Polycarbonate polyols, methods for making the same, and compositions thereof

Abstract

A polycarbonate polyol having an ester bond and a urethane bond, and having an acid value of 0.01 mgKOH / g to 5.0 mgKOH / g. Also, a method for producing the polycarbonate polyol described above, which uses a transesterification catalyst, at least one carbonate represented by formula (3), at least one diol represented by formula (4), and a cyclic amide represented by formula (5). Thus, a polycarbonate polyol that is easy to operate and that improves the mechanical properties and solvent resistance of a polyurethane resin obtained from the polycarbonate polyol is provided.

Description

Technical Field

[0001] This invention relates to polycarbonate polyols, their manufacturing methods, and compositions thereof. Background Technology

[0002] Similar to polyester polyols and polyether polyols, polycarbonate polyols are useful as raw materials for manufacturing polyurethane resins by reacting with polyisocyanate compounds, as well as for engineering plastics, adhesives, coatings, etc., and can also be used as modifiers for polyester resins, etc.

[0003] For the modification of polycarbonate diol, the reaction of polycarbonate diol with lactone is known (e.g., Patent Document 1). The product has fewer carbonate bonds and more ester bonds compared to polycarbonate diol.

[0004] To modify the properties of polycarbonate, the following examples are known: when polycarbonate is synthesized by reacting a polyol with a dialkyl carbonate, a urethane bond is introduced by reacting with a cyclic amide compound (for example, see Patent Document 2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2014 / 069563

[0008] Patent Document 2: U.S. Patent Application Publication No. 2018 / 0251597 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The polycarbonate diol in Patent Document 1 lacks solvent resistance during urethane esterification, thus requiring further improvement in solvent resistance.

[0011] Furthermore, the polycarbonate in Patent Document 2 has a molecular weight of over 20,000 g / mol, resulting in high viscosity and difficult handling. Moreover, the polycarbonate in Patent Document 2 does not explicitly specify the presence or absence of molecular end structures such as hydroxyl groups that can react with isocyanates, nor does it mention its derivatization into polyurethane as a polycarbonate diol.

[0012] The objective of this invention is to provide a polycarbonate polyol that is easy to operate and can improve the mechanical properties and solvent resistance of polyurethane resins obtained from polycarbonate polyols.

[0013] Methods for solving problems

[0014] Specifically, the present invention is described below.

[0015] 1. A polycarbonate polyol having ester bonds and urethane bonds, and having an acid value of 0.01 mg KOH / g to 5.0 mg KOH / g.

[0016] 2. The polycarbonate polyol as described in 1 above, wherein the molar ratio of the urethane bond to the ester bond (urethane / ester) is 0.8 to 1.2.

[0017] 3. The polycarbonate polyol as described in 1 or 2 above, wherein the content of carbonate bonds is 3% to 35% by mass relative to the total amount of polycarbonate polyol.

[0018] 4. The polycarbonate polyol as described in any one of 1 to 3 above, wherein the content of ester bonds is 1.5% to 15% by mass relative to the total amount of polycarbonate polyol, and the content of urethane bonds is 2% to 20% by mass relative to the total amount of polycarbonate polyol.

[0019] 5. The polycarbonate polyol as described in any one of 1 to 4 above, wherein the content of ester bonds and urethane bonds as shown in formula (I) below is 10 mol% to 90 mol%.

[0020] (E+U) / (E+U+C)×100(I)

[0021] E: The number of molar ester bonds in polycarbonate polyols

[0022] U: The number of molars of urethane bonds in polycarbonate polyols

[0023] C: The number of molars of carbonate bonds in polycarbonate polyols

[0024] 6. The polycarbonate polyol as described in any one of 1 to 5 above, wherein the hydroxyl value is 25 mg KOH / g to 250 mg KOH / g.

[0025] 7. The polycarbonate polyol as described in any one of 1 to 6 above, having repeating units as shown in formula (1) and repeating units as shown in formula (2).

[0026] [Chemistry 1]

[0027]

[0028] [Chemistry 2]

[0029]

[0030] (where R is in the formula) 1 and R 2 (This refers to hydrocarbon groups with 2 to 20 carbon atoms.)

[0031] 8. The polycarbonate polyol as described in 7 above, wherein, in formula (1) above, R 1 It is a straight-chain or branched alkylene group with 4 to 7 carbon atoms.

[0032] 9. The polycarbonate polyol as described in any one of 1 to 8 above, wherein the number average molecular weight is 400 g / mol to 4500 g / mol.

[0033] 10. The polycarbonate polyol as described in any one of 1 to 9 above, which is liquid at room temperature (25°C).

[0034] 11. A method for manufacturing a polycarbonate polyol, comprising a polycarbonate polyol having ester bonds and urethane bonds and an acid value of 0.01 mg KOH / g to 5.0 mg KOH / g, wherein...

[0035] The method uses an ester exchange catalyst, at least one carbonate of formula (3) below, at least one diol of formula (4) below, and a cyclic amide of formula (5) below.

[0036] [Chemistry 3]

[0037]

[0038] [Chemistry 4]

[0039]

[0040] [Chemistry 5]

[0041]

[0042] (where R is in the formula) 1 and R 2 This represents a hydrocarbon group with 2 to 20 carbon atoms. In the formula, R... 3 It represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 5 to 8 carbon atoms, with 2 Rs in the same molecule. 3 They can be the same or different, or two Rs 3 They can together form alkylene rings with 1 to 4 carbon atoms.

[0043] 12. The method for manufacturing polycarbonate polyols as described in 11 above, wherein the transesterification catalyst is a titanium compound and / or an alkali metal compound.

[0044] 13. A composition for forming a polyurethane resin comprising the polycarbonate polyol (A) and the polyisocyanate (C) described in any one of 1 to 10 above.

[0045] 14. A polyurethane resin having a structure derived from the polycarbonate polyol (A) of any one of the above 1 to 10 and a structure derived from the polyisocyanate (C).

[0046] 15. An aqueous polyurethane resin dispersion comprising the polyurethane resin described in 14 above.

[0047] 16. A coating composition comprising the polyurethane resin described in 14 above.

[0048] 17. A coating composition comprising the polyurethane resin described in 14 above.

[0049] 18. An adhesive composition comprising the polyurethane resin described in 14 above.

[0050] 19. A polyurethane resin film comprising the polyurethane resin described in 14 above.

[0051] 20. A synthetic leather comprising the polyurethane resin described in 14 above.

[0052] 21. A thermoplastic polyurethane comprising the polyurethane resin described in 14 above.

[0053] 22. A thermosetting cast polyurethane comprising the polyurethane resin described in 14 above.

[0054] The effects of the invention

[0055] According to the present invention, a polycarbonate polyol that is easy to operate and can improve the mechanical properties and solvent resistance of polyurethane resins obtained from polycarbonate polyols can be provided. Detailed Implementation

[0056] [Polycarbonate polyols]

[0057] The polycarbonate polyol of the present invention has ester bonds and urethane bonds, and an acid value of 0.01 mg KOH / g to 5.0 mg KOH / g. Therefore, it is possible to provide a polycarbonate polyol that is easy to handle and can improve the mechanical properties and solvent resistance of polyurethane resins obtained from polycarbonate polyols. Preferably, the polycarbonate polyol of the present invention is a polycarbonate diol having hydroxyl groups at the ends of both molecules.

[0058] It should be noted that in this invention, "easy to operate" means that at least one of the following 1) and 2) is satisfied.

[0059] 1) Its viscosity at 75℃ is below 3000 cP. 2) It is a liquid at room temperature (25℃).

[0060] Because of its ease of operation, polycarbonate polyols can be readily used as raw materials for polyurethane resins and the like.

[0061] <Ester bond>

[0062] The content of ester bonds relative to the total amount of polycarbonate polyol is preferably 1.5% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and even more preferably 8% by mass or more. Furthermore, the content of ester bonds relative to the total amount of polycarbonate polyol is preferably 15% by mass or less, more preferably 14% by mass or less, and even more preferably 12% by mass or less. The content of ester bonds relative to the total amount of polycarbonate polyol is preferably 1.5% to 15% by mass, more preferably 3% to 14% by mass, and even more preferably 5% to 12% by mass. Within this range, polycarbonate polyols that are easy to handle and improve the mechanical properties and chemical resistance of polyurethane resins can be obtained.

[0063] <Carbamate bond>

[0064] The content of urethane bonds relative to the total amount of polycarbonate polyol is preferably 2% by mass or more, more preferably 4% by mass or more, further preferably 9% by mass or more, and even more preferably 13% by mass or more. Furthermore, the content of urethane bonds relative to the total amount of polycarbonate polyol is preferably 20% by mass or less, more preferably 19% by mass or less, and even more preferably 16% by mass or less. The content of urethane bonds relative to the total amount of polycarbonate polyol is preferably 2% to 20% by mass, more preferably 4% to 19% by mass, and even more preferably 9% to 16% by mass. Within this range, polycarbonate polyols that are easy to handle and improve the mechanical properties and chemical resistance of polyurethane resins can be obtained.

[0065] <carbonate bond>

[0066] The content of carbonate bonds relative to the total amount of polycarbonate polyol is preferably 3% by mass or more, more preferably 6% by mass or more, further preferably 11% by mass or more, and even more preferably 14% by mass or more. Furthermore, the content of carbonate bonds relative to the total amount of polycarbonate polyol is preferably 35% by mass or less, more preferably 32% by mass or less, and even more preferably 23% by mass or less. The content of carbonate bonds relative to the total amount of polycarbonate polyol is preferably 3% to 35% by mass, more preferably 6% to 32% by mass, and even more preferably 11% to 23% by mass. Within this range, polycarbonate polyols that are easy to handle and improve the mechanical properties and chemical resistance of polyurethane resins can be obtained. The polycarbonate polyol of the present invention has ester bonds, urethane bonds, and carbonate bonds, and when the content of each bond is within the above-mentioned range, the general characteristics of polycarbonate can be fully utilized, and polycarbonate polyols with superior chemical resistance and handling properties can be obtained, therefore it is particularly preferred.

[0067] <Proportion of each bond>

[0068] The molar ratio of urethane bonds to ester bonds (urethane / ester) is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. Within this range, polycarbonate polyols that are easy to handle and improve the mechanical properties and solvent resistance of polyurethane resins can be obtained.

[0069] Furthermore, the content of ester bonds and urethane bonds shown in the following formula (I) is preferably 10 mol% to 90 mol%. Within this range, polycarbonate polyols that are easy to handle and improve the mechanical properties and solvent resistance of polyurethane resins can be obtained.

[0070] (E+U) / (E+U+C)×100(I)

[0071] E: The number of molar ester bonds in polycarbonate polyols

[0072] U: The number of molars of urethane bonds in polycarbonate polyols

[0073] C: The number of molars of carbonate bonds in polycarbonate polyols

[0074] <Determination of the content of ester bonds, carbamate bonds and carbonate bonds>

[0075] It can also be used to determine the polycarbonate polyols. 1 HNMR, using integral values, quantifies the content of ester bonds, urethane bonds, and carbonate bonds in polycarbonate polyols.

[0076] In addition, the content of ester bonds, urethane bonds and carbonate bonds in polycarbonate polyols can also be calculated from the amount of raw materials used in the polycarbonate polyols.

[0077] <Acid Value>

[0078] In the polycarbonate polyol of the present invention, the acid value is 0.01 mg KOH / g to 5.0 mg KOH / g. When used as a raw material within this range, a polyurethane resin with particularly good physical properties can be obtained. The acid value is preferably 0.01 KOH / g to 1.0 mg KOH / g, more preferably 0.01 KOH / g to 0.5 mg KOH / g. Within this range, a polycarbonate polyol that is easy to handle, improves the mechanical properties of the polyurethane resin, and has good solvent resistance can be obtained.

[0079] In this specification, the acid value is determined according to the indicator titration method of JIS K 1557.

[0080] <Hydroxy value>

[0081] In the polycarbonate polyol of the present invention, the hydroxyl value can be from 25 mg KOH / g to 250 mg KOH / g. If it falls within this range, a polyurethane resin with particularly good physical properties can be obtained by using it as a raw material.

[0082] <Repeating Unit>

[0083] The polycarbonate polyol preferably has repeating units as shown in formula (1) and repeating units as shown in formula (2).

[0084] [Chemistry 6]

[0085]

[0086] [Chemistry 7]

[0087]

[0088] In the formula, R 1 and R 2 It represents a divalent hydrocarbon group with 2 to 20 carbon atoms.

[0089] R 1 Preferably, it is a straight-chain, branched, or cyclic aliphatic hydrocarbon group with 4 to 8 carbon atoms or an aromatic hydrocarbon group with 8 to 12 carbon atoms; more preferably, it is a straight-chain, branched, or cyclic alkylene group with 4 to 8 carbon atoms; even more preferably, it is a straight-chain or branched alkylene group with 4 to 7 carbon atoms; and even more preferably, it is a straight-chain alkylene group with 5 or 6 carbon atoms.

[0090] R 2 Preferably, it is an aliphatic or aromatic hydrocarbon group with 5 to 12 carbon atoms, more preferably a straight-chain or branched alkylene group with 6 to 12 carbon atoms, and even more preferably a straight-chain alkylene group with 6 carbon atoms.

[0091] R 1 and R 2 It can be one of the above-mentioned hydrocarbon groups. For example, the above-mentioned polycarbonate polyol can have R 1 A repeating unit of a 5-carbon alkylene group, and R 1 It is a repeating unit of an alkylene group with 6 carbon atoms.

[0092] By making R 1 and R 2 The above-mentioned divalent hydrocarbon groups can be used to obtain polycarbonate polyols that are easy to handle and can improve the mechanical properties and solvent resistance of polyurethane resins.

[0093] Examples of the aforementioned hydrocarbon groups include straight-chain or branched alkylene groups with 2 to 20 carbon atoms, such as ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, propylene, isobutylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylpentamethylene, isononamethylene, 2-methylnonamethylene, etc.; and substituted or unsubstituted cycloalkylene groups with 3 to 20 carbon atoms, such as cyclopentylene, cyclohexylene, 1,2-dimethylenecyclopentylene, 1 ,3-Dimethylenecyclopentyl, 1,2-Dimethylenecyclohexyl, 1,3-Dimethylenecyclohexyl, 1,4-Dimethylenecyclohexyl, 4,4'-Dimethylenedicyclohexyl, 2,2-Dimethylenepropane, etc.; substituted or unsubstituted aryl groups with 6 to 20 carbon atoms, such as phenylene, 1,2-Dimethylenephenyl, 1,3-Dimethylenephenyl, 1,4-Dimethylenephenyl, naphthylene, 4,4'-Dimethylenediphenylene, 2,2-Dimethylenepropane, etc., repeating units.

[0094] <Average molecular weight>

[0095] In the polycarbonate polyol of the present invention, the number-average molecular weight Mn is preferably 400 g / mol to 4500 g / mol. Within this range, it is easy to obtain flowability (e.g., viscosity 500 cP to 10000 cP) upon heating (e.g., 75°C), exhibiting excellent operability. The number-average molecular weight Mn is more preferably 500 g / mol to 3500 g / mol, and even more preferably 500 to 3000. In this specification, the number-average molecular weight Mn is the number-average molecular weight calculated based on the hydroxyl value determined according to JIS K 1577. Specifically, the hydroxyl value is determined by the terminal group quantification method, using (56.1 × 1000 × valence) / hydroxyl value (where the unit of hydroxyl value is [mgKOH / g]). In the above formula, the valence is the number of hydroxyl groups in one molecule.

[0096] In the polycarbonate polyol of the present invention, the weight-average molecular weight Mw is preferably 500 g / mol to 30000 g / mol. More preferably, the weight-average molecular weight Mw is 1000 g / mol to 13000 g / mol. In this specification, the weight-average molecular weight Mw is a value determined by GPC.

[0097] In the polycarbonate polyol of the present invention, the dispersion Mw / Mn is preferably 1.0 to 3.0. The dispersion Mw / Mn is preferably 2.0 to 2.3. If the dispersion is greater than 3.0, the size deviation between the hard and soft segments in the obtained polyurethane becomes larger, and the mechanical properties of the polyurethane may sometimes decrease.

[0098] <Physical Properties>

[0099] The water content of the polycarbonate polyol of the present invention is preferably 1 ppm to 10,000 ppm. If the water content is greater than 10,000 ppm, the amount of urea groups generated as a byproduct of the reaction between water and isocyanate during the synthesis of polyurethane will increase, which may sometimes impair the flexibility of polyurethane.

[0100] The glass transition temperature of the polycarbonate polyol of the present invention is preferably -80°C to +50°C. If the glass transition temperature is below -80°C, the strength of the obtained polyurethane is insufficient; if it is above 50°C, it may become brittle near room temperature.

[0101] The viscosity of the polycarbonate polyol of the present invention is preferably 10 cP to 90,000 cP (75°C), more preferably 50 cP to 10,000 cP (75°C), and even more preferably 100 cP to 3,000 cP (75°C). If the viscosity is higher than 3,000 cP (75°C), the processability during the synthesis of polyurethane may sometimes deteriorate.

[0102] To modify the properties of polycarbonate polyols, methods such as changing the raw material diol and modifying the synthesized polycarbonate polyol are known. If a diol compound with fewer carbon atoms is used as the raw material for the polycarbonate polyol, the concentration of carbonate bonds in the polycarbonate polyol increases, resulting in improved solvent resistance of the polyurethane due to the high cohesive force of the carbonate bonds. On the other hand, polycarbonate polyols composed of structures derived from diols with fewer carbon atoms and carbonate bonds are known to have high viscosity. In this invention, such a problem can also be solved using a polycarbonate polyol having ester bonds and urethane bonds and a certain acid value.

[0103] [Manufacturing Method]

[0104] The manufacturing method of the present invention is a method for manufacturing polycarbonate polyol, which is a method for manufacturing polycarbonate polyol having ester bonds and urethane bonds and an acid value of 0.01 mg KOH / g to 5.0 mg KOH / g, wherein an ester exchange catalyst, at least one carbonate of the following formula (3), at least one diol of the following formula (4), and a cyclic amide of the following formula (5) are used.

[0105] Preferred method for manufacturing polycarbonate polyol: reacting at least one carbonate of formula (3) with at least one diol of formula (4) in the presence of an ester exchange catalyst, and reacting the resulting product with a cyclic amide of formula (5). Alternatively, it is preferred to react the carbonate of formula (3), at least one diol of formula (4), and the cyclic amide of formula (5) simultaneously.

[0106] [Chemistry 8]

[0107]

[0108] [Chemistry 9]

[0109]

[0110] [Chemistry 10]

[0111]

[0112] In the formula, R 1 and R 2 Same meaning as above.

[0113] In the formula, R 3 Representing alkyl groups with 1 to 4 carbon atoms, or aryl groups with 5 to 8 carbon atoms, and two R groups in the same molecule. 3 They can be the same or different, or two Rs 3 They can together form alkylene rings with 1 to 4 carbon atoms. R 3 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.

[0114] <Diol>

[0115] Examples of diols include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol, which are straight-chain diols of alkanes with 2 to 20 carbon atoms.

[0116] In addition, other examples include branched diols of alkanes with 2 to 20 carbon atoms, such as 2-methyl-1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol. Diols with alicyclic structures and 6 to 20 carbon atoms, such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl)cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,7-norbornanediol; and diols with aromatic cyclic structures and 6 to 20 carbon atoms, such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, and 2,7-naphthalenedimethanol.

[0117] <carbonate>

[0118] Examples of carbonates (hereinafter also referred to as carbonates) include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate; aromatic carbonates such as diphenyl carbonate; and cyclic carbonates such as ethylene carbonate. From the perspective of easily removing unwanted byproducts, aliphatic carbonates or cyclic carbonates are preferred, and dimethyl carbonate or ethylene carbonate are particularly preferred.

[0119] <Cyclic amides>

[0120] Examples of cyclic amides include aliphatic cyclic amides with 5 to 12 carbon atoms, such as 2-pyrrolidone, piperidinone, N-methylpyrrolidone, ε-caprolactam, N-methylcaprolactam, dodecanoic acid, etc., with ε-caprolactam being preferred.

[0121] It should be noted that compounds containing 5 to 12 aliphatic or aromatic hydrocarbon, amino, and carboxyl groups in the same molecule can also be used instead of the above-mentioned cyclic amides.

[0122] <Catalyst>

[0123] In manufacturing the polycarbonate polyol of the present invention, a catalyst can be used. The catalyst described above can be a catalyst commonly used as a transesterification catalyst. Preferably, as the transesterification catalyst, are alkali metal compounds, alkaline earth metal compounds, aluminum compounds, zinc compounds, manganese compounds, nickel compounds, antimony compounds, zirconium compounds, titanium compounds, organotin compounds, and more preferably titanium compounds and / or alkali metal compounds. These catalysts can be used in combination.

[0124] Examples of alkali metal compounds include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metal carboxylates (lithium acetate, sodium acetate, potassium acetate, etc.), and alkali metal alkoxides (lithium methoxide, sodium methoxide, potassium tert-butoxide, etc.). Examples of alkaline earth metal compounds include alkaline earth metal hydroxides (magnesium hydroxide, etc.) and alkaline earth metal alkoxides (magnesium methoxide, etc.).

[0125] Examples of aluminum compounds include aluminum alkoxides (aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, etc.) and aluminum acetylacetonate.

[0126] Examples of zinc compounds include zinc carboxylates (such as zinc acetate) and zinc acetylacetonate.

[0127] Examples of manganese compounds include manganese carboxylates (such as manganese acetate) and manganese acetylacetone.

[0128] Examples of nickel compounds include nickel carboxylates (such as nickel acetate) and nickel acetylacetonate.

[0129] Examples of antimony compounds include antimony carboxylates (antimony acetate, etc.) and antimony alkoxides.

[0130] Examples of zirconium compounds include zirconium alkoxides (zirconium propoxide, zirconium butoxide, etc.) and zirconium acetylacetone.

[0131] Examples of titanium compounds include titanium alkoxides (tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetracyclohexyltitanium, tetrabenzyltitanium, etc.), titanium acylates (tributoxytitanium stearate, isopropoxytitanium stearate, etc.), and titanium chelates (diisopropoxydiacetylacetonate titanium, dihydroxydilactate titanium, etc.).

[0132] Examples of organotin compounds include dibutyltin oxide, dibutyltin diacetate, and dibutyltin dilaurate.

[0133] It should be noted that each carboxylate is preferably a carboxylate with 2 to 30 carbon atoms, more preferably a carboxylate with 2 to 18 carbon atoms, and each alkoxide is preferably an alkoxide with 1 to 30 carbon atoms in the alkoxy group, more preferably an alkoxide with 2 to 18 carbon atoms.

[0134] Among the catalysts described above, titanium compounds, organotin compounds, and alkali metal compounds are preferred; titanium compounds and / or alkali metal compounds are more preferred; and titanium alkoxides, alkali metal hydroxides, and / or alkali metal carbonates are even more preferred. These catalysts can be used in combination.

[0135] Among titanium alkoxides, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, and other tetraalkoxy titanium are preferred, with tetrabutoxy titanium being even more preferred.

[0136] It should be noted that the above-mentioned diols, carbonates, cyclic amides and catalysts can be used alone or in combination of two or more.

[0137] <Method>

[0138] The following method can be used as a method for manufacturing the polycarbonate polyol of the present invention.

[0139] 1. There is a method for manufacturing by mixing all the diol compound shown in formula (4), the cyclic amide shown in formula (5), and the carbonate shown in formula (3), and extracting alcohols while conducting an ester exchange reaction.

[0140] 2. A method exists in which the diol compound shown in formula (4) undergoes an ester exchange reaction with the carbonate shown in formula (3), followed by the addition of the cyclic amide shown in formula (5), and then, as needed, the addition of the diol compound shown in formula (4) to carry out the reaction.

[0141] 3. A method exists in which the cyclic amide of formula (5) and the diol compound of formula (4) are polymerized, and then the diol compound of formula (4) and the carbonate of formula (3) are added to react them.

[0142] Among these, the method described in 2 above is preferred because it is possible to synthesize a variety of products by changing the amount of cyclic amide added by using a polycarbonate polyol obtained by transesterification of the diol compound shown in formula (4) and the carbonate shown in formula (3) as a common raw material.

[0143] The method for manufacturing the polycarbonate polyol described above (2) will be explained. This manufacturing method consists of a two-stage reaction.

[0144] First stage: The diol compound shown in formula (4) undergoes an ester exchange reaction with the carbonate shown in formula (3).

[0145] Second stage: Add the cyclic amide of formula (5) to the obtained reaction solution, and then add the diol compound of formula (4) as needed to react it.

[0146] (The first phase of the response)

[0147] For the diol compound shown in formula (4) and the carbonate shown in formula (3), it is preferable to carry out the transesterification reaction while distilling off alcohols from the carbonate in the presence of a catalyst.

[0148] The reaction temperature varies depending on the type of diol compound and carbonate used, but is preferably 90°C to 230°C.

[0149] There are no particular restrictions on the pressure within the reaction system, but a reduced pressure of 30 mmHg to 500 mmHg is preferred. It should be noted that the reaction can be carried out in an atmosphere or gaseous stream of air, carbon dioxide, or inert gases (nitrogen, argon, helium, etc.), preferably in an atmosphere or gaseous stream of inert gases.

[0150] In addition, when a catalyst is added, the amount of catalyst added is preferably 1 ppm to 20,000 ppm relative to the total amount added.

[0151] (Second-stage response)

[0152] The polycarbonate polyol of the present invention is obtained by adding a cyclic amide of formula (5) to the product (polycarbonate polyol) obtained above, and then adding a diol compound of formula (4) as needed, and reacting it while distilling off by-product alcohols as needed.

[0153] The preferred reaction temperature is one in which the cyclic amides shown in formula (5) do not substantially distill, and more preferably 90°C to 230°C.

[0154] There are no particular restrictions on the pressure within the reaction system, but a reduced pressure of 30 mmHg to 500 mmHg is preferred. It should be noted that the reaction can be carried out in an atmosphere or gaseous stream of air, carbon dioxide, or inert gases (nitrogen, argon, helium, etc.), preferably in an atmosphere or gaseous stream of inert gases.

[0155] Alternatively, the catalyst can be newly added as described above, or the catalyst used in the first stage of the reaction can be used directly. Furthermore, compounds containing 5 to 12 aliphatic or aromatic hydrocarbon, amino, and carboxyl groups in the same molecule can be used instead of the aforementioned cyclic amides.

[0156] [Composition for forming polyurethane resin]

[0157] The aforementioned polycarbonate polyol (A) is used as a raw material in the formation of polyurethane resin, and therefore can be incorporated into a polyurethane resin forming composition. The polyurethane resin forming composition of the present invention comprises polycarbonate polyol (A) and polyisocyanate (C), preferably comprising polycarbonate polyol (A), polyol (B) (excluding the aforementioned polycarbonate polyol (A)) and polyisocyanate (C).

[0158] The above-mentioned polyurethane resin forming compositions are available in single-component and two-component types.

[0159] The single-component type comprises the polycarbonate polyol (A), polyol (B), and polyisocyanate (C) of the present invention.

[0160] In the composition for forming polyurethane resin, from the perspective of mechanical properties during urethane esterification, the proportion of polycarbonate polyol (A) to the total amount of polycarbonate polyol (A) and polyol (B) is preferably more than 0 and less than 95% by mass, more preferably 1% to 90% by mass, and even more preferably 2% to 85% by mass.

[0161] The two-component type consists of a first liquid containing the above-mentioned polycarbonate polyol (A) and the above-mentioned polyol (B) and a second liquid containing polyisocyanate (C), and is sold, for example, as a kit consisting of the first liquid and the second liquid.

[0162] Here, polyol (B) is a polyol other than the polycarbonate polyol (A) mentioned above. For example, high molecular weight polyols and low molecular weight polyols can be used as polyol (B). From the perspective of ease of manufacture, high molecular weight diols and low molecular weight diols are preferred.

[0163] There are no particular limitations on the high molecular weight diol, but a number-average molecular weight of 400 g / mol to 8000 g / mol is preferred. If the number-average molecular weight is within this range, suitable viscosity and good workability are easily obtained. It is easy to ensure the performance of the soft segment, and when forming a coating using the obtained composition containing polyurethane resin, crack initiation is easily suppressed, resulting in sufficient reactivity with polyisocyanate (C), and efficient production of polyurethane resin is also possible. The number-average molecular weight of the polyol (B) is more preferably 400 g / mol to 4000 g / mol. It should be noted that the number-average molecular weight is a value determined using the method described in the examples.

[0164] Examples of high molecular weight diols include polycarbonate polyols other than the polycarbonate polyol (A) mentioned above, polyester polyols, and polyether polyols. From the perspective of the light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance of the resulting polyurethane resin-containing composition and the resulting coating, polycarbonate polyols other than the polycarbonate polyol (A) mentioned above are preferred.

[0165] As a low molecular weight diol, examples of diols that are the same as those shown in formula (4) above can be given, preferably 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol.

[0166] As for polyisocyanates (C), there are no particular limitations, and examples include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, etc.

[0167] As aromatic polyisocyanates, examples include 1,3-phenyl diisocyanate, 1,4-phenyl diisocyanate, 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, 1,5-naphthalene diisocyanate, 4,4',4”-triphenylmethane triisocyanate, m-isocyanate benzenesulfonyl isocyanate, and p-isocyanate benzenesulfonyl isocyanate.

[0168] As aliphatic polyisocyanates, examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methylhexanoate, bis(2-isocyanate ethyl) fumarate, bis(2-isocyanate ethyl) carbonate, and 2-isocyanate ethyl-2,6-diisocyanate hexanoate.

[0169] As alicyclic polyisocyanates, examples include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexene diisocyanate, methylcyclohexene diisocyanate (hydrogenated TDI), bis(2-isocyanate ethyl)-4-dichlorohexene-1,2-dicarboxylic acid ester, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate.

[0170] Each molecule of a polyisocyanate typically has two isocyanate groups, but within the range where the polyurethane resin in this invention does not gel, polyisocyanates with three or more isocyanate groups, such as triphenylmethane triisocyanate or isocyanurate derivatives, may also be used.

[0171] Polyisocyanates can be used alone or in combination of two or more. The above-mentioned polyurethane resin forming compositions may contain end-capping agents, wetting agents, heat stabilizers, light stabilizers, plasticizers, inorganic fillers, lubricants, colorants, silicone oils, foaming agents, flame retardants, etc., depending on the purpose.

[0172] <Polyurethane Resin>

[0173] The polyurethane resin forming composition of the present invention comprises polycarbonate polyol (A) and polyisocyanate (C), preferably comprising polycarbonate polyol (A), polyol (B) (excluding the above-mentioned polycarbonate polyol (A)) and polyisocyanate (C).

[0174] A polyurethane resin is obtained by reacting at least the above-mentioned polycarbonate polyol (A) and polyisocyanate (C). Therefore, the polyurethane resin of the present invention has a structure derived from polycarbonate polyol (A) and a structure derived from polyisocyanate (C), preferably having a structure derived from polycarbonate polyol (A), a structure derived from polyol (B) (wherein excluding the above-mentioned polycarbonate polyol (A)), and a structure derived from polyisocyanate (C).

[0175] Catalysts can also be used in the reaction. There are no particular limitations on the catalyst; examples include tin-based catalysts (trimethyltin laurylate, dibutyltin dilaurate, etc.), lead-based catalysts (lead octanoate, etc.), salts of metals with organic and inorganic acids, organometallic derivatives, amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), and diazabicycloundecene-based catalysts. From a reactivity perspective, dibutyltin dilaurate and dioctyltin dilaurate are preferred.

[0176] There are no particular restrictions on the reaction temperature, but it is preferably 40℃~120℃, more preferably 60℃~100℃.

[0177] [use]

[0178] By using a polyurethane resin forming composition, waterborne polyurethane resin dispersions, coating compositions, coating agent compositions, polyurethane resin films, adhesive compositions, synthetic leather, thermoplastic polyurethane (TPU), and thermosetting / cast polyurethane (TSU) can be obtained using known methods. That is, the waterborne polyurethane resin dispersion, coating composition, coating agent composition, ink composition, polyurethane resin film, adhesive composition, synthetic leather, thermoplastic polyurethane (TPU), and thermosetting / cast polyurethane (TSU) all contain the aforementioned polyurethane resin.

[0179] Example

[0180] The present invention will now be described in more detail with reference to embodiments and comparative examples. However, the present invention is not limited to the embodiments described below. It should be noted that the room temperature is 25°C.

[0181] <Determination Method>

[0182] [Acid Value]

[0183] The substance was prepared by dissolving 10 g of the sample in a 50 / 50 (mass ratio) toluene / ethanol solution, and then titrated with a 0.1 N KOH ethanol solution. The acid value was determined by the following formula: 5.61 × (CB 1 Calculate B by multiplying f / s. Here, B... 1 C is the volume (mL) of 0.1N KOH ethanol standard solution required to neutralize the blank control, f is the factor of 0.1N KOH ethanol standard solution required to neutralize the sample, and s is the mass (g) of the sample.

[0184] [Content of ester bonds, carbamate bonds, and carbonate bonds]

[0185] The content of ester bonds, urethane bonds, and carbonate bonds in polycarbonate polyols is calculated based on the amount of raw materials used in the polycarbonate polyol.

[0186] [Viscosity of polycarbonate polyols]

[0187] Viscosity was measured using an LVDV II+Pro cone and a Brookfield plate viscometer in combination with a spindle cone model CPE-41, under molten conditions at 75°C.

[0188] (Properties at room temperature)

[0189] Regarding the properties of polycarbonate polyols at room temperature, the state of a sample heated at 80°C for 3 hours and then placed at 25°C for 24 hours was visually confirmed. A state where no solid is visible to the naked eye and there is no cloudiness was considered transparent.

[0190] The determination of whether it is liquid is made as follows: after heating the polycarbonate polyol at 80°C for 3 hours, place it at 25°C for 24 hours, and confirm whether it is transparent and fluid at this time.

[0191] [Polyurethane molecular weight]

[0192] The equivalent molecular weight (number-average molecular weight and weight-average molecular weight) of polystyrene was determined using GPC under the following conditions.

[0193] Column: TSKgel HZ1000+Hz 3000 (Tosoh Manufacturing) (40℃)

[0194] Mobile phase: THF, flow rate 0.6 ml / min

[0195] Detector: RI (40℃)

[0196] [Hydroxy value]

[0197] The hydroxyl value was determined by titration according to JIS K 1557. Here, the unit for the hydroxyl value is mgKOH / g.

[0198] [Elastic modulus, stress at fracture, and elongation at fracture]

[0199] According to ISO 527, the test was conducted at a temperature of 23°C and a humidity of 50%. Specifically, for test specimens of polyurethane resin films with a thickness of 0.05 mm to 0.10 mm, the elastic modulus, tensile strength, and elongation at break were determined at a test width of 5 mm, a test length of 20 mm, and a test speed of 100 mm / min.

[0200] [Chemical resistance test]

[0201] Cotton soaked in chemicals was placed on the polyurethane resin membranes obtained in each example and comparative example, and the membranes were covered and left to stand at room temperature. After 24 hours, the polyurethane resin membranes were visually inspected for any changes, and evaluated according to the following criteria.

[0202] Advantages: No change

[0203] Good: The polyurethane resin film turned slightly white.

[0204] Fair: The polyurethane resin film has turned noticeably whiter.

[0205] Poor: The polyurethane resin film is white in color and peels off easily.

[0206] [Swelling test, solubility resistance test]

[0207] The polyurethane resin film with its initial mass determined was immersed in a solvent at 25°C for 10 minutes. After removal, the solvent was quickly wiped off, and the mass after immersion was measured. The swelling rate was evaluated using the following formula.

[0208] Swelling rate = 100 × (mass after impregnation - initial mass) / initial mass (%)

[0209] The closer the swelling rate is to 0%, the better the solvent resistance.

[0210] Pendulum hardness test

[0211] The determination was performed using the ISO 1522 Persoz pendulum method.

[0212] In this embodiment, the following compounds are referred to by abbreviation.

[0213] TBT: Tetrabutoxytitanium

[0214] KOH: Potassium hydroxide

[0215] NaOH: Sodium hydroxide

[0216] K2CO3: Potassium carbonate

[0217] LiOH: Lithium hydroxide

[0218] (Example 1: Synthesis of polycarbonate polyol (1))

[0219] 170g of polycarbonate diol (manufactured by Ube Industries, Inc., ETERNACOLL (registered trademark) UH-200N) (hydroxyl value: 57.6mgKOH / g), 6.07g of 1,6-hexanediol (manufactured by Ube Industries, Inc.), 94.02g of ε-caprolactam (manufactured by Ube Industries, Inc.), and 0.4991g of tetrabutoxytitanium (manufactured by TCI) as a catalyst were mixed and reacted at 190°C under normal pressure for 8 hours to obtain polycarbonate polyol (1) which is solid at room temperature.

[0220] It should be noted that, by NMR, the peak of ε-caprolactam in the starting material disappeared, and new peaks from ester and carbamate bonds were generated, thus confirming the acquisition of the target compound.

[0221] The obtained polycarbonate polyol (1) has a hydroxyl value of 64.5 mgKOH / g and an acid value of 0.17 mgKOH / g.

[0222] (Examples 2-11; Synthesis of polycarbonate polyols)

[0223] Except for changes to the quality of the raw materials, the type and amount of the catalyst, and the reaction temperature and time as described in Table 1, the reaction was carried out using the same method as in Example 1 to obtain a polycarbonate polyol that is solid at room temperature. The polycarbonate polyol obtained in Example 11 is liquid at room temperature.

[0224] In addition, for the polycarbonate polyol obtained in Example 11, the following was determined: 1 H NMR was used to quantify the contents of ester bonds, urethane bonds, and carbonate bonds in polycarbonate polyols by integrating the values. The results showed that the contents of ester bonds were 9.5 wt%, urethane bonds were 12.9 wt%, and carbonate bonds were 17.5 wt%, with a molar ratio of urethane bonds to ester bonds (urethane / ester) of 1.0.

[0225] [Table 1]

[0226]

[0227] (Example 12; Synthesis of single-component polyurethane resin and its film)

[0228] 30.0 g of polycarbonate polyol (1) synthesized in Example 1, 2.89 g of 1,4-butanediol (manufactured by Merck), 108.45 g of dimethylformamide (manufactured by Merck), 0.023 g of dibutyltin dilaurate (manufactured by Merck) (500 ppm relative to solid content) and 13.59 g of 4,4'-diphenylmethane diisocyanate (manufactured by Merck) (isocyanate group / hydroxyl group = 0.99 (molar ratio)) were mixed and reacted at 80°C for 4 hours to obtain a polyurethane resin solution.

[0229] The obtained polyurethane resin solution (30% by mass of solids) was coated onto a glass plate, dried at 60°C for 1 hour, dried at 120°C for 4 hours, and then peeled off from the glass plate to obtain a polyurethane resin film.

[0230] (Examples 13-15, Comparative Examples 1-3: Synthesis of single-component polyurethane resins and their films)

[0231] As shown in Table 2, the type of polycarbonate polyol and the quality of the raw materials were changed. Otherwise, the reaction was carried out using the same method as in Example 12 to obtain a polyurethane resin solution.

[0232] The obtained polyurethane resin solution (30% by mass of solids) was coated onto a glass plate, dried at 60°C for 1 hour, dried at 120°C for 4 hours, and then peeled off from the glass plate to obtain a polyurethane resin film.

[0233] The evaluation results of the polyurethane resin films obtained in each embodiment and comparative example are shown in Table 2. Additionally, other evaluation results of the polyurethane resin films obtained in each embodiment are shown in Table 3.

[0234] [Table 2]

[0235]

[0236] In the table above, the abbreviations refer to the following compounds, etc.

[0237] HDL: 1,6-Hexanediol

[0238] PDL: 1,5-Pentanediol

[0239] UH-200: (Manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200, a polycarbonate diol made from HDL and dimethyl carbonate) Number average molecular weight 2000 g / mol Viscosity 2300 cP (75℃)

[0240] UH-200N: (Manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UH-200N, a polycarbonate diol made from HDL and dimethyl carbonate) Number average molecular weight 2000 g / mol Viscosity 2300 cP (75℃)

[0241] PH-200N: (Manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) PH-200N, a polycarbonate diol made from HDL, PDL (HDL:PDL = 1:1 (molar ratio)) and dimethyl carbonate) Number average molecular weight 2000 g / mol Viscosity 2800 cP (75℃)

[0242] UHC50-200: (Manufactured by Ube Industries, Ltd., ETERNACOLL (registered trademark) UHC50-200, a polycarbonate diol made from 1,6-hexanediol, dimethyl carbonate, and caprolactone) Number average molecular weight 2000 g / mol

[0243] PCLO-2000: (Manufactured by Sigma-Aldrich, polycaprolactone diol) Number average molecular weight 2000 g / mol

[0244] [Table 3]

[0245]

[0246] As can be seen from the comparison of Examples 12-15 and Comparative Examples 1-3, polyurethanes with high elastic modulus, low swelling rates of hexane and toluene, i.e., high solvent resistance, can be obtained by using polycarbonate polyols with ester bonds and urethane bonds.

[0247] As can be seen from the comparison of Examples 12-15, a polyurethane with low swelling rate of toluene can be obtained by increasing the content of ester bonds and urethane bonds.

[0248] As can be seen from the results in Table 3, the polyurethane obtained from the polycarbonate polyol of the present invention also shows practical effects in the tests of breaking strength, elongation at break, and chemical resistance.

[0249] Industrial applicability

[0250] According to the present invention, a polycarbonate polyol that is easy to operate and can improve the mechanical properties and solvent resistance of polyurethane resins obtained from polycarbonate polyols can be provided.

Claims

1. A polycarbonate polyol having an ester bond and a urethane bond, an acid value of 0.01 mgKOH / g to 5.0 mgKOH / g, and a molar ratio of the urethane bond to the ester bond, urethane / ester, of 0.8 to 1.

2.

2. The polycarbonate polyol of claim 1, wherein, The content of the carbonate bond is 3 mass% to 35 mass% relative to the total amount of the polycarbonate polyol.

3. The polycarbonate polyol of claim 1 or 2, wherein, The content of the ester bond is 1.5 mass% to 15 mass% relative to the total amount of the polycarbonate polyol, and the content of the urethane bond is 2 mass% to 20 mass% relative to the total amount of the polycarbonate polyol.

4. The polycarbonate polyol of claim 1 or 2, wherein, The content of the ester bond and the urethane bond represented by the following formula (I) is 10 mole% to 90 mole%, (E + U) / (E + U + C) x 100 (I) In the formula, E is the number of moles of the ester bond in the polycarbonate polyol, U is the number of moles of the urethane bond in the polycarbonate polyol, C is the number of moles of the carbonate bond in the polycarbonate polyol.

5. The polycarbonate polyol of claim 1 or 2, wherein, The hydroxyl value is 25 mgKOH / g to 250 mgKOH / g.

6. The polycarbonate polyol according to claim 1 or 2, having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), [Chem. 11] [Chem. 12] In the formula, R 1 and R 2 represent a hydrocarbon group having 2 to 20 carbon atoms.

7. The polycarbonate polyol of claim 6, wherein, In the above formula, R 1 is a linear or branched alkylene group having 4 to 7 carbon atoms.

8. The polycarbonate polyol according to claim 1 or 2, having a number average molecular weight of 400 g / mol to 4500 g / mol.

9. The polycarbonate polyol according to claim 1 or 2, which is a liquid at room temperature of 25°C.

10. A method for producing a polycarbonate polyol having an ester bond and a urethane bond and an acid value of 0.01 mgKOH / g to 5.0 mgKOH / g, wherein, an ester exchange catalyst, at least one carbonate represented by the following formula (3), at least one diol represented by the following formula (4), and a cyclic amide represented by the following formula (5) are used, [Chem. 13] [Chem. 14] [Chem. 15] wherein R 1 and R 2 represent a hydrocarbon group having 2 to 20 carbon atoms; wherein R 3 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 5 to 8 carbon atoms, and two R 3 may be the same or different, or two R 3 may form a ring together as an alkylene group having 1 to 4 carbon atoms.

11. The method of making a polycarbonate polyol according to claim 10, wherein, The ester exchange catalyst is a titanium compound and / or an alkali metal compound.

12. A polyurethane resin-forming composition comprising the polycarbonate polyol (A) according to any one of claims 1 to 9 and a polyisocyanate (C).

13. A polyurethane resin having a structure from the polycarbonate polyol (A) according to any one of claims 1 to 9 and a structure from a polyisocyanate (C).

14. An aqueous polyurethane resin dispersion comprising the polyurethane resin according to claim 13.

15. A coating composition comprising the polyurethane resin according to claim 13.

16. A coating agent composition comprising the polyurethane resin according to claim 13.

17. An adhesive composition comprising the polyurethane resin according to claim 13.

18. A polyurethane resin film comprising the polyurethane resin according to claim 13.

19. A synthetic leather comprising the polyurethane resin according to claim 13.

20. A thermoplastic polyurethane comprising the polyurethane resin according to claim 13.

21. A thermosetting and cast polyurethane comprising the polyurethane resin according to claim 13.

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