Hydrogenated unsaturated dibasic acid composition, method for producing hydrogenated unsaturated dibasic acid composition, polyester composition, and polyamide composition

Abstract

To provide a hydrogenated unsaturated dibasic acid composition exhibiting superior thermal stability, a production method thereof, and a polyester composition and a polyamide composition obtained by reaction of the hydrogenated unsaturated dibasic acid composition.SOLUTION: The present invention provides a hydrogenated unsaturated dibasic acid composition satisfying the following (A) and (B). (A) An iodine value is 55 or more. (B) In a 1H-NMR measurement, a ratio (Olefin Hα / ArHα) of an integral value (Olefin Hα) of a peak corresponding to olefin protons to an integral value (ArHα) of a peak corresponding to aromatic protons is 0.10 or more and 0.80 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel hydrogenated unsaturated dibasic acid composition, a method for producing the same, a polyester composition, and polyamide compositions. [Background technology]

[0002] As the unsaturated dibasic acid composition, a compound obtained by dimerizing an unsaturated fatty acid having 10 to 22 carbon atoms is used. Dimer acids containing dibasic acids as the main component are known. Examples of dimer acids include: Natural or plant-derived fats such as rice bran fatty acids, soybean oil fatty acids, tall oil fatty acids, rapeseed oil fatty acids Acids and their refined forms, such as oleic acid, linoleic acid, linolenic acid, and erucic acid, are obtained from raw materials. Dimer acids that can be used are known.

[0003] Dimer acids are widely used in various applications. For example, These resins are used in various applications as polyamide resins, polyester resins, etc. Various dimer acids are known, and hydrogenated dimer acids are also known. (See, for example, Patent Documents 1 to 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-002085 [Patent Document 2] Japanese Patent Application Publication No. 08-113549 [Patent Document 3] Special Publication No. 08-503453 [Patent Document 4] Japanese Patent Application Publication No. 63-258830 Summary of the Invention [Problem to be solved by the invention]

[0005] Resins with a dimer acid skeleton have a wide range of uses, for example, those used in high-temperature environments. Therefore, the dimer acid used as the raw material is also required to have thermal stability.

[0006] In Patent Documents 1 to 4, the thermal stability of dimer acid and hydrogenated dimer acid is Naturally, the iodine value, olefin protons, and aromatic protons have not been studied. The relationship between the ratio of amines and thermal stability was not investigated at all.

[0007] Therefore, the present invention provides a hydrogenated unsaturated dibasic acid composition having excellent thermal stability, a method for producing the same, and a method for producing the same. and a method for producing the hydrogenated unsaturated dibasic acid composition. The present invention aims to provide a triamide composition. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that a hydrogenated unsaturated dibasic acid composition can be produced under specific conditions. By satisfying the above conditions, the inventors have surprisingly found that excellent thermal stability is exhibited. This led to the completion of the Ming Dynasty.

[0009] That is, the present invention relates to a hydrogenated unsaturated dibasic acid composition that satisfies the following (A) and (B): do. (A) The iodine value is 55 or higher. (B) 1 In H-NMR measurement, the integral value of the peak corresponding to the olefin proton (Ol The ratio of the integrals of the peaks corresponding to aromatic protons (ArHα) to those of the peaks corresponding to aromatic protons (Ole fin Hα / ArHα) is between 0.10 and 0.80.

[0010] The hydrogenated unsaturated dibasic acid composition is selected from the group consisting of oleic acid, linoleic acid, and / or linolenic acid. Preferably, the feed composition is a partial hydrogenation product containing the dimerization product of

[0011] the hydrogenated unsaturated dibasic acid composition comprises a monobasic acid; The content of the monobasic acid is determined by the area ratio of gas chromatography. It is preferably 10% or less relative to 100% of the composition.

[0012] The present invention also provides a hydrogenated unsaturated dibasic acid composition obtained by reacting the hydrogenated unsaturated dibasic acid composition with a polyol component. A polyester composition, comprising the hydrogenated unsaturated dibasic acid composition reacted with a polyamine component. The present invention relates to a polyamide composition.

[0013] The present invention also provides a method for hydrogenating a raw material composition containing an unsaturated dibasic acid using a hydrogenation catalyst. The present invention also relates to a method for producing the hydrogenated unsaturated dibasic acid composition, which comprises a hydrogenation step.

[0014] It is preferable to include a step of treating the composition after the hydrogenation step with an acid and clay.

[0015] Preferably, the acid is citric acid.

[0016] The hydrogenation catalyst is preferably a nickel catalyst. [Effects of the Invention]

[0017] The hydrogenated unsaturated dibasic acid composition of the present invention has a specific iodine value and 1 H-NMR The integral value of the peak corresponding to the olefin proton (Olefin Hα) in the measurement The ratio of the integrals of the peaks corresponding to aromatic protons (ArHα) (Olefin Hα / ArH When α) is in a specific range, the hydrogenated unsaturated diolefin copolymer of the present invention has excellent thermal stability. The base-acid composition has excellent thermal stability and is therefore useful as an additive for lubricating oils, fuel oils, rust inhibitors, It can be used in a wide range of applications, such as ink compositions and flux compositions. A polyester composition or a polyamide composition obtained by reacting the hydrogenated unsaturated dibasic acid composition of It also has excellent thermal stability and is used in drilling fluids, adhesives, resin compositions, hot melt composites, etc. The composition can be used in a wide range of applications, such as in coating compositions, primer compositions, polyurethane compositions, etc. DETAILED DESCRIPTION OF THE INVENTION

[0018] 1. Hydrogenated unsaturated dibasic acid composition The hydrogenated unsaturated dibasic acid composition of the present invention satisfies the following (A) and (B). (A) The iodine value is 55 or higher. (B) 1 In H-NMR measurement, the integral value of the peak corresponding to the olefin proton (Ol The ratio of the integrals of the peaks corresponding to aromatic protons (ArHα) to those of the peaks corresponding to aromatic protons (Ole fin Hα / ArHα) is between 0.10 and 0.80.

[0019] The hydrogenated unsaturated dibasic acid composition of the present invention is an unsaturated dibasic acid that satisfies the above requirements (A) and (B). It is sufficient if the composition is a basic acid composition. unsaturated dibasic acid obtained by hydrogenating a raw material unsaturated dibasic acid composition such as dimer acid In order to distinguish the dibasic acid composition from the raw unsaturated dibasic acid composition, the unsaturated The dibasic acid composition is labeled "hydrogenated" and the unsaturated bonds in the raw material unsaturated dibasic acid composition are This represents a state in which some bonds have been converted back to saturated bonds.

[0020] The dimer acid is obtained by dimerizing a monobasic unsaturated fatty acid having 10 to 22 carbon atoms. It is preferable that the raw material contains a dibasic acid. Examples of unsaturated fatty acids include oleic acid, elaidic acid, and erucic acid. Among these are the dimerization products of oleic acid, linoleic acid, and / or linolenic acid. It is preferable that

[0021] Most commercially available dimer acids are made from unsaturated fatty acids with 18 carbon atoms, so the main component is The dimer acid is a dibasic acid with 36 carbon atoms. Examples of the structure of dimer acids include the following: It is not limited to these. [ka]

[0022] As the dimer acid, either a synthetic product or a commercially available product can be used. Specifically, the monobasic acid (unreacted and isomers, etc.), dibasic acids (main components), tribasic acids, etc. (by-products), There are various standards depending on the content ratio, etc.

[0023] When the dimer acid contains a monobasic acid, the content of the monobasic acid is not particularly limited. It is preferable that the area ratio of the dimer acid in the chromatographic analysis is 10% or less relative to 100% of the dimer acid. It's nice.

[0024] When the dimer acid contains a tribasic acid, the content of the tribasic acid is not particularly limited. It is preferable that the area ratio of the dimer acid in the chromatographic analysis is 10% or less relative to 100% of the dimer acid. It's nice.

[0025] Commercially available dimer acids include, for example, Tsunodyme 228 and Tsunody me 205, Tsunodyme 216, Tsunodyme 395, Tsuno dyme 398 (hereinafter referred to as Td228, Td205, Td216, Td395, Both are manufactured by Tsuno Oleochemicals Co., Ltd.) and Haridimer 200 (H Among these, Td228, Td395, Td398 is preferred.

[0026] The compositions of the above commercially available products are as follows. Each composition is determined by liquid chromatography or gas chromatography. Although it can be measured by gas chromatography, in this disclosure, The analytical conditions for gas chromatography are as described in the examples. do.

[0027] [Table 1]

[0028] The method for producing the hydrogenated unsaturated dibasic acid composition of the present invention is not particularly limited. As a method, for example, a non-hydrogenated raw material such as the above-mentioned synthetic or commercially available dimer acid can be used. The unsaturated dibasic acid composition is not completely hydrogenated, but is hydrogenated under mild conditions (e.g., hydrogen pressure 1.0 MPa). G or less), and then partially hydrogenate it (partial hydrogenation) under the above conditions (A ) and (B). In other words, it is possible to satisfy both the above conditions (A) and (B). This improves the thermal stability of the hydrogenated unsaturated dibasic acid composition. If the above synthetic or commercially available products are not hydrogenated, the thermal stability is poor. Dimer acids that are not dimeric do not satisfy either or both of the above conditions (A) and (B).

[0029] The iodine value of the hydrogenated unsaturated dibasic acid composition of the present invention is 55 or more, preferably 58 or more. The iodine value is preferably 200 or less, more preferably 60 or more. Here, the iodine value is the iodine value added to 100 g of the hydrogenated unsaturated dibasic acid composition. The higher the degree of unsaturation of the hydrogenated unsaturated dibasic acid composition, the higher the iodine content. The iodine value increases as the iodine value increases. When the iodine value is in the above range, excellent thermal stability can be obtained. .

[0030] The hydrogenated unsaturated dibasic acid composition of the present invention 1 In H-NMR measurements, olefin protons The integral value of the peak corresponding to the aromatic proton (Olefin Hα) and the peak corresponding to the aromatic proton The ratio of the integral value (ArHα) of ArHα (Olefin Hα / ArHα) is 0.10 or more and 0.80 or more. When the ratio is less than 0.12, excellent thermal stability can be obtained. It is more preferably 15 or more, and is preferably 0.75 or less, and more preferably 0.70 or less.

[0031] The hydrogenated unsaturated dibasic acid composition of the present invention is a monobasic acid (a partially or fully hydrogenated monobasic acid). In the case where the raw material contains a monobasic acid and a monobasic acid and its isomers, The content is determined by gas chromatography based on 100% of the hydrogenated unsaturated dibasic acid composition. The volume ratio is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less.

[0032] The hydrogenated unsaturated dibasic acid composition of the present invention is a tribasic acid (a partially or fully hydrogenated tribasic acid). In the case where the raw material contains a tribasic acid and a tribasic acid and its isomers, The content is determined by gas chromatography based on 100% of the hydrogenated unsaturated dibasic acid composition. A volume ratio of 10% or less is preferable.

[0033] The hydrogenated unsaturated dibasic acid composition of the present invention is reacted with a polyol component to form a polyester. A composition (including a polyester polyol composition) can be obtained. The composition can be used as a urethane resin for adhesives, coating agents, paints, etc.

[0034] As the polyol component, a conventional one used in the production of polyesters can be used. For example, ethylene glycol, diethylene glycol, triethylene glycol, Aliphatic diols such as propylene glycol and neopentyl glycol; 1,2,3-propanol Aliphatic tolubricants such as panthenol, 1,2,4-butanetriol, and trimethylolpropane 1,2-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol alicyclic diols such as 1,4-cyclohexanedimethanol; 4,4'-methylenediphenyl These polyols may be used alone. Alternatively, two or more types may be used in combination.

[0035] The hydrogenated unsaturated dibasic acid composition of the present invention may also be reacted with a polyamine component such as a diamine. The polyamide composition can be obtained by, for example, It can be used as a binder, ink binder, hot melt adhesive, etc.

[0036] As the diamine, a diamine generally used in the production of polyamides can be used, for example, For example, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, etc. aliphatic diamines such as cyclohexanediamine; alicyclic diamines such as cyclohexanediamine; xylylenediamine, Examples of the diamine include aromatic diamines such as benzenediamine. They may be used alone or in combination of two or more.

[0037] 2. Method for producing hydrogenated unsaturated dibasic acid composition The method for producing the hydrogenated unsaturated dibasic acid composition of the present invention is not particularly limited. For example, a step of hydrogenating a raw material composition containing the unsaturated dibasic acid before hydrogenation using a hydrogenation catalyst; A manufacturing method including the steps of:

[0038] The hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst. From the viewpoint of ease of carrying out subsequent post-treatment, heterogeneous catalysts are preferred.

[0039] The hydrogenation catalyst is not particularly limited, but may be an iridium catalyst, a nickel catalyst, a para Examples of catalysts include rhodium catalysts, platinum catalysts, rhodium catalysts, and ruthenium catalysts. Among these, nickel catalysts are preferred from the viewpoint of economy.

[0040] Nickel catalysts include nickel metal powder, alloys with other metals, oxides, and hydroxides. The catalyst may be an inorganic salt, an organic salt, a Raney catalyst, or any of these supported on a carrier. Such catalysts include, for example, metallic nickel, reduced nickel, stabilized nickel, nickel -Diatomaceous earth, Raney nickel, modified Raney nickel, nickel formate, Urushibara nickel, Nickel oxide, nickel complex, nickel-copper-diatomaceous earth, nickel-zirconium Nia-diatomaceous earth, nickel-alumina, nickel-silica-alumina, nickel-cobalt , nickel-copper-cobalt, nickel-iron, nickel-iron-cobalt, nickel-iron-lithium Nickel oxide-silica, nickel oxide-magnesium oxide-alumina and nickel oxide Examples include molybdenum trioxide-alumina and the like.

[0041] Among these, stabilized nickel catalysts using diatomaceous earth as a support have suitable catalytic activity for hydrogenation reactions. Specifically, the commercially available stabilized nickel catalyst SN-110 , SN-150, SN-250, SN-300, SN-750 (Sakai Chemical Co., Ltd.), Ni -5123P, Ni-5136P, Ni-5256P, Ni-0104T, Ni-326 6. Ni-3288E, Ni-3737T, Ni-5256E (N.E. Chemcat Among these, SN-750 is preferred.

[0042] The amount of the nickel catalyst used is determined based on the hydrogenated unsaturated disodium salt that satisfies the above conditions (A) and (B). The amount is not particularly limited as long as it can form a basic acid composition. For example, The content is preferably 0.1 to 20% by weight, more preferably 0.5 to 1% by weight, based on the raw material composition (100% by weight) containing the compound. By setting the content within the above range, the above conditions (A) and (B) are satisfied. This is preferred because it allows the formation of a hydrogenated unsaturated dibasic acid composition.

[0043] The raw material composition containing the unsaturated dibasic acid before hydrogenation as the raw material is the dimer acid Among the dimer acids, oleic acid, linoleic acid, and / or linoleic acid are preferred. Dimer acids of carboxylic acids are preferred.

[0044] The hydrogenation time is, for example, preferably 1 to 50 hours, more preferably 3 to 48 hours. By setting the range, a hydrogenated unsaturated dibasic acid composition that satisfies the above conditions (A) and (B) can be formed. This is preferable because it can be achieved.

[0045] The hydrogenation temperature is, for example, preferably 100 to 250°C, more preferably 150 to 200°C. By setting the above range, it is possible to obtain a hydrogenated unsaturated dibasic alcohol that satisfies the above conditions (A) and (B). This is preferred because it allows the formation of an acid composition.

[0046] The hydrogenation is preferably carried out under hydrogen pressure. The hydrogen pressure is preferably 0.1 MPaG or more. The upper limit of the hydrogen pressure is determined by the pressure vessel to be used, etc. The hydrogen pressure is determined by, for example, 1.0 MPaG or less. If the temperature exceeds this range, complete hydrogenation is likely to occur, which is not preferable.

[0047] After the hydrogenation step, a step of treating the composition after the hydrogenation step with an acid and clay may be included. .

[0048] The acid may be citric acid, phytic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, etidronic acid, lactic acid, succinic acid, malic acid, fumaric acid, Among these, the most popular are those that are economical and have the potential to remain in the product. Citric acid is preferred from the viewpoint of less noise.

[0049] The amount of the acid used is not particularly limited. For example, The amount is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total weight of the acid composition. It's nice.

[0050] The acid can be added as an aqueous solution, and the concentration of the aqueous solution is not particularly limited. For example, For example, it is preferably 0.1 to 50% by weight, and can be about 0.1 to 30% by weight. More preferable.

[0051] Examples of the white clay include activated white clay obtained by activating white clay or acid white clay with an acid such as a mineral acid. Examples of activated clay include Galleon Earth V2 and Galleon Earth. V2R, Galleon Earth NV, Galleon Earth NVZ, Galleon Knight #251, Galleona Ito #212, Galleonite #136, Galleonite #336, Galleonite #436 ( Mizusawa Chemical Industry Co., Ltd.), activated clay SA85, activated clay SA1 (Toshin Kasei Co., Ltd.), Tonsil SUPREME134FF, Tonsil OPTIMUM231S, Tonsil OPTI Examples of commercially available products include MUM230FF (manufactured by Clariant).

[0052] The amount of the clay used is not particularly limited. For example, The content is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight.

[0053] By treating with the acid and clay, fatty acid salts formed by the hydrogenation catalyst are removed. This is preferable because it can

[0054] The hydrogenation step and the step of treating with acid and clay can be repeated two or more times.

[0055] The reduction rate of the iodine value due to the hydrogenation (iodine value after hydrogenation / iodine value of raw material before hydrogenation) ) is preferably 0.3 or more and 0.9 or less, and more preferably 0.4 or more and 0.85 or less. The range is preferable because excellent thermal stability is obtained.

[0056] By the hydrogenation 1 The peak integral ratio in H-NMR (Olefin Hα / Ar The reduction rate of Hα (integral value ratio after hydrogenation / integral value ratio of raw material before hydrogenation) is 0.05 or more. It is preferable that the ratio is 0.6 or less, and more preferably 0.1 or more and 0.5 or less. This is preferable because of its excellent stability.

[0057] According to the production method of the present invention, a hydrogenated unsaturated dibasic acid satisfying the above conditions (A) and (B) can be obtained. The hydrogenated unsaturated dibasic acid composition obtained has excellent thermal stability. This is what is done. [Example]

[0058] The present invention will be described in more detail below with reference to examples and comparative examples. The examples are not intended to be limiting.

[0059] [Raw materials for hydrogenated unsaturated dibasic acid composition] The starting dimer acids used in the production of the hydrogenated unsaturated dibasic acid composition are as follows: (dimer acid) Td228: Product name, manufactured by Tsuno Oleochemicals Co., Ltd. Td395: Product name, manufactured by Tsuno Oleochemicals Co., Ltd. Td398: Product name, manufactured by Tsuno Oleochemicals Co., Ltd. Empol 1061: Product name, manufactured by Emery Empol 1062: Product name, manufactured by Emery Pripol 1013: Trade name, manufactured by Cargill Pripol 1098: Trade name, manufactured by Cargill OLEON975: Product name, manufactured by Oleon (Among the above dimer acids, the compositions of Td228, Td395, and Td398 are shown in Table 1 above.) The composition of the other dimer acids is as shown in Table 2 below. The analytical conditions are as described below.) [Table 2]

[0060] Example 1 Dimer acid (trade name: Td395, manufactured by Tsuno Oleochemicals Co., Ltd.) and 1% by weight of Ni catalyst (product name: SN-750, manufactured by Sakai Chemical Industry Co., Ltd.) was added to the autoclave. The mixture was charged and heated to 180°C. The mixture was pressurized with hydrogen to 0.7 MPaG and hydrogenated for 3 hours. A composition containing hydrogenated dimer acid was obtained. After the hydrogenation was completed, the Ni catalyst was removed by filtration. After that, 20 wt% citric acid aqueous solution and Galleon Earth (registered trademark) V2 were hydrogenated. The dimer acid was added in amounts of 1.3% by weight and 2.0% by weight, and the mixture was heated to 90°C. After dehydration under reduced pressure of 5 Torr for 1 hour, filtration was carried out to obtain a hydrogenated unsaturated dibasic acid composition.

[0061] The obtained hydrogenated unsaturated dibasic acid composition was subjected to gas chromatography measurement under the conditions described below. The results showed that the content of monobasic acids was 0.6% (relative area) and the content of dibasic acids was 98. 9% (relative area), the tribasic acid content is 0.5% (relative area), and the raw material dimer acid It was found that the contents of monobasic, dibasic, and tribasic acids were almost the same as those of the

[0062] Examples 2 to 4 The same procedure as in Example 1 was carried out except that the hydrogenation time was changed to the time shown in Table 3. A dibasic acid composition was obtained.

[0063] Example 5 The hydrogenated unsaturated dibasic acid composition obtained in Example 4 was mixed with 1% by weight of a Ni catalyst (product number 1001001001). Add SN-750 (manufactured by Sakai Chemical Industry Co., Ltd.) and place in an autoclave at 180°C. The mixture was heated and pressurized to 0.7 MPaG with hydrogen and hydrogenated for another 24 hours. After the hydrogenation was completed, the Ni catalyst was removed by filtration. After that, 20% by weight of citric acid aqueous solution and Galleon Earth (registered trademark) V2 were added to the above two The amount of the hydrogenated unsaturated dibasic acid composition was 1.3% by weight and 2.0% by weight. The mixture was heated to 90°C. After dehydration under reduced pressure at 0 to 5 Torr for 1 hour, the mixture was filtered and the hydrogenated residue was removed. A saturated dibasic acid composition was obtained.

[0064] Example 6 The same procedure as in Example 4 was repeated except that the amount of Ni catalyst added was 7% by weight based on the dimer acid. A chlorinated unsaturated dibasic acid composition was obtained.

[0065] (Examples 7 to 14) Hydrogenation was carried out in the same manner as in Example 1, except that the type of dimer acid and the hydrogenation time were changed as shown in Table 3. A hydroxylated unsaturated dibasic acid composition was obtained.

[0066] (Comparative Examples 1 to 8) The dimer acids used in the examples and commercially available dimer acids were used as they were without hydrogenation. Various physical properties were also measured.

[0067] Comparative Example 9 In Example 4, the Ni catalyst was replaced with 2 wt % of a Pd catalyst (metal loading: 5%, palladium The same procedure as in Example 4 was carried out except that the carbon (AD, manufactured by Kawaken Fine Chemical Co., Ltd.) was used. After hydrogenation by the method, the Pd catalyst was removed by filtration. Treatment with aqueous citric acid and Galleon Earth® V2 was not performed.

[0068] (Comparative Example 10) A hydrogenated unsaturated dibasic acid composition was prepared in the same manner as in Comparative Example 9, and the Pd catalyst was removed by filtration. After removing the citric acid solution, 20% by weight of the citric acid solution and Galleon Earth (registered trademark) V2 were added to the water. The mixture was added in amounts of 1.3% by weight and 2.0% by weight based on the amount of chlorinated dimer acid, and heated to 90°C. After dehydration under reduced pressure at 0 to 5 Torr for 1 hour, the mixture was filtered to obtain a hydrogenated unsaturated dibasic acid composition. Ta.

[0069] (Comparative Examples 11 and 12) The same procedure as in Comparative Example 9 was repeated except that the type of dimer acid was changed as shown in Table 4. A base acid composition was obtained.

[0070] Regarding the obtained hydrogenated unsaturated dibasic acid composition and unhydrogenated dimer acid (raw material) The following evaluations were carried out.

[0071] [Evaluation method] <Composition analysis using gas chromatography> As a pretreatment for gas chromatography analysis, the raw material dimer acid and the obtained hydrogenated unsaturated fatty acid were The saturated dibasic acid composition was subjected to dimethylation by a conventional method. The gas chromatography of the dimer acid and unsaturated dibasic acid composition treated as above showed the following: Measurement was performed under the following conditions. Analytical column: A non-polar capillary column chemically bonded with dimethylpolysiloxane (column length: 5m) Heating conditions: After holding at 100°C for 1 minute, heat to 350°C at 20°C / min and hold for 20 minutes Detector and temperature: Flame ionization detector (FID), 380°C Injected sample: 1.0 μL (hexane solution) (evaluation) Among the gas chromatograms obtained under the above analytical conditions, peaks with retention times of 4.5 to 7.0 minutes were The peak at 9.0 - 14.7 minutes was regarded as dibasic acid, and the peak at 14.7 - 18.8 minutes was regarded as tribasic acid, with the peak at one minute being monobasic acid.

[0072] <Evaluation method of iodine value (IV)> It was measured according to JIS K 0070.

[0073] <Calculation method of Olefin Hα and ArHα> The 1H-NMR spectra of Olefin Hα and ArHα were measured under the following conditions. · NMR apparatus: manufactured by Bruker BioSpin · Spectrometer: AVANCE III HD 400 manufactured by Bruker BioSpin · Number of data points: 64k · Number of dummy scans: 2 times · Observed nucleus: 1H · Number of integrations: 16 times · Observed frequency: 400.26 MHz · NMR sample tube: 5 mm φ · Sample amount: 5 - 20 mg <00005​​​​​​​​​​​​​​​​​​​​​​​​​​​​​The weight after the elapse of time was measured (Bg). Heat resistance was evaluated according to the following formula. Heat resistance (weight loss %)=(A-B) / A×100 The lower the value, the better the heat resistance.

[0075] <Thermal decomposition start temperature (℃)> The thermal decomposition onset temperature of the obtained hydrogenated unsaturated dibasic acid composition and the unhydrogenated dimer acid was performed using a thermal analyzer ("Thermo plus TG8120", manufactured by Rigaku). In a nitrogen atmosphere, with a sample weight of 10 mg, the temperature rise rate was 10°C / min (maximum temperature reached: 500°C). The TG curve obtained was compared with the tangent of the TG curve at 100°C, and the curve that rapidly overlapped on the high temperature side. The temperature at which the tangents to the inflection points of the TG curve where the amount of carbon dioxide decreases intersect was taken as the thermal decomposition starting temperature.

[0076] Example 13 The hydrogenated unsaturated dibasic acid composition obtained in Example 4 and the hydrogenated unsaturated dibasic acid composition The mixture was 96.5% by weight of PEG400 (polyethylene glycol with a molecular weight of approximately 400 g / mol). The mixture was placed in a separable flask equipped with a stirrer, a thermometer, a dehydration tube and a condenser. The mixture was heated to 0°C. The pressure was reduced and the condensed water was removed from the system, while the reaction was carried out for 5 hours under a nitrogen stream. The hydroxyl value of this polyester was determined according to JIS K 0070 (neutralization titration) The hydroxyl value was measured in accordance with the method and found to be 39.4 mg KOH / g.

[0077] Example 14 The hydrogenated unsaturated dibasic acid composition obtained in Example 4 and the hydrogenated unsaturated dibasic acid composition 5.6% by weight of 1,2-ethanediamine was added to a separator equipped with a stirrer, thermometer, and reflux condenser. The contents were placed in a rubble flask and heated to 240°C. While removing the condensed water from the system at normal pressure, Polymerization was carried out for 4 hours under a nitrogen stream to obtain a polyamide. The amine value of this polyamide was calculated according to the JIS When measured according to K 7237 (indicator titration method), the amine value was 1 mg KOH / It was g.

[0078] [Table 3]

[0079] [Table 4]

[0080] From the above results, it is clear that the hydrogenated unsaturated dibasic acid composition of the present invention has excellent thermal stability. On the other hand, the hydrogenated unsaturated dibasic acid composition of the comparative example and the raw material dimer acid were inferior in heat resistance. The thermal decomposition starting temperature was also lower than in the examples, indicating poor thermal stability.

Claims

1. A hydrogenated unsaturated dibasic acid composition that satisfies the following (A) and (B): (A) The iodine value is 55 or more. (B) １ In the H-NMR measurement, the integral value of the peak corresponding to the olefin proton (O The ratio of the integral value of the peak corresponding to the aromatic proton (ArHα) to the integral value of the peak corresponding to the aromatic proton (Ole fin Hα / ArHα) is 0.10 or more and 0.80 or less.

2. A portion of the raw material composition comprising dimerization products of oleic acid, linoleic acid, and / or linolenic acid. The hydrogenated unsaturated dibasic acid composition according to claim 1, which is a partially hydrogenated product.

3. the hydrogenated unsaturated dibasic acid composition comprises a monobasic acid; The content of the monobasic acid is determined by the area ratio of gas chromatography.

3. The hydrogenated unsaturated dibasic acid compound according to claim 1, wherein the amount of the hydrogenated unsaturated dibasic acid compound is 10% or less based on 100% of the composition. Acid composition.

4. A hydrogenated unsaturated dibasic acid composition according to claim 1 or 2, which is reacted with a polyol component. A polyester composition.

5. A hydrogenated unsaturated dibasic acid composition according to claim 1 or 2, which is reacted with a polyamine component. A polyamide composition.

6. A hydrogenation step of hydrogenating a raw material composition containing an unsaturated dibasic acid using a hydrogenation catalyst. A method for producing the hydrogenated unsaturated dibasic acid composition according to claim 1 or 2.

7. 7. The hydrogenation method according to claim 6, further comprising treating the composition after the hydrogenation step with an acid and clay. Method for producing a substituted unsaturated dibasic acid composition.

8. The method for producing a hydrogenated unsaturated dibasic acid composition according to claim 7, wherein the acid is citric acid.

9. The hydrogenated unsaturated dibasic acid composition according to claim 6, wherein the hydrogenation catalyst is a nickel catalyst. Manufacturing method.

Images