Polycarbonate diol and polyurethane using same

Abstract

The present invention relates to a polycarbonate diol comprising a structural unit derived from a compound represented by the following formula (A) and a structural unit derived from a compound represented by the following formula (B), wherein the hydroxyl value is from 20 to 450 mg-KOH/g:
HO—R.sup.1—OH  (A)
HO—R.sup.2—OH  (B) the glass transition temperature of said polycarbonate diol as measured by a differential operating calorimeter is −30° C. or less and the average carbon number of a dihydroxy compound obtained by hydrolyzing said polycarbonate diol is from 3 to 5.5.

Claims

1. A polycarbonate diol, comprising: structural units derived from at least one compound (A) selected from the group consisting of 1,3-propanediol and 1,4-butanediol; and structural units derived from at least one compound (B) selected from the group consisting of 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; wherein: the polycarbonate diol has a hydroxyl value of 30 to 230 mg-KOH/g; and a molar ratio of total structural units derived from compound (A) and compound (B) to all structural units in the polycarbonate diol is at least 70 mol % wherein the polycarbonate diol does not contain a structural unit derived from 2-methyl-1,8-octanediol.

2. The polycarbonate diol as claimed in claim 1, wherein the molar ratio of total of structural units derived from compound (A) and compound (B) to all structural units in the polycarbonate diol is at least 80 mol %.

3. The polycarbonate diol as claimed in claim 1, wherein a molar ratio of structural units derived from compound (A) to structural units derived from compound (B) in the polycarbonate diol is 50:50 to 99:1.

4. The polycarbonate diol as claimed in claim 1, wherein an average carbon number of a dihydroxy compound obtained by hydrolyzing the polycarbonate diol is 4 to 5.5.

5. The polycarbonate diol as claimed in claim 1, wherein the polycarbonate diol has a hydroxyl value of 30 to 60 mg-KOH/g.

6. A polyurethane formed using the polycarbonate diol claimed in claim 1.

7. An artificial leather, synthetic leather, a coating material, a coating agent, an aqueous polyurethane coating material, an aqueous polyurethane coating material, a pressure sensitive adhesive or adhesive produced using the polyurethane claimed in claim 6.

8. An active energy ray-curable polymer composition formed using the polycarbonate diol claimed in claim 1.

9. A method for producing the polycarbonate diol of claim 1, the method comprising polycondensing the compound (A), the compound (B), and a carbonate compound, through a transesterification reaction, to produce the polycarbonate diol.

10. The polycarbonate diol as claimed in claim 3, wherein the molar ratio of structural units derived from compound (A) to structural units derived from compound (B) in the polycarbonate diol is 60:40 to 99:1.

11. The polycarbonate diol as claimed in claim 1, which does not contain a structural unit derived from a branched chain-containing diol.

12. The polycarbonate diol as claimed in claim 1, consisting of structural units derived from compound (A) and structural units derived from compound (B).

13. The polycarbonate diol as claimed in claim 1, wherein the structural units derived from compound (B) are derived from at least one compound selected from the group consisting of 1,10-decanediol and 1,12-dodecanediol.

14. The polycarbonate diol as claimed in claim 10, wherein the molar ratio of structural units derived from compound (A) to structural units derived from compound (B) in the polycarbonate diol is 80:20 to 99:1.

15. The polycarbonate diol as claimed in claim 1, wherein the polycarbonate diol does not contain a structural unit derived from 1,6-hexanediol.

16. The polycarbonate diol as claimed in claim 1, wherein the molar ratio of total of structural units derived from compound (A) and compound (B) to all structural units in the polycarbonate diol is at least 90 mol %.

17. The polycarbonate diol as claimed in claim 1, wherein the molar ratio of total of structural units derived from compound (A) and compound (B) to all structural units in the polycarbonate diol is at least 95 mol %.

Description

EXAMPLES

(1) The present invention is described in greater detail below by referring to Examples and Comparative Examples, bus the present invention is not limited to these Examples as long as the gist thereof is observed.

(2) The evaluation methods for respective physical values described below are as follows.

(3) [Evaluation Method: Polycarbonate Diol]

(4) <Quantitative Determination of Phenoxy Group Amount, Dihydroxy Compound Content and Phenol Content>

(5) Polycarbonate diol was dissolved in CDCl.sub.3, and 400 MHz .sup.1H-NMR (AL-400, manufactured by JEOL Ltd.) was measured, whereby a phenoxy group, a dihydroxy compound and phenol ere identified based on signal positions of respective components and the content of each component was calculated from the integral value. At this time, the detection limit is 100 ppm for the weight of phenol relative to the weight of the entire sample and 0.1 wt % for a dihydroxy compound such as compound represented by formula (A) and compound represented by formula (B). The proportion of phenoxy group is calculated from the ratio between an integral value for one proton portion of phenoxy group and an integral value for one proton portion of the entire terminal, and the detection limit for phenoxy group is 0.05% relative to the entire terminal.

(6) <Hydroxyl Value>

(7) The hydroxyl value of the polycarbonate diol was measured by the method using an acetylation reagent in conformity with JIS K1557-1 (2007).

(8) <Measurement of APHA Value>

(9) The APHA value was measured by the comparison with a standard solution prepared by putting polycarbonate diol in a colorimetric tube, in conformity with JIS K0071-1 (1998). Color Standard Solution 1000° (1 mgPt/mL) (produced by Kishida Chemical Co., Ltd.) was used as the reagent.

(10) <Measurement of Melt Viscosity>

(11) Polycarbonate diol was heated at 80° C. and thereby melted and thereafter, the melt viscosity was measured at 80° C. by using a E-type viscometer (DV-II+Pro, manufactured by BROOKFIELD, cone: CPE-52).

(12) <Measurement of Glass Transition Temperature (Tg), Melting Peak Temperature and Melting Heat Quantity>

(13) About 10 mg of polycarbonate diol was sealed in an aluminum pan, and an operation of raising and lowering the temperature from 30° C. to 150° C. at a rate of 20° C./min, from 150° C. to −120° C. at a rate of 40° C./imin, and from −120° C. to 120° C. at a rate of 20° C./min was performed in a nitrogen atmosphere by using EXSTAR DSC6200 (manufactured by Seiko Instrument, Inc.). The glass transition temperature (Tg) was obtained from the inflection point at the time of second temperature rise, and the melting peak temperature and melting heat quantity were determined from the melting peak.

(14) <Molar Fraction of Dihydroxy Compound after Hydrolysis>

(15) About 0.5 g of polycarbonate diol was precisely weighed, put in a 100-mL conical flask and dissolved by adding 5 mL of tetrahydrofuran. Thereafter, 45 mL of methanol and 5 mL of an aqueous 25 wt % sodium hydroxide solution was added. A condenser was set in a 100 mL conical flack, and hydrolysis was performed under heating for 30 minutes in a water bath at 75 to 80° C. After allowing to cool at room temperature, sodium hydroxide was neutralized by adding 5 mL of 6N hydrochloric acid to make the pH be 7. The entire amount was transferred to a 100-mL measuring flask, and the washing obtained by washing the inside of the conical flask twice with an appropriate amount of methanol was also transferred to the 100-mL measuring flask. An appropriate amount of methanol was added to make 100 mL, and the solution was mixed in the measuring flask. The supernatant was sampled, filtered through a filter, and analyzed by gas chromatography (GC). As for the concentration of each dihydroxy compound, a calibration curve was previously prepared from each known dihydroxy compound as a standard substance, and wt % was calculated from the area ratio obtained by the gas chromatography (GC).

(16) (Analysis Conditions)

(17) Apparatus: Agilent 6850 (manufactured by Agilent Technologies Japan Ltd.)

(18) Column: Agilent J&W GC column DB-WAX, inner diameter: 0.25 mm, length: 60 m, film pressure: 0.25 mm

(19) Detector: Hydrogen flame ionization detector (FID)

(20) Programmed temperature rise: 150° C. (2 minutes), from 150° C. to 280° C. (10° C./min, 9 minutes), 240° C. (10 minutes)

(21) The molar fraction of the dihydroxy compound was calculated from wt % obtained by gas chromatography above and the molecular weight of each dihydroxy compound.

(22) [Evaluation Method: Polyurethane]

(23) <Measurement of Isocyanate Group Concentration>

(24) After diluting 20 mL of a di-n-butylamine/toluene (weight ratio: 2/25) mixed solution with 90 mL of acetone, the resulting solution was titrated with an aqueous 0.5 N hydrochloric acid solution, and the amount of the aqueous hydrochloric acid solution required for neutralization was measured and taken as a blank value. Subsequently, from 1 to 2 g of the reaction solution was extracted, 20 mL of a di-n-butylamine/toluene mixed solution was added thereto, followed by stirring at room temperature for 30 minutes, the resulting solution was diluted with 90 mL of acetone, similarly to the blank measurement, and titrated with an aqueous 0.5 N hydrochloric acid solution, the amount of the aqueous hydrochloric acid solution required for neutralization was measured, and the amount of the remaining amine was quantitatively determined. From the volume of the aqueous hydrochloric acid solution required for neutralization, the isocyanate group concentration was determined according to the following formula:
Isocyanate group concentration (wt %)=A*42.02/D A: the isocyanate group (mol) contained in the sample used for this measurement,
A=(B−C)×0.5/1,000×f B: amount (mL) of aqueous 0.5 N hydrochloric acid solution required in blank measurement, C: amount (mL) of aqueous 0.5 N hydrochloric acid solution required in this measurement, D: sample (g) used in this measurement, and f: titer of aqueous hydrochloric acid solution.
<Measurement of Solution Viscosity>

(25) A polyurethane was dissolved in dimethylformamide to obtain a solution (concentration: 30 wt %), and the solution viscosity of the resulting polyurethane solution was measured at 25° C. by means of VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) provided with a rotor of 3°×R14.

(26) <Measurement of Molecular Weight>

(27) As for the molecular weight of polyurethane, a dimethylacetamide solution was prepared to afford a polyurethane concentration of 0.14 wt %, and the number average molecular weight (Mn) and weight average molecular weight (Mw), in terms of standard polystyrene, were measured using a GPC apparatus [manufactured by Tosoh Corporation, product name: “HLC-8220” (column: TskgelGMH-XL×2)].

(28) <Evaluation Method of Oleic Acid Resistance>

(29) A polyurethane solution was coated on a fluororesin sheet (fluorine tape NITOFLON 900, produced by Nitto Denko Corp., thickness: 0.1 mm) by a 9.5-mil applicator, dried at 60° C. for 1 hour and subsequently at 100° C. for 0.5 hours, further dried at 100° C. for 0.5 hours in a vacuum state and at 80° C. for 15 hours, and then left standing still at a constant temperature and a constant humidity of 23° C. and 55% RH for 12 hours or more, and a specimen of 3 cm×3 cm was cut out from the obtained film, charged into a glass vial having a volume of 250 ml and containing 50 ml of a test solvent, and left standing still in a constant temperature bath at 80° C. in a nitrogen atmosphere for 1 week or 16 hours. After the test, the front and back of the specimen was lightly wiped with a paper wiper and by performing a weight measurement, the percentage of weight increase from before test was calculated. A weight change ratio closer to 0% indicates that the oleic acid resistance is better.

(30) <Evaluation Method of Ethanol Resistance of Polyurethane>

(31) A urethane film was prepared by the same method as described in <Evaluation Method of Oleic Acid Resistance> above, the urethane film was cut out into a specimen of 3 cm×3 cm. After measuring the weight of the specimen by a precision balance, the specimen was charged into a glass-made petri dish having an inner diameter of 10 cmϕ and containing 50 ml of a test solvent and immersed in the solvent at room temperature of about 23° C. for 1 hour. After the test, the specimen was taken out and lightly wiped with a paper wiper and by performing a weight measurement, the percentage of weight increase from before test was calculated.

(32) <Measurement Method of Glass Transition Temperature (Tg)>

(33) About 5 mg of a polyurethane film piece prepared in the same manner as in the evaluation of oleic acid resistance was sealed in an aluminum pan, and an operation of raising and lowering the temperature from −100° C. to 250° C., from 250° C. to −100° C., and from −100° C. to 250° C., at a rate of 10° C./min, was performed in a nitrogen atmosphere by using EXSTAR DSC6200 (manufactured by Seiko Instrument, Inc.). The inflection point at the time of second temperature rise was taken as the glass transition temperature (Tg).

(34) <Room-Temperature Tensile Test Method>

(35) In conformity with JIS K6301 (2010), a polyurethane specimen in a strip shape having a width of 10 mm, a length of 100 mm and a thickness of about 50 μm was subjected to a tensile test by using a tensile tester [manufactured by Orientec, Co. Ltd., product name: “Tensilon UTM-III-100”] under the conditions of a chuck-to-chuck distance of 50 mm, a tensile speed of 500 mm/min and a temperature of 23° C. (relative humidity: 55%), and the stress when the specimen was elongated by 100% was measured. The Young's modulus was defined as a gradient of the stress value at the initial elongation, and specifically, a stress value at an elongation of 1% was employed.

(36) <Low-Temperature Tensile Test Method>

(37) In conformity with JIS K6301 (2010), a polyurethane specimen in a strip shape having a width of 10 mm, a length of 100 mm and a thickness of about 50 μm was tested by using a tensile tester [manufactured by Shimadzu Corporation, product name: “Autograph AG-X 5 kN”]. More specifically, the film was placed with a chuck-to-chuck distance of 50 mm in a constant temperature bath [manufactured by Shimadzu Corporation, product name: “THERMOSTATIC CHAMBER TCR2W-200T”] set to −10° C., then left standing still at −10° C. for 3 minutes, and subsequently subjected to a tensile test at a tensile speed of 500 mm/min. The stress when the specimen was elongated by 100% was measured. The Young's modulus was defined as a gradient of the stress value at the initial elongation, and specifically, a stress value at an elongation of 1% was employed.

(38) <Low-Temperature Cycle Test Method of Polyurethane>

(39) In conformity with JIS K6301 (2010), a polyurethane specimen in a strip shape having a width of 10 mm, a length of 100 mm and a thickness of about 90 μm was tested by using a tensile tester [manufactured by Shimadzu Corporation, product name: “Autograph AG-X 5 kN”. Load Cell 100N]. More specifically, the film was placed with a chuck-to-chuck distance of 50 mm in a constant temperature bath [manufactured by Shimadzu Corporation, product name: “THERMOSTATIC CHAMBER TCR2W-200T”] set to −10° C. and left standing still at −10° C. for 3 minutes, and subsequently, an operation of stretching the film to 300% at a tensile speed of 500 mm/min and then contracting it to the original length at the same speed, was repeated twice. The ratio of the stress at 250% elongation at the time of first contraction to the stress at 250% elongation at the time of first stretching (hereinafter, sometimes referred to as “ratio 1”) was determined. In addition, the stress at 250% elongation at the time of second stretching relative to the stress at 250% elongation at the time of first stretching (hereinafter, sometimes referred to as “ratio 2”) was determined.

(40) <Evaluation of Heat Resistance>

(41) A polyurethane film prepared in the same manner as in the evaluation of oleic acid resistance was formed into a strip shape having a width of 100 mm, a length of 100 mm and a thickness of approximately 50 μm and heated in a gear oven at a temperature of 120° C. for 400 hours, and the weight average molecular weight (Mw) of the sample after heating was measured by the method described in <Measurement of Molecular Weight>.

(42) <Raw Material Used>

(43) The raw materials used for the production of polycarbonate diol in this Example are as follows.

(44) 1,4-Butanediol (hereinafter, sometimes simply referred to as 1,4BD): produced by Mitsubishi Chemical Corporation

(45) 1,5-Pentanediol (hereinafter, sometimes simply referred to as 1,5PD): produced by Tokyo Chemical Industry Co., Ltd.

(46) 1,3-Propanediol (hereinafter, sometimes simply referred to as 1,3PDO): produced by Wako Pure Chemical Industries, Ltd. or DuPont Kabushiki Kaisha

(47) 1,6-Hexanediol (hereinafter, sometimes simply referred to as 1,6HD): produced by BASF

(48) 1,10-Decanediol (hereinafter, sometimes simply referred to as 1,10DD): produced by Hokoku Corporation

(49) 1,9-Nonanediol (hereinafter, sometimes simply referred to as 1,9ND): produced by Tokyo Chemical Industry Co., Ltd.

(50) 1,12-Dodecanediol (hereinafter, sometimes simply referred to as 1,12DDD): produced by Wako Pure Chemical Industries, Ltd.

(51) 2-Methyl-1,3-propanediol (hereinafter, sometimes simply referred to as 2M1,3PDO): produced by Tokyo Chemical Industry Co., Ltd.

(52) 3-Methyl-1,5-pentanediol (hereinafter, sometimes simply referred to as 3M1,5PD): produced by Wako Pure Chemical Industries, Ltd.

(53) Diphenyl carbonate (hereinafter, sometimes simply referred to as DPC): produced by Mitsubishi Chemical Corporation

(54) Ethylene carbonate (hereinafter, sometimes simply referred to as EC): produced by Mitsubishi Chemical Corporation

(55) Magnesium acetate tetrahydrate: produced by Wako Pure Chemical Industries, Ltd.

(56) Lead(II) acetate trihydrate: produced by Wako Pure Chemical Industries, Ltd.

(57) Lead(IV) acetate: produced by Nacalai Tesque, Inc.

Example 1-1

(58) <Production and Evaluation of Polycarbonate Diol>

(59) Into a 5-L glass separable flask equipped with a stirrer, a distillation trap and a pressure adjusting device, 1,4-butanediol (1,4BD): 768.5 g, 1,10-decanediol (1,10DD): 768.5 g, diphenyl carbonate: 2,563.0 g, and an aqueous magnesium acetate tetrahydrate solution: 6.6 mL (concentration: 8.4 g/L, magnesium acetate tetrahydrate: 55 mg) were charged as raw materials. After purging with nitrogen gas, the contents were heated and dissolved under stirring by raising the internal temperature to 160° C. Thereafter, the pressure was reduced to 24 kPa over 2 minutes, and the reaction was allowed to proceed for 90 minutes while removing phenol outside the system. The reaction was continued by reducing the pressure to 9.3 kPa over 90 minutes and further to 0.7 kPa over 30 minutes, and then, the reaction was allowed to proceed for 60 minutes by raising the temperature to 170° C. while removing phenol and unreacted dihydroxy compounds outside the system, whereby a polycarbonate diol-containing composition was obtained.

(60) The polycarbonate diol-containing composition obtained was fed to a thin-film distillation apparatus at a flow rate of 20 g/min, and thin-film distillation (temperature: from 180 to 190° C., pressure: from 40 to 67 Pa) was performed. As the thin-film distillation apparatus, Molecular Distillation Apparatus Model MS-300, manufactured by Sibata Scientific Technology Ltd., equipped with an internal condenser having a diameter of 50 mm, a height of 200 mm and an area of 0.0314 m.sup.2 and a jacket, was used. The same applies also to the following Examples and Comparative Examples.

(61) The properties of the polycarbonate diol obtained by thin-film distillation and the evaluation results of physical properties are shown in Table 1.

(62) <Production and Evaluation of Polyurethane>

(63) The specific polyurethane was produced by the following operation using the polycarbonate diol obtained by the method above.

(64) (Prepolymer (PP) Forming Reaction)

(65) Into a separable flask provided with a thermocouple and a cooling tube, 90.57 g of the above-described polycarbonate diol previously heated to 80° C. was charged. After immersing the flask in an oil bath at 60° C., 22.69 g of 4,4′-dicyclohexylmethane diisocyanate (hereinafter H12MDI, produced by Tokyo Chemical Industry Co., Ltd. and 0.332 g of triisooctyl phosphite (hereinafter TiOP, produced by Tokyo Chemical Industry Co., Ltd.) as a reaction retarder were added, and the temperature was raised to 80° C. over about 1 hour while stirring the contents in the flask at 60 rpm in a nitrogen atmosphere. After raising the temperature to 80° C., 9.3 mg (81.9 wt ppm relative to the total weight of polycarbonate diol and isocyanate) of NEOSTANN U-830 (hereinafter referred to as U-830, produced by Nitto Kasei Co., Ltd.) was added, and when heat generation was settled, the temperature of the oil bath was raised to 100° C., followed by stirring for about another 2 hours. The concentration of the isocyanate group was analyzed, and it was confirmed that the theoretical amount of isocyanate group was consumed.

(66) (Chain Extension Reaction)

(67) After diluting 106.62 g of the obtained prepolymer (PP) with 11.46 g of dehydrated toluene (produced by Wako Pure Chemical Industries, Ltd.), 237.36 g of dehydrated N,N-dimethylformamide (hereinafter DMF, produced by Wako Pure Chemical Industries, Ltd.) was added. The flask was immersed in an oil bath at 55° C., and the prepolymer was dissolved under stirring at about 200 rpm. The concentration of the isocyanate group in the prepolymer solution was analyzed. Thereafter, the flask was immersed in an oil bath set to 35° C., and 6.06 g of isophoronediamine (hereinafter IPDA, produced by Tokyo Chemical Industry Co., Ltd.), which is the necessary amount calculated from the remaining isocyanate, was added in parts under stirring at 150 rpm, After stirring for about 1 hour, 0.623 g of morpholine (produced by Tokyo Chemical Industry Co., Ltd.) as a terminal stopper was added, and the system was further stirred for 1 hour to obtain a polyurethane solution having a viscosity of 125 Pa*s and a weight average molecular weight of 151,000. The properties of this polyurethane and the evaluation results of physical properties are shown in Table 3.

Examples 1-2 to 1-13

(68) <Production and Evaluation of Polycarbonate Diol>

(69) Polycarbonate diol-containing compositions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polycarbonate diol of Example 1-1 except that the kind and charged amount of the PCD polymerization raw material were changed to the kind and charged amount of raw material shown in Table 1.

(70) Each of the obtained polycarbonate diol-containing compositions was subjected to thin-film distillation by the same method as in Example 1-1. The properties of polycarbonate diol obtained by thin-film distillation and the evaluation results of physical properties are shown in Table 1.

(71) <Production and Evaluation of Polyurethane>

(72) Polyurethane solutions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polyurethane of Example 1-1 except that the kind of polycarbonate diol (PCD) used and the amount of each raw material charged were changed to PCD and charged amount shown in Table 3. The properties of the polyurethane obtained and the evaluation results of physical properties are shown in Table 3.

Comparative Examples 1-1 and 1-5

(73) <Production and Evaluation of Polycarbonate Diol>

(74) Polycarbonate diol-containing compositions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polycarbonate diol of Example 1-1 except that the kind and charged amount of the PCD polymerization raw material were changed to the kind and charged amount of raw material shown in Table 2.

(75) Each of the obtained polycarbonate diol-containing compositions was subjected to thin-film distillation by the same method as in Example 1-1.

(76) The properties of polycarbonate diol obtained by thin-film distillation and the evaluation results of physical properties are shown in Table 2.

(77) <Production and Evaluation of Polyurethane>

(78) Polyurethane solutions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polyurethane of Example 1-1 except that the amounts of polycarbonate diol (PCD) used and each raw material charged were changed to the charged amounts shown in Table 3. The properties of the polyurethane obtained and the evaluation results of physical properties are shown in Table 3.

Comparative Examples 1-2 to 1-4 and 1-6

(79) <Evaluation of Polycarbonate Diol>

(80) Polycarbonate diols shown below were used, respectively. The properties of each polycarbonate diol and the evaluation results of physical properties are shown in Table 2.

Comparative Example 1-2

(81) Polycarbonate diol produced using 1,6HD as a raw material (“Duranol (registered trademark)” produced by Asahi Kasei Chemicals Corporation, grade: T-6002)

Comparative Example 1-3

(82) Polycarbonate diol produced using 1,4BD and 1,6HD as raw materials (“Duranol (registered trademark)” produced by Asahi Kasei Chemicals Corporation, grade: T-4672)

Comparative Example 1-4

(83) Polycarbonate diol produced using 1,5PD and 1,6HD as raw materials (“Duranol (registered trademark)” produced by Asahi Kasei Chemicals Corporation, grade: T-5652)

Comparative Example 1-6

(84) Polycarbonate diol using 1,9ND and 2M1,8OD as raw materials (trade name: Kuraray Polyol C-2065N, produced by Kuraray Co., Ltd.)

(85) <Production and Evaluation of Polyurethane>

(86) Polyurethane production was performed using the polycarbonate diol above as PCD that is a production raw material of polyurethane.

(87) Polyurethane solutions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polyurethane of Example 1-1 except that the polycarbonate diol used as a raw material and the amount of raw material charged were changed to the kind and respective charged amounts of raw materials shown in Table 3. The properties of the polyurethane obtained and the evaluation results of physical properties are shown in Table 3.

Comparative Example 1-71

(88) <Production and Evaluation of Polycarbonate Diol>

(89) A polycarbonate diol-containing composition was obtained by performing the reaction by using entirely the same method as in the production of polycarbonate diol of Example 1-1 except that the raw material and the charged amount of raw material were changed to the raw material (1,6H1-D and 3M1,5PD) and the charged amount of raw material shown in Table 2.

(90) The polycarbonate diol-containing composition obtained was subjected to thin-film distillation by the same method as in Example 1-1.

(91) The properties of polycarbonate diol obtained by thin-film distillation and the evaluation results of physical properties are shown in Table 2.

(92) <Production and Evaluation of Polyurethane>

(93) The polycarbonate diol obtained by the method above and the polycarbonate diol (trade name: Kuraray Polyol C-2065N, produced by Kuraray Co., Ltd.) used in Comparative Example 1-6 were mixed in a ratio of 75:25 by weight and used as a raw material (PCD) for the production of a polyurethane.

(94) A polyurethane solution was obtained by performing the reaction by using entirely the same conditions and method as in the production of polyurethane of Example 1-1 except that the raw material (PCD) obtained by the mixing above was used and the amount of raw material charged was changed to the charged amount shown in Table 3. The properties of the polyurethane obtained and the evaluation results of physical properties are shown in Table 3.

(95) In “Stress at −10° C..Math.100% Elongation” of Table 3, the value of Examples is small as compared with that of Comparative Examples, revealing good flexibility at low temperatures. In addition, since the values in “80° C. Oleic Acid Resistance, Weight Change Ratio” and “Room Temperature Ethanol Resistance, Weight Change Ratio” are small, it is understood that the chemical resistance is good. Furthermore, since the value in “Change Ratio of Polystyrene-Reduced Weight Average Molecular Weight After Heat Resistance Test” is small, it is understood that the heat resistance is good, and Examples reveal that these physical properties are good. Accordingly, compared with the conventional polycarbonate diol, the polycarbonate diol of the present invention is proved to be a polycarbonate diol as a raw material of a polyurethane excellent in the physical property balance among chemical resistance, low-temperature characteristics and heat resistance.

Examples 2-1 to 2-6

(96) <Production and Evaluation of Polycarbonate Diol>

(97) Polycarbonate diol-containing compositions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polycarbonate diol of Example 1-1 except that the kind and charged amount of the PCD polymerization raw material were changed to the kind and charged amount of raw material shown in Table 4.

(98) Each of the obtained polycarbonate diol-containing compositions was subjected to thin-film distillation by the same method as in Example 1-1. The properties of polycarbonate diol obtained by thin-film distillation and the evaluation results of physical properties are shown in Table 4.

(99) <Production and Evaluation of Polyurethane>

(100) Polyurethane solutions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polyurethane of Example 1-1 except that the kind of polycarbonate diol (PCD) used and the amount of each raw material charged were changed to the kind and the charged amount shown in Table 6. The properties of the polyurethane obtained and the physical properties are shown in Table 6.

Comparative Examples 2-1 and 2-2

(101) <Production and Evaluation of polycarbonate Diol>

(102) Polycarbonate diol-containing compositions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polycarbonate diol of Example 1-1 except that the kind and charged amount of the PCD polymerization raw material were changed to the raw material and the charged amount of raw material shown in Table 5.

(103) Each of the obtained polycarbonate diol-containing compositions was subjected to thin-film distillation by the same method as in Example 1-1.

(104) The properties of polycarbonate diol obtained by thin-film distillation and the evaluation results of physical properties are shown in Table 5.

(105) <Production and Evaluation of Polyurethane>

(106) Polyurethane solutions were obtained by performing the reaction by using entirely the same conditions and method as in the production of polyurethane of Example 1-1 except that the amounts of polycarbonate diol (PCD) used and each raw material charged were changed to the charged amounts shown in Table 6. The properties of the polyurethane obtained and the evaluation results of physical properties are shown in Table 6.

(107) In “Stress at −10° C..Math.100% Elongation” of Table 6, the value of Examples is small as compared with that of Comparative Examples, revealing good flexibility at low temperatures. In addition, since the values in “80° C. Oleic Acid Resistance, Weight Change Ratio” and “Room Temperature Ethanol Resistance, Weight Change Ratio” are small, it is understood that the chemical resistance is good. Furthermore, it is seen from “Ratio 1, Ratio 2” that the low-temperature characteristics are good. Accordingly, compared with the conventional polycarbonate diol, the polycarbonate diol of the present invention is proved to be a polycarbonate diol as a raw material of a polyurethane excellent in the physical property balance between chemical resistance and low-temperature characteristics.

(108) Abbreviations in Tables 1 and 2 and Tables 4 and 5 have the following meanings.

(109) 1,4BD: 1,4-Butanediol

(110) 1,5PD: 1,5-Pentanediol

(111) 1,3PDO: 1,3-Propanediol

(112) 1,6HD: 1,6-Hexanediol

(113) 1,10DD: 1,10-Decanediol

(114) 1,9ND: 1,9-Nonanediol

(115) 1,12DDD: 1,12-Dodecanediol

(116) 2M1,3PDO: 2-Methyl-1,3-propanediol

(117) 2M1,8OD: 2-Methyl-1,8-octanediol

(118) 3M1,5PD: 3-Methyl-1,5-pentanediol

(119) DPC: Diphenyl carbonate

(120) TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 Charged amount 1,4BD [g] 768.5 879.5 993.8 1120.2 1211.9 1272.8 975.8 of PCD 1,5PD [g] — — — — — — — polymerization 1,3PDO [g] — — — — — — — raw material 1,6HD [g] — — — −0 — — — 1,10DD [g] 768.5 597.6 421.9 277.4 133.8 40.0 414.2 1,9ND [g] — — — — — — — 1,12DDD [g] — — — — — — — 2M1,3PDO [g] — — — — — — — 3M1,5PD [g] — — — — — — — DPC [g] 2563.0 2622.8 2684.4 2802.5 2854.4 2887.2 2709.9 Aqueous catalyst 6.6 6.7 6.9 7.2 7.3 7.3 6.7 solution [mL] Outer appearance white white white white white white white solid solid solid solid solid solid solid Structural Compound of 1,4BD 1,4BD 1,4BD 1,4BD 1,4BD 1,4BD 1,4BD unit (kind) formula (A) Compound of 1,10DD 1,10DD 1,10DD 1,10DD 1,10DD 1,10DD 1,10DD formula (B) Ratio (A:B) of structural unit derived from 64:36 71:29 80:20 88:12 94.6 98:2 80:20 compound of formula (A) and structural unit derived from compound of formula (B) [molar ratio] Average carbon number of dihydroxy 6.2 5.7 5.2 4.7 4.4 4.1 5.1 compound after hydrolysis Hydroxyl value [mg-KOH/g] 53.1 51 52.1 51.5 52 55.3 37.4 Phenoxy group terminal not not not not not not not detected detected detected detected detected detected detected APHA 30 30 30 40 30 30 30 Melt viscosity [mPa .Math. s] 1960 2250 2590 2920 3550 3980 7670 DSC Glass transition not −48 −47 −47 −45 −42 −46 temperature [° C.] detected Melting peak 26 32 37 46 54 59 39 temperature [° C.] Melting heat 23.4 13.8 7.32 4.13 3.6 2.5 2.08 quantity [J/g] Molecular weight Mn 3446 3395 3341 3303 3275 3243 4863 and molecular Mw 7192 7029 6539 7226 7003 6740 9780 weight Mw/Mn 2.09 2.07 1.96 2.19 2.14 2.08 2.01 distribution Example Example Example Example Example Example 1-8 1-9 1-10 1-11 1-12 1-13 Charged amount 1,4BD [g] 1057.7 1028.1 984.9 — — — of PCD 1,5PD [g] — — — — — 1305.7 polymerization 1,3PDO [g] — — — 756.0 558.5 — raw material 1,6HD [g] — — — — — — 1,10DD [g] — — — 608.4 548.2 115.0 1,9ND [g] 385.2 — — — — — 1,12DDD [g] — 375.7 390.2 — — — 2M1,3PDO [g] — — — — — — 3M1,5PD [g] — — — — — — DPC [g] 2757.1 2596.2 2624.8 2635.6 2143.3 2579.3 Aqueous catalyst 7.2 6.8 6.6 6.9 5.4 6.7 solution [mL] Outer appearance white white white transparent transparent white solid solid solid viscous viscous solid liquid liquid Structural Compound of 1,4BD 1,4BD 1,4BD 1,3PDO 1,3PDO 1,5 PD unit (kind) formula (A) Compound of 1,9ND 1,12DDD 1,12DDD 1,10DD 1,10DD 1,10DD formula (B) Ratio (A:B) of structural unit derived from 82:18 84:16 84:16 72:28 67:33 94:6 compound of formula (A) and structural unit derived from compound of formula (B) [molar ratio] Average carbon number of dihydroxy 4.9 5.3 5.3 5.0 5.3 5.2 compound after hydrolysis Hydroxyl value [mg-KOH/g] 52.7 53 37 54.5 37.1 53.7 Phenoxy group terminal not not not not not not detected detected detected detected detected detected APHA 30 30 30 30 30 30 Melt viscosity [mPa .Math. s] 2250 2650 7520 2660 6800 2290 DSC Glass transition −45 −48 −49 −46 −46 −50 temperature [° C.] Melting peak not 42 41 not not not temperature [° C.] detected detected detected detected Melting heat not 35.8 42.3 not not not quantity [J/g] detected detected detected detected Molecular weight Mn 3500 3495 4814 3354 5161 2999 and molecular Mw 6826 6728 10168 6860 10715 6251 weight Mw/Mn 1.95 1.93 2.11 2.05 2.08 2.08 distribution

(121) TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Comparative Example Example Example Example 1-1 1-2 1-3 1-4 Charged amount 1,4BD [g] 1234.3 of PCD 1,5PD [g] — polymerization 1,3PDO [g] — raw material 1,6HD [g] — 1,10DD [g] — 1,9ND [g] — 1,12DDD [g] — 2M1,3PDO [g] — 3M1,5PD [g] — DPC [g] 2765.7 Aqueous catalyst 7.0 solution [mL] Outer appearance white solid white solid transparent transparent viscous viscous liquid liquid Structural Diol (1) 1,4BD 1,6HD 1,4BD 1,5PD unit (kind) Diol (2) — — 1,6HD 1,6HD Ratio ((1):(2)) of structural units in — — 70:30 50:50 PCD when using two kinds of diols as PCD polymerization raw material Average carbon number of dihydroxy 4 6 4.6 5.5 compound after hydrolysis [molar ratio] Hydroxyl value [mg-KOH/g] 52.1 56.1 55 56.4 Phenoxy group terminal not detected not detected not detected not detected APHA 50 — — — Melt viscosity [mPa .Math. s] 4160 1800 3760 2050 DSC Glass transition −44 −57 −50.0 −54 temperature [° C.] Melting peak 62 47 not detected not detected temperature [° C.] Melting heat 39.2 45 not detected not detected quantity [J/g] Molecular weight Mn 3195 3310 3521 3339 and molecular Mw 6319 7185 7108 7416 weight Mw/Mn 1.98 2.17 2.02 2.22 distribution Comparative Comparative Comparative Example Example Example 1-5 1-6 1-7 Charged amount 1,4BD [g] — — of PCD 1,5PD [g] — — polymerization 1,3PDO [g] — — raw material 1,6HD [g] 860.8 657.6 1,10DD [g] 358.1 — 1,9ND [g] — — 1,12DDD [g] — — 2M1,3PDO [g] — — 3M1,5PD [g] — 657.6 DPC [g] 1781.1 2184.9 Aqueous catalyst 4.8 5.7 solution [mL] Outer appearance white solid transparent transparent transparent viscous viscous viscous liquid liquid liquid Structural Diol (1) 1,6HD 1,9ND 1,6HD 1,9ND unit (kind) Diol (2) 1,10DD 2M1,8OD 3M1,5PD 2M1,8OD Ratio ((1):(2)) of structural units in 77:28 65:35 50:50 65:35 PCD when using two kinds of diols as PCD polymerization raw material Average carbon number of dihydroxy 6.8 9 6 9 compound after hydrolysis [molar ratio] Hydroxyl value [mg-KOH/g] 57.1 57.1 55.6 57.1 Phenoxy group terminal not detected not detected not detected not detected APHA 40 — 30 — Melt viscosity [mPa .Math. s] 1250 1270 1850 1270 DSC Glass transition −56 −56 −50 −56 temperature [° C.] Melting peak 20 24 not detected 24 temperature [° C.] Melting heat 46 37 not detected 37 quantity [J/g] Molecular weight Mn 3254 3459 3250 3459 and molecular Mw 6460 7064 6686 7064 weight Mw/Mn 1.99 2.04 2.06 2.04 distribution

(122) TABLE-US-00003 TABLE 3 Example Example Example Example Example Example Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 PP PCD [g] 90.57 91.0 82.11 90.3 90.55 91.00 90 Forming H12MDI [g] 22.69 21.9 20.4 22.06 22.33 22.60 16.5 reaction TiOP [g] 0.332 0.335 0.392 0.338 0.335 0.338 0.320 U-830 [mg] 9.3 7.2 9.1 9.3 6.7 7.3 5.0 Chain PP [g] 106.62 109.00 94.53 103.59 105.97 108.50 103.59 extension IPDA [g] 6.06 5.74 5.53 5.80 5.82 5.86 4.77 reaction Toluene [g] 11.46 11.46 10.35 10.78 11.22 10.82 9.62 DMF [g] 237.36 234.90 213.00 230.93 235.46 233.75 231.86 Morpholine [g] 0.623 0.550 0.466 0.561 0.671 0.630 0.597 Polyurethane Melt viscosity 142 130 125 122 146 135 181 solution [Pa .Math. s/25° C.] Polystyrene-reduced 146000 149000 151000 153000 163000 152000 134000 weight average molecular weight Physical Glass transition −39 −38 −36 −34 −31 −30 −40 properties, temperature [° C.] etc. of Stress at 23° C. .Math. 100% 5.4 5.5 5.3 6.0 5.8 6.0 3.1 polyurethane elongation [MPa] Stress at −10° C. .Math. 100% 9.4 8.6 9.5 8.7 12.1 12.6 4.6 elongation [MPa] 80° C. Oleic acid 80 49 34 36 31 28 35 resistance, weight change ratio [%] Room temperature 22 21 20 18 18 18 16 ethanol resistance, weight change ratio [%] Change ratio of 66 — 45 — 24 — — polystyrene-reduced weight average molecular weight after heat resistance test [%] Example Example Example Example Example Example 1-8 1-9 1-10 1-11 1-12 1-13 PP PCD [g] 74.9 74.82 90.11 77.05 90.75 75 Forming H12MDI [g] 18.65 18.82 15.73 19.92 15.97 19.06 reaction TiOP [g] 0.279 0.285 0.317 0.291 0.321 0.280 U-830 [mg] 8.3 12.5 7.1 5.8 8.8 4.7 Chain PP [g] 86.25 93.64 96.86 91.62 99.34 91.29 extension IPDA [g] 4.86 5.11 4.08 5.09 4.22 5.41 reaction Toluene [g] 9.27 0.00 10.32 10.17 10.30 0.00 DMF [g] 191.91 211.59 215.68 203.61 221.52 213.01 Morpholine [g] 0.516 0.461 0.393 0.496 0.454 0.395 Polyurethane Melt viscosity 162 148 185 209 220 160 solution [Pa .Math. s/25° C.] Polystyrene-reduced 153000 163000 173000 171000 182000 171000 weight average molecular weight Physical Glass transition −34 −36 −38 −37 −40 −34 properties, temperature [° C.] etc. of Stress at 23° C. .Math. 100% 5.4 5.7 3.4 6.0 3.6 5.5 polyurethane elongation [MPa] Stress at −10° C. .Math. 100% 11.7 11.4 4.4 12.3 5.0 11.3 elongation [MPa] 80° C. Oleic acid 49 54 37 42 41 41 resistance, weight change ratio [%] Room temperature 19 21 17 21 21 22 ethanol resistance, weight change ratio [%] Change ratio of — 24 — 17 — 85 polystyrene-reduced weight average molecular weight after heat resistance test [%] Comparative Comparative Comparative Comparative Comparative Comparative Comparative Example Example Example Example Example Example Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 PP PCD [g] 94.02 94.07 90.01 90.47 75 75 91.1 Forming H12MDI [g] 23.28 25.77 23.3 24.39 20.33 20.48 24.14 reaction TiOP [g] 0.380 0.363 0.342 0.352 0.286 0.272 0.362 U-830 [mg] 12.4 5.5 4.7 5.6 4.7 7.3 7.8 Chain PP [g] 109.14 109.60 100.78 109.10 92.58 92.79 108.12 extension IPDA [g] 6.28 6.91 6.09 6.65 5.42 5.89 6.53 reaction Toluene [g] 12.04 12.38 10.24 12.07 0.00 0.00 11.87 DMF [g] 242.75 243.01 224.58 242.49 216.03 216.51 240.58 Morpholine [g] 0.402 0.757 0.785 0.889 0.500 0.620 0.600 Polyurethane Melt viscosity 189 203 162 130 144 171 152 solution [Pa .Math. s/25° C.] Polystyrene-reduced 168000 142000 138000 144000 140000 146000 164000 weight average molecular weight Physical Glass transition −28 −41 −34 −40 −45 −48 −40 properties, temperature [° C.] etc. of Stress at 23° C. .Math. 100% 6.2 6.1 7.1 6.5 6.1 5.5 6.2 polyurethane elongation [MPa] Stress at −10° C. .Math. 100% 13.4 14.4 13 12.6 11.2 10.8 11.7 elongation [MPa] 80° C. Oleic acid 26 61 32 63 unmeasurable unmeasurable unmeasurable resistance, weight change ratio [%] Room temperature 18 26 20 24 25 26 24 ethanol resistance, weight change ratio [%] Change ratio of 30 55 129 — — — 45 polystyrene-reduced weight average molecular weight after heat resistance test [%]

(123) TABLE-US-00004 TABLE 4 Example Example Example Example Example Example 2-1 2-2 2-3 2-4 2-5 2-6 Charged amount 1,4BD [g] 975.8 984.9 — 1311.2 1214.3 611.3 of PCD 1,5PD [gl — — — — — — polymerization 1,3PDO [g] — — 558.5 — — — raw material 1,6HD [g] — — — — — — 1,10DD [g] 414.2 — 548.2 — — — 1,9ND [g] — — — — — — 1,12DDD [g] — 390.2 — — — — 2M1,3PDO [g] — — — — — 611.3 3M1,5PD [g] — — — — — — DPC [g] 2709.9 2624.8 2143.3 2988.8 2785.7 2777.5 Aqueous catalyst 6.7 6.6 5.4 7.4 6.9 6.9 solution [mL] Outer appearance white white transparent white white white solid solid viscous solid solid solid liquid Structural Diol (1) 1,4BD 1,4BD 1,3PDO 1,4BD 1,4BD 1,4BD/ unit (kind) 2M1,3PDO Diol (2) 1,10DD 1,12DDD 1,10DD — — — Ratio ((1):(2)) of structural units in PCD 80:20 84:16 67:33 — — (50:50) when using two kinds of diols as PCD polymerization raw material [molar ratio] Average carbon number of dihydroxy 5.1 5.3 5.3 4.0 4.0 4.0 compound after hydrolysis Hydroxyl value [mg-KOH/g] 37.4 37 37.1 37.1 30.4 35.9 Phenoxy group terminal not not not not not not detected detected detected detected detected detected APHA 30 30 30 30 30 30 Melt viscosity [mPa .Math. s] 7670 7520 6800 13200 23900 18200 DSC Glass transition −46 −49 −46 −42 −40 −31 temperature [° C.] Melting peak 39 41 not 62 64 not temperature [° C.] detected detected Melting heat 2.08 42.3 not 77 68.9 not quantity [J/g] detected detected Molecular weight Mn 4863 4814 5161 4015 5510 4293 and molecular Mw 9780 10168 10715 8841 11536 8694 weight Mw/Mn 2.01 2.11 2.08 2.20 2.09 2.03 distribution

(124) TABLE-US-00005 TABLE 5 Comparative Comparative Example Example 2-1 2-2 Charged amount 1,4BD [g] 1234.3 — of PCD 1,5PD [g] — — polymerization 1,3PDO [g] — — raw material 1,6HD [g] — 1197.8 1,10DD [g] — — 1,9ND [g] — — 1,12DDD [g] — — 2M1,3PDO [g] — — 3M1,5PD [g] — — DPC [g] 2765.7 2052.2 Aqueous catalyst 7.0 5.2 solution[mL] Outer appearance white solid white solid Structural unit (kind) 1,4BD 1,6HD Average carbon number of dihydroxy 4 6 compound after hydrolysis Hydroxyl value [mg-KOH/g] 52.1 37.6 Phenoxy group terminal not detected not detected APHA 50 30 Melt viscosity [mPa .Math. s] 4160 6400 DSC Glass transition −44 −51 temperature [° C.] Melting peak 62 53 temperature [° C.] Melting heat 39.2 40 quantity [J/g] Molecular weight Mn 3195 5004 and molecular Mw 6319 10881 weight Mw/Mn 1.98 2.17 distribution

(125) TABLE-US-00006 TABLE 6 Comparative Comparative Example Example Example Example Example Example Example Example 2-1 2-2 2-3 2-4 2-5 2-6 2-1 2-2 PP PCD [g] 90 90.11 90.75 114.06 93.25 92.7 94.02 91.24 Forming H12MDI [g] 16.5 15.73 15.97 20.21 13.3 15.81 23.28 16.22 reaction TiOP [g] 0.320 0.317 0.321 0.402 0.313 0.312 0.380 0.323 U-830 [mg] 5.0 7.1 8.8 13.7 7.6 9.5 12.4 5.5 Chain PP [g] 103.59 96.86 99.34 117.22 96.96 100.11 109.14 100.23 extension IPDA [g] 4.77 4.08 4.22 5.04 3.23 4.05 6.28 4.18 reaction Toluene [g] 9.62 10.32 10.30 12.17 10.62 10.69 12.04 10.70 DMF [g] 231.86 215.68 221.52 261.84 215.82 222.92 242.75 223.25 Morpholine [g] 0.597 0.393 0.454 0.343 0.401 0.355 0.402 0.480 Poly- Melt viscosity 181 185 220 204 191 111 189 145 urethane [Pa .Math. s/25° C.] solution Polystyrene-reduced 134000 173000 182000 184000 190000 199000 168000 153000 weight average molecular weight Physical Glass transition −40 −38 −40 −31 −32 −24 −28 −42 properties, temperature [° C.] etc. of Stress 3.1 3.4 3.6 3.9 3.3 3.9 6.2 3.2 poly- at 23° C. .Math. 100% urethane elongation [MPa] Stress 4.6 4.4 5.0 6.4 4.1 12.3 13.4 5.8 at −10° C. .Math. 100% elongation [MPa] 80° C. Oleic acid 35 37 41 21 17 24 26 80 resistance, weight change ratio [%] Room temperature 16 17 21 14 14 17 18 20 ethanol resistance, weight change ratio [%] Ratio 1 — — — 0.13 — — 0.06 — Ratio 2 — — — 0.61 — — 0.49 —

(126) While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. This application is based on (Patent Application No. 2012-283163) filed on Dec. 26, 2012, Japanese Patent Application (Patent Application No. 2013-29212) filed on Feb. 18, 2013, Japanese Patent Application (Patent Application No. 2013-29213) filed on Feb. 18, 2013, Japanese Patent Application (Patent Application No. 2013-30250) filed on Feb. 19, 2013, Japanese Patent Application (Patent Application No. 2013-30251) filed on Feb. 19, 2013, Japanese Patent Application (Patent Application No. 2013-30252) filed on Feb. 19, 2013, Japanese Patent Application (Patent Application No. 2013-89345) filed on Apr. 22, 2013, and Japanese Patent Application (Patent Application No. 2013-89346) filed on Apr. 22, 2013, the contents of which are incorporated herein by way of reference.