JP6880767B2 - Polycarbonate polyol - Google Patents

Description

The present invention relates to novel polycarbonate polyols. Polycarbonate polyol is a compound useful as a raw material for various polyurethane resins.

Conventionally, polycarbonate polyols have been actively used as raw materials for various polyurethane resins.
Among them, the polycarbonate polyol derived from 2-methyl-1,3-propanediol is known as an amorphous polycarbonate polyol.
For example, a method of reacting 2-methyl-1,3-propanediol with dimethyl carbonate in the presence of sodium methoxide to obtain a polycarbonate diol as a viscous liquid is disclosed (see, for example, Patent Document 1). ..
A method of reacting 2-methyl-1,3-propanediol with ethylene carbonate in the presence of lead acetate to obtain a polycarbonate diol as a viscous liquid is disclosed (see, for example, Patent Document 2).
Further, by reacting 2-methyl-1,3-propanediol with other alkylene polyols and ethylene carbonate in the presence of lead acetate, 5-methyl-1,3-dioxane-2-one (cyclic carbonate) is allowed to react. ) Is disclosed (see, for example, Patent Document 3).
Further, a method of reacting 2-methyl-1,3-propanediol with diethyl carbonate in the presence of sodium ethoxide to obtain a polycarbonate diol as a viscous liquid is disclosed (see, for example, Patent Document 4). ..

Japanese Unexamined Patent Publication No. 2005-325219 Japanese Unexamined Patent Publication No. 2006-225543 International Publication No. 2006/088152 (Patent No. 5068159) Japanese Unexamined Patent Publication No. 2012-46659 (Patent No. 5614637)

Patent Document 1 discloses a polycarbonate diol derived from 2-methyl-1,3-propanediol as an example (only two cases), but the function and property thereof and the function and property of polyurethane derived from the same are disclosed. Was not disclosed at all.

Patent Document 2 has a problem that lead acetate, which is highly toxic and has a problem in safety, must be used for the production of polycarbonate diol derived from 2-methyl-1,3-propanediol. It is disclosed that the properties of the polyurethane film derived from the copolymer obtained from 2-methyl-1,3-propanediol, 1,4-butanediol and ethylene carbonate are poor (Comparative Example 7). ).

Patent Document 3 has a problem that lead acetate, which is highly toxic and has a problem in safety, must be used for the production of polycarbonate diol derived from 2-methyl-1,3-propanediol.

Patent Document 4 discloses a polycarbonate diol derived from 2-methyl-1,3-propanediol (only in Example 4), but only the reaction rate of urethanization is disclosed, and it was obtained. Nothing was disclosed about the function or characteristics of urethane.

As described above, in any of the patent documents, the polyurethane derived from the polycarbonate diol derived from 2-methyl-1,3-propanediol has hardly been evaluated. That is, even in the case of the polycarbonate polyol, detailed studies have not been made on what kind of composition the repeating unit exhibits an effective function as polyurethane.
Therefore, there has been a demand for a polycarbonate polyol derived from 2-methyl-1,3-propanediol that satisfies a desired function when made into a derivative such as polyurethane.

An object of the present invention is to provide a polycarbonate polyol derived from 2-methyl-1,3-propanediol, which solves the above-mentioned problems and exhibits a useful effect when derivatized into polyurethane.

An object of the present invention is a polycarbonate polyol having a repeating unit represented by the following formula (A), a repeating unit of at least one of the following formulas (B) and (C), and a terminal hydroxyl group.
For all repeating units in polycarbonate polyols
The ratio of the following formula (A) is 99.0 to 99.8 mol%.
The ratio of the following formula (B) is 0.5 mol% or less,
It is solved by the polycarbonate polyol in which the ratio of the following formula (C) is 0.2 mol% or less.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polycarbonate polyol having high breaking point elongation and breaking point stress and excellent solvent resistance and tack performance when derivatized into polyurethane.

(Polycarbonate polyol)
The polycarbonate polyol of the present invention
It consists of a repeating unit represented by the following formula (A) and at least one of the following formula (B) and the following formula (C), and both ends are hydroxyl groups.
For all repeating units in polycarbonate polyols
The ratio of the following formula (A) is 99.0 to 99.8 mol%.
The ratio of the following formula (B) is 0.5 mol% or less,
A polycarbonate polyol having a proportion of the following formula (C) of 0.2 mol% or less.

(Repeating unit)
The total repeating unit in the polycarbonate polyol is a component derived from the monomers constituting the polycarbonate polyol, and the total number of repeating units corresponds to the number of the monomers.
Therefore, by measuring the number of monomers contained in the polycarbonate, the total number of repeating units (total number of moles of all monomers) and the number of each repeating unit (number of moles of each monomer) can be calculated.

As a method for measuring the monomer, for example, a polycarbonate polyol, ethanol and a base are mixed, and the mixed solution is heated to decompose with alcohol to obtain a monomer, and the obtained monomer is analyzed by gas chromatography. Can be measured by.
The polycarbonate polyol can also be directly measured by a proton nuclear magnetic resonance spectrum ( ¹ H-NMR).

Examples of the monomer constituting the repeating unit of the formula (A) are 2-methyl-1,3-propanediol.
The monomer constituting the repeating unit of the formula (B) is, for example, 1,4-butanediol.
Examples of the monomer constituting the repeating unit of the formula (C) are γ-butyrolactone, hydroxybutanoic acid and an ester thereof.

(Repeating unit of formula (A))
Specifically, the repeating unit represented by the formula (A) is a repeating unit composed of, for example, a reaction between 2-methyl-1,3-propanediol and a carbonic acid ester.
The ratio of the repeating unit represented by the formula (A) to all the repeating units in the polycarbonate polyol is 99.0 to 99.8 mol%, preferably 99.1 to 99.7 mol%, and more preferably 99.2 to 99.2. It is 99.6 mol%.
Within this range, high flexibility of polyurethane derived from polycarbonate polyol, that is, high breaking point elongation and high breaking point stress is exhibited. Moreover, good tack performance can be obtained.

(Repeating unit of equation (B))
Specifically, the repeating unit represented by the formula (B) is a repeating unit composed of, for example, a reaction between 1,4-butanediol and a carbonic acid ester.
The ratio of the repeating unit represented by the formula (B) to all the repeating units in the polycarbonate polyol is 0.5 mol% or less, preferably 0.1 to 0.5 mol%, more preferably 0.1 to 0.4. It is mol%, more preferably 0.1 to 0.3 mol%.
Within this range, higher flexibility, ie, higher breaking point elongation and higher breaking point stress, is exhibited without degrading the tack performance of the polyurethane derived from the polycarbonate polyol.

(Repeating unit of formula (C))
The repeating unit represented by the formula (C) is a repeating unit composed of ring opening of γ-butyrolactone, condensation of hydroxybutanoic acid, dealcoholization of hydroxybutanoic acid, and the like.
The ratio of the repeating unit represented by the formula (C) to all the repeating units in the polycarbonate polyol is 0.2 mol% or less, preferably 0.01 to 0.2 mol%, and more preferably 0.01 to 0.15. It is mol%, more preferably 0.02 to 0.15 mol%.
Within this range, the solvent resistance of polyurethane derived from polycarbonate polyol, particularly the durability against oleic acid, which is a component of sweat (oleic acid resistance), is improved.

(Other repeating units)
The polycarbonate polyol of the present invention may be referred to as a repeating unit other than the repeating units of the formulas (A) to (C) (hereinafter, "other repeating units"" as long as the content ratio of each repeating unit is satisfied. ) May be included. Examples of the monomer (other monomer) constituting the other repeating unit include 1,2-ethanediol, 1,3-propanediol, 3-oxa-1,5-pentanediol (diethylene glycol), and 2,2-. Dimethyl-1,3-propanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 2-methyl-1,3-pentanediol, 1,5-hexanediol, 1,6-hexane Diols, 1,4-cyclohexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, and other diols with 2 to 12 carbon atoms; valerolactone, caprolactone, etc. Lactones having 5 to 12 carbon atoms; hydroxycarboxylic acids having 5 to 12 carbon atoms such as hydroxypentaneic acid and hydroxyhexaneic acid, or isomers thereof.
The other repeating units can be formed by the methods shown in the repeating units of the formulas (A) to (C) depending on the type of the monomer.
The ratio of the other repeating units in the polycarbonate polyol is the ratio obtained by subtracting the total ratio of the repeating units of the formulas (A) to (C) from all the repeating units, preferably 0.09 to 0.89 mol%. Is.
Within this range, the function of the polycarbonate polyol of the present invention is not impaired.

More preferably, the polycarbonate polyol of the present invention
It consists of the repeating unit represented by the formula (A), the formulas (B) and the formula (C), and both ends are hydroxyl groups.
For all repeating units in polycarbonate polyols
The ratio of the following formula (A) is 99.0 to 99.8 mol%.
The ratio of the following formula (B) is 0.1 to 0.5 mol%.
It is a polycarbonate polyol having a ratio of the following formula (C) of 0.01 to 0.2 mol%.

(Number average molecular weight of polycarbonate polyol)
The number average molecular weight of the polycarbonate polyol of the present invention can be appropriately adjusted depending on the intended purpose, but is preferably 100 to 5000, more preferably 200 to 4000, and even more preferably 300 to 3000.
The number average molecular weight shall be the number average molecular weight calculated based on the hydroxyl value measured in accordance with JIS K 1557. Specifically, the hydroxyl value is measured and calculated using (56.1 × 1000 × valence) / hydroxyl value by the terminal group quantification method (in this formula, the unit of the hydroxyl value is [mgKOH / g]. Is). In the above formula, the valence is the number of hydroxyl groups in one molecule.
Within this range, the polycarbonate polyol becomes a liquid that can be easily handled, and the low temperature characteristics of the polyurethane derived from the polycarbonate polyol become good.

(Manufacturing of polycarbonate polyol)
The method for producing the polycarbonate polyol of the present invention (hereinafter, also referred to as “reaction of the present invention”) is not particularly limited, but for example, 2-methyl-1,3-propanediol (component of the formula (A)). And 1,4-butanediol (component of formula (B)) and β-butanediol (component of formula (C)), or one of the other monomers (components of other repeating units). , Carbonate ester and catalyst are mixed and reacted while distilling off low boiling point components (for example, alcohol produced as a by-product).
The reaction of the present invention may be carried out in a plurality of times, for example, once a prepolymer of a polycarbonate polyol (lower molecular weight than the target polycarbonate polyol) is obtained, and then the reaction is carried out in order to further increase the molecular weight. it can.

(Carbonate ester)
The carbonate ester used in the reaction of the present invention is, for example, dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate; diaryl carbonate such as diphenyl carbonate; ethylene carbonate, propylene carbonate (4-methyl-1,3-dioxolane-). Cyclic carbonates such as 2-one, trimethylene carbonate), butylene carbonate (4-ethyl-1,3-dioxolan-2-one, tetramethylene carbonate) and 5-methyl-1,3-dioxane-2-one are listed. However, dimethyl carbonate, diethyl carbonate, and ethylene carbonate are preferably used.
In addition, these carbonic acid esters may be used individually or in mixture of 2 or more types.

The amount of the carbonic acid ester used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1.5 mol, based on 1 mol of 2-methyl-1,3-propanediol.
Within this range, the desired polycarbonate polyol can be efficiently obtained at a sufficient reaction rate.

(Reaction temperature and reaction pressure)
The reaction temperature in the reaction of the present invention can be appropriately adjusted according to the type of carbonic acid ester, but is preferably 50 to 250 ° C, more preferably 70 to 230 ° C.
Further, the reaction pressure in the reaction of the present invention is not particularly limited as long as the pressure is such that the reaction is carried out while removing the low boiling point component, and the reaction is preferably carried out under normal pressure or reduced pressure.
Within this range, the desired polycarbonate polyol can be efficiently obtained without causing sequential reactions or side reactions.

(catalyst)
Known ester exchange catalysts can be used as the catalyst used in the reaction of the present invention, for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, etc. Metals such as cobalt, germanium, tin and cerium, and their hydroxides, alkoxides, carboxylates, carbonates, hydrogen carbonates, sulfates, phosphates, nitrates and organic metals are preferred. Sodium hydride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxyde, dibutyltin oxide are used.
These catalysts may be used alone or in combination of two or more.

The amount of the catalyst used is preferably 0.001 to 0.1 mmol, more preferably 0.005 to 0.05 mmol, and more preferably 0, based on 1 mol of 2-methyl-1,3-propanediol. It is 0.01 to 0.03 mmol.
Within this range, the desired polycarbonate polyol can be efficiently obtained without complicating post-treatment.
The catalyst may be used collectively at the start of the reaction, or may be used (added) in two or more portions at the start of the reaction and after the start of the reaction.

(Polyurethane)
Polyurethane can be obtained by reacting the polycarbonate diol of the present invention obtained as described above with a polyisocyanate (hereinafter, also referred to as "polyurethaneization reaction").
The polyurethane derived from the polycarbonate polyol of the present invention is an extremely useful material having high breaking point elongation and breaking point stress, and excellent solvent resistance and tack performance.

(Polyisocyanate)
The polyisocyanate can be appropriately selected depending on the purpose and application, and for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1. , 5-Diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediocyanate, polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), phenylenedi isocyanate and other aromatic aliphatic diisocyanates; 4,4'-methylenebiscyclohexyl An aliphatic diisocyanate such as diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,2-diylbis (methylene) diisocyanate, or trimethylhexamethylene diisocyanate is used.
These polyisocyanates may be used alone or in admixture of two or more, and a part or all of the structure may be derivatized such as isocyanurate-forming, carbodiimide-forming, or biuret-forming.

Regarding the amount of polyisocyanate used, the ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polycarbonate polyol (isocyanate group / hydroxyl group (molar ratio)) is preferably 0.8 to 1.2, more preferably 0.9 to 1. .1.

(Chain extender)
In the polyurethane-forming reaction, a chain extender can be used for the purpose of increasing the molecular weight. The chain extender to be used can be appropriately selected according to the purpose and application, and for example,
water;
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, tricyclodecanedimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl ] Propane, low molecular weight polyols such as bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane;
High molecular weight polyols such as polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, and polyolefin polyols;
Polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine are used.
For the chain extender, for example, "Latest Polyurethane Applied Technology" (CMC Co., Ltd., published in 1985) can be referred to, and for the polymer polyol, for example, "Polyurethane form" (polymer). Publications, 1987) can be referred to.

(Urethane catalyst)
In the polyurethaneization reaction, a known polymerization catalyst can be used to improve the reaction rate, and for example, a tertiary amine or an organometallic salt such as tin or titanium is used.
For the polymerization catalyst, refer to pages 23 to 32 of "Polyurethane Resin" by Keiji Yoshida (published by Nihon Kogyo Shimbun, 1969).

(solvent)
The polyurethaneization reaction can be carried out in the presence of a solvent, for example, esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, γ-valerolactone, δ-caprolactone; dimethylformamide, diethylformamide, dimethylacetamide. Amides such as; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, 2-ethoxyethanol; ketones such as methylisobutylketone and cyclohexanone; aromatic hydrocarbons such as benzene and toluene are used.

The polyurethaneization reaction can be carried out by adding a terminal terminator to adjust the molecular weight.
Further, the polyurethane may contain a heat stabilizer, a light stabilizer, a plasticizer, an inorganic filler, a lubricant, a colorant, a silicone oil, a foaming agent, a flame retardant and the like, depending on the purpose.

The obtained polyurethane can be a flexible polyurethane foam, a rigid polyurethane foam, a thermoplastic polyurethane, a solvent-based polyurethane solution, an aqueous polyurethane dispersion, or the like. In addition, these can be used to process artificial leather, synthetic leather, heat insulating materials, cushioning materials, adhesives, paints, coating agents, molded products such as films, and the like.

[Aqueous polyurethane resin dispersion]
Specifically, the aqueous polyurethane resin dispersion is obtained by reacting, for example, the polycarbonate polyol, polyisocyanate, and acidic group-containing polyol of the present invention in the presence or absence of a solvent to obtain a urethane prepolymer. , A step of neutralizing the acidic group in the prepolymer with a neutralizing agent, a step of dispersing the neutralized prepolymer in an aqueous medium, and a step of reacting the prepolymer dispersed in the aqueous medium with a chain extender. It can be manufactured by sequentially performing.
In each step, the reaction can be promoted and the amount of by-products can be controlled by using a catalyst as needed.
The aqueous polyurethane resin dispersion derived from the polycarbonate polyol of the present invention provides a film having excellent adhesion, flexibility, and tactile sensation, and is therefore particularly applicable to artificial leather and synthetic leather.

As the polycarbonate polyol, polyisocyanate, solvent, and chain extender, those described above can be used.

(Polyol containing acidic group)
When producing an aqueous polyurethane resin dispersion, an acidic group-containing polyol can be used to disperse the dispersion in an aqueous medium. Therefore, the amount of the polyisocyanate used is the molar ratio (isocyanate) of the isocyanate group of the polyisocyanate to the total hydroxyl group of the polyol (polypolypolyol, all polyols such as acid group-containing polyol described later, and low molecular weight polyol described later). It can be designed with a group / hydroxyl group (mol), and the molar ratio is preferably 0.8 to 2.0, more preferably 0.9 to 1.8.

Examples of the acidic group-containing polyol include dimethylol alkanoic acids such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid; N, N-bishydroxyethylglycine and N, N-bishydroxyethyl. Examples thereof include alanine, 3,4-dihydroxybutane sulfonic acid, 3,6-dihydroxy-2-toluene sulfonic acid, etc., preferably dimethylol alkanoic acid, more preferably 4 to 12 carbon atoms containing two methylol groups. Alkane acid is used.
These acidic group-containing polyols may be used alone or in combination of two or more, and the amount used is not particularly limited as long as the polyurethane resin can be dispersed in an aqueous medium.

(Neutralizer)
Examples of the neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine and N-methyl. Organic amines such as morpholin and pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide and ammonia can be mentioned, but organic amines are preferably used, and tertiary amines are more preferably used.
These neutralizing agents may be used alone or in combination of two or more, and the amount used is not particularly limited as long as the amount of the acidic group in the polyurethane resin can be neutralized.

(Aqueous medium)
Examples of the aqueous medium include water such as clean water, ion-exchanged water, distilled water, and ultrapure water, and a mixed medium of water and a hydrophilic organic solvent.

Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl ketone; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; ethers such as diethyl ether and dipropylene glycol dimethyl ether; methanol, ethanol, and the like. Alcohols such as n-propanol, isopropanol, ethylene glycol, diethylene glycol; amides such as β-alkoxypropionamide represented by "Equamid" manufactured by Idemitsu Kosan Co., Ltd .; 2- (dimethylamino) -2-methyl-1-propanol Examples thereof include hydroxyl group-containing tertiary amines such as (DMAP).
The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by mass.

(Low molecular weight polyol)
In the urethanization reaction of the present invention, a low molecular weight polyol can be present in order to adjust the molecular weight. Examples of low molecular weight polyols that can be used include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 1,4-butanediol. , 1,5-Pentanediol, 3-methyl-1,5-Pentanediol, 1,6-hexanediol and the like.
In addition, these low molecular weight polyols may be used individually or in mixture of 2 or more types.

The polycarbonate polyol of the present invention also has a solid content of about 30% after mixing the polycarbonate polyol and 4,4'-dicyclohexylmethane diisocyanate so that the isocyanate group / hydroxyl group = 0.99 (molar ratio). The polyurethane film has a breaking point elongation of 890% or more and a breaking point stress of 50 MPa or more when the mixture obtained by diluting and reacting with γ-butyrolactone is applied onto a glass plate and cured. Is a polycarbonate polyol.

Further, the polycarbonate polyol of the present invention has a solid content of about 30% after mixing the polycarbonate polyol and 4,4'-dicyclohexylmethanediisocyanate so that the isocyanate group / hydroxyl group = 0.99 (molar ratio). The swelling rate when the polyurethane film obtained by diluting with γ-butyrolactone and reacting so as to be obtained by applying it on a glass plate and curing it and immersing it in oleic acid at 45 ° C. for 1 week is obtained. It is also a polycarbonate polyol that is less than 15%.

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

(Number average molecular weight)
The number average molecular weight was calculated based on the following formula.
Number average molecular weight = (56100 × 2) / hydroxyl value The hydroxyl value of the polycarbonate polyol was determined by titration in accordance with JIS K 1557. Here, the unit of the hydroxyl value is mgKOH / g.

(Repeating unit in polycarbonate polyol)
1 g of polycarbonate polyol, 30 g of ethanol and 4 g of potassium hydroxide were mixed and stirred at 95 to 105 ° C. for 1 hour.
After completion of stirring, the mixture was neutralized with hydrochloric acid, the produced sodium chloride was filtered, and the filtrate was diluted 3-fold with ethanol and analyzed by gas chromatography.
The detected 2-methyl-1,3-propanediol, 1,4-butanediol, γ-butyrolactone, hydroxybutanoic acid ester, and other monomers were quantified by a calibration curve method, and the total amount of all monomer components was calculated. Each repeating unit (mol%) was calculated as 100%.
For the quantification of other monomers, 3-methyl-1,5-pentanediol was used as a standard substance.

The analysis conditions by gas chromatography are as follows.
Equipment: Gas chromatograph GC-2010 (manufactured by Shimadzu Corporation)
Column: DB-WAX (manufactured by J & W, USA), film thickness 0.25 μm, length 30 m
Column temperature: 60 ° C (hold for 5 minutes) → 250 ° C (hold)
Heating rate; 10 ° C / min Carrier gas; Helium detector: Flame ionization detector (FID)
Injection volume; 1 μL

(Example 1: Synthesis of polycarbonate polyol)
In a glass round bottom flask equipped with a rectification tower, stirrer, thermometer and nitrogen introduction tube,
425.5 g of 2-methyl-1,3-propanediol (4.72 mol, purity of 99% or more), 0.86 g of 1,4-butanediol (0.0095 mol, purity of 99% or more), dimethyl carbonate 448. 8 g (4.98 mol, 99% or more) and 0.003 g (0.13 mmol) of lithium hydroxide were mixed and reacted at 120 to 200 ° C. for 12 hours under normal pressure while distilling off low boiling point components.
Further, under reduced pressure (0.1 to 6.7 kPa), the reaction was carried out at 150 to 170 ° C. for 8 hours while distilling off the components containing 2-methyl-1,3-propanediol to prepare a polycarbonate polyol as a viscous liquid. (1) was obtained.

The obtained polycarbonate polyol had a number average molecular weight of 2093 and a hydroxyl value of 53.6, and had the following composition.
Repeat unit (A); 99.3 mol%
Repeat unit (B); 0.2 mol%
Repeat unit (C); 0 mol%
Other repeating units; 0.5 mol%

(Example 2; Synthesis of polycarbonate polyol)
In a glass round bottom flask equipped with a rectification tower, stirrer, thermometer and nitrogen introduction tube,
24-methyl-1,3-propanediol 425.5 g (4.72 mol, purity 99% or more), γ-butyrolactone 0.41 g (0.0047 mol, purity 99% or more), dimethyl carbonate 448.8 g (4) .98 mol, 99% or more) and 0.003 g (0.13 mmol) of lithium hydroxide were mixed and reacted at 120 to 200 ° C. for 12 hours under normal pressure while distilling off low boiling point components.
Further, under reduced pressure (0.1 to 6.7 kPa), the reaction was carried out at 150 to 170 ° C. for 8 hours while distilling off the components containing 2-methyl-1,3-propanediol to prepare a polycarbonate polyol as a viscous liquid. (2) was obtained.

The obtained polycarbonate polyol had a number average molecular weight of 2109 and a hydroxyl value of 53.2, and had the following composition.
Repeat unit (A); 99.4 mol%
Repeat unit (B); 0 mol%
Repeat unit (C); 0.1 mol%
Other repeating units; 0.5 mol%

(Example 3; Synthesis of polycarbonate polyol)
In a glass round bottom flask equipped with a rectification tower, stirrer, thermometer and nitrogen introduction tube,
425.5 g of 2-methyl-1,3-propanediol (4.72 mol, purity of 99% or more), 0.86 g of 1,4-butanediol (0.0095 mol, purity of 99% or more), γ-butyrolactone 0 .41 g (0.0048 mol, purity 99% or more), dimethyl carbonate 448.8 g (4.98 mol, 99% or more) and lithium hydroxide 0.003 g (0.13 mmol) are mixed, and the pressure is low under normal pressure. The reaction was carried out at 120 to 200 ° C. for 12 hours while distilling off the boiling point component.
Further, under reduced pressure (0.1 to 6.7 kPa), the reaction was carried out at 150 to 170 ° C. for 8 hours while distilling off the components containing 2-methyl-1,3-propanediol to prepare a polycarbonate polyol as a viscous liquid. (3) was obtained.

The obtained polycarbonate polyol had a number average molecular weight of 2097 and a hydroxyl value of 63.5, and had the following composition.
Repeat unit (A); 99.2 mol%
Repeat unit (B); 0.2 mol%
Repeat unit (C); 0.1 mol%
Other repeating units; 0.5 mol%

Comparative Example 1 (Synthesis of Polycarbonate Polyol)
In a glass round bottom flask equipped with a rectification tower, stirrer, thermometer and nitrogen introduction tube,
425.5 g of 2-methyl-1,3-propanediol (4.72 mol, purity of 99% or more), 448.8 g of dimethyl carbonate (4.98 mol, 99% or more) and 0.003 g of lithium hydroxide (0. 13 mmol) was mixed, and the mixture was reacted at 120 to 200 ° C. for 12 hours under normal pressure while distilling off low boiling point components.
Further, under reduced pressure (0.1 to 6.7 kPa), the reaction was carried out at 150 to 170 ° C. for 8 hours while distilling off the components containing 2-methyl-1,3-propanediol to prepare a polycarbonate polyol as a viscous liquid. (4) was obtained.

The obtained polycarbonate polyol had a number average molecular weight of 2093 and a hydroxyl value of 53.6, and had the following composition.
Repeat unit (A); 99.9 mol%
Repeat unit (B); 0 mol%
Repeat unit (C); 0 mol%
Other repeating units; 0.1 mol%

(Comparative Example 2; Synthesis of Polycarbonate Polyol)
In a glass round bottom flask equipped with a rectification tower, stirrer, thermometer and nitrogen introduction tube,
425.5 g of 2-methyl-1,3-propanediol (4.72 mol, purity of 99% or more), 5.6 g of 1,4-butanediol (0.062 mol, purity of 99% or more), dimethyl carbonate 448. 8 g (4.98 mol, 99% or more) and 0.003 g (0.13 mmol) of lithium hydroxide were mixed and reacted at 120 to 200 ° C. for 12 hours under normal pressure while distilling off low boiling point components.
Further, under reduced pressure (0.1 to 6.7 kPa), the reaction was carried out at 150 to 170 ° C. for 8 hours while distilling off the components containing 2-methyl-1,3-propanediol to prepare a polycarbonate polyol as a viscous liquid. (5) was obtained.

The obtained polycarbonate polyol had a number average molecular weight of 2086 and a hydroxyl value of 53.8, and had the following composition.
Repeat unit (A); 98.2 mol%
Repeat unit (B); 1.3 mol%
Repeat unit (C); 0 mol%
Other repeating units; 0.5 mol%

(Example 4; Synthesis of polycarbonate polyol)
In Example 3, except for changing the amount of 2-methyl-1,3-propanediol, the same procedure was followed as in Example 3 to obtain polycarbonate polyol (6).

The obtained polycarbonate polyol had a number average molecular weight of 2097 and a hydroxyl value of 53.5, and had the following composition.
Repeat unit (A); 99.6 mol%
Repeat unit (B); 0.1 mol%
Repeat unit (C); 0.05 mol%
Other repeating units; 0.25 mol%

(Example 5; Synthesis of polycarbonate polyol)
In Example 3, except for changing the amount of 2-methyl-1,3-propanediol Lumpur及beauty 1,4-butanediol, the reaction was carried out in the same manner as in Example 1, a polycarbonate polyol (7) Obtained.

The obtained polycarbonate polyol had a number average molecular weight of 2097 and a hydroxyl value of 53.5, and had the following composition.
Repeat unit (A); 99.1 mol%
Repeat unit (B); 0.1 mol%
Repeat unit (C); 0 mol%
Other repeating units; 0.8 mol%

(Polyurethane synthesis)
70.6 g of the polycarbonate polyols synthesized in Examples and Comparative Examples and 10.5 g of 4,4′-dicyclohexylmethanediisocyanate (adjusted to have an isocyanate group / hydroxyl group = 0.99 (molar ratio)) were added to a solid content of 30. It was diluted with γ-butyrolactone so as to be%, and 0.08 g of dibutyltin dilaurate was mixed and reacted at 75 to 85 ° C. for 10 hours to obtain a γ-butyrolactone solution of polyurethane.
The obtained polyurethane solution was applied onto a glass plate and dried at 70 ° C. for 1 hour and 120 ° C. for 3 hours to obtain a polyurethane film.
The obtained polyurethane film was measured for breaking point elongation, breaking point stress, olein resistance, and tack performance by the following evaluation methods.

(Elongation at break point, stress at break point)
A polyurethane film having a thickness of about 0.05 mm was formed, and this film was cut into strips of 10 mm × 80 mm and cured in a thermostatic chamber at 23 ° C. and 50% RH for one day as an evaluation sample.
The sample was pulled in a thermostatic chamber at 23 ° C. and 50% RH using a Tensilon tensile tester (RTC-1250A, manufactured by ORIENTEC) at a chuck distance of 20 mm and a tensile speed of 100 mm / min, and the elongation at break (%) and Breaking point stress The stress (MPa) was measured.

(Olein resistant acidity)
Polyurethane having a thickness of about 0.05 mm was immersed in oleic acid at 45 ° C. for 1 week, and the swelling rate (%) at that time was measured. Olein acid resistance was evaluated according to the following criteria according to the degree of swelling rate.
⊚; swelling rate is less than 10% ○; swelling rate is 10% or more and less than 15% Δ; swelling rate is 15% or more

(Tack performance)
The polyurethane solution was applied onto a 10 cm × 10 cm glass plate to form a polyurethane film, and then glass plates of the same size were overlapped with each other, and a 5 kg weight was placed on the glass plate and left for 1 hour.
After that, the force required to peel off both glass plates was evaluated as the tack performance according to the following criteria.
○; No tack (easily peeled off with almost no force applied)
△: Slightly tacky (can be peeled off with a little force)
×; Tacky (cannot be peeled off without applying considerable force)

The above results are shown in Table 1.

From the above results, it was found that the polycarbonate polyol whose repeating unit is within the range of the present invention has good fracture point elongation, fracture point stress, olein resistance, and tack performance when induced in polyurethane. ..

By having a repeating unit (A) of 99.0 to 99.8 mol% and a repeating unit (B) of 0.5 mol% or less, a higher breaking point elongation (900% or more) and a higher breaking point stress (55 MPa or more) was expressed (comparison between Examples 1 and 3 to 4 and Comparative Example 1). Further, it was found that the tack performance was slightly impaired as the number of repeating units (B) increased (Comparative Example 2).

It was found that high olein-resistant acidity was exhibited by having the repeating unit (A) in an amount of 99.0 to 99.8 mol% and the repeating unit (C) in an amount of 0.2 mol% or less (Examples 2 to 4). And comparison with Comparative Examples 1 and 2).

In particular, the polycarbonate polyol has a repeating unit (A) of 99.0 to 99.8 mol%, a repeating unit (B) of 0.1 to 0.5 mol%, and a repeating unit (C) of 0.01 to 0. It was found that by having 2 mol%, the tack performance was good, higher breaking point elongation (900% or more) and higher breaking point stress (55 MPa or more) were exhibited, and high olein acid resistance was exhibited. (Examples 3 and 4).

As described above, a specific ratio of the repeating unit (A) derived from 2-methyl-1,3-propanediol, the repeating unit (B) derived from 1,4-butanediol, and the repeating unit (C) derived from γ-butyrolactone. It was clarified that high performance is exhibited when polyurethane is used.

The polycarbonate polyol of the present invention has high breaking point elongation and breaking point stress when made into polyurethane, and is also excellent in tack performance and olein acid resistance. Therefore, the present invention relates to a novel polycarbonate polyol. Polycarbonate polyol is a compound useful as a raw material for various polyurethane resins used for coating sheets and leather.

Claims (6)

Formula (A), consists of a Repetitive returns units of formula (B) and the following formula (C), a polycarbonate polyol having terminal hydroxyl groups,
For all repeating units in polycarbonate polyols
The ratio of the following formula (A) is 99.0 to 99.8 mol%.
The ratio of the following formula (B) is 0.1 to 0.5 mol% .
The ratio of the following formula (C) is 0.01 to 0.2 mol% .
Polycarbonate polyol.

Polycarbonate polyol and 4,4'-dicyclohexylmethane diisocyanate are mixed so that isocyanate group / hydroxyl group = 0.99 (molar ratio), and then diluted with γ-butyrolactone so that the solid content is about 30%. The first aspect of claim 1, wherein the polyurethane film has a breaking point elongation of 890% or more and a breaking point stress of 50 MPa or more when the mixture obtained by the reaction is applied onto a glass plate and cured. Polycarbonate polyol. Polycarbonate polyol and 4,4'-dicyclohexylmethane diisocyanate are mixed so that isocyanate group / hydroxyl group = 0.99 (molar ratio), and then diluted with γ-butyrolactone so that the solid content is about 30%. A claim that the polyurethane film obtained by applying the mixture obtained by the reaction on a glass plate and being cured is immersed in oleic acid at 45 ° C. for 1 week, and the swelling rate at that time is less than 15%. The polycarbonate polyol according to 1 or 2. A polyurethane obtained by using the polycarbonate polyol according to any one of claims 1 to 3. Synthetic leather obtained by using the polycarbonate polyol according to any one of claims 1 to 3. An aqueous polyurethane resin dispersion obtained by using the polycarbonate polyol according to any one of claims 1 to 3.