JP2003147057A - Polycarbonate diol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate diol capable of imparting mechanical strength such as good tensile strength to polyurethanes, prolonging durable period of polyurethanes and suitably usable for not only unexpandable elastomer, but also for polyurethane foam. SOLUTION: This polycarbonate diol has a structural unit represented by formula (I) (wherein n is an integer of 2-6) and a structural unit represented by formula (II) (wherein m is an integer of 2-4; x is an integer of 2-15). In the diol, the molar ratio of the structural unit represented by formula (I) to the structural unit represented by formula (II) is (2/8) to (9/1). The diol has hydroxy groups at both ends and has 400-3,000 number-average molecular weight. A polyurethane using the polycarbonate polyol as a raw material is also provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to polycarbonate diols and polyurethanes. More specifically, for example, a polyurethane foamed elastomer or a polyurethane foam that can be suitably used as a shock absorber, a sound absorber, a vibration absorber, a cushion material, etc. used in a seat, a bed, a toy, a shoe sole, an automobile, a bicycle with a motor, etc. And a polycarbonate diol used as a raw material therefor.

[0002]

Polyurethanes are manufactured by reacting an isocyanate component with a polyol composition.

The polyol, which is the main raw material in the polyol composition, is a compound that greatly affects the properties of polyurethane. Typical examples thereof include polyester polyols obtained by dehydration condensation of glycols such as ethylene glycol, diethylene glycol and 1,4-butanediol and dibasic acids such as adipic acid, propylene oxide and tetrahydrofuran. A polyether polyol obtained by ring-opening polymerization of alkylene oxide is used.

However, the polyurethane using the polyester polyol as a raw material has the following properties: tensile strength, tear strength,
Good abrasion resistance, but on the other hand, low water resistance,
It has a short service life because it is contacted with water and hydrolyzed by moisture in the atmosphere.

Polyurethanes using polyether polyol as a raw material have good water resistance, so that they have a long service life, but have a drawback that they are inferior in mechanical strength such as tensile strength.

Therefore, as a polyol having improved physical properties and water resistance, for example, polyhexa having a terminal hydroxyl group obtained by condensing 1,6-hexanediol and dimethyl carbonate during a demethanol reaction. Methylene polycarbonate (hereinafter simply referred to as "polyhexamethylene polycarbonate") is known.

However, since this polyhexamethylene polycarbonate has a high melting point and a high viscosity,
It is not suitable for injection molding (hereinafter simply referred to as "injection molding"), which is a general molding method adopted when manufacturing a foam. Therefore, the use of this polyhexamethylene polycarbonate is limited, and for example, synthetic leather or TPU obtained by a method of melting a polyol composition by heating or dissolving it in an appropriate solvent and then reacting it with an isocyanate compound. It is used for non-foaming elastomers such as (thermoset polyurethane) and adhesives.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides polyurethane with mechanical strength such as good tensile strength to prolong the service life of polyurethane and is suitable for use not only in non-foamed elastomers but also in polyurethane foams. It is an object of the present invention to provide a possible polycarbonate diol.

[0009]

The present invention provides a compound of formula (I):

[0010]

[Chemical 5]

(Wherein n represents an integer of 2 to 6) and a structural unit represented by the formula (II):

[0012]

[Chemical 6]

(Wherein, m is an integer of 2 to 4 and x is an integer of 2 to 15), and the structural unit is represented by the formula (I) / the formula (II) A polycarbonate diol having a molar ratio of structural units represented by the following formula (hereinafter referred to as "molar ratio M") of 2/8 to 9/1, having hydroxyl groups at both ends and having a number average molecular weight of 400 to 3000. And a polyurethane obtained by using the polycarbonate diol as a raw material.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate diol of the present invention is a polycarbonate diol which is liquid at room temperature and has a viscosity capable of injection molding and is excellent in so-called liquidity. Further, the polyurethane produced using the same exhibits suitable mechanical strength such as tensile strength and excellent water resistance.

Further, since the polycarbonate diol of the present invention contains an oxyalkylene unit, it has a higher degree of molecular freedom and a so-called liquidity, as compared with a general polycarbonate diol consisting of only alkylene units. .

The polycarbonate diol of the present invention has the formula
It has a structural unit represented by (I) and a structural unit represented by formula (II), and has hydroxyl groups at both ends thereof. formula
Both the structural unit represented by (I) and the structural unit represented by the formula (II) may be bonded randomly or in a block form.

In the formula (I), n is an integer of 2 to 6, but from the viewpoint of liquidity, 4 to 6 is preferable, and 6 is particularly preferable.

In the formula (II), m is an integer of 2 to 4, but from the viewpoint of liquidity, 2 to 3 is preferable, and 2 is particularly preferable. Further, x is an integer of 2 to 15, but 2 is preferable from the viewpoint of liquidity and physical properties of the urethane obtained.

The molar ratio M is 2/8 to 9/1, preferably 4/6 to 8 from the viewpoint of maintaining the liquidity at room temperature and reducing the volume change due to water when it becomes polyurethane.
/ 2, more preferably 4/6 to 6/4.

The number average molecular weight of the polycarbonate diol is preferably 400 or more, more preferably 500 or more, still more preferably 800 or more from the viewpoint of exhibiting elasticity as a soft segment, and preferably from the viewpoint of lowering the viscosity. Is 3000 or less, more preferably 2200 or less, still more preferably 1500 or less. From this viewpoint, the number average molecular weight of the polycarbonate diol is preferably 400
~ 3000, more preferably 500-2200, even more preferably 80
It is 0 to 1500.

The number average molecular weight of the polycarbonate diol is represented by the formula: [number average molecular weight] = [56108] ÷ [(hydroxyl value (mgKOH /
g)) + (acid value (mgKOH / g))] × 2 (wherein 56108 is mg per mol of potassium hydroxide)
It means the number) (the same applies below).

The viscosity of the polycarbonate diol is preferably 100 to 20,000 mPa · s, more preferably 200 to 10,000 mPa · s at a viscosity of 40 ° C. from the viewpoint that injection molding is possible and the fluidity of the injected liquid is secured. , 200 to 5,00
0 mPa · s is particularly preferable.

Examples of the method for producing the polycarbonate diol of the present invention include (A) a method in which alkylene glycol and oxyalkylene glycol are transesterified in the presence of a carbonate ester, and (B) oxyalkylene glycol and carbonate. Method for producing by adding alkylene glycol to carbonate diol obtained by reacting with ester and transesterifying, (C) oxyalkylene on polycarbonate diol obtained by reacting alkylene glycol and carbonate ester Examples thereof include a method of producing by adding glycol and transesterifying.

As the alkylene glycol, for example,
Examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-methylpentanediol, neopentyl glycol, etc. They can be used alone or in combination of two or more. Among these,
While reducing the viscosity of the polycarbonate diol,
From the viewpoint of imparting good mechanical strength to the polyurethane foam, 1,5-pentanediol and 1,6-hexanediol are preferable, and 1,6-hexanediol is particularly preferable.
When 1,6-hexanediol is used, the formula (I)
In, a polycarbonate diol in which n is 6 is obtained.

Examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polytetrahydrofuran, etc. These may be used alone or in admixture of two or more. Can be used. Of these, considering the reactivity with the isocyanate component, the terminal hydroxyl group is preferably primary, and from the viewpoint of imparting good mechanical strength when urethanized, a low molecular weight oxyalkylene Glycol is preferred and diethylene glycol is more preferred.

Examples of the carbonate ester include, for example,
Examples thereof include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like, and these can be used alone or in combination of two or more kinds.

The polycarbonate diol can be produced, for example, as follows when the method (A) is adopted.

First, alkylene glycol and oxyalkylene glycol are mixed.

Next, from the viewpoint of accelerating the reaction, a base such as sodium methoxide or triethylamine or a catalyst such as titanium tetraisopropoxide may be added to the obtained mixture. From the viewpoint of accelerating the reaction and facilitating the removal, the amount of the catalyst is preferably 0.0001 to 1 part by weight, more preferably 0.001 part by weight based on 100 parts by weight of the obtained mixture.
001 to 0.5 parts by weight.

Next, the temperature of this mixture is raised to 120 to 250 ° C. After the temperature is raised, the carbonate ester is gradually added to this mixture. The amount of carbonate ester is preferably adjusted appropriately according to the desired final molecular weight of the polycarbonate diol. Generally, the amount of carbonate ester is 0.5 parts by weight per 100 parts by weight of the mixture.
It is preferably about 4 parts by weight. Further, the rate of adding the carbonate ester is preferably 0.001 to 0.5 per 100 parts by weight of the mixture from the viewpoint of reducing the rate at which the carbonate ester is distilled out of the system in an unreacted state.
The amount is parts by weight / h, more preferably 0.01 to 0.2 parts by weight / h.

During the reaction, a carbonate ester and an alcohol or glycol based on the carbonate ester are distilled out, and these are distilled out of the system. Further, it is preferable that the catalyst and the like existing in the system after the addition of the carbonate ester is completed and before proceeding to the next step are removed by an adsorbent or the like.

Next, when the catalyst is subjected to adsorption treatment with an adsorbent, the resulting reaction mixture is filtered to separate the crude product by filtration. The crude product is heated to a temperature of 120 to 250 ° C., and alkylene glycol, oxyalkylene glycol and carbonate ester are distilled off under reduced pressure to obtain a polycarbonate diol having a desired hydroxyl value.

The hydroxyl value of the polycarbonate diol is
From the viewpoint of sufficiently lowering the viscosity and functioning as a soft segment, preferably 35 to 280 mgKOH / g, more preferably 50 to 225 mgKOH / g, and most preferably 75 to 140 m.
It is gKOH / g.

The polycarbonate diol thus obtained can be suitably used as a raw material for polyurethane such as non-foamed polyurethane elastomer and foamed polyurethane elastomer, as well as polyurethane foam.

For example, when using a polycarbonate diol as a raw material for a polyurethane foam to produce a polyurethane foam, such a polyurethane foam is
It can be produced by reacting a polycarbonate diol, a polyol composition containing a chain extender, a pigment, a foam stabilizer, a foaming agent, a urethanization catalyst, a stabilizer and the like as other optional components with an isocyanate component.

Typical examples of the isocyanate component include tolylene diisocyanate and isocyanate prepolymer.

The isocyanate prepolymer is obtained by reacting an isocyanate monomer and a polyol in the presence of an excess of the isocyanate monomer by stirring and reacting by a conventional method.

Specific examples of the isocyanate monomer include tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, 3,3'-Dimethyl-4,4'-biphenylene diisocyanate, 3,3'-Dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-Dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene Examples thereof include isocyanate compounds such as diisocyanate, and modified products thereof, such as carbodiimide modified products. These can be used alone or in combination of two or more.

Among the isocyanate monomers, 4,4'-
Diphenylmethane diisocyanate used alone or 4,4 '
The combined use of diphenylmethane diisocyanate and its carbodiimide modified product is preferable from the viewpoint of maintaining mechanical strength.

A polyurethane foam can be produced by mixing, stirring and foaming the polyol composition and the isocyanate component with a molding machine. More specifically, for example, after adjusting the temperature of each of the polyol composition and the isocyanate component to about 40 ° C. using a tank or the like, a foaming machine such as an automatic mixing injection type foaming machine or an automatic mixing injection type foaming machine. A polyurethane foam can be molded by reacting with.

The polyurethane represented by the polyurethane foam of the present invention is excellent in mechanical strength such as tensile strength as compared with polyurethane in which other polyol composition is used, and has a high strength retention rate even under wet heat conditions. And has a low impact resilience.

Therefore, this polyurethane can be suitably used for applications such as seats, beds and cushions.

[0043]

EXAMPLES [Synthesis of Polycarbonate Diol for Polyol Composition] Example 1 33.29 parts of 1,6-hexanediol (parts by weight, the same applies hereinafter) and diethylene glycol 33.29 under a nitrogen gas atmosphere.
Parts were placed in a reaction vessel and stirring was started.

In the reaction vessel, add 28 ml of sodium methoxide.
0.13 parts by weight of a methanol solution was added, and the temperature was raised to 160 ° C. After raising the temperature, 33.29 parts of dimethyl carbonate were added to 5.55 parts.
Drops were made at a ratio of parts / hour. After the completion of the dropping, the mixture was cooled to 80 ° C. when the distillation of dimethyl carbonate and methanol from the system stopped.

In order to remove the catalyst by adsorption, 8.32 parts of an adsorbent [Kyowa Chemical Industry Co., Ltd., trade name: Kyoward 600S] was added to the reaction vessel and stirred for 2 hours.

Next, the obtained mixture was filtered, the crude product was returned to the reaction vessel, and the temperature was raised to 240 ° C. After the temperature rise, the pressure inside the reaction vessel was reduced to 0.0013 MPa, and unreacted dimethyl carbonate, diethylene glycol, 1,6-hexanediol, etc. were distilled off so that the hydroxyl value of the polycarbonate diol produced was 112 ± 2. I left.

Thus, the polycarbonate diol A28.3
I got a part. The physical properties of the obtained Polycarbonate diol A include acid value, hydroxyl value, viscosity at various temperatures and 25
The properties at ° C were investigated. The results are shown in Table 1.

The acid value is JIS K 0070 and the hydroxyl value is J
IS K 0070, the viscosity was measured based on JIS Z 8803 [using a B type (Brookfield) viscometer].

Incidentally, in the measurement of the viscosity at 40 ° C., No. 3
Rotor speeds were adjusted to 30, 12, and 6 rpm for the isocyanate component, the polycarbonate polyol having a molecular weight of about 1000, and the polycarbonate polyol having a molecular weight of about 2000, respectively, using the rotor of No. When measuring the viscosity at 75 ° C, use the No. 3 rotor and rotate at 30 rpm.
It was adjusted to rpm and measured.

The properties at 25 ° C. were examined according to the following evaluation methods. [Properties at 25 ° C] Immediately after the production of the polycarbonate diol, one drop of the polycarbonate diol was dropped on the flat plate (which was kept at 25 ° C) and left at 25 ° C for 1 hour, then the flat plate was erected vertically. When liquid sagging was observed, it was evaluated as "liquid", and when liquid sagging was not observed, it was evaluated as "solid".

The ¹ H-NMR spectrum of the produced polycarbonate diol A is shown in FIG. From the results shown in FIG. 1, the polycarbonate diol A has n of 6 in the formula (I), m of 2 in the formula (II), x of 2, and a molar ratio M of 7/3. It was confirmed. The number average molecular weight of Polycarbonate diol A was determined to be 989.
Met.

¹ H-NMR was measured at room temperature using deuterated dimethyl sulfoxide (DMSO-d ₆ ) as a solvent (the same applies to the following Examples).

Example 2 Under a nitrogen gas atmosphere, 133.3 parts of diethylene glycol was placed in a reaction vessel and stirring was started. To this, 0.26 parts of a 28% by weight sodium methoxide solution in methanol was added.
The temperature was raised to 0 ° C. After heating, dimethyl carbonate 6
6.7 parts was dropped into the reaction vessel at a rate of 11.1 parts / hour.

After completion of the dropping, the mixture was cooled to 80 ° C. when the distillation of dimethyl carbonate and methanol from the system stopped.

In order to remove by-produced sodium by adsorption, an adsorbent [Kyowa Chemical Industry Co., Ltd.
Manufactured, trade name: KYOWARD 600S] 16.6 parts were added and stirred for 2 hours.

Next, the resulting mixture was filtered, the crude product was returned to the reaction vessel, and the temperature was raised to 80 ° C. After the temperature was raised, the pressure in the reaction vessel was reduced to 0.0040 MPa, and unreacted dimethyl carbonate, diethylene glycol, etc. were distilled off so that the hydroxyl value of the polycarbonate diol produced was 280 ± 2.

Thus, 84.0 parts of an intermediate of polycarbonate diol was obtained (acid value 0.04 mg KOH / g, hydroxyl value 280.1 mg KO).
H / g, viscosity 560 mPa · s (40 ℃), liquid at 25 ℃).

Next, 80 parts of the obtained polycarbonate diol intermediate and 20 parts of 1,6-hexanediol were placed in a reaction vessel, stirring was started, and 0.001 part of titanium tetraisopropoxide was added thereto. The temperature was raised to 240 ° C.

After the temperature was raised, the mixture was stirred for 2 hours, and the inside of the reaction vessel was
The pressure was reduced to 0.0013 MPa and diethylene glycol, 1,6-hexanediol and the like were distilled off so that the hydroxyl value was 112 ± 2 mgKOH / g to obtain 62.8 parts of polycarbonate diol B. The physical properties of the obtained polycarbonate diol B were examined in the same manner as in Example 1. The results are shown in Table 1.

The ¹ H-NMR spectrum of the polycarbonate diol B produced is shown in FIG. From the results shown in FIG. 2, the polycarbonate diol B has n of 6 in the formula (I), m of 2 in the formula (II), x of 2, and a molar ratio M of 4/6. It was confirmed. Also, the number average molecular weight of the polycarbonate diol B was determined to be 984.
Met.

Comparative Example 1 As the polycarbonate diol C, polyhexamethylene polycarbonate (hydroxyl group: 112 ± 2 mgKOH / g, having no diethyl glycol) was prepared. The physical properties of Polycarbonate Diol C were examined in the same manner as in Example 1. The results are shown in Table 1.

The number average molecular weight of the polycarbonate diol C was 990.

[Synthesis of Polycarbonate Diol for Isocyanate Component] Example 3 In Example 1, unreacted dimethyl carbonate, diethylene glycol, so that the hydroxyl value was 56 ± 2,
Polycarbonate diol D was obtained in the same manner as in Example 1 except that 1,6-hexanediol and the like were distilled off. The physical properties of the obtained polycarbonate diol D were examined in the same manner as in Example 1. The results are shown in Table 1.

The ¹ H-NMR spectrum of the produced polycarbonate diol D is shown in FIG. From the results shown in FIG. 3, the polycarbonate diol D has n of 6 in the formula (I), m of 2 in the formula (II), x of 2, and a molar ratio M of 8/2. It was confirmed. In addition, when the number average molecular weight of Polycarbonate diol D was determined,
Met.

Example 4 In Example 2, unreacted dimethyl carbonate, diethylene glycol and 1,6- were used so that the hydroxyl value would be 56 ± 2.
26.2 parts of polycarbonate diol E was obtained in the same manner as in Example 1 except that hexanediol and the like were distilled off. The physical properties of the obtained polycarbonate diol E were examined in the same manner as in Example 1. The results are shown in Table 1.

The ¹ H-NMR spectrum of the produced polycarbonate diol E is shown in FIG. From the results shown in FIG. 4, the polycarbonate diol E has n of 6 in the formula (I), m of 2 in the formula (II), x of 2, and a molar ratio M of 4/6. It was confirmed. Further, the number average molecular weight of Polycarbonate Diol E was determined to be 1989
Met.

Comparative Example 2 Polycarbonate diol F was polyhexamethylene polycarbonate having a hydroxyl group of 56 ± 2 mgKOH / g (that is,
(A structure that does not contain diethyl glycol at all compared to A and B) was prepared. Polycarbonate diol F
Were examined in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

The number average molecular weight of Polycarbonatediol F was calculated to be 1995.

[0069]

[Table 1]

[Preparation of Polyol Composition] Preparation Examples 1 to 5 Polycarbonate diol, ethylene glycol, pigment [Nippon Pigment Co., Ltd. ), Product number: NV
-7-478], a 33.3 wt% ethylene glycol solution of triethylenediamine (hereinafter referred to as "TEDI"), a foam stabilizer [Toray Dow Corning Silicone Co., Ltd., product number: SRX-
253] and water were mixed with stirring to obtain a polyol composition.
As the physical properties of the obtained polyol composition, the acid value and the hydroxyl value were examined in the same manner as in Example 1. Also, the water content of the polyol composition was examined. The results are shown in Table 2.

[0071]

[Table 2]

[Production of Isocyanate Component] Production Examples 1 to 5 4,4′-diphenylmethane diisocyanate dissolved by heating to 60 ° C. under a nitrogen atmosphere while controlling the temperature to 40 ° C. and a polyol The mixture was mixed so as to have the composition shown in Table 3, and mixed and stirred for 2 hours while controlling the reaction temperature to 50 to 60 ° C. Then, a carbodiimide modified product [Nippon Polyurethane Co., Ltd.] was added to the obtained mixture.
Product name: Coronate-MX] and triphenylphosphite were added in the amounts shown in Table 3 and the mixture was further stirred for 0.5 hour to obtain an isocyanate component. Table 3 shows the physical properties of the obtained isocyanate component.

[0073]

[Table 3]

Examples 5 to 6 and Comparative Examples 3 to 5 The polyol compositions obtained in each of the preparation examples and the isocyanate component obtained in each of the production examples were charged into respective raw material tanks and adjusted to a temperature of 40 ° C.

On the other hand, on the inner surface of the molding die having a desired inner surface shape, a mold release agent [Kao Corporation, trade name: PLA POWER 206
0] 0.002 g / cm ³ was applied and adjusted to a temperature of 50 ± 1 ° C.

Next, the polyol composition and the isocyanate component were mixed at the weight ratio shown in Table 4, and the resulting mixture was injected into a molding machine [manufactured by Polyurethane Engineering Co., Ltd., model number: MU-203S], After discarding once, it is injected into the molding die for the second time, and after 10 minutes have elapsed, it is demolded,
A sheet-like molded body having a size of 100 mm × 300 mm × 10 mm (thickness) was taken out.

The physical properties of the obtained molded product were measured according to the following methods. The results are shown in Table 2.

[Molding Density] The mass of a molded body of 100 mm × 300 mm × 10 mm (thickness) was measured, and the mass was measured to have a volume of 300 cm ³
The density was calculated by dividing by.

[Hardness] Measured with an Asker C hardness meter.

[Tensile Strength] The tensile strength was measured according to the method described in JIS K-6301 using a dumbbell No. 2 type test piece.

[Elongation] According to the method described in JIS K-6301,
The measurement was performed using a dumbbell-shaped type 2 test piece.

[Strength Retention Ratio] The strength retention ratio in the moist heat condition is an index of hydrolysis resistance, that is, long-term durability.
In the test, 6 test pieces were punched out from a sheet-like molded body of 100 mm x 300 mm x 10 mm (thickness), and the tensile strength x (MPa) of 3 of the test pieces was measured, and the average value (hereinafter, ""Tensile strength before standing") was calculated.

Next, the remaining three test pieces were allowed to stand in an atmosphere having a temperature of 80 ° C. and a relative humidity of 95% for 7 days, and then the test pieces were taken out from this atmosphere and air-dried at room temperature for 2 days. The tensile strength y (MPa) of this test piece was measured, and its average value (hereinafter,
"Tensile strength after leaving for 7 days" was calculated. The tensile strength was measured as described above.

The strength retention rate was calculated based on the formula: [strength retention rate] = [tensile strength before standing−tensile strength after standing for 7 days] / [tensile strength before standing] × 100.

[Measurement Method of Repulsion Resilience] It was measured based on JIS K-6301 using a sheet-like molded body of 100 mm × 300 mm × 10 mm (thickness).

[0086]

[Table 4]

From the results shown in Table 4, it can be seen that the polyurethane foams obtained in Examples 5 to 6 have high tensile strength and strength retention. Moreover, when the impact resilience was measured, it was found that the polyurethane foams obtained in Examples 5 to 6 had low impact resilience.

[0088]

The polycarbonate diol of the present invention is
It provides polyurethane with good mechanical strength such as tensile strength, hardness, elongation and the like. Further, the polyurethane of the present invention has mechanical strength such as good tensile strength, hardness and elongation, and has an effect of a long service life. Further, since the polyurethane of the present invention has low impact resilience, it can be suitably used as a shock absorber, a sound absorber, a vibration absorber, a cushioning material and the like.

[Brief description of drawings]

FIG. 1 is a chart showing the ¹ H-NMR measurement results of the polycarbonate diol obtained in Example 1.

FIG. 2 is a chart showing ¹ H-NMR measurement results of the polycarbonate diol obtained in Example 2.

FIG. 3 is a chart showing ¹ H-NMR measurement results of the polycarbonate diol obtained in Example 3.

FIG. 4 is a chart showing ¹ H-NMR measurement results of the polycarbonate diol obtained in Example 4.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J029 AA08 AB01 AC03 AD01 AE17                       BA02 BA03 BA04 BA05 BA07                       BA10 BF09 BF10 BF17 BF18                       BF25 HA01 HC04A HC05A                       HC06 JB131 JC031 JF031                       JF321                 4J034 BA03 CA04 CB03 CB07 CC03                       DA01 DB04 DB07 DF03 HA01                       HA02 HA06 HA07 HB16 HB17                       HC03 HC12 HC17 HC22 HC46                       HC52 HC61 HC63 HC64 HC67                       HC71 HC73 JA42 KA01 KB02                       KD12 KE02 NA03 NA08 QC01

Claims (4)

[Claims] 1. Formula (I): (In the formula, n represents an integer of 2 to 6) and a structural unit represented by the formula (II): (In the formula, m represents an integer of 2 to 4, and x represents an integer of 2 to 15)
A structural unit represented by the formula (I) and a molar ratio of the structural unit represented by the formula (I) / the structural unit represented by the formula (II) is from 2/8 to 9/1.
It has hydroxyl groups at both ends and its number average molecular weight is 40.
A polycarbonate diol that is 0 to 3000. 2. The formula (I), wherein n is 6.
Polycarbonate diol as described. 3. Formula (I): (In the formula, n represents an integer of 2 to 6) and a structural unit represented by the formula (II): (In the formula, m represents an integer of 2 to 4, and x represents an integer of 2 to 15)
A structural unit represented by the formula (I) and a molar ratio of the structural unit represented by the formula (I) / the structural unit represented by the formula (II) is from 2/8 to 9/1.
It has hydroxyl groups at both ends and its number average molecular weight is 40.
Polyurethane obtained by using as a raw material a polycarbonate diol of 0 to 3000. 4. The formula (I), wherein n is 6. 3.
Polyurethane as described.