JP4560373B2 - Polycarbonate / polyether block copolymer having a hydroxyl group at the terminal - Google Patents

Description

  The present invention relates to a polycarbonate / polyether block copolymer having a hydroxyl group at a terminal.

Conventionally, aliphatic polycarbonate diol is a diol with good hydrolysis resistance and heat resistance, so it has been used as a raw material for high-performance polyurethane in the fields of spandex, fiber treatment agents, coating agents, synthetic leather, molded products, etc. ing.
Generally, a polycarbonate diol having a hexamethylene group obtained from 1,6-hexanediol and dialkyl carbonate or alkylene carbonate is superior in hydrolysis resistance and mold resistance to polyester diol, and polyether diol. Compared to its excellent light resistance, heat resistance, and oil resistance, it is used as a raw material for producing highly durable polyurethane.

However, since this carbonate diol has crystallinity, a polyurethane using the carbonate diol has a defect that it is poor in flexibility and elastic recovery, and these properties are further deteriorated at low temperatures.
In addition, polycarbonate diol itself, or derivatives such as terminal isocyanate prepolymers and urethane acrylate prepolymers using the same tend to produce crystals at temperatures of 50 ° C. or lower because the polycarbonate diol chain portion has a melting point. In addition, the fluidity of the product is hindered and the handling becomes extremely difficult.
As techniques for improving this point, Patent Document 1 discloses copolymer polycarbonate diols using diols having 5 and 6 carbon atoms as raw materials, and Patent Document 2 discloses copolymer polycarbonate diols using diols having 4 and 6 carbon atoms as raw materials. Proposed. Since these copolymer polycarbonate diols are liquid at room temperature, they are easy to handle when synthesizing polyurethane and urethane prepolymers, and the obtained polyurethane and urethane prepolymers are flexible.

However, a polycarbonate-based diol having a further reduced viscosity is desired depending on the application. In particular, in the field of UV / EB curable resins and water-based urethane coating resins, there is a strong demand for polycarbonate diols with reduced viscosity. In the case of urethane acrylate used as UV / EB curable resin, if the polyol as the raw material is made low viscosity, the product urethane acrylate can be made low viscosity, so the low temperature fluidity becomes good, Furthermore, it is easy to apply urethane acrylate to the base material, and the film after curing is advantageous in that it is flexible and can be maintained even at low temperatures. In the field of water-based polyurethane, if the viscosity of polyurethane or urethane prepolymer can be reduced, there is an advantage that the process of dispersing in water becomes easy, and the film is flexible and can be maintained even at low temperatures. .
Japanese Patent Laid-Open No. 4-7327 JP-A-5-25264

  An object of the present invention is to provide a polycarbonate-based diol copolymer that can solve the problems of the prior art, and using this as a raw material, a urethane prepolymer, a solvent-based polyurethane, a water-based polyurethane, a bulk-polymerized polyuritan, a urethane Products such as acrylates can be reduced in viscosity in the molten state, and when these products are used, mechanical operations such as coating, molding, and stirring are easy, and when polyurethane is used, there is little decrease in light resistance, and polycarbonate diol It is an object of the present invention to provide a copolymer which can be used as a compatibilizing agent in the case of mixing both of them because of good affinity with both of them and polyether diol.

In order to solve the above-mentioned problems, the present invention provides a polycarbonate / polyether block copolymer having a terminal hydroxyl group obtained by block copolymerization of a copolymerized polycarbonate chain composed of an aliphatic diol component having 5 and 6 carbon atoms and a polyoxyalkylene chain. The present inventors have found that the polymer has a low viscosity and have made the present invention.
That is, the present invention is the following (1) to (10).
(1) The repeating unit formula (I) including the following repeating unit formula (I), formula (II) and formula (III), wherein the polycarbonate chain portion has 5 methylene chains and the number of methylene chains is 6 A copolymer chain consisting of repeating unit formula (II) is formed, and the ratio of carbon number 5 to carbon number 6 is 1/9 to 9/1, and the polycarbonate chain and repeating unit formula (III) The ether chain forms a block copolymer chain, and the range of the number average degree of polymerization of the copolymer polycarbonate chain comprising the repeating unit formulas (I) and (II) is 2 or more and 36 or less, and the repeating unit formula (III The range of the number average polymerization degree of the polyether chain of 2) to 70 is the sum of the number of repeating unit formulas (I) and (II) contained in the product c, repeating unit formula (III) If the number of e is , Carbonate composition ratio c / (c + e) is 0.1 to 0.9, having terminal hydroxyl groups, a number average molecular weight of 300 to 50,000 polycarbonate / polyether block copolymer.

(R is an oxytetramethylene group and / or an oxy 2,2-dimethyltrimethylene group)
(2) The polycarbonate / polyether block copolymer of the above (1) wherein the repeating unit formula (III) is an oxytetramethylene group (3) The repeating unit formula (III) is an oxytetramethylene group and an oxy 2,2- The polycarbonate / polyether block copolymer of the above (1) which is a dimethyltrimethylene group.
(4) The polycarbonate / polyether block copolymer according to (1), (2) or (3), wherein the repeating unit formula (III) has a number average degree of polymerization of 2 or more and 14 or less.
(5) The polycarbonate / polycarbonate of the above (1), (2) or (3), wherein the copolymer polycarbonate chain comprising the repeating unit formulas (I) and (II) has a number average degree of polymerization of 2 or more and 22 or less. Ether block copolymer.
(6) The polycarbonate / polyether block copolymer according to (1), (2) or (3), wherein the polycarbonate / polyether block copolymer has a number average molecular weight of 300 to 5,000.

(7) A process for producing the polycarbonate / polyether block copolymer of the above (2) by transesterifying a copolymer polycarbonate diol comprising repeating unit formulas (I) and (II) with polyoxytetramethylene glycol. .
(8) Transesterification of a copolymerized polycarbonate diol composed of repeating unit formulas (I) and (II) with a copolymerized polyoxyalkylene glycol composed of oxytetramethylene group and oxy 2,2-dimethyltrimethylene group To produce the polycarbonate / polyether block copolymer of (3) above.
(9) The method according to (7), wherein the polyoxytetramethylene glycol has a number average polymerization degree of 2 or more and 14 or less.
(10) The method according to (8), wherein the polyoxyalkylene glycol has a number average degree of polymerization of 2 or more and 14 or less.

  Since the polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention has a characteristic of low viscosity, a urethane prepolymer, a solvent-based polyurethane, a water-based polyurethane, a bulk-polymerized polyuritan, and a urethane are used as a raw material. Products such as acrylates can be reduced in viscosity in the molten state, and when these products are used, there is an advantage that mechanical operations such as coating, molding, and stirring are easy, and there is little reduction in light resistance when polyurethane is used. Moreover, since the affinity with both polycarbonate diol and polyether diol is good, it is possible to provide a copolymer that can be used as a compatibilizing agent in the case of mixing both.

The present invention will be specifically described below. In the polycarbonate / polyether block copolymer of the present invention, the polycarbonate chain and the polyether chain form a block copolymer having a hydroxyl group at the terminal. The number of methylene chains in the repeating unit formula (I) is 5, and the number of methylene chains in the repeating formula (II) is 6, but these repeating units form a copolymer chain and have 5 carbon atoms. And the ratio of 6 carbon atoms is 1/9 to 9/1. When it is out of these ranges, the crystallinity of the portion composed of the repeating unit containing a carbonate bond increases, which is not preferable. A preferred range of the number average degree of polymerization of the copolymer polycarbonate chain comprising the repeating unit formulas (I) and (II) is 2 or more and 36 or less. When it exceeds 36, the viscosity of the urethane prepolymer such as a polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention or a terminal isocyanate urethane prepolymer, which is an application of this, becomes high. Therefore, handling becomes difficult. A more preferable range is 2 or more and 22 or less.
The polyether chain consisting of repeating unit formula (III) is a copolymer of oxytetramethylene group formula (IV) or oxytetramethylene group formula (IV) and oxy 2,2-dimethyltrimethylene group formula (V) shown below. Consists of chains.

  The ratio (number ratio) IV / (IV + V)) in the formula (IV) is preferably 0.1 or more and 1 or less. Outside this range, flexibility is reduced when polyurethane is used. A preferred range of the number average polymerization degree of the repeating unit formula (III) is 2 or more and 70 or less. When it exceeds 70, the viscosity of the urethane prepolymer such as a polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention or a terminal isocyanate urethane prepolymer, which is an application of this, becomes high. Therefore, handling is likely to be difficult. A more preferable range is 2 or more and 42 or less, and further preferably 2 or more and 28 or less. In order to increase the probability that both a carbonate bond and an ether bond are contained in one molecule of a polycarbonate / polyether block copolymer having a hydroxyl group at the end of the present invention, the number average degree of polymerization of the repeating unit (III) is: 2 to 14 is most preferable. The number average molecular weight of the polycarbonate / polyether block copolymer of the present invention is from 300 to 50,000. If it is less than 300, the properties of the polyurethane as a soft segment are lost, and if it is 50000 or more, the viscosity of the block copolymer becomes remarkably high, which makes it difficult to handle. More preferably, it is 300 or more and 5000 or less.

Polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention A block part consisting of a copolymerized polycarbonate chain and a block part consisting of a polyether chain in each molecule may be present alone or in plural. May be. The terminal may be any one of — (CH ₂ ) ₆ OH, — (CH ₂ ) ₅ OH, — (CH ₂ ) ₄ OH, and —CH ₂ C (CH ₃ ) ₂ CH ₂ —OH. Moreover, the terminal other than these as an impurity may be contained. Examples of terminals other than these include — (CH ₂ ) ₂ —OH, secondary hydroxyl terminal, alkyl group terminal and the like. When the terminal as an impurity is inert to the isocyanate, the final molecular weight of the polyurethane is lowered. Therefore, it is preferable that the purity of the terminal primary hydroxyl group having good reactivity with the isocyanate is as high as possible. Specifically, the purity of the terminal primary hydroxyl group is preferably 95% or more, more preferably 97% or more, when calculated by the number thereof. The terminal primary hydroxyl group purity can be measured by the method described in WO01 / 90213. The total number of carbonate repeating units (I) and (II) contained in the polycarbonate / polyether block copolymer product having a hydroxyl group at the terminal of the present invention is c, and the number of ether repeating units (III) is e. In this case, the carbonate composition ratio c / (c + e) is 0.1 or more and 0.9 or less. When it is less than 0.1, the light resistance is lowered when polyurethane is used, and when it is more than 0.9, the fluidity of the polyol is lowered.

  The terminal hydroxyl group of the polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention can be converted into various functional groups depending on the application. For example, an acryloyl group or a methacryloyl group can be introduced at the terminal, and this can be used as an ultraviolet-electron beam (UV-EB) curable prepolymer. This ultraviolet-electron beam curable prepolymer is used as a paint or an adhesive. Since the aliphatic polycarbonate diol has a high affinity for the aromatic polycarbonate resin, it is particularly suitable as a UV-EB curable adhesive for the aromatic polycarbonate resin. As a method for introducing an acryloyl group or a methacryloyl group at a terminal, a method in which a terminal hydroxyl group is directly reacted with acryloyl chloride or methacryloyl chloride, or a terminal is reacted with an aromatic or aliphatic polyisocyanate to convert the terminal to an isocyanate. Then, there is a method of reacting with hydroxyalkyl alkylate or hydroxyalkyl methacrylate such as hydroxyethyl acrylate or hydroxyethyl methacrylate.

Those having an isocyanate group introduced at the terminal can be used as a urethane prepolymer. As a method for introducing an isocyanate group at the terminal, the terminal hydroxyl group may be reacted with an aromatic polyisocyanate or an aliphatic polyisocyanate equivalent to or equivalent to an OH equivalent or in excess of the OH equivalent.
Those having an alkoxysilane or silanol introduced at the end can be used as a 25 ° C. cross-linked prepolymer. In order to introduce an alkoxysilane group at the terminal, for example, it is reacted with an aromatic or aliphatic polyisocyanate to make the terminal isocyanate, and then reacted with a silane coupling agent having an amino group such as aminoalkylalkoxysilane. That's fine.

Those having an epoxy group or oxetanyl group introduced at the end can be used as an additive for an epoxy resin or a cationically curable prepolymer. In order to introduce an epoxy group or an oxetane group, for example, it may be reacted with an aromatic or aliphatic polyisocyanate to make the terminal isocyanate, and then reacted with an epoxy compound having a hydroxyl group or an oxetane compound having a hydroxyl group.
The polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention can be converted into a polyol having an average number of functional groups exceeding two functions. As this method, for example, depolymerization may be performed with a low molecular or high molecular alcohol having 3 or more hydroxyl groups in one molecule, or reaction with a polyisocyanate having 3 or more functional groups may be performed.

The polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention can be synthesized by reacting a carbonate compound with 1,5-pentanediol, 1,6-hexanediol, or polyoxyalkylene glycol. As the carbonate compound, dialkyl carbonate, alkylene carbonate, and diaryl carbonate can be used. More specifically, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, ethylene carbonate, 4-methyl-1,3-dioxolan-2-one, 1,3-propylene carbonate, diphenyl carbonate, etc. It can be illustrated. The reaction of 1,5-pentanediol, 1,6-hexanediol, polyoxyalkylene glycol, and carbonate compound is a polycondensation reaction by transesterification, and a monoalcohol or diol corresponding to the carbonate compound as shown in the following formula The polymerization reaction proceeds by distilling out of the reaction system.
(n + 1) HO-R-OH + n R ₁ -OCOO-R ₁ → HO- (R-OCOO-) _n -R-OH + 2n R ₁ -OH
(HO-R-OH represents 1,5-pentanediol, 1,6-hexanediol, or polyoxyalkylene glycol.)
In order to further increase the molecular weight after the monoalcohol or diol corresponding to the carbonate compound on the left side in the above formula is distilled, a self-condensation polymerization reaction shown in the following formula is used.
HO- (R-OCOO-) _a -R-OH + HO- (R-OCOO-) _b -R-OH → HO- (R-OCOO-) _{a + b} -R-OH + HO-R-OH

At this time, the raw material diol is distilled from the reaction system, and as a result, the molecular weight increases. The temperature of these reactions is usually 100-250 ° C. In these reactions shown above, a transesterification catalyst can be used. A catalyst generally used as the transesterification catalyst can be used. Alkali metal alcoholates, organic acids, inorganic acids, ion exchange resins, transition metal alcoholates, metal oxides and the like can be exemplified. More specifically, sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, acetic acid Lead, titanium tetraalkoxide, calcium oxide, zinc oxide SnO (OR) _{3 and the} like are suitable. As raw materials, low molecular polyols other than 1,5-pentanediol, 1,6-hexanediol, and polyoxyalkylene glycol can be used in combination with the diol compound. In addition, when a trifunctional or higher polyhydric alcohol is used, the target product can be a polyfunctional alcohol. Examples of these low molecular diols include polyols having 2 to 10 carbon atoms. More specifically, ethylene glycol, propylene glycol, propylene 1,2-diol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-hexanediol, heptanediol, octanediol, Nonanediol, decanediol, trimethylolpropane, pentaerythritol and the like can be exemplified.

As another production method of the polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention, a method by depolymerization represented by the following formula can be employed.
a HO- (R-OCOO-) _n -R-OH + b HO-R-OH → c HO- (R-OCOO-) _p -R-OH (p <n)
This method is a method in which a copolymerized polycarbonate diol composed of repeating units (I) and (II) is transesterified with polyoxyalkylene glycol. Also in this method, a block copolymer of polycarbonate and polyether is formed in the same manner as described above. There is no particular limitation on the number average degree of polymerization of the copolymer polycarbonate diol composed of the repeating units (I) and (II), but the viscosity increases as the number average degree of polymerization increases, so that it is easy to charge into the reactor. Usually, it is preferably 2 or more and 36 or less.
A preferred range of the number average degree of polymerization of the repeating unit (III) is 2 or more and 28 or less. In order to increase the probability that both a carbonate bond and an ether bond are contained in one molecule of a polycarbonate / polyether block copolymer having a hydroxyl group at the end of the present invention, the number average degree of polymerization of the repeating unit (III) is: 2 to 14 is most preferable.

  The reaction temperature is usually 100-250 ° C. In the transesterification reaction, that is, the depolymerization reaction, a transesterification catalyst similar to that described above can be used. In order to accurately control the molecular weight distribution and avoid the thermal decomposition reaction of the polyether as much as possible, this transesterification reaction is preferably employed. It is also possible to use a low molecular polyol in combination with polyoxyalkylene glycol. In addition, when a trifunctional or higher polyhydric alcohol is used, the target product can be a polyfunctional alcohol. Examples of these low molecular diols include polyols having 2 to 10 carbon atoms. Specifically, ethylene glycol, propylene glycol, propylene 1,2-diol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, Examples include 1,5-hexanediol, heptanediol, octanediol, nonanediol, decanediol, trimethylolpropane, pentaerythritol, and glycerin.

  The polycarbonate / polyether block copolymer having a hydroxyl group at the terminal of the present invention includes a urethane prepolymer, a solvent-based polyurethane, a water-based polyurethane, a bulk-polymerized polyurethane, a urethane acrylate, a thermoplastic polyurethane, a thermosetting polyurethane, and a polyurethane-based powder resin. It can be used as a raw material for polyurethane. More specifically, chipping-resistant paints for automobiles, solvent-based adhesives, water-based adhesives, polyurethane moldings, shoe soles, packings, polyurethane foams, sports equipment, sealing agents, semiconductor sealants, epoxy resin modifiers, UV / EB curable adhesive, UV / EB curable resin, resin coating, slush molding powder, wood coating, powder coating, UV curable powder coating, water-based UV curable coating, fiber treatment agent, Examples include use as a raw material for synthetic leather, artificial leather, spandex, etc., and use as a compatibilizing agent in the case of mixing polycarbonate diol and polyether diol.

The present invention will be described based on examples.
[Example 1]
A reactor capable of depressurization equipped with a stirrer and a distillation column was charged with 100 parts by weight of 1,6-hexanediol, 88.1 parts by weight of 1,5-pentanediol, 74.6 parts by weight of ethylene carbonate, and 0.0187 parts by weight of titanium tetrabutoxide. The transesterification reaction was started at normal temperature and the reaction temperature was gradually raised to 200 ° C., and at the same time the pressure was gradually reduced to 5 Torr. At this time, in the first half of the reaction, ethylene glycol was distilled off from the top of the distillation column with a small amount of azeotropic ethylene carbonate, and in the second half of the reaction, 1,6-hexanediol and 1,6-hexanediol produced by the self-condensation reaction were distilled. 5-Pentanediol distilled off. After completion of the reaction, the product copolymerized polycarbonate diol (PCD-A) remained in the reactor. The number average molecular weight of PCD-A was determined by hydroxyl group quantification by the acetylation method and found to be 2004 (OH value = 56 mgKOH / g). When PCD-A was decomposed with an aqueous caustic soda solution and the composition ratio of the repeating units (I) and (II) was determined, it was 48/52.

A reactor equipped with a stirrer was charged with 198.8 parts by weight of PCD-A and 51.33 parts by weight of polyoxytetramethylene glycol (PTMG) (PolyTHF250 manufactured by BASF, number average molecular weight = 253, OH number = 443.7 mgKOH / g) at 150 ° C. A transesterification reaction (depolymerization reaction) was performed for 4 hours. The reaction system was a two-phase system in the first half, but became uniform in the second half. The obtained polycarbonate / polyether block copolymer (PCPED-1) having a hydroxyl group at the terminal is a colorless or pale yellow transparent viscous liquid at room temperature, and the number average molecular weight is 828 (OH value = 135.5 mgKOH / g). there were. When the viscosity at 37 ° C. was measured with a B-type viscometer No. 4 rotor (Tokyo Keiki), it was 1700 mPa · s, which was lower than that of PCD-C in Comparative Example 1. The carbonate composition ratio c / (c + e) in the product PCPED-1 is 0.674. Table 1 shows the carbonate composition ratio and the viscosity at 37 ° C.
The results of measuring GPC and IR are shown in FIGS. These measurement conditions are as follows.
GPC measuring device Tosoh HLC-8820, column TSKgel G4000HXL × 1 G3000HXL × 1 G2000HXL × 2
Guard column, eluent THF, flow rate 1 mL / min, temperature 40 ° C, detector RI.
IR
Measuring equipment JASCO FT-IR430, KBr crystal plate

  Since the polycarbonate / polyether block copolymer having a hydroxyl group at the terminal in Example 1 has a characteristic of low viscosity, a urethane prepolymer, a solvent-based polyurethane, a water-based polyurethane, and a bulk-polymerized polyuritan using this as a raw material. Products such as urethane acrylate can be reduced in the molten state, and when these products are used, there is an advantage that mechanical operations such as coating, molding, and stirring are easy, and light resistance is reduced when polyurethane is used. In addition, since the affinity with both the polycarbonate diol and the polyether diol is good, a copolymer that can be used as a compatibilizing agent when mixing both of them can be provided.

[Example 2]
In the same manner as in Example 1, 100 parts by weight of 1,6-hexanediol, 88.1 parts by weight of 1,5-pentanediol, 74.6 parts by weight of ethylene carbonate, and 0.0187 parts by weight of titanium tetrabutoxide were reacted to give a number average molecular weight of 989 ( A copolymer polycarbonate diol (PCD-B) having an OH number of 113.5 mgKOH / g) was obtained. When PCD-B was decomposed with an aqueous caustic soda solution and the composition ratio of the repeating units (I) and (II) was determined, it was 49/51.
In the same manner as in Example 1, 152.5 parts by weight of PCD-B and 97.69 parts by weight of polyoxytetramethylene glycol (PTMG) (PolyTHF650 manufactured by BASF, number average molecular weight = 655, OH value = 171.2 mgKOH / g) were charged. The transesterification reaction (depolymerization reaction) was performed at 150 ° C. for 4 hours. The reaction system was a two-phase system in the first half, but became uniform in the second half. The obtained polycarbonate / polyether block copolymer (PCPED-2) having a hydroxyl group at the terminal is a colorless or pale yellow transparent viscous liquid at room temperature, and the number average molecular weight is 825 (OH value = 136.0 mgKOH / g). there were. When the viscosity at 37 ° C. was measured with a B-type viscometer No. 4 rotor (Tokyo Keiki), it was 1040 mPa · s, which was lower than that of PCD-C in Comparative Example 1. The carbonate composition ratio c / (c + e) in the product PCPED-2 is 0.428. Table 1 shows the carbonate composition ratio and the viscosity at 37 ° C. The results of measuring GPC and IR are shown in FIGS.

Example 3
Copolymer polyoxyalkylene containing 152.2 parts by weight of PCD-B and oxytetramethylene glycol unit and oxy 2,2-dimethyltrimethylene glycol unit in this order in a ratio of 90 to 10 in the same manner as in Example 1. 97.61 parts by weight of glycol (number average molecular weight = 652, OH value = 172.1 mgKOH / g) was charged, and transesterification (depolymerization reaction) was performed at 150 ° C. for 4 hours. The reaction system was a two-phase system in the first half, but became uniform in the second half. The obtained polycarbonate / polyether block copolymer (PCPED-3) having a hydroxyl group at the terminal is a colorless or pale yellow transparent viscous liquid at room temperature, and the number average molecular weight is 823 (OH value = 136.4 mgKOH / g). there were. When the viscosity at 37 ° C. was measured with a B-type viscometer No. 4 rotor (Tokyo Keiki), it was 1005 mPa · s, which was lower than that of PCD-C in Comparative Example 1. The carbonate composition ratio c / (c + e) in the product PCPED-3 is 0.433. Table 1 shows the carbonate composition ratio and the viscosity at 37 ° C.

[Comparative Example 1]
In the same manner as in Example 1, 100 parts by weight of 1,6-hexanediol, 88.1 parts by weight of 1,5-pentanediol, 74.6 parts by weight of ethylene carbonate, and 0.0187 parts by weight of titanium tetrabutoxide were charged, and the number average molecular weight 826 (OH Copolycarbonate diol (PCD-C) having a value of 135.8 mg KOH / g) was obtained. PCD-C was a colorless or pale yellow transparent viscous liquid at room temperature. When PCD-C was decomposed with an aqueous caustic soda solution and the composition ratio of the repeating units (I) and (II) was determined, it was 50/50. The viscosity at 37 ° C. measured with a B-type viscometer No. 4 rotor (Tokyo Keiki) was 2580 mPa · s. Table 1 shows the carbonate composition ratio and the viscosity at 37 ° C.

  The present invention can be suitably used in the fields of water-based polyurethane, solvent-based polyurethane, polyurethane resin, urethane prepolymer, urethane acrylate and the like.

It is GPC of PCPED-1 described in Example 1. 2 is an IR spectrum of PCPED-1 described in Example 1. It is GPC of PCPED-2 described in Example 2. 2 is an IR spectrum of PCPED-2 described in Example 2.

Claims (10)

The repeating unit formula (I) comprising the following repeating unit formula (I), formula (II) and formula (III), wherein the polycarbonate chain moiety is a repeating unit formula (I) wherein the number of methylene chains is 5 and the number of methylene chains is 6 Forming a copolymer chain consisting of unit formula (II) , wherein the ratio of carbon number 5 to carbon number 6 is 1/9 to 9/1 and the polyether chain consisting of repeating unit formula (III); Forms a block copolymer chain, and the range of the number average degree of polymerization of the copolymer polycarbonate chain comprising the repeating unit formulas (I) and (II) is from 2 to 36, and the repeating unit formula (III) The range of the number average degree of polymerization of the ether chain is 2 or more and 70 or less, the total number of repeating unit formulas (I) and (II) contained in the product is c, and the number of repeating unit formulas (III) is e Boneto composition ratio c / (c + e) is 0.1 to 0.9, having terminal hydroxyl groups, a number average molecular weight of 300 to 50,000 polycarbonate / polyether block copolymer.

(R is an oxytetramethylene group and / or an oxy 2,2-dimethyltrimethylene group)   The polycarbonate / polyether block copolymer according to claim 1, wherein the repeating unit formula (III) is an oxytetramethylene group.   The polycarbonate / polyether block copolymer according to claim 1, wherein the repeating unit formula (III) is an oxytetramethylene group and an oxy2,2-dimethyltrimethylene group.   4. The polycarbonate / polyether block copolymer according to claim 1, wherein the repeating unit formula (III) has a number average degree of polymerization of 2 or more and 14 or less.   The copolymer / polyether block copolymer of claim 1, 2 or 3, wherein the copolymer polycarbonate chain comprising the repeating unit formulas (I) and (II) has a number average degree of polymerization of 2 or more and 22 or less. Coalescence.   4. The polycarbonate / polyether block copolymer according to claim 1, wherein the polycarbonate / polyether block copolymer has a number average molecular weight of 300 or more and 5000 or less.   A process for producing the polycarbonate / polyether block copolymer according to claim 2, wherein the copolymerized polycarbonate diol comprising the repeating unit formulas (I) and (II) is transesterified with polyoxytetramethylene glycol.   A copolymer polycarbonate diol comprising repeating unit formulas (I) and (II) and a copolymer polyoxyalkylene glycol comprising oxytetramethylene group and oxy 2,2-dimethyltrimethylene group are subjected to a transesterification reaction. 3. A process for producing a polycarbonate / polyether block copolymer.   The method according to claim 7, wherein the polyoxytetramethylene glycol has a number average degree of polymerization of 2 or more and 14 or less. The method according to claim 8, wherein the polyoxyalkylene glycol has a number average polymerization degree of 2 or more and 14 or less.

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