Method for producing polyurethane

Abstract

The purpose of the present invention is to provide a method for efficiently manufacturing high-quality polyurethane. This method for manufacturing polyurethane is characterized by including: a step in which a specific fluorocarbonate compound and a dihydric alcohol compound are caused to react to obtain a biscarbonate compound; and a step in which the biscarbonate compound and a bivalent amino compound are caused to react to obtain polyurethane.

Description

Technical Field

[0001] The present invention relates to a method for efficiently producing high-quality polyurethane.

Background Art

[0002] Polyurethane is excellent in flexibility and elasticity, so it can be used as a raw material for highly stretchable resins and fibers. On the other hand, by adjusting its chemical structure, it can also be made hard and tough. In addition, it is an extremely excellent material with excellent low-temperature characteristics, abrasion resistance, impact resistance, oil resistance, etc.

[0003] Polyurethane is generally produced by reacting a diisocyanate compound with a dihydric alcohol compound. However, there are concerns about the toxicity of isocyanate compounds, and they are highly reactive and easily react with water, so strict storage conditions such as low humidity and low temperature are required. In addition, polyurethane can also be produced using phosgene instead of isocyanate compounds. Isocyanate compounds themselves are also synthesized industrially by reacting primary amine compounds with phosgene (Patent Document 1, etc.). However, phosgene is a toxic compound as it easily reacts with water to generate hydrogen chloride and has a history of being used as a poisonous gas. In addition, a chlorine component remains in the compound produced using phosgene. For example, Non-Patent Document 1 describes that polycarbonate produced from phosgene contains chloride compounds in the range of several tens to several hundreds of ppm even after thorough purification. A chlorine component also remains in the polyurethane produced using phosgene, and the chlorine component remaining in the polyurethane causes yellowing of the polyurethane and has an adverse effect on metals and living organisms. Therefore, technologies for producing polyurethane without using isocyanate compounds or phosgene have been studied.

[0004] For example, Patent Document 2 and Non-Patent Documents 2 and 3 disclose a technique for producing polyurethane by reacting diphenyl carbonate, which may be substituted with a nitro group or a fluoro group, with a diamino compound. However, diphenyl carbonate itself is generally synthesized by reacting phosgene with phenol, and the method for synthesizing diphenyl carbonate without using phosgene has a large number of steps (Non-Patent Document 4). On the other hand, the present inventors have developed a method capable of safely and efficiently producing carbonate derivatives such as diphenyl carbonate (Patent Documents 3 and 4).

[0005] Note that Patent Document 5 discloses a biscarbonate compound that may have a fluoro group as a non-aqueous solvent for a non-aqueous electrolyte for a secondary battery.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0007]

Non-Patent Document 1

Non-Patent Document 2

[0008] As described above, technologies for producing polyurethane using diphenyl carbonate without using isocyanate compounds or phosgene have already been developed. However, the inventors have found that in the above reaction, although phenol is by - produced, it cannot be completely removed from the biscarbonate compound or polyurethane, remains in the polyurethane, and this residual phenol is easily oxidized, causing discoloration of the polyurethane and a decrease in the degree of polymerization, thereby degrading the quality of the polyurethane. The inventors have also experimentally found that such residual phenol inhibits the polymerization reaction. Therefore, an object of the present invention is to provide a method for efficiently producing high - quality polyurethane. [Means for Solving the Problems]

[0009] The inventors have conducted intensive research to solve the above problems. As a result, they have found that if a specific fluorocarbonate compound is used as a raw material to produce polyurethane, the residual amount of the by - produced fluoroalcohol compound can be reduced, and even if the fluoroalcohol compound remains, it rather imparts favorable properties to the polyurethane, thus completing the present invention. The present invention is shown below.

[0010] [1] A method for producing polyurethane, comprising A step of obtaining a biscarbonate compound represented by the following formula (III) by reacting a fluorocarbonate compound represented by the following formula (I) with a dihydric alcohol compound represented by the following formula (II), and [Chemical formula] [In the formula, Rf 1 independently represents an aliphatic hydrocarbon group having a fluoro group, R 1 represents a divalent organic group.] A method characterized by including a step of obtaining a polyurethane represented by the following formula (V) by reacting the biscarbonate compound represented by the above formula (III) with a diamino compound represented by the following formula (IV). [Chemical formula] [In the formula, Rf 1 and R 1 have the same meanings as described above, R 2 represents a divalent organic group.] [2] The method according to [1] above, wherein the fluorocarbonate compound represented by formula (I) and the dihydric alcohol compound represented by formula (II) are reacted in the presence of a base. [3] The method according to [1] or [2] above, wherein R 1 is a C 2-10 alkanediyl group which may be substituted with a halogeno group. [4] The method according to [1] or [2] above, wherein R 1 is a divalent organic group represented by the formula -R 3 -[-X-R 3 -] m -(wherein X represents O or S, and R 3 represents a C 1-8 alkanediyl group which may be substituted with a halogeno group, and m represents an integer of 1 or more and 180 or less). [5] R 2 is a C 2-10The method according to any one of [1] to [4] above, which is an alkanediyl group. [6] R 2 is C 1-6 Alkanediyl-C 6-12 Aryldiyl-C 1-6 The method according to any one of [1] to [4] above, which is an alkanediyl group. [7] A biscarbonate compound characterized by being represented by the following formula (III-1). [Chemical formula] [In the formula, Rf 2 represents H or an aliphatic hydrocarbon group having a fluoro group, Rf 3 and Rf 4 each independently represent an aliphatic hydrocarbon group having a fluoro group, R 1 represents a divalent organic group.] [Advantages of the Invention]

[0011] According to the method of the present invention, polyurethane can be produced without using a toxic isocyanate compound. Further, it is not necessary to use diphenyl carbonate, which is a substitute for phosgene, and there is no room for the residue of phenol, which is a by-product derived from diphenyl carbonate and causes coloring and reduction of the degree of polymerization of polyurethane. Instead, fluoroalcohol may remain, but the residual amount is less than the phenol residual amount when diphenyl carbonate is used, and the remaining fluoroalcohol can impart preferable properties to the polyurethane. Therefore, the present invention is very useful industrially as a technology capable of safely and efficiently producing high-quality polyurethane. [Modes for Carrying Out the Invention]

[0012] The method for producing a polyurethane according to the present invention includes a step of obtaining a biscarbonate compound represented by formula (III) by reacting a fluorocarbonate compound represented by formula (I) with a dihydric alcohol compound represented by formula (II), and a step of obtaining a polyurethane represented by formula (V) by reacting the biscarbonate compound represented by formula (III) with a diamino compound represented by formula (IV). Hereinafter, each step will be described, but the present invention is not limited to the following specific examples. Hereinafter, "the compound represented by formula (x)" will be abbreviated as "compound (x)".

[0013] 1. Step for producing biscarbonate compound In this step, a biscarbonate compound (III) is obtained by reacting a fluorocarbonate compound (I) with a dihydric alcohol compound (II). In the present invention, due to the combination of the R group in the diamino compound (IV) and the R in the biscarbonate compound (III), it becomes possible to impart desired properties such as high strength, flexibility, and water repellency to the polyurethane. 2 group and the R in the biscarbonate compound (III) 1 It is possible to impart desired properties such as high strength, flexibility, and water repellency to the polyurethane.

[0014] Conventionally, when diphenyl carbonate, which was developed as a substitute for phosgene, is reacted with a dihydric alcohol compound (II), a biscarbonate compound (III) is produced. However, in that case, phenol derived from diphenyl carbonate is by-produced. Since phenol is a solid at room temperature, for example, when trying to remove it from the biscarbonate compound (III) by distillation, the viscosity of the crude composition increases as the distillation progresses, and it becomes difficult to completely remove it. According to the experimental findings of the present inventors, the remaining phenol inhibits the polymerization reaction and also remains in the target polyurethane. Since the remaining phenol is very easily oxidized, it causes the coloring of the polyurethane.

[0015] In contrast, the present invention uses a fluorocarbonate compound (I). In the reaction between the fluorocarbonate compound (I) and the dihydric alcohol compound (II), fluoroalcohol is by-produced, but fluoroalcohol is more easily distilled off than phenol. Further, even if fluoroalcohol remains in the polyurethane, it is clearly less likely to be oxidized than phenol and will not adversely affect the transparency of the polyurethane. Instead, favorable properties resulting from the fluoro group, such as water repellency, antifouling property, weather resistance, and abrasion resistance, can be imparted to the polyurethane.

[0016] Rf in the fluorocarbonate compound (I) independently represents an aliphatic hydrocarbon group having a fluoro group. Examples of the aliphatic hydrocarbon group having a fluoro group include a C 1-10 monovalent chain aliphatic hydrocarbon group, a C 3-10 monovalent cyclic aliphatic hydrocarbon group, and a monovalent organic group formed by bonding two or more and five or less of these groups.

[0017] The "C 1-10 monovalent chain aliphatic hydrocarbon group" refers to a linear or branched monovalent saturated or unsaturated aliphatic hydrocarbon group having 1 or more and 10 or less carbon atoms. For example, C 1-10 As the monovalent chain aliphatic hydrocarbon group, C 1-10 an alkyl group, C 2-10 an alkenyl group, and C 2-10 an alkynyl group can be mentioned.

[0018] C 1-10 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2,2-dimethylethyl, n-pentyl, n-hexyl, 2-hexyl, 3-hexyl, 4-methyl-2-pentyl, n-heptyl, n-octyl, n-decyl, etc. Preferably, it is a C 2-8 alkyl group, and more preferably a C 4-6 alkyl group.

[0019] C 2-10Examples of the alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), butenyl, hexenyl, octenyl, decenyl, and the like. Preferably, it is a C 2-8 alkenyl group, more preferably a C 4-6 alkenyl group.

[0020] C 2-10 Examples of the alkynyl group include ethynyl, propynyl, butynyl, hexynyl, octynyl, pentadecynyl, and the like. Preferably, it is a C 2-8 alkynyl group, more preferably a C 2-6 alkynyl group.

[0021] The "C 3-10 monocyclic aliphatic hydrocarbon group" refers to a cyclic saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. For example, C 3-10 cycloalkyl group, C 4-10 cycloalkenyl group, and C 4-10 cycloalkynyl group can be mentioned.

[0022] Examples of the monovalent organic group in which two or more and five or less C 1-10 monovalent chain aliphatic hydrocarbon groups are bonded to a C 3-10 monocyclic aliphatic hydrocarbon group include, for example, a C 3-10 monocyclic aliphatic hydrocarbon group-C 1-10 divalent chain aliphatic hydrocarbon group, and a C 1-10 monovalent chain aliphatic hydrocarbon group-C 3-10 divalent cyclic aliphatic hydrocarbon group-C 1-10 divalent chain aliphatic hydrocarbon group.

[0023] In the aliphatic hydrocarbon group having a fluoro group, the number of substituted fluoro groups is not particularly limited as long as substitution is possible. However, the more fluoro groups there are, the higher the reactivity of the fluorocarbonate compound (I). Therefore, 2 or more is preferable, and 3 or more is more preferable. Regarding the upper limit of the number of substituted groups, for example, it can be 20 or less, and 15 or less is preferable. As the aliphatic hydrocarbon group, a sec-alkyl group or a tert-alkyl group is preferable, and a sec-perfluoroalkyl group or a tert-alkyl group in which all hydrogen atoms at carbons other than the first carbon are substituted with fluoro groups is more preferable. Further, the fluorocarbonate compound (I) may be substituted with a halogeno group selected from a chloro group, a bromo group, and an iodo group, which are also electron-withdrawing groups, in addition to the fluoro group.

[0024] As the fluorocarbonate compound (I), if a commercially available product is available, a commercially available product may be used, or it may be synthesized. The fluorocarbonate compound (I) can be synthesized, for example, by a conventional method using phosgene, but it can also be synthesized by the reaction of a fluoroaliphatic hydrocarbon ester of trichloroacetic acid with a fluoroalcohol or by the method described in WO2018 / 211953 that does not use phosgene.

[0025] Examples of the fluorocarbonate compound (I) include bis(2,2,2-trifluoroethyl) carbonate, bis(2,2,3,3-tetrafluoropropyl) carbonate, bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, bis(1,1,1,2,2,4,5,5,5-nonafluoro-4-trifluoromethyl-3-pentyl) carbonate, bis[1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl] carbonate, bis(2,2,3,3,3-pentafluoropropyl) carbonate, bis(2,2,3,3,4,4,5,5-octafluoropentyl) carbonate, and bis(2,2,3,3,4,4,5,5-octafluorocyclopentyl) carbonate.

[0026] R in the dihydric alcohol compound (II)1 R represents a divalent organic group. 1 For example, C 1-10 Divalent chain aliphatic hydrocarbon group, C 3-10 Divalent cycloaliphatic hydrocarbon radical, C 6-15 Examples of the divalent aromatic hydrocarbon group include a divalent organic group having two or more and five or less of these groups bonded thereto.

[0027] "C 1-10 The term "divalent chain aliphatic hydrocarbon group" refers to a linear or branched divalent saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. For example, 1-10 As the divalent chain aliphatic hydrocarbon group, C 1-10 Alkanediyl group, C 2-10 Alkenyl groups, and C 2-10 An example is an alkynediyl group.

[0028] C 1-10 Examples of the alkanediyl group include methylene, ethylene, n-propylene, isopropylene, n-butylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, and n-decylene. 2-10 Alkanediyl group or C 1-8 Alkanediyl groups, more preferably C 1-6 Alkanediyl group or C 1-4 It is an alkanediyl group.

[0029] C 2-10 Examples of the alkene diyl group include ethenylene (vinylene), 1-propenylene, 2-propenylene (arylene), butenylene, hexenylene, octenylene, and decenylene. 2-8 Alkenyl groups are preferred, and C 2-6 Alkenyl group or C 2-4 It is an alkenediyl group.

[0030] C 2-10Examples of the alkynediyl group include ethynylene, propynylene, butynylene, hexynylene, octynylene, pentadecynylene, and the like. Preferably, it is a C 2-8 alkynediyl group, more preferably a C 2-6 alkynediyl group or a C 2-4 alkynediyl group.

[0031] The "C 3-10 divalent cyclic aliphatic hydrocarbon group" refers to a cyclic divalent saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. For example, C 3-10 cycloalkanediyl group, C 3-10 cycloalkenediyl group, and C 3-10 cycloalkynediyl group can be mentioned. Examples of the C 3-10 cycloalkanediyl group include cyclobutanediyl, cyclopropanediyl, cyclohexanediyl, and adamantanediyl.

[0032] The "C 6-15 divalent aromatic hydrocarbon group" refers to a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms. For example, phenylene, indenylene, naphthylene, biphenylene, phenalenylene, phenanthrenylene, anthracenylene, etc., preferably a C 6-12 divalent aromatic hydrocarbon group, more preferably phenylene.

[0033] Examples of the divalent organic group in which 2 to 5 groups selected from C 1-10 divalent chain aliphatic hydrocarbon group, C 3-10 divalent cyclic aliphatic hydrocarbon group, and C 6-15 divalent aromatic hydrocarbon group are bonded include, for example, C 3-10 divalent cyclic aliphatic hydrocarbon group-C 1-10 divalent chain aliphatic hydrocarbon group, C 1-10 divalent chain aliphatic hydrocarbon group-C 3-10 divalent cyclic aliphatic hydrocarbon group, C 6-15 divalent aromatic hydrocarbon group-C 1-10 divalent chain aliphatic hydrocarbon group, C 1-10 divalent chain aliphatic hydrocarbon group-C 6-15A divalent aromatic hydrocarbon group, C 1-10 A divalent linear aliphatic hydrocarbon group - C 3-10 A divalent cycloaliphatic hydrocarbon group - C 1-10 A divalent linear aliphatic hydrocarbon group, C 3-10 A divalent cycloaliphatic hydrocarbon group - C 1-10 A divalent linear aliphatic hydrocarbon group - C 3-10 A divalent cycloaliphatic hydrocarbon group, and C 1-10 A divalent linear aliphatic hydrocarbon group - C 6-15 A divalent aromatic hydrocarbon group - C 1-10 Examples of the divalent linear aliphatic hydrocarbon group include those mentioned below.

[0034] The above divalent organic group in the divalent alcohol compound (II) may be substituted with one or more halogeno groups selected from fluoro, chloro, bromo, and iodo. Also, C 3-10 The divalent cycloaliphatic hydrocarbon group and C 6-15 The divalent aromatic hydrocarbon group may contain an ether group (-O-), and further, in addition to the halogeno group, it may be substituted with a C 1-6 alkyl group. As the substituent, fluoro is preferable.

[0035] Examples of the divalent alcohol compound (II) include ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and isosorbide.

[0036] R in the divalent alcohol compound (II) 1 can include a divalent organic group represented by the following formula (VI).

[0037]

Chemical formula

[0038] [In the formula, R 11 and R 12 are independently, -(CR 14 R 15 ) m3 -, or -(-O-(CR14 R 15 ) m4 -) m5 -(wherein R 14 and R 15 each independently represents H or a C 1-6 alkyl group, m3 represents an integer of 0 or more and 10 or less, m4 represents an integer of 1 or more and 10 or less, m5 represents an integer of 1 or more and 10 or less, and when m3 or m4 is an integer of 2 or more, a plurality of R 14 and R 15 may be the same as or different from each other), R 13 represents any of the following divalent organic groups,

[0039]

Chemical formula

[0040] (wherein, R 16 and R 17 each independently represents H, a halogeno group, a C 1-20 aliphatic hydrocarbon group which may have a substituent β, a C 1-20 alkoxy group which may have a substituent β, a C 6-20 aromatic hydrocarbon group which may have a substituent γ, or R 16 and R 17 are bonded to form a C 3-20 carbocyclic ring or a 5- to 12-membered heterocyclic ring, R 18 and R 19 each independently represents H or a C 1-6 alkyl group, and when m6 is an integer of 2 or more, a plurality of R 18 and R 19 may be the same as or different from each other, R 20 ~R 27 each independently represents a halogeno group, a C 1-20 aliphatic hydrocarbon group which may have a substituent β, a C 1-20 alkoxyl group which may have a substituent β, or a C 6-12 aromatic hydrocarbon group which may have a substituent γ, R28 represents a C alkane diyl group which may have a substituent β, 1-9 and m6 represents an integer of 1 or more and 20 or less, m7 represents an integer of 1 or more and 500 or less.) Substituent α 1 and substituent α 2 each independently represent one or more substituents selected from the group consisting of a halogeno group, a C 1-20 aliphatic hydrocarbon group, a C 1-20 alkoxy group, a C 3-20 cycloalkyl group, a C 6-20 aromatic hydrocarbon group, a C 7-20 aralkyl group, a C 6-20 aromatic hydrocarbon oxy group, and a C 3-20 cycloalkoxyl group, m1 and m2 each independently represent an integer of 0 or more and 4 or less, Substituent β is one or more substituents selected from a C 1-6 alkoxy group, a C 1-7 acyl group, a halogeno group, a nitro group, a cyano group, and a carbamoyl group, Substituent γ is one or more substituents selected from a C 1-6 alkyl group, a C 1-6 alkoxyl group, a C 1-7 acyl group, a halogeno group, a nitro group, a cyano group, and a carbamoyl group.)

[0041] As for -Ph-R 13 -Ph- in the divalent organic group (VI), examples of the divalent organic group excluding the hydroxyl group in bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol S, bisphenol TMC, and bisphenol Z can be mentioned.

[0042] As for the -(CR 14 R 15 ) m3 - group in the divalent organic group (VI), examples include a single bond and a C 1-2 alkyl group, or -(-O-(CR 14 R15 ) m4 -) m5 Examples of the - group include -(-O-CH2CH2-) m5 -, -(-O-CH(CH3)CH2-) m5 -, and -(-O-CH2CH(CH3)-) m5 - etc.

[0043] In addition, R in the dihydric alcohol compound (II) 1 Examples of - include the formula -R 3 -[-X-R 3 -] m -(where X represents O or S, O is preferred, R 3 represents an alkane diyl group, m represents an integer of 1 or more and 180 or less, and when m is an integer of 2 or more, a plurality of X and R 1-8 may be the same as or different from each other.) The divalent organic group represented by the formula is exemplified. 3 Examples of R include an ethylene group (-CH2CH2-), a propylene group [-CH(CH3)CH2- or -CH2CH(CH3)-], and a tetramethylene group (-CH2CH2CH2CH2-).

[0044] R 3 Examples of - include an ethylene group (-CH2CH2-), a propylene group [-CH(CH3)CH2- or -CH2CH(CH3)-], and a tetramethylene group (-CH2CH2CH2CH2-).

[0045] m is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, and preferably 160 or less, more preferably 150 or less.

[0046] When reacting the fluorocarbonate compound (I) with the dihydric alcohol compound (II), a solvent may be used. The solvent is not particularly limited as long as it is liquid at normal temperature and pressure and does not adversely affect the reaction. For example, nitrile solvents such as acetonitrile; ether solvents such as diethyl ether, glyme, diglyme, triglyme, tetraglyme, tetrahydrofuran, dioxane; ketone solvents such as acetone, methyl ethyl ketone; ester solvents such as ethyl acetate; halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, etc. may be mentioned. However, when at least one of the fluorocarbonate compound (I) or the dihydric alcohol compound (II) is liquid under the reaction conditions, a solvent may not be used. From the viewpoints of cost and environmental load, it is preferable not to use a solvent.

[0047] The amounts of the fluorocarbonate compound (I) and the dihydric alcohol compound (II) may be appropriately adjusted. For example, when the synthesis of one of the fluorocarbonate compound (I) or the dihydric alcohol compound (II) is difficult or expensive, the molar ratio of the other to one of them can be used in an amount of 5 times molar or more and 20 times molar or less. As the molar ratio, 15 times molar or less is preferable, and 12 times molar or less is more preferable. Alternatively, the above molar ratio can also be 0.5 times molar or more and 1.5 times molar or less.

[0048] In this step 1, the fluorocarbonate compound (I) and the dihydric alcohol compound (II) may be reacted in the presence of a base. Examples of the base include organic bases such as pyridine, triethylamine, ethyldiisopropylamine, diazabicycloundecene (DBU), N-methylmorpholine; inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate. From the viewpoints of solubility in the reaction solution and appropriate basicity, an organic base is preferable. The amount of the base used may be appropriately adjusted. For example, it can be used in an amount of 0.01 times molar or more and 1 times molar or less based on the one with the smaller number of moles among the fluorocarbonate compound (I) and the dihydric alcohol compound (II). However, from the viewpoints of cost and residue, it is preferable not to use a base.

[0049] The reaction temperature can be adjusted as appropriate. For example, it can be 30°C or higher and 120°C or lower. Also, depending on the solvent used, etc., the reaction may be carried out under heating reflux conditions. The reaction time can also be adjusted as appropriate. It can be until the consumption of at least one of the fluorocarbonate compound (I) or the dihydric alcohol compound (II) is confirmed by chromatography or the like, or it can be determined by preliminary experiments or the like. For example, it can be 1 hour or longer and 50 hours or shorter.

[0050] After the reaction, usual post-treatment can be carried out. For example, an immiscible solvent with water such as diethyl ether, chloroform, ethyl acetate, etc. and water are added to the reaction solution for liquid separation, and the target compound, the biscarbonate compound (III), is extracted into the organic phase. The organic phase may be washed with water, saturated brine, etc., or dried with anhydrous sodium sulfate, anhydrous magnesium sulfate, etc. By concentrating the organic phase, the biscarbonate compound (III) can be obtained. The obtained biscarbonate compound (III) may be further purified by chromatography, recrystallization, etc., or it may be used as it is in the following step 2.

[0051] Among the biscarbonate compounds (III), in the case of the above-mentioned biscarbonate compound (III-1), since the fluoroalcohol is particularly likely to be eliminated during the reaction, the reaction proceeds rapidly. Especially when R 1 does not contain a fluoro group, the reaction may be difficult to proceed. However, since the biscarbonate compound (III-1) has particularly high reactivity, even in such a case, it is possible to produce polyurethane well by using the biscarbonate compound (III-1).

[0052] 2. Process for producing polyurethane In this step, the polyurethane (V) is obtained by reacting the biscarbonate compound (III) obtained in the above step 1 with the dihydric amino compound (IV).

[0053] In the dihydric amino compound (IV), R 2represents a divalent organic group. R in the divalent amino compound (IV) 2 is the same divalent organic group as R in the divalent alcohol compound (II). However, R in the divalent amino compound (IV) 1 may be the same as or different from R in the divalent alcohol compound (II). From the perspective of various properties of the target compound polyurethane (V), it is preferable that R 2 is different from R 1 in the divalent alcohol compound (II). From the perspective of various properties of the target compound polyurethane (V), it is preferable that R 1 and R 2 are different from each other.

[0054] When reacting the biscarbonate compound (III) with the divalent amino compound (IV), a solvent may be used. The solvent is not particularly limited as long as it is liquid at normal temperature and pressure and does not have an adverse effect on the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene, and chlorobenzene; nitrile solvents such as acetonitrile; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate; halogenated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride; hydrocarbon solvents such as pentane and hexane; ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, etc. However, when at least one of the biscarbonate compound (III) and the divalent amino compound (IV) is liquid under the reaction conditions, a solvent may not be used. However, from the perspective of cost and environmental load, it is preferable not to use a solvent.

[0055] The amounts of the biscarbonate compound (III) and the divalent amino compound (IV) may be adjusted as appropriate. For example, the molar ratio of the divalent amino compound (IV) to 1 mol of the biscarbonate compound (III) can be set to 0.5 times mol or more and 1.5 times mol or less. As the molar ratio, 0.8 times mol or more is preferable, 0.9 times mol or more is more preferable, 1.2 times mol or less is preferable, and 1.1 times mol or less is more preferable.

[0056] The reaction temperature of this process 2 can be adjusted as appropriate. For example, it can be 10°C or higher, 200°C or higher. Also, depending on the solvent used, etc., the reaction may be carried out under heating reflux conditions. The reaction time can also be adjusted as appropriate, and it can be until at least one of the biscarbonate compound (III) or the divalent amino compound (IV) is confirmed to be consumed by chromatography or the like, or it can be determined by preliminary experiments, etc. For example, it can be 30 minutes or longer, 10 hours or shorter.

[0057] After the reaction, normal post-treatment can be carried out. For example, the target compound, polyurethane (V), is a polymer and is insoluble in the solvent, so it may be washed with an inert solvent such as n-hexane. Also, it may only be dried after washing or without washing.

[0058] According to the present invention, polyurethane can be produced simply, safely, and efficiently without using a highly toxic isocyanate compound. Also, the polyurethane produced by the present invention has two divalent organic groups in its molecular structural unit, namely R in the biscarbonate compound (III) 1 and R in the divalent amino compound (IV) 2 By the combination of the groups, it becomes possible to have desired properties such as high strength, flexibility, and water repellency. Furthermore, the quality of the polyurethane may be enhanced by the fluoroalcohol that may remain.

[0059] This application claims the benefit of priority based on Japanese Patent Application No. 2020-83148 filed on May 11, 2020. The entire contents of the specification of Japanese Patent Application No. 2020-83148 filed on May 11, 2020 are incorporated herein by reference for reference purposes.

Examples

[0060] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is of course not limited by the following examples, and it is of course possible to make appropriate modifications and implement them within the range that can conform to the gist of the foregoing and following descriptions, and all of them are included in the technical scope of the present invention.

[0061] Example 1: Synthesis of a difficult-to-yellow thermoplastic polyurethane (1) Synthesis of 1,6 - hexamethylene bis(1,1,1,2,2,4,5,5,5 - nonafluoro - 4 - (trifluoromethyl) - 3 - pentyl carbonate) [Chemical formula] Chloroform (50 mL, 620 mmol) was placed in a three - necked cylindrical flask (φ42 mm × 200 mm). While blowing oxygen at 1.0 mL / min for 3 hours at 0 °C, it was irradiated with light using a low - pressure mercury lamp (20 W, φ24 mm × 120 mm, containing ultraviolet light of 253.7 nm and 184.9 nm) installed at a position 2 cm from the bottom of the flask. Subsequently, the light irradiation was stopped, the reaction solution was cooled to - 30 °C, 1,1,1,2,2,4,5,5,5 - nonafluoro - 4 - (trifluoromethyl)pentanol (3.2 g, 10 mmol) and pyridine (3.2 mL, 30 mmol) were added in sequence, and stirring was carried out for 2 hours. Subsequently, in order to remove the photodecomposition gas such as phosgene dissolved in the reaction solution from the system, the reaction solution was heated to 50 °C and stirred for 2 hours. The generated gas was passed through a saturated aqueous sodium hydrogen carbonate solution, decomposed into carbon dioxide gas and then discharged. Thereafter, 1,6 - hexanediol (0.35 g, 3 mmol) was added and stirred at 30 °C for 15 hours. Dichloromethane and water were added to the reaction solution, separated, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the target compound, which is a colorless liquid, was obtained by distillation using a glass tube oven (yield: 60%, yield: 1.4 g, 1.8 mmol). 1 H NMR (400 MHz, CDCl3, 20 °C): δ / ppm = 6.01 (ttt, J = 19 Hz, 6.6 Hz, 3.6 Hz, 2H, methine), 4.29 (t, J = 6.6 Hz, 4H, methylene), 1.72 (t, J = 6.6 Hz, 4H, methylene), 1.40 (tt, J = 6.6 Hz, 4H, methylene) 1919F NMR (376 MHz, CDCl3, 20 °C): δ ppm = -73.87 (m, 6F, -CF3), -83.06 (m, 3F, -CF3), -122.90 (m, 2F, -CF2-), -182.84 (m, 1F, -CF-) 13 13C NMR (125 MHz, CDCl3, 20 °C): δ ppm = 152.36, 119.92, 119.50, 119.261, 110.79, 89.65, 70.64, 67.84, 28.28, 25.11 IR (ATR): 2972, 2871, 1780, 1302, 1206, 1171, 1115, 970 cm -1 FAB-MS: m / z calculated for [M+H] + (C 20 H 14 F 24 O6) 807.04, found 806.91

[0062] (2) Synthesis of a hardly yellowing thermoplastic polyurethane [Chemical formula] Into a 10 mL sample bottle, 1,6 - hexamethylene bis(1,1,1,2,2,4,5,5,5 - nonafluoro - 4 - (trifluoromethyl) - 3 - pentyl carbonate) (0.20 g, 0.5 mmol), m - xylylenediamine (0.07 g, 0.5 mmol), and toluene (3 mL) as a solvent were added, and the mixture was stirred at 100 °C for 1 hour. After washing the reaction product with n - hexane, it was suction - filtered and vacuum - dried at 60 °C for 2 hours to obtain the target product as a pale yellow solid (yield: 61%, amount: 93 mg, 0.3 mmol). 1 1H NMR (400 MHz, DMSO - d6, 20 °C): δ 7.64 (br., 2H, NH), 7.35 - 7.09 (br., 4H, Phenyl), 4.14 (d, 4H, methylene), 3.94 (t, 4H, methylene), 1.53 (br., 4H, methylene), 1.31 (br., 4H, methylene) IR (ATR): 3304, 2931, 1686, 1523, 1240, 1135, 1048 cm -1 Average molecular weight by HPLC (polystyrene standard): M n = 3100, M w = 5200, M w / M n = 1.7

[0063] Example 2: Synthesis of a difficult-to-yellow thermoplastic polyurethane (1) Synthesis of PPG bis(2,2,2-trifluoroethyl carbonate) [B3FEC + polypropylene glycol 400 (PPG)] [Chemical formula] Bis(2,2,2-trifluoroethyl carbonate) (3.39 g, 15.0 mmol) and potassium carbonate (55 mg, 0.4 mmol) were added to acetonitrile (2 mL) and mixed to prepare a solution. Polypropylene glycol 400 (2.0 g, 5.0 mmol) was added to the solution, and the mixture was stirred at 50 °C for 3 hours. Dichloromethane and water were added to the reaction solution, and the layers were separated. The organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain the target product as a pale yellow oil (yield: 90%, yield: 2.92 g, 4.47 mmol). 1 1H NMR (400 MHz, CDCl3, 293 K): δ / ppm = 4.94 (sext, J = 6.0 Hz, 2H, methine), 4.50 (q, J = 8.3 Hz, 4H, methylene), 3.39 - 3.62 (m, methylene, methine), 1.31 (dd, J = 6.8 Hz, 3.2 Hz, 6H, methyl), 1.13 (m, methyl) 19 19F NMR (376 MHz, CDCl3, 293 K): δ / ppm = -74.20 IR (ATR): ν = 2974, 2876, 1759, 1296, 1246, 1166, 1102, 991, 956 cm -1 ESI-FT-MS: m / z calculated for [M+Na] + [C 12 H 16 F6O7(C3H6O) n 409.07+n(58.04)(n≧3), found 583.20(n = 3), 641.24(n = 4), 699.28(n = 5), 757.32(n = 6), 815.37(n = 7), 873.41(n = 8), 931.45(n = 9)

[0064] (2) Synthesis of yellowing-resistant thermoplastic polyurethane

Chem.

[0065] Example 3: Synthesis of a heat-resistant yellowing thermoplastic polyurethane (1) Synthesis of 1,6 - hexamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate)

Chemical formula

[0066] (2) Synthesis of a heat - resistant yellowing thermoplastic polyurethane

Chemical formula

[0067] Example 4: Synthesis of a heat - resistant yellowing - resistant thermoplastic polyurethane (1) Synthesis of polypropylene glycol bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate)

Chemical formula

[0068] (2) Residual Chlorine Measurement The obtained bis-carbonate (50 mg) was burned with P as the internal standard in an automatic sample combustion apparatus (“AQF-2100” manufactured by Mitsubishi Analytic Co., Ltd.) and absorbed into the absorption solution. As the absorption solution, 25 mM NaOH + 0.1% H2O2 was used. The obtained absorption solution was analyzed by ion chromatography (“ICS-2100” manufactured by Thermo Fisher Scientific Co., Ltd., column: AS11HC) to quantify Cl and P in the absorption solution. As a result, the chlorine concentration was 132 wtppm. The mixed chlorine is considered to be derived from the impurities contained in BHFC used as the raw material.

[0069] (3) Synthesis of Light-Resistant Yellowing Thermoplastic Polyurethane

Chemical Structure

[0070] When the chlorine content remaining in the obtained polyurethane was measured by the same method as in (2) above, it was as low as 30 wtppm. Also, although fluoroalcohol is generated during the reaction, fluoroalcohol is volatile and was not detected in the obtained polyurethane.

[0071] Comparative Example 1: Synthesis of Polyurethane Using Diphenyl Carbonate (1) Synthesis of Polypropylene Glycol Bis(phenyl carbonate)

Chemical Structure

[0072] (2) Synthesis of polyurethane

Chemical formula

[0073] Example 5: Synthesis of a non-yellowing thermoplastic polyurethane [Chemical formula] Into a 50 mL eggplant flask, polypropylene glycol bis(1,1,1,3,3,3-hexafluoroisopropyl carbonate) (2.3 g, 3.0 mmol) and 1,6-hexamethylenediamine (0.35 g, 3.0 mmol) were added, and the mixture was stirred at 150 °C for 3 hours under an argon atmosphere. The reaction solution was vacuum dried at 50 °C for 2 hours to obtain a pale yellow oily target product (yield: >99%, yield: 1.81 g, 3.2 mmol). Although fluoroalcohol is generated during the progress of the reaction, fluoroalcohol is volatile and no fluoroalcohol was detected in the obtained polyurethane. 1 1H NMR (400 MHz, CDCl3, 293 K): δ / ppm = 4.93 - 4.87 (br., 2H, methine), 3.65 - 3.30 (br., 22H, methylene + methine), 3.14 - 3.13 (br., 4H, methylene), 1.50 - 1.47 (br., 4H, methylene), 1.34 - 1.30 (br., 4H, methylene), 1.23 (d, J = 6.4 Hz, 6H, methyl), 1.14 (d, J = 5.2 Hz, 18H, methyl) IR (ATR): 3329, 2972, 2931, 2862, 1697, 1530, 1453, 1374, 1252, 1200, 1097, 1016 cm -1 Average molecular weight by HPLC (polystyrene standard): M n = 10800, M w = 17500, M w / M n = 1.62

[0074] Comparative Example 2: Synthesis of polyurethane using diphenyl carbonate Into a 50 mL single-neck eggplant flask, bis(phenyl carbonate) (1.92 g, 3.0 mmol) obtained in Comparative Example 1(1) and 1,6-hexamethylenediamine (0.35 g, 3.0 mmol) were added, and the mixture was stirred at 150 °C for 3 hours. To remove the eliminated alcohol, it was dried under vacuum at 120 °C for 4 hours using an oil rotary pump. 1 The formation of the corresponding polyurethane was confirmed by 1H NMR spectrum. When the average molecular weight was estimated by GPC, M n = 2791, M w = 5804, M w / M n = 2.08. Also, 62% of the phenol remained in the obtained polyurethane with respect to the total phenol eliminated by the reaction. As a result of the above, despite drying under vacuum at a high temperature, phenol remained in the polyurethane. For the same polyurethane, the molecular weight was smaller and the molecular weight distribution was larger compared to Example 5, which is presumably because the by-produced phenol was not removed and inhibited the polymerization reaction.

[0075] Example 6: Synthesis of non-yellowing thermoplastic polyurethane

Chemical formula

[0076] Example 7: Synthesis of non - yellowing thermoplastic polyurethane

Chemical formula

[0077] Example 8: Synthesis of non-yellowing thermoplastic polyurethane

Chemical formula

[0078] Example 9: Synthesis of non-yellowing thermoplastic polyurethane [Chemical formula] Into a 50 mL eggplant flask, polypropylene glycol bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate) (0.39 g, 0.5 mmol) and isophoronediamine (0.09 g, 0.5 mmol) were added, and the mixture was stirred at 150 °C for 1 hour. The reaction solution was vacuum dried at 50 °C for 2 hours to obtain the target product as a pale yellow oily substance (yield: 97%, amount: 0.30 g, 0.48 mmol). 1 1H NMR (400 MHz, CDCl3, 293 K): δ / ppm = 4.95 - 4.87 (m, 2H, methine), 3.59 - 3.39 (m, 22H, methylene), 2.94 - 2.88 (br., 2H, methylene), 1.75 - 1.50 (br., 6H), 1.24 (d, J = 5.6 Hz, 6H, methyl), 1.16 - 1.14 (d, J = 6.0 Hz, 18H, methyl), 1.07 - 0.83 (m, 10H) IR (ATR): 3326, 2970, 2931, 1699, 1530, 1460, 1374, 1302, 1240, 1098, 1027 cm -1 Average molecular weight by HPLC (polystyrene standard): M n = 8800, M w = 16000, M w / M n = 1.82

[0079] Example 10: Synthesis of a difficult - yellowing thermoplastic polyurethane (1) Synthesis of polypropylene glycol bis(2,2,3,3 - tetrafluoropropyl carbonate) using an inorganic base [Chemical formula] Bis(2,2,3,3-tetrafluoropropyl) carbonate (78.33 g, 270 mmol), propylene glycol 400 (36 mL, 90 mmol), potassium carbonate (1.3 g, 9 mmol), and acetonitrile (150 mL) as a solvent were added to a one-necked eggplant flask and stirred at 50 °C for 3 hours. Then, after distilling off the solvent of the reaction solution under reduced pressure using an evaporator, ethyl acetate, hexane, and pure water were added and liquid separation was performed, and the organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was filtered off, the filtrate was concentrated under reduced pressure using an evaporator, and vacuum dried at 100 °C for 2 hours to obtain a colorless transparent oily target product (yield: 85%, yield: 39.12 mmol). 1 1H NMR (400 MHz, CDCl3, 293 K): δ / ppm = 5.94 (tt, J = 53.0 Hz, 4.0 Hz, 2H, methine), 4.86 - 4.97 (m, methylene), 4.61 (tt, J = 12.6 Hz, 1.2 Hz, 2H, methylene), 3.39 - 3.62 (m, methylene and methine), 1.31 (dd, J = 6.8 Hz, 3.2 Hz, 6H, methyl), 1.13 (m, methyl) 19 19F NMR (376 MHz, CDCl3, 293 K): δ / ppm = -124.6, -138 IR (ATR): 2977, 2879, 1454, 1383, 1268, 1099, 992, 921, 786 cm -1 FT-MS: m / z calculated for [M+Na] + [C 14 H 18 F8O7(C3H6O) n 473.08 + 58.06n, found 763.28 (n = 5), 821.32 (n = 6), 879.36 (n = 7), 937.40 (n = 8), 995.44 (n = 9), 1053 (n = 10), 1111.52 (n = 11)

[0080] (2) Synthesis of polypropylene glycol bis(2,2,3,3-tetrafluoropropyl carbonate) using an organic base To a one-necked eggplant flask, bis(2,2,3,3-tetrafluoropropyl) carbonate (14.5 g, 50 mmol), propylene glycol 400 (4.0 g, 10 mmol), and triethylamine (0.2 g, 2 mmol) were added, and the mixture was stirred at 90 °C for 13 hours. Then, after distilling off the low-boiling components of the reaction solution under reduced pressure using an evaporator, the product was vacuum dried at 120 °C for 1 hour to obtain a colorless and transparent oily target product (yield: 94%).

[0081] (3) Synthesis of polypropylene glycol bis(2,2,3,3-tetrafluoropropyl carbonate) using an organic base To a one-necked eggplant flask, polypropylene glycol 400 (0.4 g, 1.0 mmol), bis(2,2,3,3-tetrafluoropropyl) carbonate (0.72 g, 2.5 mmol), and 1,4-diazabicyclo(2,2,2)octane (hereinafter, DABCO) (0.01 g, 0.1 mmol) were added, and the mixture was stirred at 100 °C for 13 hours. The obtained oily reaction solution was vacuum dried at 100 °C for 2 hours using an oil rotary pump to distill off the eliminated alcohol and DABCO generated in the reaction, thereby obtaining a transparent oily target product (yield 96%).

[0082] (4) Synthesis of a yellowing-resistant thermoplastic polyurethane

Chemical formula

[0083] (5) Synthesis of heat-resistant yellowing thermoplastic polyurethane To a one-necked eggplant flask, polypropylene glycol bis(2,2,3,3-tetrafluoropropyl carbonate) (0.73 g, 1.0 mmol) and m-xylylenediamine (0.14 g, 1.0 mmol) were added, and the mixture was stirred at 100 °C for 13 hours. The obtained oily reaction solution was vacuum dried at 100 °C for 1 hour using a diaphragm pump. 1 The formation of the corresponding polyurethane was confirmed by 1H NMR spectrum. When the average molecular weight was estimated by GPC, M n = 4195, M w = 5900, M w / M n = 1.40. Also, no fluoroalcohol eliminated by the reaction was detected from the obtained polyurethane.

[0084] Comparative Example 3 In Example 10(5), polyurethane was produced in the same manner except that bis(phenyl carbonate) (0.64 g, 1.0 mmol) obtained in Comparative Example 1(1) was used instead of polypropylene glycol bis(2,2,3,3-tetrafluoropropyl carbonate) (0.73 g, 1.0 mmol). 1The formation of the corresponding polyurethane was confirmed by 1H NMR spectrum. When the average molecular weight was estimated by GPC, M n = 1318, M w = 1715, M w / M n = 1.30. Also, 5% of phenol remained in the obtained polyurethane with respect to the total phenol eliminated by the reaction. As a result of the above, despite vacuum drying at high temperature, phenol remained in the polyurethane. The fact that for the same polyurethane, the molecular weight was smaller and the molecular weight distribution was larger compared to Example 10(5) is presumably because the by-produced phenol was not removed and the polymerization reaction was inhibited.

[0085] Example 11: Synthesis of a difficult-yellowing type thermoplastic polyurethane using a solvent Into a 50 mL one-neck eggplant flask, polypropylene glycol bis(2,2,3,3-tetrafluoropropyl carbonate) (1.0 g, 1.37 mmol), m-xylylenediamine, and the solvent shown in Table 1 were added, and heating and stirring were carried out under the conditions shown in Table 1. 1 The formation of the corresponding polyurethane was confirmed by 1H NMR spectrum, and the average molecular weight was estimated by GPC. The results are shown in Table 1.

[0086] [Table 1]

[0087] Compared with Example 10(4) without using a solvent, there was no significant change in the average molecular weight of the obtained polyurethane, and it was found that the reaction proceeded well even when a solvent was used.

[0088] Example 12: Synthesis of a difficult-yellowing type thermoplastic polyurethane using a solvent To a 50 mL single-necked eggplant flask, polypropylene glycol bis(2,2,3,3-tetrafluoropropyl carbonate) (1.0 g, 1.37 mmol), THF (444 μL), and the diamine shown in Table 1 were added, and the mixture was stirred at 50 °C for 332 hours. 1 The formation of the corresponding polyurethane was confirmed by 1H NMR spectrum, and the average molecular weight was estimated by GPC. The results are shown in Table 2.

[0089]

Table 2

[0090] Compared with Example 10(4) without using a solvent, there was no significant change in the average molecular weight of the obtained polyurethane, and it was found that the reaction proceeded well even when a solvent was used.

[0091] Example 13: Synthesis of non-yellowing thermoplastic polyurethane

Chemical formula

[0092] Example 14: Synthesis of a Difficult-to-Discolor Thermoplastic Polyurethane Using a Solvent Into a 50 mL one-necked eggplant flask, polypropylene glycol bis(2,2,3,3-tetrafluoropropyl carbonate) (1.0 g, 1.37 mmol), 1,6-hexamethylenediamine (0.11 g, 1.00 mmol), and the solvents shown in Table 1 were added, and further, the bases shown in Table 1 were added as appropriate, and heating and stirring were carried out under the conditions shown in Table 1. 1 The formation of the corresponding polyurethane was confirmed by 1H NMR spectrum, and the average molecular weight was estimated by GPC. The results are shown in Table 3.

[0093]

Table 3

[0094] As shown in the results in Table 3, compared with Example 13, the average molecular weight of the polyurethane produced by using a solvent increased. It is considered that the reaction was accelerated due to the increased fluidity of the polymer. Also, it was found that the reaction was further accelerated by adding a base.

[0095] Example 15 (1) Synthesis of 1,6-Hexamethylene Bis(2,2,2-Trifluoroethyl Carbonate)

Chemical Formula

[0096] Example 16 (1) Synthesis of bis(hydroxyethyl)bisphenol A bis(2,2,2-trifluoroethyl carbonate)

Chemical formula

[0097] Example 17 (1) Synthesis of isosorbide bis(2,2,2-trifluoroethyl carbonate) [Chemical formula] Bis(3,3,3-trifluoroethyl) carbonate (11.3 g, 50.0 mmol) and potassium carbonate (688 mg, 5.0 mmol) were added to acetonitrile (25 mL) in a one-necked eggplant flask and mixed. Isosorbide (2.44 g, 16.7 mmol) was added to the resulting solution, and the mixture was stirred at 50 °C for 1 hour. Diethyl ether and water were added to the reaction solution, and the layers were separated. The organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was filtered off, and the filtrate was concentrated under reduced pressure using an evaporator and then further dried under vacuum at 80 °C for 2 hours to obtain the target product as a brown oil (yield: 82%, amount: 5.5 g, 13.7 mmol). 1 H NMR (500 MHz, CDCl3, 293 K): δ / ppm = 5.08 - 5.16 (m, 2H), 4.87 - 4.99 (m, 1H), 4.49 - 4.61 (m, 5H), 4.06 - 4.12 (m, 1H), 3.97 - 4.04 (m, 2H), 3.87 - 3.94 (m, 1H) 13 C NMR (125 MHz, CDCl3, 293 K): δ / ppm = 153.42, 153.11, 122.47, 122.39, 85.73, 82.12, 81.08, 77.83, 72.97, 70.77, 64.24, 63.66 19 F NMR (376 MHz, CDCl3, 293 K): δ / ppm = -74.25 IR (ATR): 2983, 2885, 1759, 1416, 1291, 1237, 1162, 1095, 990, 973, 778 cm -1 FAB-MS: m / z calculated for [M + H] + (C 12 H 12 F6O8) 399.04, found 399.00

[0098] Example 18 (1) Synthesis of 2,2'-thiodiethylene bis(1,1,1,3,3,3-hexafluoroisopropyl carbonate) [Chemical formula] Bis(1,1,1,3,3,3-hexafluoropropan-2-yl) carbonate (1.81 g, 5 mmol), 2,2'-thiodiethanol (0.12 g, 1 mmol), and triethylamine (0.1 mmol, 13.8 μL) were added to a one-necked eggplant flask and stirred at 90 °C for 16 hours. Then, chloroform and water were added and separated by liquid separation, and the organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was filtered off, and the filtrate was concentrated under reduced pressure using an evaporator and then further dried under vacuum at 50 °C for 3 hours to obtain a colorless oily target product (yield: 75%, yield: 0.38 g, 0.75 mmol). 1 H NMR (400 MHz, CDCl3, 293 K): δ / ppm = 5.57 (m, 2H, methine), 5.05 - 4.97 (m, 2H, methine), 3.65 - 3.38 (m, 19H, methylene and methine), 1.35 - 1.32 (m, 6H, methyl), 1.14 - 1.10 (m., 15H, methyl) 13 C NMR (125 MHz, CDCl3, 293 K): δ / ppm = 152.8, 120.3, 70.5, 69.0, 30.5 19 F NMR (376 MHz, CDCl3, 293 K): δ / ppm = -73.52 IR (ATR): 1774, 1382, 1296, 1253, 1238, 1197, 1189, 1140, 1106, 939, 929, 686, 677, 594, 565 cm -1 FAB MS: m / z calculated for [M] + (C 12 H 10 F 12 O6S) 510.00, found 509.93

[0099] Example 19 (1) Synthesis of polytetramethylene ether glycol bis(1,1,1,3,3,3-hexafluoroisopropyl carbonate) [Chem.] Bis(1,1,1,3,3,3-hexafluoropropan-2-yl) carbonate (3.62 g, 10 mmol), polytetramethylene ether glycol (PTMG1500) (1.5 g, 1 mmol), and triethylamine (0.1 mmol, 13.8 μL) were added to a one-necked eggplant flask and stirred at 90 °C for 16 hours. Then, chloroform and water were added and separated by liquid-liquid extraction, and the organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was filtered off, the filtrate was concentrated under reduced pressure, and then vacuum dried at 60 °C for 1 hour to quantitatively obtain 1.93 g (1.0 mmol) of the target white solid. 1 H NMR (400 MHz, CDCl3, 293 K): δ / ppm = 5.56 (m, 2H, methine), 4.32 (t, J = 5.2 Hz, 4H, methylene), 3.45 - 3.36 (m, 82H, methylene), 1.83 (m, 4H, methylene), 1.68 - 1.57 (m, 82H, methylene) 19 F NMR (376 MHz, CDCl3, 293 K): δ / ppm = -73.52 IR (ATR): 2942, 2862, 1777, 1371, 1253, 1199, 1106, 1065, 1012, 996, 617, 607, 594, 582, 567, 554 cm -1 FT-MS: m / z calculated for [M+Na] + [C 12 H 10 F 12 O6(C4H8O) n501.02 + 72.07n, found 789.25 (n = 4), 861.31 (n = 5), 933.36 (n = 6), 1005.42 (n = 7), 1077.48 (n = 8), 1149.53 (n = 9), 1221.59 (n = 10), 1365.71 (n = 11), 1365.71 (n = 12), 1437.76 (n = 13), 1509.82 (n = 14), 1581.88 (n = 15), 1653.94 (n = 16), 1725.99 (n = 17), 1798.05 (n = 18), 1870.11 (n = 19)

[0100] Example 20 (1) Synthesis of 1,1'-thiodiethylene bis(2,2,3,3-tetrafluoropropyl carbonate) [Chemical formula] To a one-necked eggplant flask, bis(2,2,3,3-tetrafluoropropyl) carbonate (16 mL, 90 mmol), 1,1'-thiodiethanol (3.7 g, 30 mmol), potassium carbonate (0.42 g, 3 mmol), and acetonitrile (50 mL) as a solvent were added, and the mixture was stirred at 50 °C for 3 hours. Then, after concentration under reduced pressure using an evaporator, dichloromethane and pure water were added for liquid separation, and the organic layer was dried over anhydrous sodium sulfate. The anhydrous sodium sulfate was filtered off, the filtrate was concentrated under reduced pressure using an evaporator, and distillation was carried out using a glass tube oven. By collecting the fraction at 170 °C, a colorless transparent oily target product was obtained (yield: 15%, yield: 1.97 g, 8.67 mmol). 1 H NMR (400 MHz, CDCl3, 293 K): δ / ppm = 5.92 (tt, J = 53.0 Hz, 4.0 Hz, 2H, methine), 4.54 (tt, J = 12.6 Hz, 1.2 Hz, 4H, methylene), 4.36 (t, J = 6.8 Hz, 4H, methylene), 2.86 (t, J = 6.8 Hz, 4H, methylene) 19 F NMR (376 MHz, CDCl3, 293 K): δ / ppm = -124.2, -137.6 IR(ATR): 1760, 1452, 1267, 1202, 984, 835, 636, 574 cm -1 FAB-MS: m / z calculated for [M+H] + (C 11 H 12 (C₈H₈F₈O₆S) 411.01, found 411.04

[0101] Example 21 (1) Synthesis of 2,2,3,3,4,4 - hexafluoro - 1,5 - pentamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate) [Chemical formula] BHFC (24 mmol, 5.3 mL), 2,2,3,3,4,4 - hexafluoro - 1,5 - pentanediol (1,5 - HFPDL) (4.0 mmol, 0.84 g), pyridine (0.40 mmol, 32 μL), and acetonitrile (2 mL) as a solvent were added to a 50 mL eggplant - shaped flask, and the mixture was stirred at 20 °C for 6 hours. Then, the solvent was distilled off under reduced pressure, and the residue was heated to 50 °C under reduced pressure to dryness to obtain the target compound as a colorless liquid (yield: 2.2 g, 3.6 mmol, yield: 90%). 1 H NMR (400 MHz, CDCl₃, 293 K): δ 5.56 (sep, J = 5.8 Hz, 2H, CH), 4.77 (t, J = 13 Hz, 4H, CH₂) 13 C NMR (125 MHz, CDCl₃, 293 K): δ 152.4, 120.0 (q, J = 283 Hz), 113.8 (tt, J = 257, 31 Hz), 110.9 (tt, J = 261, 33 Hz), 71.2 (sep), 64.6 (t, J = 28 Hz) 19 F NMR (376 MHz, CDCl₃, 293 K, C₆F₆ as external standard): δ - 73.63 (s, 12F, CF₃), - 120.20 (s, 4F, CF₂), - 125.66 (s, 2F, CF₂) IR(ATR): 2985, 1787, 1384, 1254, 1200, 1152, 1111, 1045, 985, 906, 777, 689 cm -1

[0102] (2) Synthesis of polyurethane [Chemical formula] In a 7 mL test tube, 2,2,3,3,4,4 - hexafluoro - 1,5 - pentamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate) (0.30 g, 0.50 mmol) and m - xylylenediamine (73 μL, 0.53 mmol) were added, and the mixture was stirred at 100 °C for 2 hours. Then, an appropriate amount of methanol and hexane were added to the reaction solution, and the precipitated solid was collected by suction filtration and vacuum - dried at 50 °C for 2 hours to obtain the target compound as a pale yellow solid (yield: 0.14 g, 0.35 mmol, yield rate: 71%). 1 H NMR(400 MHz, acetone - d6, 293 K): δ 7.31 - 7.21 (m, 4H, CHAr), 4.69 (t, J = 14 Hz, 4H, CH2), 4.34 (s, 4H, CH2) 13 C NMR(125 MHz, acetone - d6, 293 K): δ 155.8, 140.3, 129.5, 127.2, 126.9, 116.2 (tt), 112.3 (tt), 60.5 (t, J = 25 Hz), 45.3 19 F NMR(376 MHz, acetone - d6, 293 K, C6F6 as external standard): δ - 120.87 (s, 4F, CF2), - 127.08 (s, 2F, CF2) IR(ATR): 3322, 1703, 1529, 1457, 1260, 1149, 1055, 967, 776 cm -1 Average molecular weight by HPLC: M n = 6500, M w = 11100, M w / M n = 1.7

[0103] Example 22: Synthesis of Polyurethane

Chemical Structure

[0104] Example 23: Synthesis of Polyurethane [Chemical formula] Into a 7 mL test tube, 2,2,3,3,4,4 - hexafluoro - 1,5 - pentamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate) (0.30 g, 0.50 mmol) and polypropylene glycol diamine (PPGDA, average molecular weight: 430) (0.22 g, 0.50 mmol) were added and stirred at 100 °C for 2 hours. Then, the reaction solution was vacuum - dried at 50 °C for 3 hours to obtain the target compound as a yellow viscous solid (yield: 0.36 g, 0.50 mmol, yield: >99%). 1 H NMR (400 MHz, acetone - d6, 293 K): δ6.58 (br., 2H, NH), 4.68 - 4.64 (br., 4H, CH2), 3.77 (m, 2H, CH), 3.60 - 3.36 (m, 19H, CH + CH2), 1.18 (br., 6H, CH3), 1.10 (br., 15H, CH3) 13 C NMR (125 MHz, acetone - d6, 293 K): δ154.9, 116.2 (tt, J = 255, 30 Hz), 112.2 (tt), 76.5 - 72.7 (m), 60.2 (t, J = 25 Hz), 48.5 - 48.2 (m), 17.7 19 F NMR (376 MHz, acetone - d6, 293 K, C6F6 as external standard): δ - 120.89 (br.), - 127.17 (br.) IR (ATR): 3330, 2974, 1873, 1721, 1534, 1428, 1375, 1240, 1098, 927, 769 cm -1 Average molecular weight by HPLC: M n = 6600, M w = 15000, M w / M n = 2.3

[0105] Example 24: Synthesis of polyurethane [Chemical formula] Into a 20 mL eggplant flask, 2,2,3,3,4,4 - hexafluoro - 1,5 - pentamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate) (0.30 g, 0.50 mmol), 4,4’ - diaminodiphenylmethane (0.50 mmol, 99 mg), and THF (2 mL) as a solvent were added, and the mixture was stirred at 60 °C for 27 days. Samples were taken from the reaction solution approximately every three days, mixed with deuterated acetone, and 1 analyzed by 1H NMR to confirm that the reaction was proceeding. Then, an appropriate amount of THF and hexane were added to the reaction solution, and the precipitated solid was collected by suction filtration and vacuum - dried at 50 °C for 3 hours to obtain the target compound as a pale - brown solid (yield: 0.21 g, 0.46 mmol, yield: 91%). 1 1H NMR (400 MHz, DMSO - d6, 293 K): δ 10.05 (s, 2H, NH), 7.38 (d, J = 7.6 Hz, 4H, CHAr), 7.14 (d, J = 7.6 Hz, 4H, CHAr), 4.82 (t, J = 15 Hz, 4H, CH2), 3.82 (s, 2H, CH2) 13 13C NMR (125 MHz, DMSO - d6, 293 K): δ 151.8, 136.2, 136.1, 128.9, 118.6, 115.0 (tt), 113.0 (tt), 59.0 (t, J = 21 Hz), 39.7 19 19F NMR (376 MHz, DMSO - d6, 293 K, C6F6 as external standard): δ - 119.20 (br., 4F, CF2), - 125.40 (br., 2F, CF2) IR (ATR): 3334, 1716, 1598, 1536, 1415, 1236, 1158, 1112, 992, 814, 762 cm -1 Average molecular weight by HPLC: M n = 6300, M w = 13400, M w / M n = 2.1

[0106] Example 25 (1) Synthesis of 2,2,3,3,4,4,5,5 - Octafluoro - 1,6 - hexamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate)

Chem.

[0107] (2) Synthesis of polyurethane

Chem.

[0108] (3) Synthesis of polyurethane Into a 50 mL eggplant flask, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexamethylene bis(1,1,1,3,3,3-hexafluoroisopropyl carbonate) (containing 9.5% carbonate oligomer) (3.25 g, 4.53 mmol), m-xylylenediamine (587 μL, 4.53 mmol), and tetrahydrofuran (12.5 mL) as a solvent were added, and the mixture was stirred at 65 °C for 2 hours. Then, the solvent was distilled off under reduced pressure, and the resulting product was dried under vacuum at 50 °C for 2 hours to obtain the target compound as a white solid (yield: 2.39 g, 4.53 mmol, yield: 99%). Average molecular weight by HPLC: M n = 7900, M w = 13900, M w / M n = 1.8

[0109] (4) Synthesis of polyurethane Into a 50 mL eggplant flask, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexamethylene bis(1,1,1,3,3,3-hexafluoroisopropyl carbonate) (containing 10.7% carbonate oligomer) (2.18 g, 3.0 mmol), m-xylylenediamine (356 μL, 2.74 mmol), and tetrahydrofuran (10 mL) as a solvent were added, and the mixture was stirred at room temperature for 34 hours. Then, the solvent was distilled off under reduced pressure, and the resulting product was dried under vacuum at 50 °C for 2 hours to obtain the target compound (containing unreacted carbonate and m-xylylenediamine) as a white solid. Average molecular weight by HPLC: M n = 5700, M w = 6600, M w / M n = 1.2

[0110] Example 26: Synthesis of polyurethane

Chemical formula

[0111] Example 27: Synthesis of Polyurethane

Chemical Structure

[0112] (2) Into a 20 mL eggplant flask, 2,2,3,3,4,4,5,5 - octafluoro - 1,6 - hexamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate) (containing 10.7% carbonate oligomer) (2.18 g, 3.0 mmol), 1,6 - hexamethylenediamine (0.349 g, 3.0 mmol), and tetrahydrofuran (15 mL) as a solvent were added, and the mixture was stirred at room temperature for 5 hours. Then, the solvent was distilled off under reduced pressure and dried in vacuo at 50 °C for 2 hours to obtain the target compound as a white solid (yield: 1.43 g, 3.0 mmol, yield: >99%). Average molecular weight by HPLC: M n = 7200, M w = 12400, M w / M n = 1.7

[0113] Example 28: Synthesis of polyurethane

Chemical formula

[0114] (2) 2,2,3,3,4,4,5,5 - Octafluoro - 1,6 - hexamethylene bis(1,1,1,3,3,3 - hexafluoroisopropyl carbonate) (0.65 g, 1.0 mmol) and polypropylene glycol diamine (PPGDA, average molecular weight: 230) (0.23 g, 1.0 mmol) were placed in a 10 mL eggplant flask, and tetrahydrofuran (2 mL) was added as a solvent. The mixture was stirred at 20 °C for 2 hours. Then, the solvent was distilled off under reduced pressure, and the residue was dried in vacuo at 50 °C for 2 hours to obtain the target compound as a pale yellow transparent viscous liquid (yield: 0.68 g, 1.0 mmol, yield: >99%, containing HFIP that had been eliminated). 1 1H NMR (400 MHz, acetone-d6, 293 K): δ 6.64 - 6.52 (br., 2H, NH), 4.75 - 4.62 (br., 4H, CH2), 3.87 - 3.75 (br., 2H, CH), 3.58 - 3.36 (m, 19H, CH + CH2), 1.18 (br., 6H, CH3), 1.10 (br., 15H, CH3) 13 13C NMR (125 MHz, acetone-d6, 293 K): δ 154.92, 116.19, 112.19, 76.54 - 72.70, 60.35, 48.34, 17.79 19 F NMR (376 MHz, acetone-d6, 293 K): δ -120.60 (br.), -124.31 (br.) IR (ATR): 3327, 2977, 2937, 2878, 2360, 1715, 1531, 1456, 1378, 1287, 1226, 1173, 1125, 1100, 983, 894, 870, 841, 771 cm -1 Average molecular weight by HPLC: M n = 13100, M w = 22400, M w / M n = 1.7

[0115] Example 29 (1) Synthesis of perfluoropolyether (1,1,1,3,3,3-hexafluoroisopropyl carbonate)

Chemical formula

[0116] (2) Synthesis of polyurethane

Chemical formula

[0117] Example 30: Synthesis of polyurethane

Chemical formula

[0118] Example 31: Synthesis of polyurethane

Chemical formula

[0119] Example 32: Synthesis of polyurethane

Chemical Structure

[0120] Example 33: Synthesis of Polyurethane (1) Synthesis of 1H,1H,11H,11H-dodecafluoro-3,6,9-trioxaundecane bis(1,1,1,3,3,3-hexafluoroisopropyl carbonate) [Chemical formula] To a 25 mL eggplant flask, add BHFC (12 mmol, 2.64 mL), 1H,1H,11H,11H-dodecafluoro-3,6,9-trioxaundecane-1,11-diol (2.0 mmol, 0.82 g), pyridine (0.20 mmol, 16 μL), and acetonitrile (1 mL) as a solvent, and heat and stir at 20 °C for 6 hours. Then, add an appropriate amount of 1 M hydrochloric acid and hydrofluoroether (manufactured by 3M, "Novec TM 7100") to the reaction solution, separate the layers, and dry the organic layer over anhydrous sodium sulfate. After distilling off the solvent from the obtained solution under reduced pressure, dry it under vacuum at 50 °C for 1.5 hours to obtain the target compound as a white solid (yield: 1.49 g, 1.9 mmol, yield: 93%). 1 1H NMR (400 MHz, CDCl3, 293 K): δ 5.55 (sep, J = 5.6 Hz, 2H, CH), 4.64 (t, J = 8.4 Hz, 4H, CH2) 13 13C NMR (100 MHz, CDCl3, 293 K): δ 152.42, 120.04, 117.57, 114.51, 111.64, 71.24, 66.20 1919F NMR (376 MHz, CDCl3, 293 K): δ -73.67 (m, 12F, CF3), -77.77 (m, 4F, CF2), -88.83 (m, 4F, CF2), -88.94 (s, 4F, CF2) IR (ATR): 2988, 2360, 1791, 1385, 1322, 1288, 1247, 1196, 1146, 1108, 1044, 990, 949, 907, 776, 690 cm -1 FT-MS: m / z calculated for [M+Na] + (C 16 H6F 24 O9) 820.9498, found 821.3282

[0121] (2) Synthesis of polyurethane [Chemical formula] Into a 10 mL eggplant-shaped flask, H,1H,11H,11H-dodecafluoro-3,6,9-trioxaundecane bis(1,1,1,3,3,3-hexafluoroisopropyl carbonate) (0.80 g, 1.0 mmol) and m-xylylenediamine (130 μL, 1.0 mmol) were added, and the mixture was stirred at 150 °C for 1 hour. Then, the insoluble matter was dissolved in tetrahydrofuran, the solvent was distilled off under reduced pressure, and the residue was dried under vacuum at 50 °C for 2 hours to obtain the target compound as a yellow solid (yield: 0.68 g, 0.99 mmol, 99%). 1 1H NMR (400 MHz, acetone-d6, 293 K): δ 7.30 - 7.21 (m, 4H, CHAr), 4.66 (t, J = 10.2 Hz, 4H, CH2), 4.34 (d, J = 6.4 Hz, 4H, CH2) 13 13C NMR (125 MHz, acetone-d6, 293 K): δ 155.62, 140.25, 129.43, 127.28, 126.96, 123.15, 115.52, 113.24, 68.08, 62.29, 45.43, 26.18 1919F NMR (376 MHz, acetone-d6, 293 K): δ -78.29 (m, 4F, CF2), -89.15 (br., 4F, CF2), -89.48 (s, 4F, CF2) IR (ATR): 3330, 2974, 2364, 1699, 1540, 1412, 1172, 1108, 1057, 962, 774, 703 cm -1 Average molecular weight by HPLC: M n = 4800, M w = 12100, M w / M n = 2.5

[0122] Comparative Example 4

Chemical Structure

[0123] Comparative Example 5

Chemical formula

Claims

1. A method for producing polyurethane, comprising a step of obtaining a biscarbonate compound represented by the following formula (III) by reacting a fluorocarbonate compound represented by the following formula (I) with a dihydric alcohol compound represented by the following formula (II); and 【Chemical Formula 1】 [In the formula, Rf 1 independently represents an aliphatic hydrocarbon group having a fluoro group, R 1 represents a divalent organic group. ] A method characterized by comprising a step of obtaining a polyurethane represented by the following formula (V) by reacting the biscarbonate compound represented by the above formula (III) with a diamino compound represented by the following formula (IV). 【Chemical Formula 2】 [In the formula, Rf 1 and R 1 have the same meanings as described above, R 2 represents a divalent organic group. ]

2. The method according to claim 1, wherein the fluorocarbonate compound represented by formula (I) is reacted with the dihydric alcohol compound represented by formula (II) in the presence of a base.

3. R 1 is a C 2-10 alkane diyl group which may be substituted with a halogeno group, according to claim 1 or 2.

4. R 1 is a divalent organic group represented by the formula -R 3 - [-X-R 3 - ] m - (X represents O or S, and R 3 represents a C 1-8 alkane diyl group which may be substituted with a halogeno group, and m represents an integer of 1 or more and 180 or less. ), according to claim 1 or 2.

5. R 2 is a C alkylene group which may be substituted with a halogeno group, the method according to any one of claims 1 to 4. 2-10

6. R 2 is a C alkylene-C aryl diyl-C alkylene group, the method according to any one of claims 1 to 4. 1-6 6-12 1-6

7. A biscarbonate compound characterized by being represented by the following formula (III-1). 【Chemical formula 3】 [In the formula, Rf 2 represents H or an aliphatic hydrocarbon group having a fluoro group, Rf 3 and Rf 4 independently represent an aliphatic hydrocarbon group having a fluoro group, R 1 represents a divalent organic group. ]​​​​

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