Pre-Processing Method

Abstract

In a pretreatment method, in first step, a sample is dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol to prepare a first solution. In second step, an organic base is added to the first solution to prepare a second solution. In third step, the second solution is heated to obtain a substance in which an anhydrous oxide structure in the sample has been decomposed. In a fourth step, an organic solvent that has a higher boiling point than that of 1,1,1,3,3,3-hexafluoro-2-propanol and is compatible (miscible) with 1,1,1,3,3,3-hexafluoro-2-propanol is added to the second solution to prepare a third solution.

Claims

1-6. (canceled)

7. A method for pretreating a sample comprising polyester or a polyester decomposition product before carrying out size exclusion chromatography of the sample, the method comprising: dissolving the sample in 1,1,1,3,3,3-hexafluoro-2-propanol to prepare a first solution; adding an organic base to the first solution to prepare a second solution; heating the second solution to obtain a substance in which an anhydrous oxide structure in the sample has been decomposed; after heating the second solution, adding an organic solvent that has a higher boiling point than that of 1,1,1,3,3,3-hexafluoro-2-propanol and is compatible with 1,1,1,3,33-hexafluoro-2-propanol to the second solution to prepare a third solution; and removing the organic solvent from the third solution to obtain a solid sample consisting of the substance.

8. The method according to claim 7, further comprising dissolving the solid sample in a solvent for the size exclusion chromatography.

9. The method according to claim 7, wherein a concentration of the organic base in the second solution is greater than 0.05 [mmol/L] and less than 0.4 [mmol/L].

10. The method according to claim 7, wherein a ratio of amount V [mL] of the organic solvent to amount “a” [ml] of the 1,1,1,3,3,3-hexafluoro-2-propanol in the third solution is V/a≥1.

11. The method according to claim 7, wherein the organic solvent comprises any of an ester bond, an ether bond, ketone, an aromatic ring, or a hydroxy group.

12. The method according to claim 7, wherein the organic solvent has a boiling point higher than 50° C.

13. The method according to claim 12, wherein removing the organic solvent from the third solution to obtain the solid sample consisting of the substance comprises removing the organic solvent from the third solution by concentration under reduced pressure to obtain the solid sample.

14. A pretreatment method comprising: preparing a first solution by dissolving a sample comprising polyester or a polyester decomposition product in 1,1,1,3,3,3-hexafluoro-2-propanol; preparing a second solution by adding an organic base to the first solution, wherein a concentration of the organic base in the second solution is greater than 0.05 [mmol/L] and less than 0.4 [mmol/L]; obtaining a substance in which an anhydrous oxide structure in the sample has been decomposed by heating the second solution; after obtaining the substance, preparing a third solution by adding an organic solvent to the second solution, the organic solvent having a boiling point higher than 50° C. and higher than that of the 1,1,1,3,3,3-hexafluoro-2-propanol and the organic solvent being compatible with the 1,1,1,3,3,3-hexafluoro-2-propanol; and obtaining a solid sample consisting of the substance by removing the organic solvent from the third solution.

15. The pretreatment method according to claim 14, further comprising dissolving the solid sample in a solvent for size exclusion chromatography.

16. The pretreatment method according to claim 14, wherein a ratio of amount V [mL] of the organic solvent to amount “a” [ml] of the 1,1,1,3,3,3-hexafluoro-2-propanol in the third solution is V/a≥1.

17. The pretreatment method according to claim 14, wherein the organic solvent comprises any of an ester bond, an ether bond, ketone, an aromatic ring, or a hydroxy group.

18. The pretreatment method according to claim 14, wherein obtaining the solid sample comprises removing the organic solvent from the third solution by concentration under reduced pressure.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0017] FIG. 1 is a flow chart for illustrating a pretreatment method according to an embodiment of the present invention.

[0018] FIG. 2 is a configurational diagram showing the molecular structure of deteriorated polyethylene terephthalate.

[0019] FIG. 3 is a characteristic diagram showing results of measurement by size exclusion chromatography to which an embodiment of the present invention was applied.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0020] Hereinafter, a pretreatment method according to an embodiment of the present invention will be described with reference to FIG. 1. This pretreatment method relates to the pretreatment of a sample consisting of polyester or a polyester decomposition product (deteriorated thermoplastic polyester) before carrying out size exclusion chromatography of the sample. The thermoplastic polyester is polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyneopentyl terephthalate, polycyclohexyl terephthalate, poly-dicyclohexylmethyl terephthalate, polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polyneopentyl isophthalate, polyethylene naphthalate, polybutylene naphthalate, or the like. Also, copolymers of these thermoplastic polyesters are included therein. Further, copolymers of polyamide (nylon 6, nylon 11, nylon 12, and nylon 66) or polyacetal and thermoplastic polyester are also included therein.

[0021] First, in first step Sol, the sample is dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) to prepare a first solution.

[0022] Next, in second step S102, an organic base is added to the first solution to prepare a second solution. The concentration of the organic base in the second solution is larger than 0.05 [mmol/L] and less than 0.4 [mmol/L]. Any of amines such as ethylamine, diethylamine, triethylamine, n-propylamine, i-propylamine (isopropylamine), n-butylamine, s-butylamine, t-butylamine, dimethylethylamine, and pyridine can be used as the organic base.

[0023] Next, in third step S103, the second solution is heated to obtain a substance in which an anhydrous oxide structure in the sample has been decomposed. This substance is dissolved in the second solution at this stage.

[0024] Subsequently, in fourth step S104, an organic solvent that has a higher boiling point than that of HFIP and is compatible (miscible) with HFIP is added to the second solution to prepare a third solution. The ratio of amount V [mL] of the organic solvent to amount “a” [ml] of HFIP in the third solution is V/a≥1. The organic solvent containing any of an ester bond, an ether bond, ketone, an aromatic ring, and a hydroxy group can be used.

[0025] Then, in fifth step S105, the solvent is removed from the third solution to obtain a solid sample consisting of the substance in which an anhydrous oxide structure in the sample has been decomposed. The solvent can be vaporized by heating and thereby removed, for example. However, when the boiling point of the organic solvent is higher than 50° C., the solvent is removed from the third solution through treatment in a range that does not allow the solution temperature to become 50° C. by concentration under reduced pressure, to obtain a solid sample.

[0026] The solid sample is thus obtained, and for subsequent size exclusion chromatography, the obtained solid sample is dissolved in a solvent (eluent) for size exclusion chromatography (sixth step).

[0027] Here, the deterioration of thermoplastic polyester will be described. As the deterioration of thermoplastic polyester progresses due to heat (heating) or light (light reception), its molecular chain scission reaction and cross-linking reaction progress, causing reduction in performance such as deterioration in strength. The course of reaction leading to molecular chain scission includes a pathway leading to molecular chain scission by only light, such as “Norrish II” reaction.

[0028] A molecular structure represented by the chemical structural formula (1) given below is converted to a molecular structure represented by the chemical structural formula (2) through photooxidation reaction and then converted to a molecular structure represented by the chemical structural formula (3) through ambient oxygen to form an acid anhydride structure which is a molecular structure weak in water. Then, the pathway leads to molecular chain scission as represented by the chemical structural formula (4) through hydrolysis.

Formulas (1) to (4)

[0029] ##STR00001##

[0030] In the course of reaction to form a cross-linked structure, a molecular structure represented by the chemical structural formula (5) given below is converted to a molecular structure represented by the chemical structural formula (7) through the withdrawal of a hydrogen radical by radical R. as represented by the chemical structural formula (6), and two molecular structures of the chemical structural formula (7) form a cross-linked structure through radicals to yield a molecular structure represented by the chemical structural formula (8). Such a course of reaction increases the number of cross-linked structures so that the thermoplastic polyester is insolubilized.

Formulas (5) to (8)

[0031] ##STR00002##

[0032] For example, when the thermoplastic polyester polyethylene terephthalate (PET) is deteriorated, as shown in FIG. 2, an acid anhydride structure 102 is formed in the middle of a molecular chain 101. Also, a cross-linked structure 103 which links two adjacent molecular chains 101 is formed, for example. The formation of such a network structure based on the cross-linked structure 103 involving the acid anhydride structure 102 is responsible for insolubilization. In such a molecular structure ascribable to deterioration, the decomposition of the acid anhydride structure 102 renders the network structure sparse, causing solubilization.

[0033] Hereinafter, embodiments of the present invention will be described in more detail with reference to experimental results. First, the addition of an organic solvent that had a higher boiling point than that of HFIP and was compatible (miscible) with HFIP was tested. In this test, solid samples were prepared by a pretreatment method under varying conditions, and the solid sample prepared under each condition was analyzed for the state of ester bonds and the state of an acid anhydride structure.

[0034] The state of ester bonds was evaluated as a decrease in the number of ester bonds by analyzing (quantifying) an increase in the number of hydroxy group ends formed through the decomposition of ester bonds in the solid sample by nuclear magnetic resonance (NMR) measurement. More specifically, .sup.1H NMR (300 MHz) was measured using the nuclear magnetic resonance device Oxford from Varian Medical Systems, Inc.

[0035] A sample was dissolved in a solvent of deuterated chloroform [containing 0.03% (v/v)Me.sub.4Si] CDCl.sub.3 and 1,1,1,3,3,3-hexafluoro-2-propanol-2d (HFIP-2d) mixed at a volume ratio of 1:1.

[0036] Measurement was carried out under a temperature condition of 50° C. For the measurement, the Me.sub.4Si peak of deuterated chloroform [containing 0.03% (v/v)Me.sub.4Si] CDCl.sub.3 was defined as 0 ppm.

[0037] Concentration C.sub.OH of hydroxy group ends was determined for repeat units from the intensity ratio between the peak of a proton on an aromatic ring (88.10 ppm) and the peak of a proton on a methylene group at hydroxy group ends (δ4.05 ppm) resulting from the decomposition of ester bonds.

[0038] The state of an acid anhydride structure was analyzed (quantified) as the presence or absence of a residual acid anhydride structure in a solid sample by infrared spectroscopy (FT-IR). More specifically, measurement was performed by reflection ATR with a single-reflection diamond ATR plate using the FT-IR analysis device Frontier Gold manufactured by PerkinElmer, Inc. The residual acid anhydride structure was confirmed from A.sub.1785/A.sub.1016 wherein the absorbance of 1785 cm.sup.−1 (light absorption by the acid anhydride structure) was normalized with the absorbance of 1016 cm.sup.−1 (light absorption by an aromatic ring).

ΔA.sub.1785/A.sub.1016=(A.sub.1785/A.sub.1016 when a deteriorated sample is pretreated)−(A.sub.1785/A.sub.1016 of an undeteriorated sample).

Sample

[0039] Light-deteriorated PET (approximately 10 mg) was used as deteriorated thermoplastic polyester.

Organic Base

[0040] Any of the following organic bases were used.

[0041] Isopropylamine (boiling point: 34° C.)

[0042] Diethylamine (boiling point: 56° C.)

[0043] n-Butylamine (boiling point: 78° C.)

[0044] Triethylamine (boiling point: 89° C.)

[0045] Pyridine (boiling point: 115° C.)

Solvent

[0046] In addition to HFIP (boiling point: 59° C.), hexane (boiling point: 69° C.), ethyl acetate (boiling point: 77° C.), tetrahydrofuran (boiling point: 66° C.), diisopropyl ether (boiling point: 69° C.), toluene (boiling point: 110° C.), 2-butanone (boiling point: 79° C.), dioxane (boiling point: 101° C.), xylene (boiling point: 144° C.), propyl acetate (boiling point: 97° C.), butyl acetate (boiling point: 126° C.), and isopropyl acetate (boiling point: 89° C.) were used as organic solvents.

Test 1

[0047] In test 1, light-deteriorated PET (10 mg) was dissolved in HFIP (2 mL) (first solution). To this solution, the organic base mentioned above was added at C mmol/L (second solution), followed by warming at 50° C. for 1 h. A small aliquot of this solution (second solution) was collected and subjected to NMR measurement, and “ΔC.sub.CH2OH before solvent removal” was calculated. Then, the solvent was removed to obtain a solid sample. The obtained solid sample was subjected to NMR measurement, and “ΔC.sub.CH2OH after solvent removal” was calculated. The calculation results are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Δ C.sub.CH2OH Δ C.sub.CH2OH before solvent after solvent Base C removal removal Triethylamine 0.25 0 2.1 (boiling point 89° C.) n-Butylamine 0.25 0 2.5 (boiling point 78° C.) Diethylamine 0.25 0 0.2 (boiling point 56° C.) Isopropylamine 0.05 0 0.1 (boiling point 34° C.) 0.10 0 0.2 0.25 0 0.3 0.30 0 0.3 0.40 0 0.7 0.50 0 0.7

[0048] As shown in Table 1, there was neither an increase in the number of hydroxy group ends nor the decomposition of ester bonds before removal of the solvent in all the cases. On the other hand, the number of hydroxy group ends was increased after removal of the solvent, demonstrating that the decomposition of ester bonds progressed during the course of removal of the solvent.

Test 2

[0049] In test 2, light-deteriorated PET (10 mg) was dissolved in HFIP (2 mL) (first solution). To this solution, the organic base mentioned above was added at C mmol/L (second solution), followed by warming at 50° C. for 1 h. To this solution (second solution), v mL of ethyl acetate was added as organic solvent, and the mixture was thoroughly stirred (third solution). Then, the obtained solution was concentrated under reduced pressure at 30° C. for the removal of the organic solvent to obtain a solid sample. The obtained solid sample was subjected to NMR measurement, and “ΔC.sub.CH2OH after solvent removal” was calculated. Also, the obtained solid sample was subjected to Fr-IR measurement, and “ΔA.sub.1785/A.sub.1016” was calculated. The results of each calculation are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Δ C.sub.CH2OH after Base C Organic solvent V solvent removal Δ A.sub.1785/A.sub.1016 Triethylamine 0.25 Ethyl acetate 2 0.4 0 (boiling point 89° C.) (boiling point 77° C.) n-Butylamine 0.25 Ethyl acetate 2 0 0 (boiling point 78° C.) (boiling point 77° C.) Diethylamine 0.25 Ethyl acetate 2 0 0 (boiling point 56° C.) (boiling point 77° C.) Isopropylamine 0.05 Ethyl acetate 2 0 0.12 (boiling point 34° C.) (boiling point 77° C.) 0.10 Ethyl acetate 2 0 0 (boiling point 77° C.) 0.25 Ethyl acetate 2 0 0 (boiling point 77° C.) 0.30 Ethyl acetate 2 0 0 (boiling point 77° C.) 0.40 Ethyl acetate 2 0.2 0 (boiling point 77° C.) 0.50 Ethyl acetate 2 0.3 0 (boiling point 77° C.) 0.25 Ethyl acetate 5 0 0 (boiling point 77° C.) 0.25 Ethyl acetate 2 0 0 (boiling point 77° C.) 0.25 Ethyl acetate 1 0.2 0 (boiling point 77° C.)

[0050] As shown in Table 2, for the combination of triethylamine and ethyl acetate, the number of hydroxy group ends was increased after removal of the solvent, revealing that the decomposition of ester bonds progressed. This is presumably because, since the boiling point of the organic base exceeded the boiling point of the organic solvent, the concentration of the solvent facilitated elevating the base concentration.

[0051] In contrast to these results, for isopropylamine which had a lower boiling point than that of ethyl acetate, the number of hydroxy group ends was increased when the amount of the base added was 0.40 mmol/L or more, demonstrating the progression of decomposition of ester bonds. On the other hand, for isopropylamine, the number of hydroxy group ends was not increased when the amount of the base added was in the range of 0.10 to 0.30 mmol/L, demonstrating that the decomposition of ester bonds did not progress.

[0052] In the case of adding 0.05 mmol/L of isopropylamine, ΔA.sub.1785/A.sub.1016>0 held, demonstrating that when the amount of the organic base added is small, the decomposition of an acid anhydride structure is not completed. When the amount of ethyl acetate added was 1 mL, the number of hydroxy groups was increased, demonstrating the decomposition of ester bonds. It is considered that if the amount of the organic solvent added is small, a portion of PET resin remains dissolved so that ester bonds have been decomposed.

[0053] From these results, it was found necessary to add an organic solvent that has a higher boiling point than that of HFIP and does not dissolve thermoplastic polyester. It was also found that the concentration of the organic base added is suitably 0.05<c<0.4. When the amount of HFIP is defined as “a” mL, it is evidently desired that amount V mL of the organic solvent added should satisfy the relationship of “V/a≥1”.

Test 3

[0054] In test 3, light-deteriorated PET (10 mg) was dissolved in HFIP (2 mL) (first solution). To this solution, dimethylamine was added at 0.25 mmol/L (second solution), followed by warming at 50° C. for 1 h. To this solution (second solution), 2 mL of an organic solvent was added, and the mixture was thoroughly stirred (third solution). Then, the obtained solution was concentrated under reduced pressure at TC for the removal of the organic solvent to obtain a solid sample. The obtained solid sample was subjected to NMR measurement, and “ΔC.sub.CH2OH after solvent removal” was calculated. The calculation results are shown in Table 3 below.

TABLE-US-00003 TABLE 3 Δ C.sub.CH2OH after solvent Base C Organic solvent V T removal Δ A.sub.1785/A.sub.1016 Isopropylamine 0.25 Hexane (boiling point 69° C.) 2 30 0.3 0 (boiling point 0.25 Ethyl acetate (boiling point 77° C.) 2 30 0 0 34° C.) 0.25 Tetrahydrofuran (boiling point 2 30 0 0 66° C.) 0.25 Diisopropyl ether (boiling point 2 30 0 0 77° C.) 0.25 Toluene (boiling point 110° C.) 2 30 0 0 0.25 2-Butanone (boiling point 79° C.) 2 30 0 0 0.25 Dioxane (boiling point 101° C.) 2 30 0 0 0.25 Xylene (boiling point 144° C.) 2 30 0 0 0.25 Xylene (boiling point 144° C.) 2 50 0 0 0.25 Xylene (boiling point 144° C.) 2 70 0 0 n-Butylamine 0.25 Xylene (boiling point 144° C.) 2 50 0 0 (boiling point 0.25 Xylene (boiling point 144° C.) 2 60 0.4 0 78° C.) 0.25 Xylene (boiling point 144° C.) 2 70 0.2 0 Pyridine (boiling 0.25 Xylene (boiling point 144° C.) 2 50 0 0 point 115° C.)

[0055] In the case of using hexane as an organic solvent, hexane was not miscible with HFIP so that the number of hydroxy group ends was increased after removal of the solvent, revealing that the decomposition of ester bonds progressed. These results demonstrated that it is necessary to use an organic solvent that contains a molecular structure such as an ester bond, an ether bond, an aromatic ring, or ketone and is sufficiently miscible with HFIP.

[0056] In the case of using isopropylamine having a low boiling point, the decomposition of ester bonds did not occur, irrespective of concentration temperature. In the case of using n-butylamine having a boiling point higher than 50° C., it was confirmed that the decomposition of ester bonds progressed under a concentration temperature condition of 60° C. or higher. These results demonstrated that even in a precipitated state of PET resin at the time of concentration, the decomposition of ester bonds progresses upon contact with a base at a high temperature. As for a base, such as pyridine, which has a high boiling point, the decomposition of ester bonds does not occur as long as concentration under reduced pressure is performed at 50° C.

[0057] From these results, it was found necessary to use an organic solvent that can be mixed with HFIP. In the case of using an organic base having a boiling point higher than 50° C., it was also found necessary to remove the solvent by concentration under reduced pressure at 50° C. or lower.

Experimental Results

[0058] Hereinafter, results of carrying out the pretreatment method of embodiments of the present invention and carrying out measurement by size exclusion chromatography will be described. In this experiment, light-deteriorated PET (10 mg) was dissolved in HFIP (2 mL) (first solution). Isopropylamine was added thereto as an organic base at 0.25 mmol/L (second solution), followed by warming at 50° C. for 1 h. Then, 2 mL of ethyl acetate was added, and the mixture was thoroughly stirred (third solution). Then, the solvent was removed by concentration under reduced pressure at 30° C. to obtain a solid sample. The obtained solid sample was measured by size exclusion chromatography.

Measurement Equipment

[0059] For measurement, the SEC device ACQUITY APC from Waters Corp. was used. Also, APC-XT, 186006995, 186006998, 186007003, and 18600754 were used as columns.

Standard Sample

[0060] Six types of commercially available polymethyl methacrylate (PMMA) standard samples having a peak top molecular weight of 102500, 56900, 24400, 10900, 8350, or 4250 were used to carry out measurement. A triple calibration curve was prepared.

Sample Preparation

[0061] The solid sample obtained by pretreatment was dissolved at 1 mg/l mL in an eluent of HFIP containing 10 mmol/L of sodium trifluoroacetate. A sample bottle of the obtained solution was capped and left standing overnight. The sample was added to a vial for measurement, filtered through a PTFE syringe filter having a pore size of 0.2 μm, and subjected to measurement.

Measurement Conditions

[0062] Eluent: HFIP containing 10 mmol/L of sodium trifluoroacetate

[0063] Column temperature: 40° C.

[0064] Flow rate: 0.25 mL/min

[0065] Sample concentration: 1 mg/mL

[0066] Injection volume: 0.2 μL/run

[0067] Detector: RI detector (40° C.)

[0068] The measurement results are shown in FIG. 3. In FIG. 3, line 201 depicts results of measuring undeteriorated PET without pretreatment. Line 202 depicts results of measuring an undeteriorated PET pretreated according to embodiments of the present invention. Line 203 depicts results of measuring light-deteriorated PET without pretreatment. Line 204 depicts results of measuring light-deteriorated PET pretreated according to embodiments of the present invention.

[0069] As described above, according to embodiments of the present invention, the decomposition of ester bonds can be suppressed in the pretreatment of a sample consisting of polyester or a polyester decomposition product for carrying out size exclusion chromatography, because an organic solvent that has a higher boiling point than that of 1,1,1,3,3,3-hexafluoro-2-propanol and is compatible with 1,1,1,3,3,3-hexafluoro-2-propanol is added.

[0070] The present invention is not limited by the embodiments described above. It is obvious that those ordinarily skilled in the art are capable of carrying out many modifications and combinations without departing from the technical brief of the present invention.

REFERENCE SIGNS LIST

[0071] 101 Molecular chain [0072] 102 Acid anhydride structure [0073] 103 Cross-linked structure [0074] 201,202,203,204 Line