KR20160026505A - Analytical Method and System for Monomer Composition of Polyamic acid having cinnamate group - Google Patents

Abstract

The present invention relates to an analyzing method of a monomer composition of polyamic acid comprising a cinnamate group, and an analyzing system using the same. The analyzing method comprises the step of: (a) preparing a first sample by hydrolysis of polyamic acid comprising a cinnamate group; (b) preparing a second sample by alcoholylysis of the polyamic acid comprising the cinnamate group; (c) collecting an organic layer through respectively liquid-liquid extracting the first sample and the second sample; and (d) respectively analyzing samples of the collected organic layer through a GC/MS analysis. According to the present invention, analysis about the monomer composition of polyamic acid comprising a cinnamate group can be easily carried out.

Description

TECHNICAL FIELD The present invention relates to a method for analyzing a monomer composition of a polyamic acid including a cinnamate group,

The present invention relates to a method and an analysis system for analyzing monomer composition of a polyamic acid containing a cinnamate group.

In a liquid crystal display (LCD), a liquid crystal alignment layer makes contact with liquid crystal molecules to uniformly orient liquid crystal molecules. The liquid crystal alignment layer is a key material of liquid crystal driving that uniformly aligns the liquid crystal in one direction so that the liquid crystal can perform the function of opening and closing polarized light well.

The liquid crystal alignment characteristic of the liquid crystal alignment film determines the display quality of the liquid crystal display. A multi-domain mode in which liquid crystal alignment directions are divided by dividing pixels into various regions in a liquid crystal alignment mode, a vertical alignment mode (VA) in which a liquid crystal alignment direction is vertical, An IPS (In-Plane-Switching) mode in which an electrode is positioned is being developed.

A photo alignment film for producing a non-contact type liquid crystal alignment film without using the rubbing method in the alignment film manufacturing process has been developed. The light scattering is a method of orienting the liquid crystal by arranging the surface molecules of the substrate in a certain direction using a photoreaction. In order to apply a photo alignment layer to a liquid crystal display, a polymer material including a cinnamate group is used.

On the other hand, in the research and development of the photo alignment layer, a composition analysis method is indispensably required to confirm the composition of the developed product. Therefore, it is necessary to identify a polyamic acid including a cinnamate group used in a photo-alignment layer. For this purpose, a monomer composition analysis method and a monomer ratio analysis method are indispensable .

In this regard, the method of analyzing the monomer composition of polyamic acid is a method using conventional Pyrolysis GC-MS or a method of analyzing polyimide film by derivatization with tetramethylammonium hydroxide (TMAH) as disclosed in Korean Patent Publication No. 1995-0029297 However, it is difficult to interpret the data due to the generation of complicated pyrolysis products, and in the case of dianhydride, the derivatization is not easily occurred, which makes it difficult to grasp the monomer components.

Korean Patent Publication No. 1995-0029297

The conventional analysis method is difficult to analyze due to complicated pyrolysis products, and the derivation of the dianhydride component is not proceeded easily.

In order to solve this problem, the present invention provides a method for analyzing monomer composition of a polyamic acid including a cinnamate group by using alcoholysis and hydrolysis as a pretreatment method do.

That is, there is provided a method for analyzing monomer composition of a polyamic acid including a cinnamate group which is free from the interference effect due to a complicated thermal decomposition product and is easily detected by detecting a desired monomer (dianhydride and diamine) as a main component .

In order to achieve the above object, the present invention provides a method for preparing polyamic acid, comprising: (a) preparing a first sample by hydrolysis of a polyamic acid containing a cinnamate group; (b) alcoholysis of a polyamic acid including a cinnamate group to prepare a second sample; (c) recovering the organic layer through liquid-liquid extraction from the first sample and the second sample, respectively; And (d) subjecting the recovered organic layer samples to GC / MS analysis, respectively, to provide a method for analyzing the monomer composition of a polyamic acid including a cinnamate group. According to a preferred embodiment of the present invention, (e) NMR measurement of polyamic acid containing a cinnamate group can be further included.

(A) a hydrolysis module for preparing a first sample by hydrolysis of a polyamic acid containing a cinnamate group; (b) an alcohol decomposition module for preparing a second sample by alcoholysis of a polyamic acid including a cinnamate group; (c) a recovery module for recovering the organic layer through liquid-liquid extraction of the first sample and the second sample, respectively; And (d) an analysis module for analyzing samples of the recovered organic layer by GC / MS. The present invention also provides a system for analyzing monomer composition of polyamic acid comprising Cinnamate group.

According to a preferred embodiment of the present invention, (e) a module for NMR measurement of polyamic acid containing a cinnamate group may be further included.

The present invention also provides a computer readable recording medium on which a program for executing the above method is recorded.

The present invention uses alcoholysis and hydrolysis methods as pretreatment methods to prevent the interference caused by a complicated thermal decomposition product and to detect a desired monomer (dianhydride and diamine) as a main component and to produce a cinnamate group) of the polyamic acid can be easily analyzed.

Further, the chemical structure of the polyamic acid including the cinnamate group can be determined by analyzing the molar ratio based on the monomer composition analysis data of the polyamic acid including the cinnamate group.

1 is a graph showing GC / MS data of a hydrolyzed sample of Example 1 of the present invention.
2 is a table showing the peaks of hydrolyzed samples of Example 1 of the present invention and the chemical formulas of the compounds.
3 is a graph showing GC / MS data of an alcohol decomposed sample of Example 1 of the present invention.
4 is a table showing the peaks of the alcohol decomposed sample and the chemical formula of the compound of the present invention.
5 is a ¹ H NMR spectrum of Example 2 of the present invention.
6 is a ¹ H edit NMR and ¹ H NMR comparison spectrum of Example 2 of the present invention.
7 is a gCOSY NMR spectrum of Example 2 of the present invention.
8 is a gHMBC NMR spectrum of Example 2 of the present invention.

Hereinafter, the present invention will be described in detail.

The method for analyzing the monomer composition of a polyamic acid comprising a cinnamate group according to the present invention comprises the steps of: (a) hydrolysis of a polyamic acid containing a cinnamate group to prepare a first sample; ; (b) alcoholysis of a polyamic acid including a cinnamate group to prepare a second sample; (c) recovering the organic layer through liquid-liquid extraction from the first sample and the second sample, respectively; And (d) GC / MS analysis of the recovered organic layer samples.

According to a preferred embodiment of the present invention, the polyamic acid including the cinnamate group may be preferably a polyamic acid including a cinnamate group used in a photo alignment layer.

The method for analyzing the monomer composition of a polyamic acid including a cinnamate group according to the present invention comprises hydrolysis of a polyamic acid containing a cinnamate group in step (a) .

The hydrolysis in step (a) is for analyzing the components of the diamine monomer in the polyamic acid including a cinnamate group, and hydrolysis is performed using a strong base.

In the present invention, the strong base is not particularly limited as long as it is a commonly used strong base, but NaOH and the like can be preferably used. The amount of the strong base to be added in the hydrolysis is not particularly limited as long as sufficient hydrolysis can be performed, but it is preferably 10 to 50 times as much as the total amount of the polyamic acid including the cinnamate group .

The hydrolysis in step (a) is preferably carried out at 100 to 150 ° C for 2 to 12 hours, more preferably at 110 to 130 ° C for 4 to 8 hours in order to obtain a sufficient hydrolysis effect . If the reaction temperature of the hydrolysis is lower than 100 ° C, there is a problem that the hydrolysis time becomes longer. When the reaction temperature is higher than 150 ° C, decomposition is promoted too much to cause an undesired compound.

In the method of analyzing the monomer composition of a polyamic acid containing a cinnamate group according to the present invention, in step (b), a polyamic acid containing a cinnamate group is subjected to alcoholysis Prepare two samples.

The alcoholysis in the step (b) is for analyzing the dianhydride monomer component of the polyamic acid including the cinnamate group. The alcoholysis is performed using strong acid and alcohol, .

In the present invention, the strong acid is not particularly limited as long as it is a commonly used strong acid, but sulfuric acid and the like can be preferably used. In the present invention, the alcohol is not particularly limited as long as it is a commonly used alcohol, and preferably at least one selected from the group consisting of methanol, ethanol, n-propanol and isopropanol, and most preferably methanol To decompose methanol. The amount of strong acid to be added in the alcoholysis is not particularly limited as long as alcoholysis is sufficiently performed, but it is preferably 10 to 50 times as much as the total amount of polyamic acid including cinnamate group . ≪ / RTI > In addition, the amount of alcohol added in the alcoholysis is not particularly limited as long as sufficient hydrolysis can be performed, but it is preferably about 50 to 200 times as much as the total amount of the polyamic acid including a cinnamate group Can be injected.

The alcoholysis in step (b) is preferably carried out at 100 to 150 ° C for 4 to 12 hours, more preferably at 4 to 8 hours at 110 to 130 ° C in order to obtain a sufficient alcoholysis effect. For a period of time. When the reaction temperature of the alcoholysis is lower than 100 ° C, alcoholysis time becomes longer. When the reaction temperature is higher than 150 ° C, decomposition is promoted too much to cause an undesired compound.

Thereafter, the method for analyzing the monomer composition of a polyamic acid containing a cinnamate group according to the present invention is characterized in that in the step (c), the samples of the steps (a) and (b) Liquid-Liquid Extraction) to recover the organic layer.

That is, in the step (c), the first sample in which the polyamic acid including the cinnamate group is hydrolyzed in the step (a) and the cinnamate group in the step (b) Liquid-Liquid Extraction is performed on each of the second alcohol-decomposed samples of polyamic acid. In the present invention, liquid-liquid extraction is carried out after the samples hydrolyzed in step (a) are cooled at room temperature so that the liquid-liquid extraction can proceed sufficiently, In step (b), the alcohol-decomposed samples are cooled at room temperature, and alcohol is volatilized under nitrogen, followed by liquid-liquid extraction.

Liquid-Liquid Extraction can separate an organic layer using an organic solvent. The organic solvent is not particularly limited as long as it is ordinarily used, but chloroform, ethyl ether, ethyl Acetate can be used. In addition, water is additionally added to the sample in addition to the organic solvent in order to remove strong acid in the liquid-liquid extraction of the alcohol-decomposed sample in the step (b).

Further, it is preferable that the organic solvent is added to the mixture and shaken for 30 minutes or more so that the liquid-liquid extraction can proceed sufficiently. Thereafter, when the liquid-liquid extraction is completed, the organic solvent layer (organic layer) is recovered after allowing the layer separation to proceed completely.

Thereafter, in the method for analyzing the monomer composition of the polyamic acid including the cinnamate group according to the present invention, the collected organic solvent layer samples are analyzed by GC / MS in step (d).

For the GC / MS analysis of the samples, the samples of the organic solvent layer obtained in the step (c) were completely dried at room temperature under nitrogen, extracted with an organic solvent and dissolved well. The obtained samples were analyzed by GC / MS do.

The analytical instrument used for the GC / MS analysis is not particularly limited as long as it is an analytical instrument used for gas chromatography and mass spectrometry. In the present invention, GC / MS (Agilent 7890A GC system with 5975C inert XL mass selective detector, Agilent Technologies Korea).

Meanwhile, the method for analyzing the monomer composition of a polyamic acid including a cinnamate group of the present invention may further include (e) NMR measurement of a polyamic acid containing a cinnamate group.

In the present invention, the molar ratio of the polyamic acid monomers including the cinnamate group can be analyzed by performing NMR measurement at this stage based on the analysis data of the GC / MS.

According to a preferred embodiment of the present invention, the NMR measurement may be carried out by including at least one selected from ¹ H NMR, ¹ H edit NMR, and 2D NMR.

However, it is not limited to the above-mentioned NMR, and it can be freely used as long as it is commonly used. The above 2D NMR may be used as long as it is commonly used, and preferably gCOSY and / or gHMBC may be used.

In order to carry out the ¹ H NMR, ¹ H edit NMR, and 2D NMR, the polyamic acid containing the cinnamate group is dissolved in a deuterium solvent such as DMSO-d6, DMF (N, N-dimethyl-foramide) And NMP (N-methylpyrrolidone) -d9 may be used as a solvent and used as a solvent. The sampling means pre-treatment, and a polyamic acid containing a cinnamate group as a sample can be dissolved in the solvent and subjected to NMR.

The ¹ H edit NMR used in the present invention can be performed by performing an experiment under the condition of number of increment 1 using HSQCAD (Heteronuclear Single Quantum Coherence ADiabatic) pulse sequence.

Specifically, the difference between ¹ H NMR and ¹ H edit experiments is as follows. In ¹ H edit NMR, the peaks CH and CH ₃ peaks appearing in ¹ H NMR are up, and CH ₂ Peaks are denoted as down, and NH and COOH peaks do not appear, thus helping to assign ¹ H (peak). HSQCAD and HSQC are the same experiments, and HSQCAD is an experiment in which adiabatic pulse (AD) is added as an advanced pulse sequence of HSQC.

That is, this ¹ H edit experiment allows discrimination between CH and CH ₃ peaks and CH ₂ peaks as compared to ¹ H NMR.

According to a preferred embodiment of the present invention, structural analysis of a polyamic acid containing a cinnamate group is carried out by performing at least one selected from the above ¹ H NMR, ¹ H edit NMR, and 2D NMR, can do.

In conclusion, the method for analyzing the monomer composition of a polyamic acid containing a cinnamate group of the present invention involves a hydrolysis process for analyzing a diamine component, and a hydrolysis process for analyzing a dianhydride component Alcoholysis) and GC / MS analysis. Analysis of the monomer composition of the polyamic acid including the cinnamate group through such a process revealed that the sample subjected to the hydrolysis process was a diamine component and the sample subjected to the alcoholysis process was a dianhydride dianhydride) is esterified and becomes a compound without interference.

Based on the monomer composition analysis data obtained by GC / MS analysis, the polyamic acid containing the cinnamate group was subjected to NMR to determine the mole ratio of each of the diamine component and dianhydride monomer component Can be obtained. Thus, the chemical structure of the polyamic acid including the cinnamate group can be confirmed.

The present specification provides a computer-readable recording medium on which a program for executing the above-described analysis method is recorded.

(A) a hydrolysis module for preparing a first sample by hydrolysis of a polyamic acid containing a cinnamate group; (b) an alcohol decomposition module for preparing a second sample by subjecting a polyamic acid containing a cinnamate group to alcoholysis (methanolysis); (c) a recovery module for recovering the organic layer through liquid-liquid extraction of the first sample and the second sample, respectively; And (d) an analysis module for analyzing samples of the recovered organic layer by GC / MS. The present invention also provides a system for analyzing the monomer composition of polyamic acid including a cinnamate group.

According to a preferred embodiment of the present invention, (e) a module for analyzing a molar ratio of polyamic acid monomers including a cinnamate group by NMR measurement of a polyamic acid containing a cinnamate group.

In the monomer composition analysis system of the polyamic acid including the cinnamate group of the present invention, the description of the structure overlapping with the monomer composition analysis method of the polyamic acid including the cinnamate group is the same Do.

Also, in the present invention, the term module refers to a unit for processing a specific function or operation, which can be realized by hardware, software, or a combination of hardware and software.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims.

Synthetic example  One

Cinnamate  Included Polyamic acid  Produce

0.5 mol of (E) -4- (3- (2,4-diaminophenethoxy) -3-oxopropyl-1-en-1-yl) 2-en-1-yl) -phenyl-4- (3-cyanopropoxy) benzoate) and 0.5 < RTI ID = 0.0 > Butoxyethanol (BE) was prepared by using 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride (CBDA) represented by the following formula (2) And N-methylpyrrolidone (NMP) at room temperature. Thereafter, 5 mL of the polyamic acid solution containing the polymerized cinnamate group was transferred to a 40 mL vial, and 30 mL of chloroform (CHCl ₃ ) was added thereto to obtain a polyamic acid solution containing a cinnamate group A precipitate of mica was obtained.

[Chemical Formula 1]

(2)

Example  One

The dianhydride and diamine components of Synthesis Example 1 were analyzed by the following (a) hydrolysis and (b) alcoholysis.

(a) Hydrolysis

50 mg of the polyamic acid sample obtained by the precipitation of Synthesis Example 1 was transferred to a 40 mL vial with a lid, 5 mL of 6N-NaOH solution was added, and the hydrolysis reaction was carried out at 120 DEG C for 6 hours. After completion of the hydrolysis reaction, the reaction mixture was cooled at room temperature, 20 mL of chloroform (CHCl ₃ ) was added thereto, shaken for 30 minutes, and subjected to liquid-liquid extraction. Thereafter, when the liquid-liquid extraction was completed, the layer was left to be sufficiently separated, and then a chloroform layer located on the lower layer was taken. The obtained chloroform layer was dried at room temperature under nitrogen, and 1 mL of chloroform was further added to dissolve the extracted sample, followed by GC / MS analysis.

(b) Alcohololysis

50 mg of the polyamic acid sample obtained by the precipitation of Synthesis Example 1 was transferred to a 40 mL vial with a lid, 5 mL of a solution of H ₂ SO ₄ / MeOH (1/10, v / v%) was added, Were subjected to alcoholysis for 6 hours. After the alcoholysis was completed, the reaction mixture was cooled at room temperature, the alcohol was volatilized under nitrogen, 20 mL of chloroform (CHCl ₃ ) and 5 mL of distilled water were added, shaking for 30 minutes, liquid-liquid extraction). When the liquid-liquid extraction was completed, the layer was left to be sufficiently separated and a chloroform layer located in the lower layer was taken. The obtained chloroform layer was dried at room temperature under nitrogen, and 1 mL of chloroform was further added to dissolve the extracted sample, followed by GC / MS analysis.

GC / MS analysis conditions are as follows.

Instrument: GC / MS (Agilent 7890A GC system with 5975C inert XL mass selective detector, Agilent Technologies Korea)

Experimental conditions

Column: HP-5ms capillary column (0.25mm ID X 30m L., 0.25μm d.f., Agilent Technologies, USA)

Injector temp .: 300 ° C

Carrier (He): 1.0 mL / min

               40: 1 s / s ratio

Oven temp .: 50 ° C / 5min-10 ° C / min-320 ° C / 15min

MSD Source / Qd temp .: 230 ° C / 150 ° C

Scan range: 18 - 600 m / z

Example  2

Synthesis Example 1 was analyzed by the following ¹ H NMR, ¹ H edit NMR and 2 H NMR.

¹ H, ¹ H edit NMR and 2D NMR experiments were performed using Agilent VNMRS 500 MHz NMR and ¹ H- ¹⁹ F / ¹⁵ N- ³¹ P 5 mm extended PFG (pulse field gradient) dual broad band probe.

¹ H, ¹ H edit For the NMR and 2D NMR experiments, a polyamic acid sample obtained by precipitation of Synthesis Example 1 was redissolved in chloroform (CHCl ₃ ), dried under nitrogen at room temperature, and then dissolved in a deutrium solvent, DMSO-d 6 solvent was sampled using a solvent.

¹ H NMR was performed under the conditions of a pulse width of 8 μsec, a recycle delay of 2 sec, and a number of scans of 16.

^{The 1} H edit experiment used a HSQCAD (pulse sequence), a recycle delay of 2 sec, a number of scans of 1024, a number of increments: 1.

2D NMR was analyzed with gCOSY and gHMBC.

gCOSY (gradient COrrelated Spectroscopy) experiments were performed under the conditions of recycle delay: 2 sec, number of scans: 4, and number of increments: 256.

The gHMBC (gradient Heteronuclear Multiple Bond Correlation) experiment was conducted under conditions of recycle delay: 2 sec, number of scans: 4, and number of increments: 512.

Example  Data analysis of 1

As the assay method of the present invention, a sample of the polyamic acid containing the cinnamate group of Synthesis Example 1 was used for GC / MS analysis (a) hydrolysis product of Example 1 and (b) GC / MS results of the hydrolysis product of Example 1 are shown in FIG. 1, and the relationship between the analytical compounds and peaks shown by the analysis is shown in FIG. 2. In FIG. 2 (b) GC / MS results of the alcohol decomposition product are shown in FIG. 3, and the relationship between each analytical compound and the peak shown by the analysis is shown in FIG.

As shown in Fig. 1 and Fig. 2, in the case of the hydrolyzate of (a) in Example 1, the peaks 1 and 2 in Fig. 1 are shown in Fig. 2, and the concentrations of buthoxyethanol, BE, 1) and N-methylpyrrolidinone (NMP, peak 2) were detected. And the diamine components were detected at the 3, 4 and 5 peaks of FIG. 1, respectively. 2, the peaks 3, 4 and 5 of FIG. 1 are shown in FIG. 2, showing the hydrolysis product (peak 3) of the diamine component, the ethylation product (peak 4) of the cinnamate decomposition product and the hydrolysis product of the cinnamate decomposition product (Peak 5).

As shown in Fig. 3 and Fig. 4, in the case of the alcohol decomposition product (b) of Example 1, the peaks 1 and 2 in Fig. 3 are shown in Fig. 4, and the amounts of butoxyethanol , Peak 1) and N-methylpyrrolidinone (NMP, peak 2) were detected. As a dianhydride component, a tetramethyl ester compound of CBDA was detected at 4 peaks in Fig. Also, the diamine component was detected at the 3, 5 and 6 peaks of Fig. 3, respectively. The peaks 3, 5 and 6 in FIG. 3 were detected in FIG. 4, and were detected in the same manner as the methylation products (peak 3 and peak 5) and cinnamate decomposition (peak 6) of the cinnamate decomposition product .

When the skeletons of the decomposed diamine monomer components are combined based on GC / MS analysis data after (1) hydrolysis and (2) alcoholysis of Example 1, The diamine component can be analyzed.

As a result, the hydrolyzed product (a) of Example 1 and the alcohol product (b) were analyzed by the GC / MS analysis in Example 1 using a sample of polyamic acid containing the cinnamate group of Synthesis Example 1 Respectively. Namely, the CBDA of Formula 2 was analyzed as a dianhydride component of a polyamic acid including a cinnamate group, and as the diamine component, 4-hydroxy Ethyl-1,3-phenylenediamine (4-hydroxyethyl-1,3-phenylenediamine) compound was analyzed.

Example  Data analysis of 2

Next, the connection relationship and the detailed structure of the structure related to Example 2 were confirmed by NMR, and the results of NMR analysis are shown in FIGS. 5 to 8.

The peak assignments of ¹ H NMR were confirmed based on the correlation between gCOSY and gHMBC. The detailed assignments were confirmed as follows.

5 is a ¹ H NMR spectrum of Example 2, and the following Formula 3 is a polyamic acid including a cinnamate group as shown in FIG. 5, FIG. 6, FIG. 7, and FIG. (4) and (5) are substructures of the polyamic acid including the cinnamate group as shown in FIG. 7 and FIG.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

Since the peaks assigned to the spectra of FIG. 5 are different from each other, carbon and peak numbers of the different positions of the above-mentioned formulas (3), (4) and (5) are described and can be confirmed.

In FIG. 5, -NH peak and -COOH peak can be confirmed. As a result, it can be seen that Synthesis Example 1 exists in the form of a polyamic acid including a cinnamate group. Therefore, these peaks were integrated to calculate the molar ratio of dianhydride to diamine, and the calculated molar ratio was 1: 1.

6 is a graph comparing the ¹ H edit NMR spectrum and the ¹ H NMR spectrum of Example 2. FIG. ¹ H edit The peak assigned to -COOH and -NH does not appear on the NMR spectrum, indicating that the assignments to -COOH and -NH in ¹ H NMR are correct Can be verified.

FIG. 7 is a gCOSY NMR spectrum of Example 2, which is based on the ³ J _HH correlation and the chemical shift shown in gCOSY NMR in the 4.6 to 1.5 ppm region. In the middle of the formula 4 and the polymer, which is phenoxypropanenitrile, It can be estimated that a structure related to the following formula (5), which is a moiety structure, exists.

In FIG. 7, the peaks associated with 4-hydroxyethyl-1,3-phenylenediamine detected by GC through the ³ J _HH correlation of 4.32 ppm and 2.92 ppm peak, And hydroxyl radicals are present in the form of an ester structure through a chemical shift.

Namely, since the compound of the formula 1 which is a compound of 4-hydroxyethyl-1,3-phenylenediamine including a cinnamate group in Example 1 is detected, the ester structure of cinnamate is also It is judged that the compound of Formula 1 exists in a form connected to 4-hydroxyethyl-1,3-phenylenediamine.

Also, the relationship between the detected monomer and the substructure can be analyzed by the following formula (6) through gHMBC.

[Chemical Formula 6]

FIG. 8 is a gHMBC NMR spectrum of Example 2, and a cinnamate double bond can be confirmed on gHMBC through 1 and 2 peaks in FIG.

The peak of 6, 7 and 8 in the above chemical formulas 6 and 8 indicates that the 4-hydroxybutanenitrile structure and its structure are connected to the aromatic structure by ³ J _HC correlation .

The presence of a nitrile group can also be confirmed by peak 11, which is the carbon peak of the ³ J _HC correlation in FIG.

Also, 3 of the formula (6) the phenoxy propanenitrile structure associated with the (Phenoxypropanenitrile) also, as shown in FIG. 8 ³ J _HC correlation of 4, and can determine through the fifth peak (peak), and in Fig 8 ^three-J _HC correlation It can be seen from the peak that the structure is linked to the carbonyl carbon of the ester.

In conclusion, as a result of NMR analysis of Example 2, it is judged that the structure of Synthesis Example 1 is a polyamic acid structure including a cinnamate group, and the structure of Synthesis Example 1 is the structure shown in Formula 6 above.

Claims (27)

(a) preparing a first sample by hydrolysis of a polyamic acid containing a cinnamate group;
(b) alcoholysis of a polyamic acid containing a cinnamate group to prepare a second sample;
(c) recovering the organic layer through liquid-liquid extraction from the first sample and the second sample, respectively; And
(d) analyzing the samples of the recovered organic layer by GC / MS, respectively, and analyzing the monomer composition of the polyamic acid containing a cinnamate group. The method according to claim 1,
(e) measuring a polyamic acid including a cinnamate group by NMR; and (e) measuring the polyamic acid including a cinnamate group. The method according to claim 1,
Wherein the polyamic acid including the cinnamate group is used in a photo alignment layer. A method for analyzing monomer composition of a polyamic acid including a cinnamate group. The method according to claim 1,
A method for analyzing monomer composition of a polyamic acid comprising a cinnamate group, wherein the hydrolysis of step (a) uses a strong base. The method of claim 4,
Wherein the strong base is NaOH. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the hydrolysis in step (a) is carried out at 100 to 150 ° C for 2 to 12 hours. A method for analyzing monomer composition of a polyamic acid comprising a cinnamate group. The method according to claim 1,
A method for analyzing monomer composition of a polyamic acid comprising a cinnamate group, wherein alcohol decomposition in step (b) is performed using a strong acid and an alcohol. The method of claim 7,
Wherein the strong acid is sulfuric acid. ≪ RTI ID = 0.0 > 11. < / RTI > The method of claim 7,
Wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol and isopropanol. A method for analyzing monomer composition of a polyamic acid comprising a cinnamate group. The method according to claim 1,
Wherein the alcohol decomposition in step (b) is carried out at 100 to 150 ° C for 4 to 12 hours. A method for analyzing monomer composition of a polyamic acid comprising a cinnamate group. The method according to claim 1,
Wherein the liquid-liquid extraction of step (c) comprises using an organic solvent. 6. A method for analyzing monomer composition of a polyamic acid comprising a cinnamate group. The method of claim 11,
Wherein the organic solvent is selected from the group consisting of chloroform, ethyl ether, and ethyl acetate. A method for analyzing monomer composition of a polyamic acid comprising a cinnamate group. The method of claim 2,
The NMR measurement is carried out by including at least one selected from ¹ H, ¹ H edit and 2D NMR,
A method for analyzing the monomer composition of a polyamic acid comprising a cinnamate group, characterized in that the polyamic acid comprising a cinnamate group is sampled using a deuterium solvent. 14. The method of claim 13,
Wherein the deuterium solvent comprises at least one selected from the group consisting of DMSO-d6, N, N-dimethyl-foramide-d7 and NMP (N-methylpyrrolidone) -d9. Method of analyzing monomer composition. 14. The method of claim 13,
The ¹ H edit NMR
HSQCAD pulse sequence and a number of increment of 1. 2. The method of claim 1, (a) a hydrolysis module for preparing a first sample by hydrolysis of a polyamic acid containing a cinnamate group;
(b) an alcohol decomposition module for preparing a second sample by alcoholysis of a polyamic acid including a cinnamate group;
(c) a recovery module for recovering the organic layer through liquid-liquid extraction of the first sample and the second sample, respectively; And
(d) an analyzing module for GC / MS analysis of the samples of the recovered organic layer, respectively; and (d) a cinnamate group-containing monomer composition analysis system for polyamic acid. 18. The method of claim 16,
(e) a module for NMR measurement of a polyamic acid containing a cinnamate group. < Desc / Clms Page number 20 > 18. The method of claim 16,
Wherein the hydrolysis of the hydrolysis module utilizes a strong base. ≪ RTI ID = 0.0 > A < / RTI > system for analyzing monomer composition of a polyamic acid comprising a cinnamate group. 18. The method of claim 16,
Wherein the strong base is NaOH. ≪ RTI ID = 0.0 > 11. < / RTI > A system for analyzing monomer composition of a polyamic acid comprising a cinnamate group. 18. The method of claim 16,
Wherein the hydrolysis of the hydrolysis module is carried out at 100 to 150 ° C for 2 to 12 hours. 18. The method of claim 16,
Wherein the alcohol decomposition of the alcohol decomposition module is carried out using a strong acid and an alcohol, and a monomer composition analysis system of a polyamic acid containing a cinnamate group. 23. The method of claim 21,
Wherein the strong acid is sulfuric acid. A system for analyzing monomer composition of a polyamic acid comprising a cinnamate group. 23. The method of claim 21,
Wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol and isopropanol. A system for analyzing monomer composition of a polyamic acid comprising a cinnamate group. 18. The method of claim 16,
Wherein the alcohol decomposition of the alcohol decomposition module is carried out at 100 to 150 ° C for 4 to 12 hours. The system for analyzing the composition of monomers of polyamic acid containing cinnamate group. 18. The method of claim 16,
Characterized in that the liquid-liquid extraction of the recovery module uses an organic solvent. ≪ RTI ID = 0.0 > A < / RTI > system for analyzing monomer composition of a polyamic acid comprising a cinnamate group. 26. The method of claim 25,
Wherein the organic solvent is selected from the group consisting of chloroform, ethyl ether and ethyl acetate. A system for analyzing monomer composition of a polyamic acid comprising a cinnamate group. A computer-readable recording medium on which a program for executing a method for analyzing monomer composition of a polyamic acid including a cinnamate group of claim 1 is recorded.

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