Method for calculating mixture ratio of organic mixture

Abstract

To provide a method for precisely calculating the mixture ratio of an organic mixture.SOLUTION: A method for calculating the mixture ratio of an organic mixture includes the step of measuring the temperature change of the mass of an organic mixture by thermal weight analysis, and the measurement step includes a step 1 of measuring the mass of the organic mixture while increasing the temperature at the rate of 50°C / minute; and a step 2 of measuring the mass of the organic mixture while increasing the temperature at the rate of 0.1°C / minutes after detecting decrease of the mass.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for calculating the mixing ratio of an organic mixture.

Background Art

[0002] In order to control the quality of a mixture prepared by mixing organic materials, the mixing ratio (mass ratio of the composition) of each component in the mixture is analyzed. As one of the methods for analyzing the composition of a substance, thermogravimetric analysis (TGA) is known (see Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] As described above, it is known to analyze the composition of a substance using thermogravimetric analysis. However, as a result of intensive studies by the present inventors, in an organic mixture prepared by mixing organic materials, when thermogravimetric analysis measurement is performed, since thermal decomposition of each component in the organic mixture occurs almost simultaneously at temperatures close to each other, there is a problem that thermal decomposition of each component cannot be detected separately.

[0005] An object of the present invention is to solve the above problems and provide a method for accurately calculating the mixing ratio of an organic mixture.

Means for Solving the Problems

[0006] The present invention includes a measurement step of measuring the temperature change of the mass of an organic mixture by thermogravimetric analysis, The measurement process relates to a method for calculating the mixing ratio of an organic mixture, which includes process 1 of measuring the mass of the organic mixture while increasing the temperature at a rate of 50 °C / min or less, and process 2 of measuring the mass of the organic mixture while increasing the temperature at a rate of 0.1 °C / min or less after detecting a mass decrease.

Advantages of the Invention

[0007] The present invention includes a measurement process of measuring the temperature change of the mass of an organic mixture by thermogravimetric analysis. The measurement process includes process 1 of measuring the mass of the organic mixture while increasing the temperature at a rate of 50 °C / min or less, and process 2 of measuring the mass of the organic mixture while increasing the temperature at a rate of 0.1 °C / min or less after detecting a mass decrease. Since it is a method for calculating the mixing ratio of an organic mixture, the mixing ratio of the organic mixture can be accurately calculated.

Brief Description of the Drawings

[0008]

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Mode for Carrying Out the Invention

[0009] The present invention includes a measurement step of measuring the temperature change of the mass of an organic mixture by thermogravimetric analysis. The measurement step includes Step 1 of measuring the mass of the organic mixture while increasing the temperature at 50°C / min or less, and Step 2 of measuring the mass of the organic mixture while increasing the temperature at 0.1°C / min or less after detecting a mass decrease. It is a method for calculating the mixing ratio of an organic mixture. By adopting such a method, the mixing ratio of the organic mixture can be calculated accurately.

[0010] The organic mixture used in the method of the present invention is prepared by mixing two or more kinds of organic materials. The organic material is not particularly limited, and any organic material can be used. For example, an organic mixture prepared by mixing one or more kinds of polymer materials and one or more kinds of organic fillers, since the thermal decomposition of each component occurs almost simultaneously at very close temperatures, when used in the method of the present invention, the effects of the present invention can be obtained more remarkably. Therefore, as the above organic mixture, those prepared by mixing one or more kinds of polymer materials and one or more kinds of organic fillers are preferred. The blending ratio of these components can be appropriately adjusted according to its use.

[0011] The above polymer material is not particularly limited, and conventionally known ones can be mentioned. For example, rubber materials, liquid polymers, composite materials in which the rubber material or the liquid polymer and a resin are combined, etc. can be applied.

[0012] Examples of the rubber material include diene rubbers such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), styrene-isoprene-butadiene rubber (SIBR), and non-diene rubbers such as butyl rubber (IIR) and halogenated butyl rubber (X-IIR). These may be used alone or in combination of two or more. Further, the rubber material may contain one or more modifying groups such as a hydroxyl group and an amino group.

[0013] Examples of the liquid polymer include an unmodified liquid polymer and a modified liquid polymer. Among them, a modified liquid polymer is preferable, and it is particularly preferable to use a modified liquid polymer obtained by modifying an unmodified liquid polymer with an unsaturated carboxylic acid and / or its derivative.

[0014] The unmodified liquid polymer is an unmodified liquid polymer (liquid diene polymer) obtained by polymerizing monomers mainly containing conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. Examples of the unmodified liquid polymer include liquid diene polymers such as liquid polybutadiene, liquid polyisoprene, liquid styrene-butadiene random copolymer, liquid styrene-butadiene block copolymer, liquid butadiene-isoprene random copolymer, liquid butadiene-isoprene block copolymer, liquid styrene-butadiene-isoprene random copolymer, and liquid styrene-butadiene-isoprene block copolymer. These may be used alone or in combination of two or more. Among them, liquid polyisoprene is preferable.

[0015] Examples of the unsaturated carboxylic acid include maleic acid, fumaric acid, itaconic acid, (meth)acrylic acid, etc. Examples of the unsaturated carboxylic acid derivative include unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; unsaturated carboxylic acid esters such as maleic acid ester, fumaric acid ester, itaconic acid ester, glycidyl (meth)acrylate, and hydroxyethyl (meth)acrylate; unsaturated carboxylic acid amides such as maleic acid amide, fumaric acid amide, and itaconic acid amide; unsaturated carboxylic acid imides such as maleic acid imide and itaconic acid imide; and the like. The modification may be carried out with one kind of the unsaturated carboxylic acid or unsaturated carboxylic acid derivative, or may be carried out with two or more kinds thereof.

[0016] The modified liquid polymer can be produced by modifying an unmodified liquid polymer as a raw material with an unsaturated carboxylic acid and / or its derivative. The modification method is not particularly limited, and it can be produced by a known method such as a method of adding an unsaturated carboxylic acid and / or its derivative to the unmodified liquid polymer as a raw material. The modified liquid polymer may be used alone or in combination of two or more.

[0017] Among these, maleic anhydride-modified liquid polymers are preferred, maleic anhydride-modified liquid diene polymers are more preferred, and maleic anhydride-modified liquid polyisoprene is even more preferred.

[0018] Examples of the liquid polymer include products of Kuraray Co., Ltd., Kray Valley Co., etc.

[0019] The number average molecular weight (Mn) of the liquid polymer is preferably 1000 or more, more preferably 5000 or more, and even more preferably 10000 or more. Also, the Mn is preferably 70000 or less, more preferably 50000 or less.

[0020] In addition, in this specification, Mn can be determined by conversion to standard polystyrene based on the measured values obtained by gel permeation chromatography (GPC) (GPC-8000 series manufactured by Tosoh Corporation, detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M manufactured by Tosoh Corporation).

[0021] The above resin is not particularly limited, and examples include those commonly used in the rubber industry, such as petroleum resins such as C5-based aliphatic petroleum resins and cyclopentadiene-based petroleum resins; polyolefin resins such as polyethylene, polypropylene, polybutene, polystyrene, ethylene-propylene copolymers, ethylene-methacrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate copolymers, and ionomer resins thereof; ethylene-vinyl alcohol copolymers, vinyl alcohol homopolymers, poly(meth)acrylic acid resins, polyamide resins, aliphatic polyamide-based resins, aromatic polyamide-based resins, polyester resins, polyvinyl alcohol-based resins, cellulose-based resins, acrylic resins, etc. These may be used alone or in combination of two or more.

[0022] The above organic filler is not particularly limited, and examples include those commonly used in the rubber industry, such as microfibrillated plant fibers, carbon fibers, carbon nanotubes (multi-walled, single-walled), graphene, etc. These may be used alone or in combination of two or more. Among these, microfibrillated plant fibers are preferred because the organic filler and the polymer material undergo thermal decomposition almost simultaneously at temperatures very close to each other, and thus the effects of the present invention can be obtained more significantly when subjected to the method of the present invention.

[0023] Examples of the microfibrillated plant fibers include cellulose microfibrils (cellulose nanofibers (CNF)), which are widely used in the rubber industry. The cellulose microfibrils are not particularly limited as long as they are derived from natural products. For example, they include resource biomass such as fruits, grains, and root vegetables, wood, bamboo, hemp, jute, kenaf, pulp, paper, cloth, agricultural crop residues, waste biomass such as food waste and sewage sludge, unused biomass such as rice straw, wheat straw, and thinned wood, and those derived from cellulose produced by organisms such as jellyfish and acetic acid bacteria. These microfibrillated plant fibers may be used alone or in combination of two or more.

[0024] In the present specification, the cellulose microfibrils typically mean cellulose fibers having an average fiber diameter within a range of 10 μm or less, and more typically, cellulose fibers having a microstructure with an average fiber diameter of 500 nm or less formed by an aggregation of cellulose molecules. Note that typical cellulose microfibrils can be formed as an aggregate of cellulose fibers having the average fiber diameter as described above, for example.

[0025] The method for producing the microfibrillated plant fibers is not particularly limited. For example, after chemically treating the raw material of the cellulose microfibrils with an alkali such as sodium hydroxide as necessary, mechanical grinding or beating is performed using a refiner, a twin-screw kneader (twin-screw extruder), a twin-screw kneading extruder, a high-pressure homogenizer, a media agitation mill, a mortar, a grinder, a vibration mill, a sand grinder, or the like. In these methods, lignin is separated from the raw material by chemical treatment, so that microfibrillated plant fibers substantially free of lignin can be obtained. Further, as other methods, a method of subjecting the raw material of the cellulose microfibrils to ultra-high pressure treatment may be mentioned.

[0026] As the microfibrillated plant fibers, products of, for example, Sugino Machine Ltd., Daicel Finechem Ltd., and the like can be used.

[0027] In addition, as the microfibrillated plant fiber, those obtained by the above production method and further subjected to oxidation treatment or various chemical modification treatments, or natural products (for example, wood, pulp, bamboo, hemp, jute, kenaf, agricultural crop residues, cloth, paper, tunic cellulose, etc.) that can be the origin of the above cellulose microfibrils can be used as cellulose raw materials, subjected to oxidation treatment or various chemical modification treatments, and then defibrated as necessary.

[0028] Examples of the above oxidation treatment mode include oxidation treatment using an N-oxyl compound. The oxidation treatment using the N-oxyl compound can be carried out, for example, by a method in which the N-oxyl compound is used as an oxidation catalyst in water and a co-oxidizing agent is allowed to act on the microfibrillated plant fiber. Examples of the N-oxyl compound include 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its derivatives. Examples of the co-oxidizing agent include sodium hypochlorite.

[0029] The above organic mixture may further contain other compounding agents (inorganic fillers such as silica, silane coupling agents, zinc oxide, stearic acid, anti-aging agents, oils, waxes, cross-linking agents such as sulfur, vulcanization accelerators, etc.) commonly used in the rubber industry field such as tire materials. The organic mixture can be produced using known kneading methods and the like.

[0030] In the present invention, thermogravimetric analysis is used to perform a measurement step of measuring the temperature change of the mass of the organic mixture. As an apparatus for performing thermogravimetric analysis, a commercially available general-purpose apparatus can be used. Thus, the method of the present invention includes a measurement step of measuring the temperature change of the mass of the organic mixture by thermogravimetric analysis.

[0031] The measurement atmosphere in the above measurement step can be an atmosphere generally used when performing thermogravimetric analysis and is not particularly limited. Examples include an inert gas atmosphere such as N2, Ar, He, and a CO2 atmosphere.

[0032] The above measurement step includes Step 1 of measuring the mass of the organic mixture while increasing the temperature at 50°C / min or less, and Step 2 of measuring the mass of the organic mixture while increasing the temperature at 0.1°C / min or less after detecting a mass decrease.

[0033] In Step 1, using a thermogravimetric analyzer, the organic mixture is heated while increasing the temperature at 50°C / min or less, and the mass of the organic mixture at that time is measured. From the viewpoint of analysis accuracy, the heating rate is preferably 40°C / min or less, more preferably 30°C / min or less, still more preferably 20°C / min or less. Also, the lower limit of the heating rate is not particularly limited, but from the viewpoints of analysis efficiency, etc., it is preferably 5°C / min or more, more preferably 7°C / min or more, still more preferably 10°C / min or more, and even more preferably 15°C / min or more.

[0034] When measuring the mass of the organic mixture while increasing the temperature at 50°C / min or less in Step 1, a mass decrease is necessarily detected at a certain temperature. This is due to some of the components in the organic mixture starting to thermally decompose. In the present invention, after such a mass decrease is detected, the process proceeds to Step 2 of measuring the mass of the organic mixture while increasing the temperature at 0.1°C / min or less. That is, in Step 2, after detecting a mass decrease in Step 1, the mass of the organic mixture is measured while increasing the temperature at 0.1°C / min or less.

[0035] As the detection of the above mass decrease, it is preferable to detect a mass decrease corresponding to 3% by mass of the mass of the organic mixture used for the measurement. That is, in the present invention, the organic mixture is heated while increasing the temperature at 50°C / min or less, and the mass of the organic mixture at that time is measured. After detecting a mass decrease corresponding to 3% by mass of the mass of the organic mixture used for the measurement, it is preferable to measure the mass of the organic mixture while increasing the temperature at 0.1°C / min or less. As the detection of the mass decrease, from the viewpoint of analysis accuracy, it is more preferable to detect a mass decrease corresponding to 1% by mass of the mass of the organic mixture used for the measurement, still more preferably 0.5% by mass, and even more preferably 0.1% by mass.

[0036] After detecting the mass decrease in the above step 1, as the timing for shifting to the above step 2, it is preferable to shift to the above step 2 as soon as possible after detecting the mass decrease in the above step 1. Specifically, it is preferable to shift to the above step 2 before the temperature rises by 10 °C from the temperature at the time when the mass decrease is detected in the above step 1, more preferably before the temperature rises by 7 °C, still more preferably before the temperature rises by 5 °C, even more preferably before the temperature rises by 3 °C, and even more preferably before the temperature rises by 1 °C.

[0037] As the temperature rising rate in the above step 2, from the viewpoint of analysis accuracy, it is preferably 0.05 °C / min or less, more preferably 0.01 °C / min or less, still more preferably 0.005 °C / min or less, and even more preferably 0.001 °C / min or less. Also, the lower limit of the temperature rising rate is not particularly limited, but in consideration of the performance of the analyzer etc., for example, it can be 0.0001 °C / min or more.

[0038] As the temperature range measured in the above measurement step, it may be measured from room temperature (23 °C) until the temperature is raised in the above step 1, the mass decrease is detected and shifted to the above step 2, and then no further mass decrease is observed. For example, it is preferably measured from room temperature to 1000 °C, more preferably from room temperature to 900 °C, still more preferably from room temperature to 800 °C, and even more preferably from room temperature to 750 °C.

[0039] The method of the present invention preferably includes a quantification step of obtaining a temperature differential curve of the mass decrease rate from the temperature change curve of the mass obtained in the above measurement step, separating peaks from the temperature differential curve, and quantifying the components in the above organic mixture by function fitting (curve fitting).

[0040] From the temperature change curve of the mass (data of mass M and the temperature T at that time) obtained in the above measurement step, the mass decrease rate M p can be obtained by the following formula. Mp =(M0 - M T ) / M0 (In the above formula, M0 represents the initial mass at room temperature. M T represents the mass at temperature T.)

[0041] Subsequently, the temperature differential curve dM p / dT of the mass reduction rate is calculated and plotted against the temperature T. When the thermal decomposition behavior occurs in multiple stages, the number of peaks corresponding to the number of stages can be confirmed. For each peak, function fitting is performed, and by calculating the integral value, each component in the organic mixture can be quantified. It should be noted that it is preferable to execute the above quantification process by a computer.

[0042] As the above function fitting, in addition to fitting by a Gaussian function, it can also be fitted by a gamma function, a Weibull function, etc.

[0043] As described above, in the method of the present invention, by thermogravimetric analysis, the mass of the organic mixture is measured while increasing the temperature at 50 °C / min or less. After detecting the mass reduction, the mass of the organic mixture is measured while increasing the temperature at 0.1 °C / min or less, and the mixing ratio of the organic mixture is calculated. Thus, the mixing ratio of the organic mixture can be accurately calculated.

Example

[0044] Based on the examples, the present invention will be specifically described, but the present invention is not limited thereto.

[0045] Various chemicals used in the examples and comparative examples will be described below. CNF: Biomass nanofiber manufactured by Sugino Machine Ltd. (product name "BiNFi-s cellulose", solid content: 2% by mass, moisture: 98% by mass, average fiber diameter: 10 - 50 nm, average fiber length: 2 - 5 μm) TEMPO: 2,2,6,6 - tetramethylpiperidine - 1 - oxyl Sodium bromide: Manufactured by Fujifilm Wako Pure Chemical Corporation Sodium hypochlorite: manufactured by Tokyo Chemical Industry Co., Ltd. NaOH: NaOH manufactured by Fujifilm Wako Pure Chemical Corporation Hydrophobic agent: Kireslite CW manufactured by Kires Co., Ltd. Polyisoprene: LIR-403 (maleic anhydride-modified liquid polyisoprene, Mn = 34000) manufactured by Kuraray Co., Ltd. Polybutene: Nisseki Polybutene HV1900 manufactured by JX Nippon Oil & Energy Corporation

[0046] (Preparation of microfibrillated plant fiber dispersion (CNF aqueous dispersion)) After dispersing 10 g of CNF, 150 mg of TEMPO, and 1000 mg of sodium bromide in 1000 ml of water, an aqueous 15% by mass sodium hypochlorite solution was added so that the amount of sodium hypochlorite was 5 mmol per 1 g of CNF (absolute dry) to initiate the reaction. During the reaction, a 3M aqueous NaOH solution was added dropwise to maintain the pH at 10.0. When no change in pH was observed, the reaction was considered complete, and the reaction product was filtered through a glass filter. Then, washing with a sufficient amount of water and filtration were repeated 5 times to obtain reaction product fibers (TEMPO-oxidized CNF) impregnated with 15% by mass of water. Further, it was diluted to obtain a 1% by mass CNF aqueous dispersion.

[0047] (Sample manufacturing method) 1000 ml of the prepared 1% by mass CNF aqueous dispersion and 5 g of the hydrophobic agent were mixed and dehydrated. Then, 500 ml of 1-butanol was added, and the mixture was stirred at room temperature (20 - 30°C) for 5 minutes using a high-speed homogenizer to disperse it, and then further dehydrated to obtain a CNF dispersion slurry. According to the formulation shown in Table 1, polyisoprene and polybutene were added to the CNF dispersion slurry, and the mixture was stirred at room temperature (20 - 30°C) for 5 minutes using a high-speed homogenizer and then dried to obtain a masterbatch (Formulations 1 - 5).

[0048]

Table 1

[0049] (Comparative Example 1) The composition 1 was heated under the following measurement conditions using a thermogravimetric analyzer ("TGA Q500" (product name) manufactured by TA Instruments) to track the temperature change of the mass. <Measurement conditions> Temperature range: room temperature to 750 °C Heating rate: 50 °C / min Measurement atmosphere: nitrogen atmosphere

[0050] (Comparative Example 2) The compositions 1 to 5 were heated under the following measurement conditions using a thermogravimetric analyzer ("TGA Q500" (product name) manufactured by TA Instruments) to track the temperature change of the mass. <Measurement conditions> Temperature range: room temperature to 750 °C Heating rate: 50 °C / min Measurement atmosphere: nitrogen atmosphere

[0051] Furthermore, from the obtained temperature change curve of the mass (data of mass M and temperature T at that time), the mass reduction rate M p was determined by the following formula. M p =(M0 - M T ) / M0 (In the above formula, M0 represents the initial mass at room temperature. M T represents the mass at temperature T.) Subsequently, the temperature differential curve dM p / dT of the mass reduction rate was calculated and plotted against temperature T. Gaussian function fitting was performed for each peak of the obtained curve.

[0052] (Example 1) The compositions 1 to 5 were heated under the following measurement conditions using a thermogravimetric analyzer ("TGA Q500" (product name) manufactured by TA Instruments) to track the temperature change of the mass. <Measurement conditions> Temperature range: room temperature to 750 °C Heating rate: 20 °C / min, provided that after detecting a mass reduction corresponding to 0.1 mass% of the mass of the sample used for the measurement, it shifts to 0.001 °C / min until the temperature is increased by 1 °C Measurement atmosphere: nitrogen atmosphere

[0053] Furthermore, from the obtained temperature change curve of the mass (data of mass M and temperature T at that time), the mass reduction rate M p was determined by the following formula. M p = (M0 - M T ) / M0 (In the above formula, M0 represents the initial mass at room temperature. M T represents the mass at temperature T.) Subsequently, the temperature differential curve dM p / dT of the mass reduction rate was calculated and plotted against temperature T. For each peak of the obtained curve, fitting was performed with a Gaussian function.

[0054] When analyzed in Comparative Example 1, a curve representing the relationship between mass and temperature is obtained (Figure 1). From Figure 1, since the curve consists of multiple steps, it can be seen that the thermal decomposition behavior occurs in multiple stages, but since each stage cannot be clearly separated, it is not suitable for quantification.

[0055] When analyzed in Comparative Example 2, a temperature differential curve of the mass reduction rate is obtained (Figures 2, 4, 6, 8, 10). In Figures 2, 4, 6, 8, 10, even when attempting fitting with a Gaussian function, the fitting of the peak at 200 - 300 °C is not successful (thin line: fitting result, thick line: experimental data), and thus it is still inferior in terms of the accuracy of quantification.

[0056] When analyzed in Example 1, a temperature differential curve of the mass reduction rate is obtained (Figures 3, 5, 7, 9, 11). In Figures 3, 5, 7, 9, 11, the fitting with a Gaussian function is performed with high accuracy (thin line: fitting result, thick line: experimental data).

[0057] Also, from the thermal decomposition behavior of each component alone, CNF decomposes below 300 °C, and components other than CNF decompose above 300 °C. Therefore, if the thermal decomposition peaks of the three components up to 300 °C are CNF, and the others are polyisoprene and polybutene, a quantitative value of CNF can be obtained. When plotting the relationship between the theoretical value and the quantitative value, in Example 1, the correlation coefficient R 2It was confirmed that it could be accurately quantified to 0.9761 (Fig. 12). On the other hand, in Comparative Example 2, it was confirmed that the correlation coefficient R 2 was 0.0397, and the quantification accuracy was much inferior to that of Example 1 (Fig. 13).

Claims

1. including a measurement step of measuring the temperature change of the mass of the organic mixture by thermogravimetric analysis, wherein the measurement step includes Step 1 of measuring the mass of the organic mixture while increasing the temperature at 50°C / min or less, and Step 2 of measuring the mass of the organic mixture while increasing the temperature at 0.1°C / min or less after detecting a mass decrease, and a method for calculating the mixing ratio of the organic mixture.

2. The method according to claim 1, including a quantification step of obtaining a temperature differential curve of the mass loss rate from the temperature change curve of the mass obtained in the measurement step, separating peaks from the temperature differential curve, and quantifying components in the organic mixture by function fitting.

3. The method according to claim 2, wherein the quantification step is executed by a computer.

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