CN107540830B - Polycarbonate diol composition - Google Patents
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Abstract
The present invention provides a polycarbonate diol composition which, when used as a constituent material of a coating material, can give a coating film having mechanical strength and flexibility without impairing chemical resistance. The aforementioned polycarbonate diol composition, which comprises: 0.05 to 5 wt% of a carbonate compound represented by the following formula (C) and a polycarbonate diol comprising a repeating unit represented by the following formula (A) and a terminal hydroxyl group, wherein 5 to 100 mol% of the repeating unit represented by the formula (A) is the repeating unit represented by the following formula (B). (in the formula (A), R1Represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms in the formula (C), wherein R is2Optionally the same or different, represents (CH)2)4Or CH2CH(CH3)CH2And m represents an integer of 2 to 8).
Description
Technical Field
The present invention relates to a polycarbonate diol composition.
Background
Polycarbonate diols are known as soft segments of, for example, polyurethanes, thermoplastic elastomers, and the like, as raw materials excellent in hydrolysis resistance, light resistance, oxidation deterioration resistance, heat resistance, and the like. However, when polycarbonate diol is used as a constituent material of a coating material, the interaction between polycarbonate diol bonds is strong, and therefore the flexibility of the coating film may be impaired.
On the other hand, various additives having a cyclic carbonate structure are disclosed. For example, an additive having a cyclic carbonate structure is disclosed which reduces the viscosity of an epoxy resin without significantly deteriorating the mechanical properties and/or solvent resistance (see, for example, patent document 1). Further, a novel cyclic carbonate useful as a solvent for an electrolytic solution or the like, a precursor of a polymer material, and an additive is disclosed (for example, see patent document 2). Further, a polycarbonate diol composition containing 5-methyl-1, 3-dioxane-2-one is disclosed (for example, see patent document 3).
Documents of the prior art
Patent document
Patent document 1: JP-A-2013-528652
Patent document 2: japanese patent No. 5479844
Patent document 3: japanese patent No. 5068159
Disclosure of Invention
Problems to be solved by the invention
However, when the cyclic carbonates described in patent documents 1 and 2 are used as a constituent material of a coating material, the mechanical strength of a coating film cannot be improved when a small amount of the cyclic carbonate is added, and bleeding may occur when a large amount of the cyclic carbonate is added, leaving room for improvement. In addition, when the polycarbonate diol composition described in patent document 3 is used as a constituent material of a coating material, there is still room for improvement in obtaining a coating film having both mechanical strength and flexibility.
As described above, in the prior art, a polycarbonate diol capable of obtaining a coating film having mechanical strength and flexibility has not been developed yet.
Accordingly, an object of the present invention is to provide a polycarbonate diol composition which, when used as a constituent material of a coating material, can give a coating film having mechanical strength and flexibility without impairing chemical resistance.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that: the object can be achieved by using a polycarbonate diol composition containing a carbonate compound having a specific structure, and the present invention has been completed.
That is, the configuration of the present invention is as follows.
[1] A polycarbonate diol composition, comprising: 0.05 to 5 wt% of a carbonate compound represented by the following formula (C), and a polycarbonate diol comprising a repeating unit represented by the following formula (A) and a terminal hydroxyl group,
5 to 100 mol% of the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (B).
(in the formula (A), R1Represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms. )
(in the formula (C), R2Optionally the same or different, represents (CH)2)4Or CH2CH(CH3)CH2,m represents an integer of 2 to 8. )
[2] The polycarbonate diol composition according to [1], wherein the carbonate compound represented by the formula (C) is a carbonate compound represented by the following formula (D).
(in the formula (D), R2Optionally the same or different, represents (CH)2)4Or CH2CH(CH3)CH2And m represents an integer of 3 to 6. )
[3] The polycarbonate diol composition according to [1] or [2], wherein 5 to 95 mol% of the repeating unit represented by the formula (A) is the repeating unit represented by the formula (E).
(in the formula (E), n represents an integer of 2-12.)
[4] The polycarbonate diol composition according to any one of [1] to [3], wherein the total content of titanium, ytterbium and zirconium is 0.0001 to 0.02% by weight when measured by ICP.
[5] The polycarbonate diol composition according to any one of [1] to [4], wherein the content of the phosphorus element is 0.0005 to 0.05% by weight as measured by ICP.
[6] The polycarbonate diol composition according to any one of [1] to [5], wherein the water content is 1 to 500 ppm.
[7] A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of [1] to [6] and an organic polyisocyanate.
[8] A coating composition comprising the polycarbonate diol composition according to any one of [1] to [6] and an organic polyisocyanate.
[9] A coating composition comprising a urethane prepolymer obtained by reacting the polycarbonate diol composition according to any one of [1] to [6] with an organic polyisocyanate, the urethane prepolymer having a terminal isocyanate group.
[10] A coating composition comprising a polyurethane resin obtained by reacting the polycarbonate diol composition according to any one of [1] to [6], an organic polyisocyanate, and a chain extender.
[11] An aqueous coating composition comprising a polyurethane obtained by reacting the polycarbonate diol composition according to any one of [1] to [6], an organic polyisocyanate and a chain extender.
ADVANTAGEOUS EFFECTS OF INVENTION
When the polycarbonate diol composition of the present invention is used as a constituent material of a coating material, a coating film having mechanical strength and flexibility can be obtained. The polycarbonate diol composition of the present invention has these characteristics, and therefore can be suitably used as a constituent material of a coating material, and further can be suitably used as a raw material of polyurethane.
Detailed Description
The present embodiment (hereinafter, simply referred to as "the present embodiment") will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.
< polycarbonate diol composition >
The polycarbonate diol composition of the present embodiment comprises 0.05 to 5% by weight of a carbonate compound represented by the following formula (C) and a polycarbonate diol comprising a repeating unit represented by the following formula (A) and a terminal hydroxyl group,
5 to 100 mol% of the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (B).
(in the formula (A), R1Represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms. )
(in the formula (C), R2Optionally the same or different, represents (CH)2)4Or CH2CH(CH3)CH2And m represents an integer of 2 to 8. )
The polycarbonate diol used in the present embodiment is a polycarbonate diol which contains a repeating unit represented by the above formula (a) and a terminal hydroxyl group, and in which 5 to 100 mol% of the repeating unit represented by the above formula (a) is the repeating unit represented by the above formula (B).
The polycarbonate diol of the present embodiment has a repeating unit represented by the formula (B), and thus can provide a coating film having mechanical strength and flexibility, and further having chemical resistance such as sweat resistance, alkali resistance, and alcohol resistance. The repeating unit represented by the formula (B) is preferably 20 to 100 mol%, more preferably 40 to 100 mol% of the repeating unit represented by the formula (a) in order to obtain higher chemical resistance. Since the viscosity of the obtained polycarbonate diol increases as the proportion of the repeating unit represented by formula (B) increases, it is preferably 90 mol% or less, more preferably 75 mol% or less of the repeating unit represented by formula (a).
As for the repeating unit represented by the formula (a), in addition to the repeating unit represented by the formula (B), 1 or 2 or more repeating units represented by the following formula (F) may be selected.
(in the formula (F), R3Represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms. Wherein the repeating unit represented by the formula (B) is not included
The repeating unit represented by the formula (F) is preferably a repeating unit represented by the following formula (E) from the viewpoint of improving the mechanical strength and flexibility of the coating film. Further, from the viewpoint of further improving the mechanical strength and flexibility of the coating film, n in the formula (E) is preferably 4 to 6.
(in the formula (E), n represents an integer of 2 to 12.)
The proportion of the repeating unit represented by the formula (E) in the repeating unit represented by the formula (A) is preferably 5 to 95 mol%. In addition, the proportion of the repeating unit represented by the formula (E) in the repeating unit represented by the formula (a) is more preferably 10 to 80 mol%, and still more preferably 25 to 60 mol%, from the viewpoint of improving the mechanical strength and flexibility of the coating film.
In the polycarbonate diol, the proportion of the repeating unit represented by the formula (a) is preferably 95 mol% or more and 100 mol% or less, more preferably 97 mol% or more and 100 mol% or less, and still more preferably 99 mol% or more and 100 mol% or less, from the viewpoint of heat resistance and hydrolysis resistance.
The polycarbonate diol used in the present embodiment may further contain a structure represented by a repeating unit of the following formula (G) in its molecule for the purpose of imparting flexibility.
(in the formula (G), R' represents an alkylene group, and the alkylene group may have 2 or more in all repeating units, and x represents an integer of 2 or more.)
The method for introducing the repeating unit of the formula (G) into the molecule of the polycarbonate diol is not particularly limited, and for example, ether polyols such as polyoxyethylene glycol, polyoxyethylene propylene glycol, polyoxyethylene tetramethylene glycol, polyoxytetramethylene glycol, and polyoxypropylene glycol may be added to the raw material diol, or alkylene oxides such as ethylene oxide and/or propylene oxide may be added during the polymerization.
The content of the repeating unit of the formula (G) in the molecule of the polycarbonate diol used in the present embodiment is not particularly limited as long as it does not affect the scope of the present invention, and if the content is increased, the heat resistance and chemical resistance of the resulting polyurethane may be lowered. Therefore, when the repeating unit represented by the formula (G) is introduced into the polycarbonate diol, the repeating unit represented by the formula (G) (having a structure derived from an ether) is preferably 0.05 to 5 mol%, more preferably 0.05 to 3 mol%, based on the repeating unit of the carbonate represented by the formula (a).
The number average molecular weight of the polycarbonate diol used in the present embodiment is preferably 300 to 5000. When the number average molecular weight of the polycarbonate diol is 300 or more, flexibility of the coating film can be obtained. When the polycarbonate diol has a number average molecular weight of 5000 or less, it is preferable because the concentration of the solid content of the coating material is not limited and the moldability of the resulting polyurethane is not lowered when it is used as a constituent material of the coating material. The number average molecular weight of the polycarbonate diol is more preferably 450 to 3000.
In the present embodiment, the number average molecular weight of the polycarbonate diol can be measured by the method described in the examples below.
The polycarbonate diol used in the present embodiment is preferably a polycarbonate diol in which the repeating unit represented by the formula (a) includes only the repeating unit represented by the formula (B), or a polycarbonate diol in which the repeating unit represented by the formula (a) includes the repeating unit represented by the formula (B) and the repeating unit represented by the formula (E).
The polycarbonate diol composition of the present embodiment contains a carbonate compound represented by the formula (C).
The carbonate compound represented by the formula (C) contains 4R's, for example, when m in the formula (C) is 42Are all tetramethylene [ (CH)2)4]Compound of (2), 3R2Is tetramethylene and 1 is 2-methyltrimethylene [ CH2CH(CH3)CH2]Compound of (1), 2R2A compound which is a tetramethylene group and 2 are 2-methyltrimethylene groups, 1R2A compound which is a tetramethylene group and 3 are 2-methyltrimethylene groups, 4R2All of which are mixtures of 2-methyltrimethylene compounds, and the proportions of the respective compounds are not particularly limited. The bonding order of the tetramethylene group and the 2-methyltrimethylene group is not particularly limited.
In the polycarbonate diol composition of the present embodiment, if the carbonate compound represented by the formula (C) is present in a specific amount together with the polycarbonate diol, each carbonate bond in the carbonate compound interacts with the carbonate bonds of a plurality of polycarbonate diols. Further, since the carbonate compound represented by the formula (C) has a large cyclic structure, when the polycarbonate diol composition of the present embodiment is used as a constituent material of a coating material, a tough and flexible coating film can be obtained.
The carbonate compound represented by the formula (C) in the present embodiment has a high carbonate density, and thus the effect obtained from the carbonate bond is high, and the distance between the carbonate bonds in the carbonate compound is within an appropriate range, whereby a strong interaction between the carbonate compound and the polycarbonate diol can be obtained2Is tetramethylene or 2-methyltrimethylene.
R in the carbonate Compound represented by the formula (C)2Preferably at least one is 2-methyltrimethylene.
That is, the polycarbonate diol composition of the present embodiment preferably contains at least one R2A carbonate compound represented by the formula (C) which is 2-methyltrimethylene.
By reacting at least one R22-methyltrimethylene, the following tendency exists: carbonic acidThe interaction between each carbonate bond in the ester compound and the carbonate bonds of the plurality of polycarbonate diols is appropriately strengthened, and a coating film having excellent flexibility and tensile elongation can be obtained.
Further, the carbonate compound of the present embodiment may also have an effect of imparting flame retardancy to the resin because it generates carbon dioxide by decomposition. In order to more remarkably exhibit the effects of mechanical strength and flexibility of the carbonate compound, the formula (C) is preferably the following formula (D), and m in the formula (D) is more preferably 4.
(in the formula (D), R2Optionally the same or different, represents (CH)2)4Or CH2CH(CH3)CH2And m represents an integer of 3 to 6. )
The polycarbonate diol composition of the present embodiment contains the carbonate compound represented by the formula (C) in an amount of 0.05 to 5% by weight in total. When the content of the carbonate compound is 0.05% by weight or more, a soft coating film can be obtained, and when the content of the carbonate compound is 5% by weight or less, the carbonate compound does not bleed out, and a tough coating film can be obtained. The content of the carbonate compound is more preferably 0.07 to 4% by weight, and still more preferably 0.08 to 3% by weight.
In this embodiment, the content of each carbonate compound can be measured by the method described in the following examples.
The method for adjusting the total content of the carbonate compound represented by the formula (C) contained in the polycarbonate diol composition of the present embodiment to fall within the above range is not particularly limited, and for example, a method in which a separately produced carbonate compound represented by the formula (C) is added to a polycarbonate diol so as to fall within the above range may be mentioned.
The carbonate compound represented by the formula (C) can be obtained, for example, by heating a polycarbonate obtained by using 1, 4-butanediol and/or 2-methyl-1, 3-propanediol as a diol raw material at a high temperature of 190 to 210 ℃ under reduced pressure, and distilling and purifying the distillate produced thereby. The carbonate compound represented by the formula (C) can be obtained by dissolving 1, 4-butanediol and/or 2-methyl-1, 3-propanediol and a carbonate used in the production of a polycarbonate diol described later in a solvent having a boiling point of 100 ℃ or higher so that the total concentration of the diol and the carbonate becomes 5 to 30% or less with respect to the whole solution to prepare a thin solution, reacting the solution at 90 to 120 ℃, and then purifying the reaction product by distillation.
The polycarbonate diol composition of the present embodiment has an effect of providing a smooth coating film without causing cloudiness due to foaming if the water content is 500ppm or less, and an effect of easily dispersing the carbonate compound in the polycarbonate diol if the water content is 1ppm or more, and therefore, it is preferably 1 to 500 ppm. In order to make the above effect more remarkable, the water content is more preferably 5 to 250ppm, and still more preferably 10 to 150 ppm.
In the present embodiment, the water content of the polycarbonate diol composition can be determined by the method described in the examples below.
The method for producing the polycarbonate diol used in the present embodiment is not particularly limited, and can be produced by various methods described in, for example, polymer reviews (ポリマー and レビューズ) by Schnell, volume 9, pages 9 to 20 (1994).
The polycarbonate diol used in the present embodiment is not particularly limited, and is produced, for example, from a diol and a carbonate as raw materials.
In the production of the polycarbonate diol of the present embodiment, 2-methyl-1, 3-propanediol is suitably used as the diol. In addition to this, other diols may also be used. The diol to be used is not particularly limited, and examples thereof include diols having no side chain such as ethylene glycol, 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; diols having a side chain such as 2-methyl-1, 8-octanediol, 2-ethyl-1, 6-hexanediol, 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; and cyclic diols such as 1, 4-cyclohexanedimethanol and 2-bis (4-hydroxycyclohexyl) propane. 1 or 2 or more of the diols may be used as a raw material for the polycarbonate diol.
Further, a compound having 3 or more hydroxyl groups in 1 molecule, for example, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, or the like may be used as a raw material of the polycarbonate diol within a range in which the performance of the polycarbonate diol used in the present embodiment is not impaired. When the compound having 3 or more hydroxyl groups in 1 molecule is used in an excessive amount as a raw material of the polycarbonate diol, crosslinking proceeds in the polymerization reaction of the polycarbonate to cause gelation. Therefore, even when a compound having 3 or more hydroxyl groups in 1 molecule is used as a raw material of the polycarbonate diol, the compound is preferably 0.1 to 5 mol% relative to the total mole number of the diols used as the raw material of the polycarbonate diol. The proportion is more preferably 0.1 to 1 mol%.
The carbonate used in the present embodiment is not particularly limited, and examples thereof include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate; diaryl carbonates such as diphenyl carbonate; alkylene carbonates such as ethylene carbonate, trimethylene carbonate, 1, 2-propylene carbonate, 1, 2-butylene carbonate, 1, 3-butylene carbonate, and 1, 2-pentylene carbonate. Among these, 1 or 2 or more carbonates can be used as a raw material for the polycarbonate diol. From the viewpoint of ease of obtaining and ease of setting conditions for the polymerization reaction, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate, and ethylene carbonate are preferably used.
In the production of the polycarbonate diol used in the present embodiment, a catalyst is preferably added. The catalyst is not particularly limited, and examples thereof include alkali metal alcoholates of alkali metals such as lithium, sodium and potassium, alkaline earth metal alcoholates of magnesium, calcium, strontium and barium, hydrides, oxides, amides, carbonates, hydroxides, nitrogen-containing borates, and basic alkali metal salts and alkaline earth metal salts of organic acids. The catalyst is not particularly limited, and examples thereof include metals, salts, alkoxides and organic compounds of aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth and ytterbium. From them, 1 or more catalysts may be selected for use. When 1 or more catalysts selected from the group consisting of sodium, potassium, magnesium, potassium, titanium, zirconium, tin, lead and ytterbium metal, salt, alkoxide and organic compound are used, the polymerization of the polycarbonate diol proceeds well, and the influence on the urethane reaction using the obtained polycarbonate diol is small, which is preferable. Titanium, ytterbium and zirconium are more preferably used as the catalyst.
The polycarbonate diol composition of the present embodiment may contain the catalyst in an amount of 0.0001 to 0.02% by weight, based on the amount of the metal element measured by ICP. When the content of the catalyst is in the above range, the polymerization of the polycarbonate diol proceeds well, and the influence on the urethane reaction using the obtained polycarbonate diol composition is small. The content of the catalyst is more preferably 0.0005 to 0.01% by weight.
The polycarbonate diol composition of the present embodiment preferably has a total content of titanium, ytterbium and zirconium, as measured by ICP, of 0.0001 to 0.02 wt%, more preferably 0.0005 to 0.01 wt%.
In the present embodiment, the content of the metal element in the polycarbonate diol composition can be measured by the method described in the examples below.
When the polycarbonate diol used in the present embodiment is used as a raw material for polyurethane, for example, it is preferable to treat a catalyst for producing the polycarbonate diol with a phosphorus compound. Examples of the phosphorus compound include, but are not particularly limited to, phosphoric acid triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyldiphenyl phosphate; acid phosphates such as methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, ditetradecyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, monobutyl phosphate, monoisodecyl phosphate, and bis (2-ethylhexyl) phosphate; phosphorous acid esters such as triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tridecyl phosphite, trioleyl phosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl phosphite, bis (2-ethylhexyl) phosphite, dilauryl phosphite, dioleyl phosphite, diphenyl phosphite, tetraphenyldipropylene glycol diphosphite, didecylpentaerythritol diphosphite, tristearyl phosphite, distearylpentaerythritol diphosphite, and tris (2, 4-di-tert-butylphenyl) phosphite; and phosphoric acid, phosphorous acid, hypophosphorous acid, and the like.
The amount of the phosphorus compound contained in the polycarbonate diol composition of the present embodiment is preferably 0.0005 to 0.05% by weight in terms of the content of phosphorus element measured by ICP. In the polycarbonate diol composition of the present embodiment, if the amount of the phosphorus compound is in the above range, for example, when the phosphorus compound is used as a raw material for polyurethane, the influence of the catalyst used in the production of the polycarbonate diol can be substantially eliminated in the production reaction of polyurethane, and the influence of the phosphorus compound on the production reaction of polyurethane and the physical properties of the reaction product is also small. Further, in the presence of a transesterification catalyst, the polycarbonate diol composition can be inhibited from decomposing the carbonate compound present therein. The content of phosphorus element in the polycarbonate diol composition of the present embodiment as measured by ICP is more preferably 0.0005 to 0.03% by weight.
Specific examples of the method for producing a polycarbonate diol used in the present embodiment are shown below. The production of the polycarbonate diol used in the present embodiment is not particularly limited, and may be carried out in two stages, for example. The diol and the carbonate are mixed at a molar ratio (diol: carbonate) of, for example, 20:1 to 1:10, preferably 10:1 to 1:2, and the first-stage reaction is carried out at 100 to 250 ℃ under normal pressure or reduced pressure. When dimethyl carbonate is used as the carbonate, the produced methanol is removed as a mixture with dimethyl carbonate to obtain a low molecular weight polycarbonate diol. When diethyl carbonate is used as the carbonate, the produced ethanol is removed as a mixture with diethyl carbonate, and a low-molecular-weight polycarbonate diol can be obtained. When ethylene carbonate is used as the carbonate, the produced ethylene glycol is removed as a mixture with ethylene carbonate, and a low-molecular-weight polycarbonate diol can be obtained. The second reaction is a reaction in which the reaction product of the first reaction is heated at 160 to 250 ℃ under reduced pressure to remove unreacted diol and carbonate and to condense low molecular weight polycarbonate diol, thereby obtaining polycarbonate diol having a specific molecular weight. The amount of the carbonate compound produced by the reaction can be suppressed to a low level by starting the reaction in the first stage at a temperature of 100 to 150 ℃, reacting for 5 hours or more at the reaction starting temperature, then raising the temperature at a rate of 15 ℃ or less per 1 hour, and performing the reaction in the second stage at a temperature of 120 to 170 ℃ under a pressure of 15kPa or less, and the amount of the carbonate compound contained in the polycarbonate diol can be controlled by adding a specific amount of the carbonate compound to the obtained polycarbonate diol, which is more preferable.
< use >
The polycarbonate diol composition used in the present embodiment can be used as a constituent material of a coating material or an adhesive, or as a raw material of a polyurethane or a thermoplastic elastomer, and can be used for applications such as a modifier for a polyester or a polyimide. In particular, when the polycarbonate diol composition of the present embodiment is used as a constituent material of a coating material, a coating film having both mechanical strength and flexibility can be obtained. When the polycarbonate diol composition of the present embodiment is used as a raw material for polyurethane or a thermoplastic elastomer, the polyurethane or the thermoplastic elastomer can be obtained which is tough, has chemical resistance, and is excellent in moldability.
The thermoplastic polyurethane of the present embodiment can be obtained by using the polycarbonate diol and the organic polyisocyanate.
The coating composition of the present embodiment includes the polycarbonate diol composition and an organic polyisocyanate.
Further, the coating composition of the present embodiment preferably contains a urethane prepolymer obtained by reacting the polycarbonate diol composition with an organic polyisocyanate, the urethane prepolymer having an isocyanate terminal group.
The coating composition of the present embodiment more preferably contains a polyurethane resin obtained by reacting the polycarbonate diol composition, the organic polyisocyanate, and the chain extender, and even more preferably contains an aqueous coating composition containing a polyurethane obtained by reacting the polycarbonate diol composition, the organic polyisocyanate, and the chain extender.
The organic polyisocyanate to be used is not particularly limited, and examples thereof include known aromatic diisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, and mixtures Thereof (TDI), crude TDI, diphenylmethane-4, 4 ' -diisocyanate (MDI), crude MDI, naphthalene-1, 5-diisocyanate (NDI), 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate, polymethylene polyphenyl isocyanate, Xylylene Diisocyanate (XDI), and phenylene diisocyanate; known aliphatic diisocyanates such as 4, 4' -methylenedicyclohexyl diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), and cyclohexane diisocyanate (hydrogenated XDI); and isocyanurated modified products, carbodiimide modified products, biuretized modified products, and the like of these isocyanates. These organic polyisocyanates may be used alone or in combination of 2 or more. In addition, these organic polyisocyanates can be used after masking the isocyanate groups with a blocking agent.
In the reaction between the polycarbonate diol composition and the organic polyisocyanate, a chain extender may be used as a copolymerization component as desired. The chain extender is not particularly limited, and for example, water, low molecular weight polyol, polyamine, and the like, which are commonly used in the polyurethane industry, can be used. Examples of the chain extender are not particularly limited, and include, for example, low molecular weight polyols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, 1-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, benzenedimethanol, bis (p-hydroxy) biphenyl, and bis (p-hydroxyphenyl) propane, and polyamines such as ethylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine, diphenyldiamine, and diaminodiphenylmethane. These chain extenders may be used alone, or 2 or more of them may be used in combination.
The method for producing the thermoplastic polyurethane of the present embodiment is not particularly limited, and a technique of a polycarbamation reaction known in the polyurethane industry can be used. For example, the thermoplastic polyurethane can be produced by reacting the polycarbonate diol composition with an organic polyisocyanate at atmospheric pressure from room temperature to 200 ℃. When the chain extender is used, it may be added from the beginning of the reaction or may be added during the reaction. For the method for producing the thermoplastic polyurethane of the present embodiment, for example, see U.S. Pat. No. 5,070,173.
In the polyurethane-forming reaction, a known polymerization catalyst and a known solvent may be used. The polymerization catalyst to be used is not particularly limited, and examples thereof include dibutyltin dilaurate.
It is preferable to add a stabilizer such as a heat stabilizer (for example, an antioxidant) or a light stabilizer to the thermoplastic polyurethane of the present embodiment. In addition, a plasticizer, an inorganic filler, a lubricant, a colorant, silicone oil, a foaming agent, a flame retardant, and the like may be added.
As a method for producing the coating composition (paint) of the present embodiment, a production method known in the art can be used. For example, a two-liquid type solvent-based coating composition in which a coating base material obtained from the polycarbonate diol composition and a curing agent containing an organic polyisocyanate are mixed immediately before coating; a one-pack solvent-based coating composition containing a urethane prepolymer having an isocyanate terminal group, which is obtained by reacting the polycarbonate diol composition with an organic polyisocyanate; a one-pack solvent-based coating composition containing a polyurethane resin obtained by reacting the polycarbonate diol composition, an organic polyisocyanate, and a chain extender; alternatively, a one-part aqueous coating composition.
The coating composition (coating material) of the present embodiment may contain, for example, a curing accelerator (catalyst), a filler, a dispersant, a flame retardant, a dye, an organic or inorganic pigment, a release agent, a fluidity modifier, a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a colorant, a solvent, and the like, depending on the application.
The solvent of the coating composition (coating material) of the present embodiment is not particularly limited, and examples thereof include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, cyclohexanone, benzene, toluene, xylene, ethyl cellosolve, ethyl acetate, butyl acetate, ethanol, isopropanol, n-butanol, and water. These solvents may be used in a single amount or in a mixture of two or more amounts.
Examples
The present invention will be described with reference to examples and comparative examples.
The following examples are given for the purpose of illustrating the present invention and are not intended to limit the scope of the present invention in any way.
The physical property values and terms shown in the following examples and comparative examples are as follows.
1. Quantitative determination of carbonate Compound
The quantitative determination of the carbonate compound was carried out in the following manner. First, the sample was dissolved in acetonitrile to make a 1% solution. The solution was analyzed by a liquid chromatography mass spectrometer (LC/MS). From the area value obtained by this analysis, the carbonate compound in the sample was quantified using a calibration curve prepared in advance using 1,3,10, 12-tetraoxycyclooctadecane-2, 11-dione. As the LC device, SIMADZU Nexera X2 (manufactured by Shimadzu corporation) equipped with Waters ACQUITY UPLC HHS C18 (manufactured by Waters) as a column was used. The flow rate in the LC device was set to 0.2 ml/min, and the measurement was performed with a gradient from 30:70 parts by weight of methanol to 100:0 parts by weight of methanol to water. The MS apparatus used BRUKER amaZon SL (manufactured by BRUKER Co.). In the MS apparatus, in the ionization: APCl +, scan range: the m/z is 70 to 1200.
2. Determination of the composition of the polycarbonate diol
The composition of the polycarbonate diol was determined as follows. First, 1g of a sample was weighed into a 100ml eggplant type flask, and 30g of ethanol and 4g of potassium hydroxide were put into the flask to obtain a mixture. The resulting mixture was heated with stirring in an oil bath at 100 ℃ for 1 hour. And cooling the mixture to room temperature, dropwise adding 1-2 drops of phenolphthalein serving as an indicator into the mixture, and neutralizing with hydrochloric acid. Thereafter, the mixture was cooled in a refrigerator for 3 hours, and after removing the precipitated salt by filtration, the filtrate was analyzed by Gas Chromatography (GC). The GC analysis was performed by using a gas chromatograph GC2014 (Shimadzu corporation) equipped with DB-WAX (30 m, 0.25 μm in thickness, manufactured by J & W Co., Ltd.) as a column, using diethylene glycol diethyl ester as an internal standard, and using a hydrogen Flame Ionization Detector (FID) as a detector. The temperature rise curve of the column was set to 60 ℃ for 5 minutes, and then the column was heated to 250 ℃ at 10 ℃/minute.
The composition of the polycarbonate diol was determined from the area value of the diol obtained by GC analysis.
3. Determination of the number average molecular weight of the polycarbonate diol
The number average molecular weight of the polycarbonate diol was determined by a "neutralization titration method (JIS K0070-1992)" using acetic anhydride and pyridine, and performing titration with an ethanol solution of potassium hydroxide, and was calculated using the following formula (4).
Number average molecular weight 2/(OH number × 1)0-3/56.1) (4)
4. Inductively Coupled Plasma (ICP) -based analysis of elements
The respective elements contained in the polycarbonate diol composition were analyzed as follows. First, a sample was taken into a teflon decomposition vessel, and high-purity nitric acid (manufactured by kanto chemical co., ltd.) was added thereto and decomposed using a microwave decomposition apparatus (manufactured by millitensegral k.k., ETHOS TC). The sample was completely decomposed, and the obtained decomposed liquid was colorless and transparent. Pure water is added to the decomposed solution to prepare a test solution. The resulting test solution was quantified from a standard solution of each element using an inductively coupled plasma analyzer (manufactured by Thermo Fisher Scientific inc., iCAP6300 Duo).
5. Measurement of moisture content of polycarbonate diol composition
The amount of water in the polycarbonate diol composition was measured by a volumetric analysis method according to JIS K0068 using a water measuring apparatus (KF-100 type, mitsubishi chemical analytical co., ltd.
6. Evaluation of coating film
(1) Perspiration resistance
The appearance of a coating film obtained from the polycarbonate diol composition after immersion in oleic acid at 23 ± 2 ℃ for 24 hours was evaluated by visual observation. The degree and amount of defects are expressed in a scale of 0 to 5 according to JIS K5600-8-1, and the sweat resistance of the coating film is determined.
(2) Alkali resistance of coating film
The appearance of a coating film obtained from the polycarbonate diol composition after immersion in a 0.1mol/L NaOH aqueous solution at 23. + -. 2 ℃ for 24 hours was evaluated by visual observation. The degree and amount of defects are expressed in a scale of 0 to 5 according to JIS K5600-8-1, and the alkali resistance of the coating film is determined.
(3) Alcohol resistance of coating film
The appearance of a coating film obtained from the polycarbonate diol composition after immersion in a 50% ethanol aqueous solution at 23 ± 2 ℃ for 4 hours was visually evaluated. The degree and amount of defects are expressed in a scale of 0 to 5 according to JIS K5600-8-1, and the ethanol resistance of the coating film is determined.
(4) Flexibility
The number of times of oscillation at an arrival amplitude angle of 3 ° or less was measured according to ISO 1522 using a charter hardness tester (BYK-Gardner) equipped with a kenisch pendulum for a coating film obtained from the polycarbonate diol composition.
(5) Wear resistance
The weight of the coating film obtained from the polycarbonate diol composition before the abrasion test and the weight change of the coated plate after the abrasion test (500 revolutions) were measured by a cone type abrasion tester No.410 (manufactured by Toyo Seiki Seisaku-Sho Ltd.) in accordance with JIS K5600-5-8.
(6) Breaking strength and elongation at break
The tensile strength (breaking strength) and tensile elongation (breaking elongation) of the coating film obtained from the polycarbonate diol composition were measured in accordance with JIS K6251, using a test specimen punched out into a short strip having a width of 10mm, a length of 50mm and a thickness of 0.05 mm. The tensile strength (breaking strength) is mechanical strength.
7. A carbonate compound represented by the formula (C)
The carbonate compound represented by the formula (C) added in examples 1 to 18 and comparative examples 1,2, 4 and 5 below was a mixture. For example, the carbonate compound in which m is 4 in the formula (C) is R of the formula (C)2A mixture of 4 of all of the compounds are tetramethylene, 3 of all of the compounds are tetramethylene and 1 is 2-methyltrimethylene, 2 of all of the compounds are tetramethylene and 2-methyltrimethylene, 1 of all of the compounds are tetramethylene and 3 of all of the compounds are 2-methyltrimethylene, and 4 of all of the compounds are 2-methyltrimethylene. The order of the tetramethylene group and the 2-methyltrimethylene group in the 2-tetramethylene and 2-methyltrimethylene group-containing compound is not particularly limited.
In addition, the carbonate compounds represented by the formula (C) added in examples 19 and 20 were those in which m was 4 and 4 Rs2All are tetramethylene compounds.
The carbonate compound represented by the formula (C) to be added in examples 1 to 18 and comparative examples 1,2, 4 and 5 is obtained by heating a polycarbonate obtained by using 1, 4-butanediol and 2-methyl-1, 3-propanediol as diol raw materials at a high temperature of 190 to 200 ℃ under a reduced pressure of 0.1 to 0.5kPa, and distilling and purifying the distillate produced at that time. The carbonate compound represented by the formula (C) to be added in examples 19 and 20 was obtained by heating a polycarbonate obtained by using 1, 4-butanediol as a diol raw material at a high temperature of 190 to 200 ℃ under a reduced pressure of 0.1 to 0.5kPa, and distilling and purifying the distillate produced at that time.
[ example 1]
Into a 2L glass flask equipped with a rectifying column packed with a regular packing and a stirring device were charged 800g (9.1mol) of ethylene carbonate, 400g (4.4mol) of 2-methyl-1, 3-propanediol, and 415g (4.6mol) of 1, 4-butanediol. 0.24g of titanium tetraisopropoxide as a catalyst was further added to the flask, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off at 140 ℃ and a pressure of 1.0 to 1.5kPa, followed by reaction for 15 hours. Thereafter, the rectifying column filled with the regular packing was replaced with a single distillation apparatus, the pressure was reduced to 0.5kPa at a temperature of 140 to 150 ℃, the diol and ethylene carbonate were distilled off, and further reacted for 12 hours. Thereafter, 0.69g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol were added 2.0g of a carbonate compound having m of 4 in the formula (C) and 2.0g of a carbonate compound having m of 5 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-1. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ examples 2 to 8]
To 400g of the polycarbonate diol obtained in example 1 was added a mixture of carbonate compounds in an amount shown in Table 1, and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. The polycarbonate diol compositions are referred to as PC-2 to 8, respectively. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ comparative examples 1 to 2]
To 400g of the polycarbonate diol obtained in example 1 was added a mixture of carbonate compounds in an amount shown in Table 1, and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. The polycarbonate diol compositions are referred to simply as PC-31 to 32, respectively.
[ Table 1]
Comparative example 3
To 400g of the polycarbonate diol obtained in example 1, 6g of 5-methyl-1, 3-dioxane-2-one was added, and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The polycarbonate diol composition obtained was analyzed. The content of 5-methyl-1, 3-dioxane-2-one was 1.5 wt%, and other results are shown in table 2. The polycarbonate diol compositions are abbreviated as PC-33, respectively.
[ example 9]
Using the apparatus used in example 1, 800g (9.1mol) of ethylene carbonate and 815g (9.1mol) of 2-methyl-1, 3-propanediol were charged. 0.24g of titanium tetraisopropoxide was added as a catalyst, and a reaction was carried out by the method of example 1. Thereafter, 0.68g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-9. The ratio (mol%) of the repeating unit represented by the formula (B) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
Comparative example 4
730g (8.3mol) of ethylene carbonate, 35g (0.4mol) of 2-methyl-1, 3-propanediol, 420g (4.0mol) of 1, 5-pentanediol, and 470g (4.0mol) of 1, 6-hexanediol were put into a 2L glass flask equipped with a rectifying column packed with a regular packing and a stirring device. 0.25g of titanium tetraisopropoxide was added as a catalyst, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off at 140 ℃ and a pressure of 1.0 to 1.5kPa, followed by a reaction for 15 hours. Thereafter, the rectifying column filled with the regular packing was replaced with a single distillation apparatus, the pressure was reduced to 0.5kPa at a temperature of 140 to 150 ℃, the diol and ethylene carbonate were distilled off, and further reacted for 12 hours. Thereafter, 0.70g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. The polycarbonate diol composition is abbreviated as PC-34.
Comparative example 5
Into a 2L glass flask equipped with a rectifying column packed with a regular packing and a stirring device, 710g (8.1mol) of ethylene carbonate, 30g (0.3mol) of 2-methyl-1, 3-propanediol, and 700g (7.8mol) of 1, 4-butanediol were charged. 0.22g of titanium tetraisopropoxide was added as a catalyst, and the resulting mixture of ethylene glycol and ethylene carbonate was distilled off at 140 ℃ and a pressure of 1.0 to 1.5kPa, followed by a reaction for 15 hours. Thereafter, the rectifying column filled with the regular packing was replaced with a single distillation apparatus, the pressure was reduced to 0.5kPa at a temperature of 140 to 150 ℃, the diol and ethylene carbonate were distilled off, and further reacted for 12 hours. Thereafter, 0.61g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-35.
[ example 10]
Polymerization was carried out under the conditions of example 1 using the apparatus used in example 1 except that 790g (9.0mol) of ethylene carbonate, 145g (1.6mol) of 2-methyl-1, 3-propanediol and 670g (7.4mol) of 1, 4-butanediol were used, to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-10. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 11]
Polymerization was carried out under the conditions of example 1 using the apparatus used in example 1 except that 790g (9.0mol) of ethylene carbonate, 300g (3.3mol) of 2-methyl-1, 3-propanediol and 510g (5.7mol) of 1, 4-butanediol were used, to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-11. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 12]
Using the apparatus used in example 1, 790g (9.0mol) of ethylene carbonate, 575g (6.4mol) of 2-methyl-1, 3-propanediol and 235g (2.6mol) of 1, 4-butanediol were charged. 0.24g of titanium tetraisopropoxide was added as a catalyst, and the mixture of ethylene glycol and ethylene carbonate thus produced was reacted for 15 hours at a temperature of 140 ℃ and a pressure of 1.0 to 1.5kPa while removing the mixture by distillation. Thereafter, the rectifying column filled with the regular packing was replaced with a single distillation apparatus, the pressure was reduced to 0.5kPa at a temperature of 140 to 150 ℃, the diol and ethylene carbonate were distilled off, and further reacted for 4 hours. Thereafter, 0.68g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-12. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 13]
The reaction was carried out under the conditions of example 12, and at a temperature of 140 to 150 ℃ and a pressure of 0.5kPa was lowered, and the reaction was further carried out for 8 hours while removing the glycol and ethylene carbonate by distillation. Thereafter, 0.68g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. The polycarbonate diol composition is abbreviated as PC-13. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 14]
The reaction was carried out under the conditions of example 13, and at a temperature of 140 to 150 ℃ and a pressure of 0.5kPa was lowered, and the reaction was further carried out for 10 hours while removing the glycol and ethylene carbonate by distillation. Thereafter, 0.68g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol was added 3.6g of a carbonate compound having m 4 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-15. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 15]
Using the apparatus used in example 1, 800g (9.1mol) of ethylene carbonate, 500g (5.6mol) of 2-methyl-1, 3-propanediol and 380g (3.7mol) of 1, 5-pentanediol were charged. 0.25g of titanium tetraisopropoxide was added as a catalyst, and a reaction was carried out by the method of example 1. Thereafter, 0.71g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol were added 2.0g of a carbonate compound having m of 4 in the formula (C) and 2.0g of a carbonate compound having m of 5 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-15. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 16]
Using the apparatus used in example 1, 790g (9.0mol) of ethylene carbonate, 385g (4.3mol) of 2-methyl-1, 3-propanediol and 560g (4.8mol) of 1, 6-hexanediol were charged. 0.26g of titanium tetraisopropoxide was added as a catalyst, and a reaction was carried out by the method of example 1. Thereafter, 0.74g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol were added 2.0g of a carbonate compound having m of 4 in the formula (C) and 2.0g of a carbonate compound having m of 5 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-16. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 17]
650g (7.2mol) of dimethyl carbonate, 330g (3.7mol) of 2-methyl-1, 3-propanediol and 710g (4.8mol) of 1, 0-decanediol were charged in the apparatus used in example 1. 0.25g of titanium tetraisopropoxide was added as a catalyst, and the mixture of methanol and dimethyl carbonate formed was distilled off while stirring at normal pressure and raising the temperature to 65 to 140 ℃ to carry out a reaction for 20 hours. Thereafter, the pressure was reduced to 17kPa, and the mixture of methanol and dimethyl carbonate was distilled off, and the reaction was further carried out at 140 to 150 ℃ for 12 hours. Thereafter, 0.72g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol were added 2.0g of a carbonate compound having m of 4 in the formula (C) and 2.0g of a carbonate compound having m of 5 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-17. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 18]
850g (7.2mol) of diethyl carbonate, 330g (3.7mol) of 2-methyl-1, 3-propanediol and 480g (4.1mol) of 3-methyl-1, 5-pentanediol were charged into the apparatus used in example 1. 0.25g of titanium tetraisopropoxide was added as a catalyst, and the mixture of ethanol and diethyl carbonate formed was distilled off while stirring at normal pressure and raising the temperature to 80 to 140 ℃ to carry out a reaction for 20 hours. Thereafter, the pressure was reduced to 17kPa, a mixture of ethanol and diethyl carbonate was distilled off, and the reaction was further carried out at 140 to 150 ℃ for 12 hours. Thereafter, 0.71g of 2-ethylhexyl acid phosphate as a phosphorus compound was added to the flask, and the mixture in the flask was heated at 105 ℃ for 5 hours to obtain a polycarbonate diol. To 400g of the obtained polycarbonate diol were added 2.0g of a carbonate compound having m of 4 and 2.0g of a carbonate compound having m of 5 in the formula (C), and the mixture was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-18. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ example 19]
To 400g of the polycarbonate diol obtained in example 1, m in the formula (C) was 4 and R was added28.8g of a carbonate compound each containing tetramethylene was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-19. The obtained polycarbonate diol has a repeating unit represented by the formula (A) and a terminal hydroxyl group, and the repeating unit represented by the formula (A)The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the element is 100 mol% is shown in table 2.
[ example 20]
To 400g of the polycarbonate diol obtained in example 1, m in the formula (C) was 4 and R was added217.2g of a carbonate compound each containing tetramethylene was stirred at 100 ℃ for 5 hours to obtain a polycarbonate diol composition. The analysis results of the obtained polycarbonate diol composition are shown in Table 2. This polycarbonate diol composition is abbreviated as PC-20. The ratio (mol%) of the repeating unit represented by the formula (B) to the repeating unit represented by the formula (E) when the repeating unit represented by the formula (a) is 100 mol% is shown in table 2.
[ Table 2]
[ application example 1]
A coating material base material was obtained by mixing and stirring 140 g of the polycarbonate diol composition PC-140 g, 0.75g of BYK-331 (manufactured by BYK Chemical inc.) as a leveling agent, 1.25g of a dibutyltin dilaurate solution obtained by dissolving 2 wt% of the polycarbonate diol composition in a diluent (xylene/butyl acetate: 70/30 (weight ratio)), and 40g of the diluent. To the resulting coating base material was added 7.7g of an organic polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei corporation, isocyanate (NCO) content: 23.1%) as a curing agent to prepare a coating liquid. The coating liquid was applied to a coated plate, and after scattering the diluent at room temperature for 2 hours, the coating liquid was cured by heating at 75 ℃ for 2 hours to obtain a coating film. The coating film was left for one week at a temperature of 23. + -. 2 ℃ and a relative humidity of 50. + -. 5%, and then physical properties were evaluated. The evaluation results are shown in table 3. In the coated sheet, a polypropylene resin sheet, a glass sheet, and an acrylonitrile-butadiene-styrene (ABS) resin sheet were used for the measurement of the breaking strength and elongation of the coating film, and for the flexibility test, and for the other resistance test.
Application examples 2 to 11, 13 and 15 to 20
A coating film was obtained in the same manner as in application example 1, except that PC-2 to 11, 13, 15 to 20 was used as the polycarbonate diol composition. The physical properties were evaluated by using the coating film. The evaluation results are shown in table 3.
[ application example 12]
A coating film was obtained in the same manner as in application example 1 except that the polycarbonate diol composition PC-1213 g, 0.30g of BYK-331 (manufactured by BYK chemical inc.) as a leveling agent, 0.40g of a dibutyltin dilaurate solution obtained by dissolving 2 wt% of the composition in a diluent (xylene/butyl acetate: 70/30 (weight ratio)), and 20g of the diluent were used. The physical properties were evaluated using the coating film. The evaluation results are shown in table 3.
[ application example 14]
A coating film was obtained in the same manner as in application example 1 except that the polycarbonate diol composition PC-1460 g, 1.0g of BYK-331 (manufactured by BYK chemical inc.) as a leveling agent, 1.75g of a dibutyltin dilaurate solution obtained by dissolving 2 wt% of the composition in a diluent (xylene/butyl acetate: 70/30 (weight ratio)), and 60g of the diluent were used. The physical properties were evaluated using the coating film. The evaluation results are shown in table 3.
[ comparative application examples 1 to 5]
A coating film was obtained in the same manner as in application example 1, except that PC-31 to 35 was used as the polycarbonate diol composition. The physical properties were evaluated using the coating film. The evaluation results are shown in table 3.
[ Table 3]
[ application example 21]
1800 g of PC-1800 g obtained in example 1 and 255g of hexamethylene diisocyanate were charged into a reactor equipped with a stirrer, a thermometer and a cooling tube, and reacted at 100 ℃ for 4 hours to obtain a urethane prepolymer having a terminal isocyanate (NCO) group. To this urethane prepolymer, 107g of 1, 4-butanediol as a chain extender and 0.05g of dibutyltin dilaurate as a catalyst were added, and a reaction was carried out at 140 ℃ for 60 minutes using a universal extruder for LABO (KR-35 type universal extruder for LABO manufactured by hama chemical research, japan) with a built-in kneader to obtain a thermoplastic polyurethane. Thereafter, the resulting thermoplastic polyurethane was pelletized by an extruder.
Industrial applicability
When the polycarbonate diol composition of the present invention is used as a constituent material of a coating material, a coating film having mechanical strength and flexibility can be obtained. The polycarbonate diol composition of the present invention has these characteristics, and therefore can be suitably used as a constituent material of a coating material, and further suitably used as a raw material of polyurethane.
Claims (11)
1. A polycarbonate diol composition, comprising: 0.05 to 5 wt% of a carbonate compound represented by the following formula (C), and a polycarbonate diol comprising a repeating unit represented by the following formula (A) and a terminal hydroxyl group,
5 to 100 mol% of the repeating unit represented by the formula (A) is a repeating unit represented by the following formula (B),
in the formula (A), R1Represents a divalent aliphatic or alicyclic hydrocarbon having 2 to 12 carbon atoms,
in the formula (C), R2Optionally the same or different, represents (CH)2)4Or CH2CH(CH3)CH2And R is2At least one is CH2CH(CH3)CH2(ii) a m represents an integer of 2 to 8,
2. the polycarbonate diol composition according to claim 1, wherein the carbonate compound represented by formula (C) is a carbonate compound represented by formula (D),
in the formula (D), R2Optionally the same or different, represents (CH)2)4Or CH2CH(CH3)CH2And R is2At least one is CH2CH(CH3)CH2(ii) a m represents an integer of 3 to 6.
3. The polycarbonate diol composition according to claim 1 or 2, wherein 5 to 95 mol% of the repeating unit represented by formula (A) is a repeating unit represented by formula (E),
in the formula (E), n represents an integer of 2 to 12.
4. The polycarbonate diol composition according to claim 1 or 2, wherein the total content of titanium, ytterbium and zirconium is 0.0001 to 0.02% by weight as measured by ICP.
5. The polycarbonate diol composition according to claim 1 or 2, wherein the content of phosphorus element as measured by ICP is 0.0005 to 0.05% by weight.
6. The polycarbonate diol composition according to claim 1 or 2, wherein the amount of water is 1 to 500 ppm.
7. A thermoplastic polyurethane obtained by using the polycarbonate diol composition according to any one of claims 1 to 6 and an organic polyisocyanate.
8. A coating composition comprising the polycarbonate diol composition of any one of claims 1 to 6 and an organic polyisocyanate.
9. A coating composition comprising a urethane prepolymer obtained by reacting the polycarbonate diol composition according to any one of claims 1 to 6 with an organic polyisocyanate, the urethane prepolymer having a terminal isocyanate group.
10. A coating composition comprising a polyurethane resin obtained by reacting the polycarbonate diol composition according to any one of claims 1 to 6, an organic polyisocyanate, and a chain extender.
11. An aqueous coating composition comprising a polyurethane obtained by reacting the polycarbonate diol composition according to any one of claims 1 to 6 with an organic polyisocyanate and a chain extender.
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| EP3960451A4 (en) * | 2019-04-24 | 2022-06-15 | Mitsubishi Chemical Corporation | Thermoplastic polyurethane resin elastomer |
| CN115044029A (en) * | 2021-03-08 | 2022-09-13 | 旭化成株式会社 | Polyester polycarbonate polyols and synthetic leather |
| JP2022166839A (en) * | 2021-04-21 | 2022-11-02 | 旭化成株式会社 | Polyol composition, polyurethane resin composition, film, and leather-like sheet |
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| WO2006088152A1 (en) * | 2005-02-18 | 2006-08-24 | Asahi Kasei Chemicals Corporation | Polycarbonate diol |
| JP5479844B2 (en) * | 2009-10-15 | 2014-04-23 | 旭化成ケミカルズ株式会社 | Cyclic carbonate |
| ES2629261T3 (en) * | 2013-07-22 | 2017-08-08 | Basf Se | Coating compositions containing a compound with at least two cyclic carbonate groups and a siloxane group |
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