KR20150121460A - Analytical Method and System for Composition of Monomer in Polyamide-Imide - Google Patents

Abstract

The present invention relates to an analysis method for composition of monomers in polyamide-imide, and a system using thereof. The method comprises: (a) a step of preparing the first sample by hydrolyzing polyamide-imide; (b) a step of preparing the second sample by methanolyzing polyamide-imide; (c) a step of collecting an organic layer by liquid-liquid extraction of the first sample and the second sample; and (d) a step of analyzing the collected samples of the organic layer collected in GC/MS.

Description

TECHNICAL FIELD The present invention relates to a method for analyzing a monomer composition of a polyamide-imide,

The present invention relates to a method and an analysis system for analyzing monomer composition of polyamide-imide.

Polyamide-imides are one of the thermoplastic polymers that are thermally superior and have excellent physical and chemical performance. Because of this feature, it is considered as one of the polymer material that exhibits good performance and maintains high price. It is also used as coating material of electric wire and insulation material of printed circuit board (PCB).

In addition to its high thermal and chemical resistance, polyamide-imide contains both polyamide and polyimide properties in that it retains high strength and is capable of melting processes. Generally, a method for producing polyamide-imide having such characteristics can be divided into the following two methods.

First, using an acid chloride route, trimellitic acid chloride (TMAC) and methylene dianiline (MDA) were used as monomers and N-methylpyrrolidone, (HCl), which is a by-product after polymerization, in a solvent such as NMP, dimethylacetamide (DMAC), dimethylformamide (DMF) or dimethylsulfoxide (DMSO) Is neutralized and removed to obtain a polymer precipitate. The resulting polymer undergoes a high-temperature imidization reaction to convert the amic acid functional group into an imide to produce polyamide-imide.

Another method is a basic method for preparing a polyamide-imide with a diisocyanate route, which comprises reacting 4,4'-methylenediphenyldiisocyanate (MDI) and trimellitic anhydride (trimellitic anhydride, TMA) to prepare imidized polyamide-imide.

On the other hand, in the research and development of the polyamide-imide film, a composition analysis method is indispensably required to confirm the composition of the developed product.

In this regard, the method of analyzing the monomer composition of the polyamide-imide can be performed by a method using a conventional Pyrolysis GC-MS or a method of analyzing a 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 anhydride acid and dianhydride, the derivatization is not easily occurred, which makes it difficult to grasp the monomer components.

Korean Patent Publication No. 1995-0029297

The present invention is based on the discovery that methanolysis can be performed to improve conventional analytical methods which are difficult to analyze due to complicated thermal decomposition products and which do not proceed with derivatization of anhydride acid and dianhydride components, And hydrolysis method were used as pretreatment methods and the analysis of monomer composition of polyamide-imide was performed by detecting the desired monomers (anhydride acid, dianhydride and diamine) as main components without any interference from complicated thermal decomposition products. And to provide a method for analyzing the monomer composition of an easy polyamide-imide.

For this purpose, the present invention provides a method for preparing a polyamide-imide, comprising: (a) hydrolysing polyamide-imide to prepare a first sample; (b) preparing a second sample by methanolysis of the polyamide-imide; (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 analyze the monomer composition of the polyamide-imide.

(A) a hydrolysis module for preparing a first sample by hydrolysis of polyamide-imide; (b) a methanol degradation module for preparing a second sample by methanolysis of polyamide-imide; (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 GC / MS analysis of the samples of the recovered organic layer.

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

According to the method for analyzing the monomer composition of the polyamide-imide of the present invention, the methanolysis and hydrolysis methods are used as the pretreatment method, so that there is no disturbance due to complicated thermal decomposition products and the desired monomer (anhydride acid, dianhydride, and diamine) is detected as a main component, which makes it easy to analyze monomer composition of polyamide-imide.

1 is a graph showing GC / MS data of a hydrolyzed sample of Example 1 of the present invention.
2 is a graph showing GC / MS data of the methanol decomposed sample of Example 1 of the present invention.
3 is a graph showing Py-GC / MS data of Comparative Example 1 of the present invention.
4 is a table showing the peaks of Example 1 and Comparative Example 1 of the present invention and the chemical formulas of the compounds.

Hereinafter, the present invention will be described in detail.

The method for analyzing the monomer composition of polyamide-imide according to the present invention comprises the steps of: (a) preparing a first sample by hydrolysis of polyamide-imide; (b) preparing a second sample by methanolysis of the polyamide-imide; (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.

In the method for analyzing the monomer composition of the polyamide-imide according to the present invention, in the step (a), the first sample is prepared by hydrolysis of the polyamide-imide.

The hydrolysis of step (a) is for analyzing the components of the diamine monomer in the polyamide-imide, and hydrolysis is carried out 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 carried out, but it is preferably 10 to 50 times as much as the total amount of the polyamide-imide.

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 for analyzing the monomer composition of the polyamide-imide according to the present invention, in the step (b), the polyamide-imide is subjected to methanolysis to prepare a second sample.

The decomposition of methanol in step (b) is for analyzing the components of anhydride-acid and dianhydride monomer in the polyamide-imide, and the methanolysis is carried out 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, but preferably selected from the group consisting of methanol, ethanol, normal propanol and isopropanol can be used. The amount of strong acid to be added in the methanol decomposition is not particularly limited as long as sufficient methanol decomposition can be carried out, but it is preferably 10 to 50 times as much as the total amount of polyamide-imide. In addition, the amount of alcohol added in the methanol decomposition is not particularly limited as long as sufficient hydrolysis can be carried out, but it is preferably 50 to 200 times based on the total amount of polyamide-imide.

The methanol decomposition in step (b) is preferably carried out at 100 to 150 ° C for 4 to 12 hours, more preferably at 110 to 130 ° C for 4 to 8 hours in order to obtain a sufficient methanol decomposing effect . If the reaction temperature is lower than 100 ° C., the decomposition time of methanol may become longer. If the reaction temperature is higher than 150 ° C., the decomposition may be promoted too much to produce undesired compounds.

The method for analyzing the monomer composition of the polyamide-imide according to the present invention may further comprise the steps of (a) and (b) , And the organic layer is recovered.

That is, in the step (c), the first sample in which the polyamide-imide is hydrolyzed in step (a) and the second sample in which the polyamide-imide is methanol-decomposed in step (b) Liquid-Liquid Extraction). 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 the step (b), the methanol-decomposed samples are cooled at room temperature, and methanol 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, in addition to the organic solvent, water is further added to the sample to remove strong acid in the liquid-liquid extraction of the methanol-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 step (d) of analyzing the monomer composition of the polyamide-imide according to the present invention, each sample of the recovered organic solvent layer is analyzed by GC / MS.

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).

As a result, the method of analyzing the monomer composition of the polyamide-imide of the present invention involves a hydrolysis process for analyzing the diamine component, and analyzes an anhydride acid and a dianhydride component To do this, GC / MS analysis is carried out through methanolysis.

When the monomer composition of the polyamide-imide is analyzed through this process, the diamine component of the hydrolysis-treated sample and the methanolysis product of the anhydride-imide (hydrolysis) dianhydride) is converted to a methyl ester, which is a compound without interference. Therefore, it can be simply analyzed.

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 polyamide-imide; (b) a methanol degradation module for preparing a second sample by methanolysis of polyamide-imide; (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 polyamide-imide.

In the monomer composition analysis system of the polyamide-imide, the description of the configuration overlapping with the method of analyzing the monomer composition of the polyamide-imide is the same.

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

Polyamide - Imide  Produce

0.5 mol of trimellitic acid chloride (TMAC) and 0.1 mol of 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (3,3', 4,4'-biphenyl tetracarboxylic dianhydride , BPDA) and 0.6 mol of 4,4'-methylene dianiline (4,4'-MDA) as monomers in a solvent of N-methylpyrrolidone (NMP) Polymerization is carried out at room temperature.

The polymerized sample solution was cast on a glass plate using a spin-coater and pre-baked at 140 ° C for 30 minutes in an air convection oven to prepare a film Respectively. The film was subjected to imidization reaction at 350 DEG C for 1 hour under a nitrogen atmosphere. The imidized film was carefully removed from the glass plate and stored in a desiccator.

Example  One

The anhydride acid, dianhydride and diamine components of Synthesis Example 1 were analyzed by the following (a) hydrolysis and (b) methanol decomposition.

(a) Hydrolysis

50 mg of the sample of Synthesis Example 1 was transferred to a 40 mL vial with a lid, 5 mL of 6N-NaOH solution was added, and hydrolysis 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) Methanolysis

50 mg of the sample of Synthesis Example 1 was transferred to a 40 mL vial with a lid, 5 mL of a H ₂ SO ₄ / MeOH (1/10, v / v%) solution was added, Decomposition reaction was carried out. After completion of the methanol decomposition reaction, the reaction mixture was cooled at room temperature, methanol 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.

Comparative Example  One

200 ㎍ of the sample of Synthesis Example 1 was transferred to a 40 ml vial with a lid, and 10 L of TMAH was added thereto, followed by reaction at 120 캜 for 30 minutes. The reacted samples were analyzed for anhydride acid, dianhydride and diamine components using Py-GC / MS.

Experimental Example  One

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  Data analysis of 1

GC / MS analysis of (a) the hydrolyzed product of Example 1 and (b) methanol products was carried out using a sample of the polyamide-imide film of the synthesis example as the assay method of the present invention, The GC / MS results of a) the hydrolysis product are shown in Fig. 1, and the GC / MS results of methanol decomposition product (b) of Example 1 are shown in Fig. FIG. 4 shows the relationship between each analytical compound and the peak shown by the analysis.

As shown in FIG. 1 and FIG. 4, the 4,4'-MDA (peak 8) as a diamine component was detected in the unmodified form in the case of hydrolysis product (a) of Example 1, (4- (4-aminobenzyl) benzonitrile, peak 14), which is a modification of the ' -MDA.

2 and 4, in the case of the (b) methanol product of Example 1, mono-methylation of trimellitic anhydride (TMA) as an anhydride-acid component, methylation compound (peak 15) and a tri-methylation compound (peak 16) were detected and the tetra-methylation compound (peak 17) of BPDA as a dianhydride component Respectively.

Comparative Experimental Example  2

Py-GC / MS analysis conditions are as follows.

Device: Py-GC / MSD

         Pyrolyzer (PY-2010iD, Frontier Laboratories, Fukushima, Japan)

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

Experimental conditions

Column: Ultra ALLOY ⁺ -5 metal capillary column (0.25 mm ID X 30m L., 0.25um df, Frontier Lab, Japan)

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

Furnace (pyrolyzer) temp .: 600 ° C

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

Scan range: 18 - 600 m / z

Comparative Example  Data analysis of 1

As a conventional analysis method, a Py-GC / MS analysis was performed using a sample of the polyamide-imide film of Comparative Example 1, and it is shown in FIG. The relationship between each analytical compound and the peak as shown by the analysis is shown in FIG.

As shown in FIGS. 3 and 4, when the diamine component is 4,4'-MDA (peak 8), mono-methylation compound (peak 9), di-methylation (Peak 10, peak 11), tri-methylation compound (peak 12) and tetra-methylation compound (peak 13), and an anhydride The dianhydride component was tried to analyze by methylation of the carboxylic group, but the amount of the dianhydride component to be detected was so small that the structural analysis was not easy.

The above-mentioned detection showed different degrees of methylation depending on the monomer components, and the structural analysis was not easy due to complicated pyrolysis products and methylation derivatives. In addition, it is expected that methylated compounds can not be analyzed accurately by analyzing unknown polyamide-imides using existing analytical methods because analytical experience must be accumulated.

In conclusion, through the above analysis, when the polyamide-imide film is analyzed by the conventional analysis method of Comparative Example 1, the anhydride acid and dianhydride components are easily detected due to thermal decomposition , And the diamine did not produce good results due to pyrolysis. In addition, methylated components are detected, but they are not easily interpreted due to trace amounts or pyrolysis products. In the case of methylation compounds, many experiences and know-how can be used to analyze the unknown samples. It was found that it was not suitable.

On the other hand, in the case of Example 1, which is the analysis method of the present invention, when the polyamide-imide film was analyzed, the diamine component was detected in the form of 4,4'-MDA in an unmodified form, mono-methylation or tri-methylation compounds of trimellitic anhydride (TMA) as an anhydride-acid component were detected. As a dianhydride component, BPDA A tetra-methylation compound was detected.

Therefore, it is easy to analyze the monomer component used in the polyamide-imide, which is much simpler and simpler to analyze than the data obtained by the conventional analysis method.

Claims (21)

(a) preparing a first sample by hydrolysis of polyamide-imide;
(b) preparing a second sample by methanolysis of the polyamide-imide;
(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 samples of the recovered organic layer, respectively. The method according to claim 1,
A method for analyzing monomer composition of polyamide-imide, wherein the hydrolysis of step (a) employs a strong base. The method of claim 2,
Wherein the strong base is NaOH. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
Wherein the hydrolysis of step (a) is carried out at 100 to 150 ° C for 2 to 12 hours. The method according to claim 1,
Wherein the decomposition of methanol in step (b) is carried out using a strong acid and an alcohol. The method of claim 5,
Wherein the strong acid is sulfuric acid. The method of claim 5,
Wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol and isopropanol. The method according to claim 1,
Wherein the decomposition of methanol in step (b) is carried out at 100 to 150 ° C for 4 to 12 hours. The method according to claim 1,
Wherein the liquid-liquid extraction of step (c) comprises using an organic solvent. The method of claim 9,
Wherein the organic solvent is selected from the group consisting of chloroform, ethyl ether and ethyl acetate. (a) a hydrolysis module for preparing a first sample by hydrolysis of polyamide-imide;
(b) a methanol degradation module for preparing a second sample by methanolysis of polyamide-imide;
(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 GC / MS analysis of the samples of the recovered organic layer, respectively. The method of claim 11,
Wherein the hydrolysis of the hydrolysis module utilizes a strong base. The method of claim 12,
Wherein the strong base is NaOH. ≪ RTI ID = 0.0 > 15. < / RTI > The method of claim 11,
Wherein the hydrolysis of the hydrolysis module is carried out at 100 to 150 ° C for 2 to 12 hours. The method of claim 11,
Wherein the methanol decomposition module of the methanol decomposition module uses a strong acid and an alcohol. 16. The method of claim 15,
Wherein the strong acid is sulfuric acid. 16. The method of claim 15,
Wherein the alcohol is selected from the group consisting of methanol, ethanol, n-propanol and isopropanol. The method of claim 11,
Wherein the methanol decomposition of the methanol decomposition module is carried out at 100 to 150 ° C for 4 to 12 hours to analyze the monomer composition of the polyamide-imide. The method of claim 11,
Wherein the liquid-liquid extraction of the recovery module uses an organic solvent. The method of claim 19,
Wherein the organic solvent is selected from the group consisting of chloroform, ethyl ether and ethyl acetate. A computer-readable recording medium on which a program for executing the method for analyzing the monomer composition of polyamide-imide of claim 1 is recorded.

Images