdered dianhydride and the adhering of dianhydride to the wall of the reaction vessel where polymerization takes place by the introduction of the dianhydride into the granular form, The amount of the remaining dianhydride or diamine remaining unreacted is minimized, thereby making it possible to increase the production yield of polyamic acid and to produce polyamic acid having a desired viscosity.

First, the diamine and dianhydride will be described in detail.

The diamine may form a polyamic acid by polymerization with dianhydride and then form a polyimide by self imidization reaction. The diamine may be in liquid or powder form. Specifically, when the diamine is in powder form, the average particle diameter (D50) may be 0.001 mm to 10.0 mm. In the above range, when the granular dianhydride is used, the production yield of the polyamic acid can be improved. The diamine may be introduced simultaneously with or after the dianhydride, but it can be easily introduced into the reaction vessel in which the polymerization takes place before the dianhydride is introduced, thereby facilitating the reaction with the dianhydride.

The diamine may include, but is not limited to, a compound represented by the following formula (1A) or (1B)

&Lt;

NH ₂ -X-Ar ₁ -Y-NH ₂

&Lt; Formula 1B >

NH ₂ -X-Ar ₁ -Z-Ar ₂ -Y-NH ₂

(Wherein Ar ₁ and Ar ₂ each independently represent a substituted or unsubstituted C6 to C20 arylene group,

X and Y are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group,

Z is a single bond, - (C = O) - , -O-, -S-, - (S = O) -, -SO 2 -, or -ORO * - * (wherein, * is connected to the element region, R is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C10 arylene group, or a substituted or unsubstituted C7 to C20 arylalkylene group).

For example, the diamine may be phenylenediamine, diaminophenylsulfone, oxydianiline, methylenedianiline, and the like. Specifically, the diamine may include any one of the following general formulas (1-1) to (1-5) and their respective isomers: wherein the "isomer" is a compound having a different amine group (-NH ₂ ) For example, para-phenylenediamine in the case of the following formula 1-1, as well as ortho-phenylenediamine, which is an isomer thereof, or meta-phenylenediamine:

&Lt; Formula 1-1 >

(1-2)

&Lt; Formula 1-5 >

The dianhydride can form a polyamic acid by polymerization with a diamine, and then form a polyimide by self imidization reaction. The dianhydrides may have a granular shape. As used herein, "granules" refers to particles having a particle diameter larger than that of the powder by agglomeration of powder-like particles unlike powders, and may mean a three-dimensional shape having a predetermined length and a cross section having a predetermined diameter. Specifically, the dianhydride may be in the form of a pellet, a bead, or a plate. Specifically, the dianhydride may have a pellet shape with an aspect ratio of 0.1 to 1,000, a cross-sectional diameter of 1 to 20 mm, specifically 4 to 10 mm, and a length of 1 to 20 mm, specifically 5 to 10 mm . Within the above range, it is possible to prevent the phenomenon of adhering dianhydride to the wall of the reaction vessel in which dust generation due to dianhydride occurs, the polymerization can occur, enable quantitative introduction of dianhydride, inhibit the sedimentation of dianhydride So that the reaction rate can be high. Particularly, in the case of using the above-mentioned powder type diamine, the production yield of polyamic acid can be increased. The aspect ratio means the ratio of the length to the diameter of the cross section of the granular shape.

By controlling the solubility in organic solvents, the dianhydride can minimize the reduction in the rate of reaction with the contrast diamine when the dianhydride on the powder is introduced.

The granular dianhydride may be prepared by granular shaping methods known to those skilled in the art. For example, powdered dianhydride may be produced in a pellet form by being poured into a die having a predetermined diameter and then pressing at a predetermined pressure.

The dianhydride may include, but is not limited to, a compound represented by the following formula 2:

(2)

(Wherein R ^d and R ^e are each independently a substituted or unsubstituted C1 to C5 alkyl group,

m and p each independently represent an integer of 0 to 3,

Z ^a represents a single bond, - (C = O) -, -O-, -S-, - (S = O) -, -SO ₂ - , R is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C10 arylene group, or a substituted or unsubstituted C7 to C20 arylalkylene group)).

For example, the dianhydride may be selected from the group consisting of biphenyl tetracarboxyl dianhydride, bis (dicarboxyphenyl) hexafluoropropanediamine hydride, bis [(dicarboxyphenoxy) phenyl] propanediamine hydride, benzophenone tetracarboxy Dianhydride, pyromellitic dianhydride, and the like.

Specifically, the dianhydride may include any of the following formulas (2-1) to (2-8), each of the isomers thereof:

&Lt; Formula (2-1)

&Lt; Formula (2-2)

Hereinafter, a method for producing the polyamic acid of the present invention will be described.

The order of introduction of diamine and dianhydride is not particularly limited. For example, a diamine may be added to a reaction vessel for polymerization, then a dianhydride may be introduced, a dianhydride may be introduced and then a diamine may be introduced, or a dianhydride and a diamine may be simultaneously introduced.

The diamine and the dianhydride may be contained in a molar ratio of the diamine: dianhydride = 1: 0.5 to 1: 2. Within this range, the production yield of polyamic acid may be high.

In the polymerization of diamine and dianhydride, the reaction temperature may be -20 ° C to 80 ° C, specifically 25 ° C to 30 ° C, and the reaction time may be 1 hour to 24 hours, specifically 1 hour to 8 hours. Within this range, the production yield of polyamic acid may be high.

Upon polymerization of diamine and dianhydride, a polyamic acid can be formed. The diamine and dianhydride may be polymerized in the presence of an organic solvent for the polyimidation of the polyamic acid, although they may be polymerized without a solvent. The organic solvent is a polar solvent in which the polyamic acid is dissolved. Examples of the organic solvent include cresol, dimethylsulfoxide, acetone, diethyl acetate, dimethylformamide, dimethylacetamide, meta-cresol, &Lt; / RTI > In addition, it may contain a low-boiling solution such as tetrahydrofuran, chloroform or a low-absorbency solvent such as gamma-butyrolactone.

The polyamic acid according to one embodiment of the present invention has a polyamic acid solution viscosity of 4,900 cps or more, specifically 4,900 cps to 7,000 cps at 25 ° C after 5 hours of polymerization, The manufacturing yield can be increased.

Hereinafter, a method for producing polyamic acid according to another embodiment of the present invention will be described.

The method for producing polyamic acid according to this embodiment is substantially the same as the method for producing polyamic acid according to one embodiment of the present invention, except that diamine is added in granular form instead of dianhydride. The diamines may be prepared in the form of pellets using methods known to those skilled in the art.

The method for producing polyamic acid according to this embodiment is substantially the same as the method for producing polyamic acid according to one embodiment of the present invention, except that both of dianhydride and diamine are added in a granular form.

The polyimide of the present invention is a high heat resistant material having a high glass transition temperature and a low thermal expansion rate and can be used as a display device. Specifically, the polyimide may have a glass transition temperature of 200 占 폚 or higher, specifically 250 占 폚 to 350 占 폚, a thermal expansion rate of 10 ppm / 占 폚 or lower, specifically, -10 ppm / 占 폚 to 5 ppm / 占 폚. In the above range, it can be used as a heat-resistant material in a display device. The polyimide of the present invention can be prepared by imidizing a polyamic acid prepared by the process for producing a polyamic acid of the present invention. Imidization depends on heat or chemicals, and specific methods are well known to those skilled in the art.

The display element of the present invention may be formed of the polyimide of the present invention and may include a coating layer, a protective layer, and the like.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples.

Manufacturing example One

Pellet-shaped dianhydride (diameter 8 mm, length 10 mm) was prepared by pressing 3,3 ', 4,4'-biphenyltetracarboxyl dianhydride (BPDA) (Formula 2-3, Mitsubishi Chemical).

Manufacturing example 2

(Diameter 5 mm, length 10 mm) was prepared by pressing 3,3 ', 4,4'-biphenyltetracarboxyl dianhydride (Mitsubishi Chemical Co., Ltd.).

Manufacturing example 3

Pellet-shaped dianhydride (diameter 5 mm, length 6 mm) was prepared by pressing 3,3 ', 4,4'-biphenyltetracarboxyl dianhydride (Formula 2-3, Mitsubishi Chemical).

(1) diamine: para-phenylenediamine (Formula 1-1, Sigma Aldrich, powder form)) (PPD)

(2) Dianhydride

(2-1) Synthesis of 3,3 ', 4,4'-biphenyltetracarboxylidyanhydride (in the form of pellets) of Production Example 1

(2-2) Synthesis of 3,3 ', 4,4'-biphenyltetracarboxyl dianhydride (pellet shape) of Production Example 2

(2-3) 3,3 ', 4,4'-biphenyltetracarboxylidyanhydride (in the form of pellets) of Production Example 3

(2-4) 3,3 ', 4,4'-biphenyltetracarboxyl dianhydride (Formula 2-3, Mitsubishi Chemical, powder form)

(3) Organic solvent: N-methyl-2-pyrrolidone (NMP)

Example One

Water jacket and a stirrer and 1,600 grams of NMP was added to a 3 L glass reactor to which nitrogen gas was connected and the temperature was maintained at 25 ° C. The stirrer was operated to set the stirring speed at 100 rpm, and 82.13 grams (0.76 mol) of PPD was added to the reactor. The funnel was used to inject PPD and the PPD loss was minimized by washing with a small amount of NMP. After confirming that all of the charged PPD was dissolved, 217.87gram (0.74 mol) of BPDA in the form of pellets of Production Example 1 was added to the reactor. The time required for all the BPDA in the pellet form to dissolve was less than 30 minutes. The reactor jacket temperature was maintained at 25 ° C., and the reaction was continued for 5 hours to prepare polyamic acid. After 5 hours of polymerization, the solution is recovered in the reactor and the viscosity of the solution is measured. The viscosity of the polymerization solution was 5,200 cps at 25 캜.

Example 2

A polyamic acid was prepared in the same manner as in Example 1, except that pellet-shaped BPDA of Production Example 2 was used instead of BPDA of Production Example 1. The time required for all of the pelletized BPDA to dissolve was less than 15 minutes. After 5 hours of polymerization, the solution was recovered in the reactor and the viscosity of the solution was 4,900 cps at 25 ° C.

Example 3

A polyamic acid was prepared in the same manner as in Example 1, except that pellet-shaped BPDA of Production Example 3 was used instead of BPDA of Production Example 1. The time required for all of the BPDA in the pellet form to dissolve was less than 5 minutes. After 5 hours of polymerization, the solution was recovered in the reactor and the viscosity of the solution was 5,100 cps at 25 ° C.

Example 4

78,028 grams of NMP was added to a 150 L glass reactor equipped with a water jacket and a stirrer and connected with nitrogen gas, and the temperature was maintained at 25 ° C. The stirrer was operated to set the stirring speed at 100 rpm, and 3,770 grams (34.86 mol) of PPD was added to the reactor. The PPD was injected using a funnel and washed with a small amount of NMP to minimize the loss of PPD. After confirming that all of the charged PPD was dissolved, 10,000 grams (33.99 mol) of BPDA in the form of pellets of Production Example 1 was added to the reactor. The time required for all the BPDA in the pellet form to dissolve was less than 30 minutes. The reactor jacket temperature was maintained at 25 ° C., and the reaction was continued for 5 hours to prepare polyamic acid. After 5 hours of polymerization, the solution is recovered in the reactor and the viscosity of the solution is measured. The viscosity of the polymerization solution was 5,200 cps at 25 캜.

Example 5

A polyamic acid was prepared in the same manner as in Example 4, except that pellet-shaped BPDA of Production Example 3 was used instead of BPDA of Production Example 1. The time required for all of the BPDA in the pellet form to dissolve was less than 5 minutes. After 5 hours of polymerization, the solution was recovered in the reactor and the viscosity of the solution was 5,100 cps at 25 ° C.

Comparative Example One

Water jacket and stirrer were attached and 1,500 grams of NMP was added to a 3 L glass reactor to which nitrogen gas was connected, and the temperature was kept at 25 ° C. The stirrer was operated to set the stirring speed at 100 rpm, and 82.13 grams (0.76 mol) of PPD was added to the reactor. The PPD was injected using a funnel and washed with a small amount of NMP to minimize the loss of PPD. After confirming that all of the charged PPD was dissolved, 217.87gram (0.74 mol) of powdery BPDA was added to the reactor. It took 10 minutes to inject BPDA. The vessel containing BPDA, the funnel used for the BPDA injection, and the BPDA on the inner wall of the reactor and the agitator bar for the polymerization were washed with NMP so as to be supplied with the BPDA. The reactor jacket temperature was maintained at 25 ° C., and the reaction was continued for 5 hours to prepare polyamic acid. After 5 hours of polymerization, the solution is recovered in the reactor and the viscosity of the solution is measured. The viscosity of the polymerization solution was 4,700 cps at 25 캜.

Comparative Example 2

In Comparative Example 1, except for the vessel containing BPDA, the funnel used for the input of BPDA, and the step of washing the BPDA on the inner wall of the reactor and the agitator rod for polymerization by NMP, And polyamic acid was prepared in the same manner. The viscosity of the polymerization solution was 3,700 cps at 25 캜.

Comparative Example 3

78,028 grams of NMP was added to a 150 L glass reactor equipped with a water jacket and a stirrer and connected with nitrogen gas, and the temperature was maintained at 25 ° C. The stirrer was operated to set the stirring speed at 100 rpm, and 3,770 grams (34.86 mol) of PPD was added to the reactor. The PPD was injected using a funnel and washed with a small amount of NMP to minimize the loss of PPD. After confirming that all of the charged PPD was dissolved, 10,000 grams (33.99 mol) of powdery BPDA was added to the reactor. The reactor jacket temperature was maintained at 25 ° C., and the reaction was continued for 5 hours to prepare polyamic acid. After 5 hours of polymerization, the solution is recovered in the reactor and the viscosity of the solution is measured. The viscosity of the polymerization solution was 3,000 cps at 25 캜.

PPD BPDA Viscosity (cps) of polyamic acid solution Input (gram) shape Input (gram) shape Example 1 82.13 powder 217.87 Pellets 5,200 Example 1 82.13 powder 217.87 Pellets 4,900 Example 3 82.13 powder 217.87 Pellets 5,100 Example 4 3,770 powder 10,000 Pellets 5,200 Example 5 3,770 powder 10,000 Pellets 5,100 Comparative Example 1 82.13 powder 217.87 powder 4,700 Comparative Example 2 82.13 powder 217.87 powder 3,700 Comparative Example 3 3,770 powder 10,000 powder 3,000

As shown in Table 1, the polyamic acid solution of the present invention had a high viscosity of the polyamic acid solution finally prepared even though dianhydride was pelletized. Accordingly, the method of the present invention for producing polyamic acid enables the production of polyamic acid having a high production yield and a desired viscosity as compared with a comparative example in which powder is added. Further, there is no problem of generation of dust as compared with the comparative example in which dianhydride is pelletized and added into powder.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

Introducing a diamine and a dianhydride, and polymerizing the diamine and a dianhydride,
Wherein at least one of the dianhydride and the diamine is charged in a granular form.

The method of producing a polyamic acid according to claim 1, wherein the granular shape is pellet, bead or plate shape.

3. The method of producing a polyamic acid according to claim 2, wherein the pellets have a cross-sectional diameter of 1 mm to 20 mm and a length of 1 mm to 20 mm.

The method for producing a polyamic acid according to claim 1, wherein the diamine is added to a reaction vessel for the polymerization, and then the dianhydride is introduced,
Wherein the diamine is in powder form and the dianhydride is in the form of a pellet.

5. The method of producing a polyamic acid according to claim 4, wherein the pellet-shaped dianhydride is produced by pressing a dianhydride powder.

The process for producing polyamic acid according to claim 1, wherein the diamine and the dianhydride are introduced at a mole ratio of 1: 0.5 to 1: 2.