Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
  • C08G71/04—Polyurethanes

Definitions

• the present invention relates to a method for efficiently producing high-quality mesh polyurethane.
• Non-Patent Document 1 summarizes a method for producing polyurethane from diisocyanate compounds and diol compounds.
• isocyanates are highly toxic, their use is beginning to be restricted in Europe. This movement is expected to spread throughout Japan and the world in the future. Furthermore, isocyanates are produced using phosgene, which is highly toxic.
• Non-Patent Document 2 hybrid non-isocyanate polyurethanes that can be produced without using phosgene or isocyanates have been developed, but they are very special (Non-Patent Document 2). It is also known that polyurethanes can be synthesized from biscarbamate compounds and diol compounds in the presence or absence of a base. Such biscarbamate compounds are called blocked isocyanates, and are used by exposing the isocyanate groups during the curing reaction.
• Non-Patent Document 3 Blocked isocyanates produced using aliphatic alcohols as blocking agents are converted to diisocyanate compounds by heating.
• the heating temperature is over 100 degrees Celsius (Non-Patent Document 3), which may cause polyurethane to become discolored and the diisocyanate compound to decompose.
• Patent Document 1 also discloses blocked isocyanates produced using fluorine-containing aliphatic alcohols, but the conversion to diisocyanate compounds is also carried out at temperatures of over 100 degrees Celsius, such as 200°C.
• Non-Patent Document 3 Blocked isocyanates produced using aromatic alcohols as blocking agents can be converted to diisocyanate compounds at relatively low temperatures (Non-Patent Document 3), but the aromatic alcohol that is eliminated cannot be removed from the polyurethane, which may result in a deterioration in the quality of the polyurethane.
• Non-Patent Document 4 discloses a method for synthesizing polyurethane by converting blocked isocyanate to a diisocyanate compound at room temperature using fluoride ions as a catalyst.
• this method is difficult to implement industrially because reagents such as n-Bu 4 NF are relatively expensive and cannot be easily removed from the synthesized polyurethane, and the fluoride ions themselves are toxic.
• isocyanate is used in the general industrial production method of polyurethane.
• isocyanate is used as a starting material compound for synthesizing blocked isocyanate, or blocked isocyanate is intentionally converted to isocyanate and then reacted with diol compound.
• isocyanate is highly toxic, and it is considered that the restrictions on its use will become increasingly strict in the future.
• an object of the present invention is to provide a method for efficiently producing a high-quality network polyurethane without using an isocyanate.
• the present inventors have conducted extensive research to solve the above problems, and as a result have found that by reacting a specific fluorinated biscarbamate compound with a polyol compound, a fluorinated polyurethane having a two- or higher-dimensional chemical structure can be produced at a relatively low temperature without isocyanate being detected at least in the reaction solution after the reaction, and that the fluorinated alcohol eliminated from the fluorinated biscarbamate compound is unlikely to remain in the fluorinated polyurethane, thereby completing the present invention.
• the present invention will now be described.
• a method for producing a reticulated polyurethane comprising the steps of: A method comprising the step of reacting a fluorine-containing biscarbamate compound represented by the following formula (I) with a polyol compound represented by the following formula (II): [Wherein, Rf1 represents a fluorine-containing C1-6 alkyl group; Rf2 represents a fluorine-containing divalent organic group; R 1 represents an n-valent organic group; R2 represents a divalent organic group; n represents an integer of 3 or more and 8 or less.
• the fluorine-containing biscarbamate compound used in the present invention can be reacted with a polyol compound at a relatively low temperature, so that coloring of the resulting fluorine-containing polyurethane is suppressed.
• the fluorine-containing alcohol generated from the fluorine-containing biscarbamate compound during the reaction has a relatively low boiling point and can be easily removed from the target compound, fluorine-containing polyurethane. Even if it remains, it may be possible to impart desirable properties such as water repellency to the fluorine-containing polyurethane.
• the mechanism of the above reaction according to the present invention is unknown, at least isocyanate is not detected in the reaction liquid after the reaction.
• the polyurethane produced by the method of the present invention has a strong chemical structure of two or more dimensions, so it is considered to be excellent in strength, heat resistance, chemical resistance, weather resistance, etc. Therefore, the present invention is industrially very excellent as a technology that can efficiently and safely produce high-quality fluorine-containing polyurethane.
• FIG. 1 is a photograph showing the appearance of polyurethane produced by the method of the present invention.
• the method for producing a fluorine-containing polyurethane according to the present invention includes a step of reacting a fluorine-containing biscarbamate compound represented by formula (I) with a polyol compound represented by formula (II).
• a fluorine-containing biscarbamate compound represented by formula (I) with a polyol compound represented by formula (II).
• a polyurethane manufacturing method has been considered in which a biscarbamate compound called a blocked isocyanate is used, which is converted to an isocyanate compound by heating in a reaction liquid and then reacted with a diol compound.
• a blocked isocyanate is used, which is converted to an isocyanate compound by heating in a reaction liquid and then reacted with a diol compound.
• high heat is generally required to convert a blocked isocyanate to an isocyanate compound, and this high heat causes discoloration of the polyurethane.
• Blocked isocyanates that use aromatic alcohols as blocking agents have also been developed as blocked isocyanates that can be converted to isocyanate compounds at relatively low temperatures, but aromatic alcohols are produced during the polymerization reaction and remain behind as they cannot be removed from the polyurethane, resulting in a decrease in the quality of the polyurethane.
• the present invention uses a fluorine-containing biscarbamate compound (I).
• a chain-type fluorine-containing alcohol is produced as a by-product, but the chain-type fluorine-containing alcohol is easier to distill off than aromatic alcohols.
• the chain-type fluorine-containing alcohol remains in the polyurethane, it is obviously less likely to be oxidized than aromatic alcohols and will not adversely affect the transparency of the polyurethane. Rather, it can impart to the polyurethane favorable properties attributable to fluoro groups, such as water repellency, stain resistance, weather resistance, and abrasion resistance.
• conventional blocked isocyanates require high heat for conversion to isocyanate compounds, the fluorine-containing biscarbamate compound (I) of the present invention can be reacted with the polyol compound (II) even at relatively low temperatures.
• Rf 1 in the fluorine-containing biscarbamate compound (I) independently represents a fluorine-containing C 1-6 alkyl group.
• the C 1-6 alkyl group refers to a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2,2-dimethylethyl, n-pentyl, n-hexyl, 2-hexyl, and 3-hexyl.
• a C 2-6 alkyl group is preferred, and a C 2-4 alkyl group is more preferred.
• the number of fluoro group substituents in the fluorine-containing C 1-6 alkyl group is not particularly limited as long as it can be substituted, but since the more fluoro groups there are, the higher the reactivity of the fluorine-containing biscarbamate compound (I) is, the more preferable the number is 2 or more, and more preferable the number is 3 or more.
• the upper limit of the number of the substituents can be, for example, 20 or less, and preferably 15 or less.
• the C 1-6 alkyl group is preferably a sec-alkyl group or a tert-alkyl group.
• Rf 1 , -CH 2 Rf 4 , -CH(Rf 4 ) 2 , or -C(Rf 4 ) 3 [wherein Rf 4 represents a perfluoro C 1-5 alkyl group, and multiple Rf 4s may be the same or different from each other. ] is preferable, and a di(trifluoromethyl)methyl group [CH(CF 3 ) 2 ] or a tri(trifluoromethyl)methyl group [C(CF 3 ) 3 ] in which all hydrogen atoms in the carbons other than the first carbon are substituted with fluoro groups is more preferable.
• the fluorine-containing biscarbamate compound (I) may be substituted with, in addition to fluoro, a halogeno group selected from chloro, bromo and iodo, which are also electron-withdrawing groups.
• the two Rf 1 s in the fluorine-containing biscarbamate compound (I) may be the same or different, but are preferably the same.
• Rf2 in the fluorine-containing biscarbamate compound (I) represents a fluorine-containing divalent organic group.
• the fluorine-containing divalent organic group include a fluorine-containing C2-10 alkanediyl group and a fluorine-containing C6-30 divalent aromatic group.
• the C2-10 alkanediyl group in the fluorinated C2-10 alkanediyl group refers to a straight-chain or branched-chain divalent saturated aliphatic hydrocarbon group having from 2 to 10 carbon atoms. Examples include ethanediyl, n-propanediyl, methylethanediyl, n-butanediyl, methylpropanediyl, n-pentanediyl, n-hexanediyl, n-heptanediyl, n-octanediyl, etc.
• a C2-8 alkanediyl group is preferred, and a C3-7 alkanediyl group is more preferred.
• the number of fluoro group substituents in the fluorine-containing C2-10 alkanediyl group is not particularly limited as long as it is substitutable, but since the more fluoro groups there are, the higher the reactivity of the fluorine-containing biscarbamate compound (I), the number is preferably 2 or more, and more preferably 3 or more.
• the upper limit of the number of the substituents can be, for example, 20 or less, and preferably 15 or less.
• Rf2 in the fluorine-containing biscarbamate compound (I) is preferably CH2 - Rf3 - CH2 (wherein Rf3 represents a fluorine-containing C1-8 alkanediyl group).
• a fluorine-containing biscarbamate compound (I) having such a group as Rf2 is more stable.
• the formula CH2- ( CF2 ) m - CH2 (wherein m represents an integer of 1 or more and 8 or less) is more preferable.
• the fluorine-containing biscarbamate compound (I) having the above group as Rf2 has a more stable Rf2 moiety and is more reactive.
• the fluorine-containing C2-10 alkanediyl group may contain an ether group (-O-). That is, examples of Rf2 include a group represented by the formula: -CH2 - Rf5 -[-O- Rf6- ] p -O- Rf7 - CH2- [wherein Rf5 to Rf7 are independently a fluorine-containing C1-4 alkanediyl group, and p is an integer of 0 to 100.]. Rf5 to Rf7 are preferably perfluoro C1-4 alkanediyl groups, and p is preferably 50 or less.
• Rf5 to Rf7 are independently -CF2- , -CF2CF2- , -CF ( CF3 ) CF2- , and -CF2CF ( CF3 )-.
• the multiple Rf 6s may be the same or different.
• the fluorine-containing C 2-10 alkanediyl group may be -CH 2 CF 2 O-[CF 2 CF 2 O]-[CF 2 O]-CF 2 CH 2 - [wherein, [CF 2 CF 2 O] and [CF 2 O] represent structural units, each of which may be polymerized 0 or more and 6 or less. ].
• the structure of the fluorine-containing C 2-10 alkanediyl group may be a block copolymer structure or a random copolymer structure.
• C6-12 divalent arylene groups such as phenylene , naphthylene, indenylene and biphenylene
• all of the hydrogen atoms in the aromatic ring may be substituted with fluoro, and an alkanediyl group bonding multiple phenylene groups, such as bisphenols, may also be substituted with fluoro, if possible.
• the fluorine-containing biscarbamate compound (I) can be produced, for example, by the following method. In the following method, it is not necessary to use an isocyanate.
• the diamino compound (IV) and carbonate compound (V) may be commercially available, or may be synthesized.
• the carbonate compound (V) may be synthesized by a conventional method using, for example, phosgene, but it may also be synthesized by reacting a fluoroaliphatic hydrocarbon ester of trichloroacetic acid with a fluorine-containing alcohol, or by using the method described in WO2018/211953 that does not use phosgene.
• H 2 N—CH 2 —Rf 3 —CH 2 —NH 2 (wherein Rf 3 represents a fluorine-containing C 1-8 alkanediyl group) or H 2 N—CH 2 —(CF 2 ) m —CH 2 —NH 2 (wherein m represents an integer of 1 or more and 8 or less) can be used.
• carbonate compounds (V) include bis(2,2,2-trifluoroethyl)carbonate, bis(2,2,3,3-tetrafluoropropyl)carbonate, bis(2,2,3,3,3-pentafluoropropyl)carbonate, bis(1,1,1,3,3,3-hexafluoroisopropyl)carbonate, and bis(1,1,1,2,2,4,5,5,5-nonafluoro-4-trifluoromethyl).
• bis(2,2,3,3,3-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.
• diamino compound (IV) and carbonate compound (V) may be adjusted as appropriate. For example, theoretically, two moles of carbonate compound (V) react with diamino compound (IV), so it is preferable to set the molar ratio of carbonate compound (V) to diamino compound (IV) to two moles or more.
• the molar ratio can be adjusted to 5 moles or more and 20 moles or less.
• the molar ratio is preferably 15 moles or less, and more preferably 10 moles or less.
• a solvent may be used in the above reaction.
• the solvent is not particularly limited, but examples thereof include fluorine-containing solvents such as Asahiklin series manufactured by AGC, Novec series manufactured by 3M, Elnova series manufactured by Tokuyama METEL, 1,3-bis(trifluoromethyl)benzene, and the like; nitrile-based solvents such as acetonitrile and benzonitrile; ether-based solvents such as diethyl ether, glyme, diglyme, triglyme, tetraglyme, tetrahydrofuran, and dioxane; ketone-based solvents such as acetone and methyl ethyl ketone; ester-based solvents such as ethyl acetate; halogenated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride; and aromatic hydrocarbon solvents such as benzene, toluene, and chlorobenzen
• a fluorine-containing solvent that has excellent solubility for fluorine-containing compounds, or a mixed solvent of a fluorine-containing solvent and another solvent is preferable.
• a solvent may not be used. From the viewpoint of cost and environmental burden, it is preferable not to use a solvent.
• a base may be used in the above reaction.
• the base include organic bases such as pyridine, triethylamine, ethyldiisopropylamine, diazabicycloundecene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), N-methylmorpholine, and N-methylimidazole; and inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium fluoride, potassium fluoride, and cesium fluoride. From the viewpoint of solubility in the reaction liquid and appropriate basicity, organic bases are preferred. After the reaction, the organic base may be removed from the reaction liquid by distillation. The amount of the base used may be adjusted as appropriate, and may be, for example, 0.1 to 5 times the molar amount of the diamino compound (IV). However, from the viewpoint of cost and residue, it may be possible not to use a base.
• the reaction conditions may be adjusted as appropriate.
• the reaction temperature may be 10°C or higher and 60°C or lower, and the reaction may be carried out at room temperature.
• the reaction time may also be adjusted as appropriate, and may be determined by a preliminary experiment or until the consumption of at least one of the diamino compound (IV) and the carbonate compound (V) is confirmed by chromatography or NMR spectrum, and may be, for example, 1 hour or higher and 50 hours or lower.
• the usual post-treatment can be carried out.
• water and/or a water-immiscible organic solvent such as a fluorine-containing solvent can be added to the reaction solution after the reaction, and the liquids can be separated.
• the resulting organic phase can be dried using anhydrous sodium sulfate or anhydrous magnesium sulfate, and the solvent can be distilled off.
• the product can be further purified by chromatography, etc.
• R 1 in the polyol compound (II) represents an organic group having a valence of n (n is an integer of 3 or more and 8 or less).
• R 1 include an n-valent C 1-10 chain aliphatic hydrocarbon group, an n-valent C 3-10 cyclic aliphatic hydrocarbon group, an n-valent C 6-15 aromatic hydrocarbon group, and an n-valent organic group to which 2 or more and 5 or less groups selected from a C 1-10 chain aliphatic hydrocarbon group, a C 3-10 cyclic aliphatic hydrocarbon group, and a C 6-15 aromatic hydrocarbon group are bonded.
• a " C1-10 tetravalent chain aliphatic hydrocarbon group” refers to a straight-chain or branched-chain tetravalent saturated aliphatic hydrocarbon group or tetravalent unsaturated aliphatic hydrocarbon group having from 1 to 10 carbon atoms.
• examples of the C1-10 tetravalent chain aliphatic hydrocarbon group include a C1-10 alkanetetrayl group, a C2-10 alkenetetrayl group, and a C2-10 alkyntetrayl group.
• C1-10 alkanetetrayl groups include methanetetrayl, ethanetetrayl, n-propanetetrayl, isopropanetetrayl, n-butanetetrayl, 1-methylpropanetetrayl, 2-methylpropanetetrayl, 1,1-dimethylethanetetrayl, 2,2-dimethylethanetetrayl, n-pentanetetrayl, n-hexanetetrayl, n-heptanetetrayl, n-octanetetrayl, n-nonanetetrayl, n-decanetetrayl, etc.
• C2-10 alkenetetrayl groups include ethenetetrayl, 1-propenetetrayl, 2-propenetetrayl, butenetetrayl, hexenetetrayl, octenetetrayl, nonenetetrayl, decenetetrayl, etc. Preferred are C2-8 alkenetetrayl groups.
• C2-10 alkynetetrayl groups include propynetetrayl, butynetetrayl, hexynetetrayl, octynetetrayl, nonynetetrayl, decynetetrayl, etc.
• Preferred is a C2-8 alkynetetrayl group.
• C3-10 tetravalent cyclic aliphatic hydrocarbon group refers to a cyclic tetravalent saturated aliphatic hydrocarbon group or tetravalent unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and the number of rings may be 1 or 2 or more. Examples include a C3-10 cycloalkanetetrayl group, a C3-10 cycloalkenetetrayl group, and a C3-10 cycloalkynetetrayl group.
• Examples of the C3-10 cycloalkanetetrayl group include cyclobutanetetrayl, cyclopropanetetrayl, cyclohexanetetrayl, and adamantanetetrayl.
• C6-15 tetravalent aromatic hydrocarbon group refers to a tetravalent aromatic hydrocarbon group having 6 or more and 15 or less carbon atoms.
• Examples include benzenetetrayl, indenetetrayl, naphthalenetetrayl, biphenyltetrayl, phenalenetetrayl, phenanthrenetetrayl, anthracenetetrayl, etc., preferably a C6-12 tetravalent aromatic hydrocarbon group, more preferably benzenetetrayl.
• Examples of the n-valent organic group to which 2 or more and 5 or less groups selected from a C1-10 chain aliphatic hydrocarbon group, a C3-10 cyclic aliphatic hydrocarbon group, and a C6-15 aromatic hydrocarbon group are bonded include a C3-10 cyclic aliphatic hydrocarbon group- C1-10 chain aliphatic hydrocarbon group, a C1-10 chain aliphatic hydrocarbon group- C3-10 cyclic aliphatic hydrocarbon group, a C6-15 aromatic hydrocarbon group- C1-10 chain aliphatic hydrocarbon group, a C1-10 chain aliphatic hydrocarbon group- C6-15 aromatic hydrocarbon group, a C1-10 chain aliphatic hydrocarbon group-C3-10 cyclic aliphatic hydrocarbon group- C1-10 chain aliphatic hydrocarbon group, a C3-10 cyclic aliphatic hydrocarbon group- C1-10 chain aliphatic hydrocarbon group, a C3-10 cyclic aliphatic hydrocarbon group- C1-10 chain
• R 1 an n-valent organic group may be substituted with one or more halogeno groups selected from fluoro, chloro, bromo, and iodo.
• the substituent is preferably fluoro.
• the n-valent C 1-10 chain aliphatic hydrocarbon group and the n-valent C 3-10 cyclic aliphatic hydrocarbon group may contain an ether group (-O-), and the n-valent C 3-10 cyclic aliphatic hydrocarbon group and the n-valent C 6-15 aromatic hydrocarbon group may be substituted with a C 1-6 alkyl group in addition to a halogeno group.
• R2 in the polyol compound (II) represents a divalent organic group having 2 or more carbon atoms.
• the present inventors have experimentally found that, although a side reaction of producing a cyclic compound occurs between the polyol compound and the fluorocarbonate compound (I) depending on the carbon number of the polyol compound, such a side reaction can be suppressed by combining R1 with R2 , which is a divalent organic group having 2 or more carbon atoms.
• R2 examples include a C2-10 divalent chain aliphatic hydrocarbon group, a C3-10 divalent cyclic aliphatic hydrocarbon group, a C6-15 divalent aromatic hydrocarbon group, and a divalent organic group to which two or more and five or less groups selected from a C1-10 divalent chain aliphatic hydrocarbon group, a C3-10 divalent cyclic aliphatic hydrocarbon group, and a C6-15 divalent aromatic hydrocarbon group are bonded.
• C2-10 divalent chain aliphatic hydrocarbon group refers to a straight-chain or branched-chain divalent saturated aliphatic hydrocarbon group or a divalent unsaturated aliphatic hydrocarbon group having from 2 to 10 carbon atoms.
• examples of C1-10 divalent chain aliphatic hydrocarbon groups include a C1-10 alkanediyl group, a C2-10 alkenediyl group, and a C2-10 alkynediyl group.
• C2-10 alkanediyl groups include ethanediyl, n-propanediyl, isopropanediyl, n-butanediyl, 1-methylpropanediyl, 2-methylpropanediyl, 1,1-dimethylethanediyl, 2,2-dimethylethanediyl, n-pentanediyl, n-hexanediyl, n-heptanediyl, n-octanediyl, n-nonanediyl, n-decanediyl, etc.
• C2-10 alkenediyl groups include ethenediyl, 1-propenediyl, 2-propenediyl, butenediyl, hexenediyl, octenediyl, nonenediyl, decenediyl, etc.
• C2-10 alkynediyl groups include ethynediyl, propynediyl, butynediyl, hexynediyl, octynediyl, nonynediyl, decynediyl, etc.
• Preferred are C2-8 alkynediyl groups, and more preferred are C2-6 alkynediyl groups or C2-4 alkynediyl groups.
• C3-10 divalent cyclic aliphatic hydrocarbon group refers to a cyclic divalent saturated or unsaturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, and the number of rings may be 1 or 2 or more.
• Examples include a C3-10 cycloalkanediyl group, a C3-10 cycloalkenediyl group, and a C3-10 cycloalkynediyl group.
• Examples of the C3-10 cycloalkanediyl group include cyclobutanediyl, cyclopropanediyl, cyclohexanediyl, and adamantanediyl.
• C6-15 divalent aromatic hydrocarbon group refers to a divalent aromatic hydrocarbon group having 6 or more and 15 or less carbon atoms. Examples include phenylene, indenylene, naphthylene, biphenylene, phenalenylene, phenanthrenylene, anthracenylene, etc., preferably a C6-12 divalent aromatic hydrocarbon group, more preferably phenylene.
• Examples of the divalent organic group to which two or more and five or less groups selected from a C1-10 divalent chain aliphatic hydrocarbon group, a C3-10 divalent cyclic aliphatic hydrocarbon group, and a C6-15 divalent aromatic hydrocarbon group are bonded include a C3-10 divalent cyclic aliphatic hydrocarbon group- C1-10 divalent chain aliphatic hydrocarbon group, a C1-10 divalent chain aliphatic hydrocarbon group-C3-10 divalent cyclic aliphatic hydrocarbon group, a C6-15 divalent aromatic hydrocarbon group-C1-10 divalent chain aliphatic hydrocarbon group, a C1-10 divalent chain aliphatic hydrocarbon group-C6-15 divalent aromatic hydrocarbon group, a C1-10 divalent chain aliphatic hydrocarbon group- C3-10 divalent cyclic aliphatic hydrocarbon group- C1-10 divalent chain aliphatic hydrocarbon group, a C3-10 divalent chain aliphatic hydrocarbon group- C6-15 divalent aromatic hydro
• R 2 divalent organic group may be substituted with one or more halogeno groups selected from fluoro, chloro, bromo, and iodo.
• the substituent is preferably fluoro.
• the C 1-10 divalent chain aliphatic hydrocarbon group and the C 3-10 divalent cyclic aliphatic hydrocarbon group may contain an ether group (-O-), and the C 3-10 divalent cyclic aliphatic hydrocarbon group and the C 6-15 divalent aromatic hydrocarbon group may be substituted with a C 1-6 alkyl group in addition to a halogeno group.
• R 2 may contain a repeating unit represented by the formula -[-O-R 4 -]- (wherein R 4 represents a C 1-8 alkanediyl group which may be substituted with a fluoro group).
• R 4 represents a C 1-8 alkanediyl group which may be substituted with a fluoro group.
• R 4 include an ethylene group (-CH 2 CH 2 -), a propylene group [-CH(CH 3 )CH 2 - or -CH 2 CH(CH 3 )-], and a tetramethylene group (-CH 2 CH 2 CH 2 CH 2 -), each of which may be substituted with a fluoro group.
• the number of repeats of the above repeating unit in each -R 2 -OH group in the polyol compound (II) is preferably 5 or more, more preferably 10 or more, even more preferably 20 or more, and is preferably 100 or less, more preferably 50 or less.
• R2s in the polyol compound (II) may be the same or different from each other.
• R2 contains the divalent polyoxyalkylene group
• the repeating units thereof may be the same or different from each other.
• a solvent When reacting the fluorine-containing biscarbamate compound (I) with the polyol compound (II), a solvent may be used.
• the solvent is not particularly limited as long as it is liquid at room temperature and normal pressure and does not adversely affect the reaction, but examples include fluorine-containing solvents such as Asahiklin series manufactured by AGC, Novec series manufactured by 3M, Elnova series manufactured by Tokuyama METEL, and 1,3-bis(trifluoromethyl)benzene; aromatic hydrocarbon solvents such as benzene, toluene, and chlorobenzene; nitrile-based solvents such as acetonitrile and benzonitrile; ether-based solvents such as diethyl ether, glyme, diglyme, triglyme, tetraglyme, tetrahydrofuran, and dioxane; ketone-based solvents such as acetone and methyl ethyl ketone; ester-
• a solvent may not be used. From the standpoint of cost and environmental impact, it is preferable not to use a solvent.
• the amount of the fluorocarbonate compound (I) and the polyol compound (II) may be adjusted appropriately.
• n times or more of the polyol compound (II) is used relative to the polyol compound (II).
• the molar number is preferably n x 1.1 times or more, more preferably n x 1.2 times or more, and even more preferably n x 1.25 times or more.
• the upper limit of the molar number is not particularly limited, but can be, for example, n x 5 times or less.
• the molar number is preferably n x 4 times or less, and more preferably n x 3 times or less. However, the molar ratio may be 1 time or more regardless of n.
• the molar ratio is preferably 1.2 times or more, and more preferably 1.5 times or more.
• the molar ratio is preferably 5 times or less or 4 times or less, and more preferably 3 times or less or 2 times or less.
• a part of the polyol compound (II) may be replaced with a diol compound.
• the fluorine-containing biscarbamate compound (I) may be reacted with the polyol compound (II) in the presence of a base.
• a base examples include organic bases such as pyridine, triethylamine, ethyldiisopropylamine, diazabicycloundecene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), N-methylmorpholine, and N-methylimidazole; and inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium fluoride, potassium fluoride, and cesium fluoride.
• organic bases such as pyridine, triethylamine, ethyldiisopropylamine, diazabicycloundecene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), N-methylmorpholine, and N
• organic bases are preferred. After the reaction, the organic base may be removed from the reaction liquid by distillation.
• the amount of the base used may be appropriately adjusted, and may be, for example, 0.01 to 1 mole times the amount of the fluorine-containing biscarbamate compound (I) or the polyol compound (II), whichever has the smaller number of moles.
• the reaction temperature may be adjusted as appropriate, and may be, for example, 10°C or higher and 200°C or lower.
• the reaction may be carried out at room temperature, or under heated reflux conditions depending on the solvent used, etc.
• the higher the reaction temperature the better the reaction may proceed.
• the reaction temperature is preferably 25°C or higher or 40°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher.
• the temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower.
• the reaction time may be adjusted as appropriate and may be determined by a preliminary experiment or the like, or until consumption of at least one of the fluorine-containing biscarbamate compound (I) or the polyol compound (II) is confirmed by chromatography or NMR spectroscopy, and may be, for example, from 1 hour to 200 hours.
• the usual post-treatment can be carried out.
• the solvent can be distilled off after the reaction.
• the fluorine-containing polyurethane can also be washed with a solvent.
• the method of the present invention can easily, safely, and efficiently produce fluorine-containing polyurethane without using highly toxic isocyanate compounds.
• the fluorine-containing polyurethane produced by the present invention has excellent heat resistance, flexibility, chemical resistance, water repellency, etc., because the main skeleton is a chain organic group having a fluoro group as a substituent.
• the quality of the polyurethane may be further improved by the fluorine-containing alcohol that may remain.
• the polyurethane produced by the present invention has a two-dimensional or three-dimensional mesh-like chemical structure, so it is considered to be even more excellent in strength, heat resistance, chemical resistance, weather resistance, etc.
• the polyurethane according to the present invention is produced by polymerizing a trivalent or higher polyol compound (II), and in the field of polymer chemistry, it is generally accepted that a polymer having a two-dimensional or three-dimensional mesh-like structure can be produced by polymerizing a trivalent or higher monomer.
• Example 1 Synthesis of network polyurethane using 8FHBC and triol type PPG1500 8FHBC (195 mg, 0.30 mmol), triol-type PPG1500 (300 mg, 0.20 mmol), DABCO (3.4 mg, 0.03 mmol), and toluene (0.5 mL) were placed in a 7 mL test tube and stirred for 4 days at 100° C. The solvent was removed from the reaction solution by distillation under reduced pressure, and the solution was dried in vacuum at 100° C. for 2 hours to quantitatively obtain the target product as a light yellow transparent solid insoluble in the solvent (yield: 395 mg).
• Example 2 Synthesis of network polyurethane using 8FHBC, diol type PPG400, and trimethylolpropane 8FHBC (195 mg, 0.30 mmol), diol type PPG400 (108 mg, 0.27 mmol), trimethylolpropane (2.7 mg, 0.02 mmol), DABCO (3.4 mg, 0.03 mmol), and toluene (0.5 mL) were placed in a 7 mL test tube and stirred for 4 days at 100° C. The solvent was removed from the reaction solution by distillation under reduced pressure, and the solution was dried in vacuum at 100° C. for 2 hours to quantitatively obtain the target product as a brown viscous liquid (yield: 196 mg).
• Example 3 Synthesis of network polyurethane using 8FHBC, diol type PPG400, and pentaerythritol 8FHBC (195 mg, 0.30 mmol), diol type PPG400 (104 mg, 0.26 mmol), pentaerythritol (2.7 mg, 0.02 mmol), DABCO (3.4 mg, 0.03 mmol), and toluene (0.5 mL) were placed in a 7 mL test tube and stirred for 4 days at 100° C. The solvent was removed from the reaction solution by distillation under reduced pressure, and the solution was dried in vacuum at 100° C. for 2 hours to quantitatively obtain the target product as a brown viscous solid insoluble in the solvent (yield: 193 mg).
• Example 4 Synthesis of network polyurethane using 8FHBC and FPEGQA40 8FHBC (195 mg, 0.30 mmol), FPEGQA40 (600 mg, 0.15 mmol), DABCO (3.4 mg, 0.03 mmol), and toluene (0.5 mL) were placed in a 7 mL test tube and stirred for two days at 100° C. The solvent was removed from the reaction solution by distillation under reduced pressure, and the solution was dried in vacuum at 100° C. for 2 hours to quantitatively obtain the target product as a white solid insoluble in the solvent (yield: 513 mg).
• Example 5 Synthesis of network polyurethane using 8FHBC, diol type PPG400, and FPEGQA40 8FHBC (195 mg, 0.30 mmol), diol type PPG400 (104 mg, 0.26 mmol), FPEGQA40 (80 mg, 0.02 mmol), DABCO (3.4 mg, 0.03 mmol), and toluene (0.5 mL) were placed in a 7 mL test tube and stirred for 5 days at 100° C. The solvent was removed from the reaction solution by distillation under reduced pressure, and the mixture was dried in vacuum at 100° C. for 2 hours to quantitatively obtain the target product as a brown viscous solid insoluble in the solvent (yield: 250 mg).

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