JPH0529648B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel aliphatic copolycarbonate diol having excellent hydrolysis resistance, light resistance, oxidative deterioration resistance, heat resistance, and flexibility. [Conventional technology] Conventionally, for example, polyurethane, urethane-based
Polyester polyols and polyether polyols having hydroxyl groups at the polymer terminals are used as soft segments for thermoplastic elastomers such as ester and amide elastomers.
(U.S. Patent No. 4362825, No. 4374535, No. 4129715
number specification etc.). Among these, polyester polyols such as adipate have poor hydrolysis resistance. For example, polyurethane made using this can cause cracks on the surface or mold growth on the surface in a relatively short period of time, making it difficult to use. subject to restrictions. On the other hand, polyurethane using polyether polyol has good hydrolysis resistance, but has the disadvantage of poor light resistance and oxidative deterioration resistance. These drawbacks are due to the presence of ester groups and ether groups in the polymer chain, respectively. In recent years, requirements for heat resistance, light resistance, hydrolysis resistance, mold resistance, oil resistance, etc., have become more sophisticated for polyester-based and polyamide-based thermoplastic elastomers, and they are facing the same problems as polyurethane. had. On the other hand, 1,6
Polycarbonate polyols of -hexanediol are commercially available, which exhibit the above-mentioned characteristics because the carbonate bonds in the polymer chains are chemically extremely stable. [Problems to be Solved by the Invention] However, since the polycarbonate polyol of 1,6-hexanediol is crystalline, it is solid at room temperature and difficult to handle. It has the disadvantage of extremely poor elastic recovery, and furthermore, when making polyurethane fibers, it lacks spinnability and is difficult to spin. Various methods have been proposed to alleviate these problems. For example, Bayer AG discloses in U.S. Patent No. 3,639,354 and European Patent No. 135,848 a method of copolymerizing 1,6-hexanediol and a diol containing an ether group, which slightly lowers the softening point of the polymer. However, although the introduction of ether groups improves flexibility when used in polyurethane, it actually worsens light resistance, chlorine resistance, and oxidation resistance. PPG Industries, in U.S. Patent Nos. 4.103070 and 4.101529,
They proposed a polycarbonate diol made by copolymerizing 1,6-hexanediol and 1,4-cyclohexanedimethanol, and claim that it is possible to suppress the crystallinity of urethane using it. However, since it contains a cyclo ring, even though the crystallinity is slightly degraded, hardness due to the cyclo ring skeleton is imparted, and the flexibility is not significantly improved. Kuraray discloses 3-methyl-
It is proposed that flexibility be imparted by copolymerization of 1,5-pentanediol and 1,6-hexanediol or 1,9-nonanediol. but,
Although having a side chain has a great effect on disrupting crystallinity, the light resistance and oxidative deterioration resistance are weak due to the side chain alkyl. The publication also states that if heat resistance, light resistance, oxidative deterioration resistance, etc. are to be improved,
50% by weight of 3-methyl-1,5-pentadiol
It is specified that it should be used in the following amounts. Also, US Patent No. 4013702 and US Patent No. 4105641
In the specification, 1,6-hexanediol and 1,
There is a description of the synthesis of copolycarbonate copolymerized with 4-butanediol. All of these disclose methods for producing copolycarbonate, but do not describe its properties, but as will be shown later in Comparative Reference Example 10, the elastic recovery properties are not sufficient and it is difficult to make polyurethane fibers. In some cases, the yarn lacked spinnability and was difficult to spin. Furthermore, as shown in Comparative Reference Example 7 below, the elastic recovery properties of the copolycarbonate of 1,6-hexanediol and 1,9-nonanediol are also not sufficient. Therefore, an object of the present invention is to provide an aliphatic copolycarbonate that can solve the above problems. [Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have found that A and B are composed of the following repeating units A and B, and the terminal group is a hydroxyl group. The copolycarbonate diol having a ratio of 9:1 to 1:9 and an average molecular weight of 300 to 50,000 is amorphous, When applied to polyurethane and other thermoplastic elastomers, the flexibility and elastic recovery properties are significantly superior to those using conventional 1,6-hexanediol-based polycarbonate polyols, and furthermore, polyurethane fibers can be manufactured. The present inventors have discovered that spinning can be easily carried out even in the case of spinnerification, leading to the present invention. The present invention will be explained in detail below. The aliphatic copolycarbonates of the present invention can be prepared by various methods described in Schnell, Polymer Reviews, Vol. 9, pp. 9-20 (1964).
- Synthesized from aliphatic diols containing hexanediol and 1,5-pentanediol as main components, and optionally containing a small amount of aliphatic polyol. In the aliphatic copolycarbonate polyol used in the present invention, in addition to 1,6-hexanediol and 1,5-pentanediol, 2
A small amount of the above hydroxyl group-containing compound may be used as a copolymer component within a range that does not impair the effects of the present invention. Although it depends on the case, for example, when polymerizing equimolar amounts of 1,6-hexanediol and 1,5-pentadiol, 1,6-hexanediol and 1,5-pentadiol are used as the third component. 1,4- 20% or less, preferably 15% or less based on the total number of moles of pentanediol
Butanediol can be used. In addition to 1,6-hexanediol and 1,5-pentadiol, the present invention also includes compounds having three or more hydroxyl groups in one molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, etc. Multifunctionalized polycarbonates are also included by using small amounts of polycarbonates. If too many compounds with 3 or more hydroxyl groups are used in one molecule, crosslinking will occur and gelation will occur.
It is best to keep it below %. Repeating unit of the copolycarbonate of the invention The idea behind the ratio is as follows. Copolycarbonate is a viscous liquid at room temperature and has no melting point in DSC measurements, so when used in polyurethane, for example, it has poor elastic recovery, flexibility, and stringiness. shows more favorable properties. If the copolycarbonate has only A and B as constituent units, the ratio of A and B is 7.5:
Since the composition exhibits amorphous property in the range of 2.5 to 1.5:8.5, a composition within this range is preferable. When a third component is included in the constituent units of A and B as a copolymer component within a range that does not impair the effect, the amorphous region expands to a range where the ratio of A and B is 9:1 to 1:9. come. The average molecular weight range of the copolycarbonate of the present invention varies depending on the use, but it is usually a number average molecular weight.
It is 300 to 50,000, preferably 600 to 20,000. The terminal groups of the copolycarbonate of the present invention can be made into various groups depending on the use. For example, when used in polyurethane applications, the copolycarbonate ends must be substantially all hydroxyl groups. When used as a polyester elastomer, carbonate elastomer, or polymer plasticizer, the copolycarbonate terminal may be replaced with a hydroxyl group, an alkyl carbonate group, an aryl carbonate group, a carboxyl group, or an ester group. When used in polyamide-based elastomer applications, substantially all of the copolycarbonate terminals can be replaced with carboxyl groups. In addition, for photosensitive resins, coating agents, and optical materials,
Substantially all of the terminal ends of the copolycarbonate are converted to allyl groups or (meth)acryloyl groups, and for sealant applications, silane groups having substituents such as halogen, alkoxy, and acyloxy that are reactive at room temperature are used. It can be used in the presence of at least one end of the copolycarbonate. In addition, it is possible to provide various functional groups such as an amino group, an aminoalkyl group, a glycidyl ether group, a cyanoethyl group, and an isocyanate group. The copolycarbonate having terminal hydroxyl groups of the present invention is a novel polymer, and a representative example thereof is represented by the general formula (1) as follows. R ₁ is an aliphatic glycol residue mainly having 5 or 6 carbon atoms, and n is an integer in the range of 2 to 200, preferably in the range of 4 to 100. In general, as described in Polymer Reviews Volume 9, pages 9-20 mentioned above, transesterification of dialkyl carbonates and aliphatic hydroxy compounds can be carried out using general transesterification catalysts. can. However, when an aliphatic polycarbonate diol is used in a thermoplastic elastomer, such as a polyester polycarbonate elastomer, for example, the hard segment polyester and the soft segment polycarbonate tend to undergo transesterification due to residual catalyst, resulting in a decrease in physical properties. . To prevent this, it is necessary to purify polycarbonate diol, but for purification,
It involves many operations and labor such as dissolution, extraction, and drying. In order to avoid this, it is preferable to produce polycarbonate diol without a catalyst. Conventionally known methods for synthesizing without a catalyst include using ethylene carbonate, which has five-membered ring strain energy, and using diphenyl carbonate, which is easily dissociated as a phenoxy group. This is possible. Furthermore, a method using dimethyl carbonate discovered by the present inventors is also possible. Among these methods, when the present inventors conducted a method in which diphenyl carbonate was reacted with an aliphatic di- and/or polyhydroxyl compound, a colored substance was produced from trace amounts of oxygen and other impurities and phenol in the reaction system. However, it was not possible to obtain colorless polycarbonate diol. Furthermore, due to phenol
Corrosion effects on the SUS reactor were also observed. Therefore, a method using dimethyl carbonate or ethylene carbonate without a catalyst is preferred. A detailed example of the method using dimethyl carbonate will be described next. That is, in this method, dimethyl carbonate and an aliphatic diphasic and/or polyhydroxy compound are reacted without using a catalyst at a temperature of 120 to 280°C under normal pressure or increased pressure while distilling off methanol, and then the temperature is further increased.
It is characterized by carrying out the reaction at 120 to 280°C under reduced pressure while distilling off methanol. The reaction temperature needs to be 120-280°C. When the reaction temperature is less than 120°C, the polymerization rate is very slow, and when it exceeds 280°C, the polymer decomposes violently. More preferably it is 150°C to 250°C. Dimethyl carbonate has a boiling point of 90°C, so in order to maintain the reaction system at 120 to 280°C, it is best to add dimethyl carbonate continuously after a small amount is added at the beginning of the reaction, or continuously from the beginning of the reaction.
Furthermore, if a pressurizable reactor is used, the reaction temperature can be freely set regardless of the amount of dimethyl carbonate present. Furthermore, in the reaction of the present invention, it is necessary to continuously extract the methanol produced to allow the reaction to proceed. In order to efficiently fractionate unreacted dimethyl carbonate and produced methanol, it is preferable to use a reactor equipped with a fractionation column. In the first stage of the reaction, the temperature is 120-280℃, preferably 150-250℃,
In addition, methanol is distilled out under normal pressure conditions, and in the latter stage of the reaction, the temperature is 120 to 280°C, preferably 150 to 250°C, and the pressure is
It is preferable to carry out the reaction while distilling methanol under conditions of 700 to 0.05 mmHg. In the latter stage of the reaction, it is also possible to shorten the reaction time by forming the reaction solution into a thin film to efficiently remove methanol. According to the method of the present invention, it is possible to freely obtain dimer, trimer or higher polycarbonate polyols by adjusting the charging ratio of diol and carbonate. A detailed example of the method using ethylene carbonate will be described below. The polycarbonate manufacturing method is carried out in two stages. That is, aliphatic di-or polyol and ethylene carbonate are mixed in a molar ratio of 20:1 to 1:10, and reacted at a temperature of 100 to 300°C under normal pressure or reduced pressure to remove by-produced ethylene glycol and unreacted Ethylene carbonate is distilled off to obtain a low molecular weight polycarbonate having 2 to 10 units, and then unreacted hydroxy compound and ethylene carbonate are distilled off under reduced pressure at a temperature of 100 to 300°C, and the low molecular weight polycarbonate is self-condensed. The raw material hydroxy compound produced during this period continues to be distilled off to obtain polycarbonate of the desired molecular weight. The composition ratio in the copolycarbonate is controlled by checking the composition of the raw material hydroxy compound to be distilled and by adding additional raw materials during the reaction. In addition, as another synthesis method, for example,
Publication No. 56-133246 (U.S. Patent No. 4508656)
discloses a method for obtaining a terminal allyl carbonate having a degree of polymerization of 1 to 10 by reacting a polyhydric alcohol with diallyl carbonate in the presence of a transesterification catalyst. If the degree of polymerization is to be further increased, it is also possible to proceed with the condensation while removing diallyl carbonate from the system under reduced pressure. Of course, it is also possible to use diallyl carbonate instead of dimethyl carbonate or ethylene carbonate, as described above for the synthesis of copolycarbonates having terminal hydroxyl groups, without using a catalyst. A method using a transesterification catalyst will be described in detail. Among the transesterification catalysts, alkali metal alcoholates, especially sodium methylate, are preferred because they are cheap and easily removed from the reaction product, for example by reaction with carbon dioxide or by simple washing. Alternatively, these catalysts are removed by treatment with organic or inorganic acids or even by flowing through a sulfonated acidic resin. Other catalysts, although somewhat less efficient, include organic or inorganic acids, such as Ti
(OR) ₄ and MgTi(OR) ₆ (where R is an organic group), transition metal alcoholates (also in the form of double salts), or metal oxides such as CaO, ZnO, SnO(OR) ₂ , etc. Or a combination of these can be used. In any case, these transesterification reaction catalysts are more expensive than alkali metal alcoholates, and moreover, they are difficult to remove from the reaction product. The amount of catalyst effective to form the copolycarbonate diol bisallyl carbonate is between 0.001 and 0.5 of the reaction mass.
% by weight, preferably 0.01% by weight. In the first step, diallyl carbonate is used in excess compared to the stoichiometry required to form the copolycarbonate diol bisallyl carbonate, with a preferred molar ratio of diallyl carbonate:polyhydric alcohol being 5:
The ratio is 1 to 10:1. The reaction temperature in the first step is generally 100 to 150°C, preferably around 120°C. The pressure at which the reaction is carried out is such that the by-product allyl alcohol can be produced and simultaneously removed by evaporation without removing or substantially removing unreacted diallyl carbonate present in the reaction solvent. . Depending on the reaction temperature, the pressure at which the operation can be effectively carried out is from about 300 to about 50 torr. Under the above reaction conditions, complete or substantially complete functionalization of the polyhydric alcohol with diallyl carbonate can be carried out, and the reaction time is generally from 0.5 to 3 hours. In fact, this first reaction step is considered to have been completed because the generation of allyl alcohol, a reaction by-product, has ended. At this stage, the pressure inside the reactor should be reduced to about 1 torr or less, and the temperature should be between 70°C and 70°C.
The second reaction step is started by heating to a temperature of 200°C. During the second reaction step, the catalyst used in the first reaction step becomes active in the same concentration range as above. Under these conditions, first, unreacted diallyl carbonate from the first reaction step is removed by evaporation,
Thereafter, a chain extension reaction of the terminal allyl carbonate having a degree of polymerization of 1 to 10 of the polyhydric alcohol produced in the first reaction step occurs, and diallyl carbonate is further removed. The preferred temperature for this second reaction step is between 90 and 150 °C.
It is ℃. The reaction in the second formulation is stopped when the final product has the desired molecular weight (easily checked by viscosity measurements). The polyurethane of the present invention using a copolycarbonate having substantially all terminals with hydroxyl groups is prepared by combining a copolycarbonate polyol, a polyisocyanate, and optionally a chain extender having at least two active hydrogen atoms capable of reacting with the polyisocyanate. synthesized from The average molecular weight range of copolycarbonate polyols used for polyurethane varies depending on the application, but the number average molecular weight is usually 500 to 30,000.
Preferably 600 to 20,000, more preferably 700 to
6000 are used. More specifically, the polyurethane used in the present invention not only has excellent abrasion resistance, impact resistance, hydrolysis resistance, oxidative deterioration resistance, light resistance, low temperature flexibility, and flexibility, but also has excellent elastic recovery. It is a polyurethane with outstanding properties and can cover a wide range of applications for which conventional polyurethanes have been used. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Copolycarbonate having hydroxyl group terminals The hydroxyl value in the examples was measured by an acetylation method. In addition, the glass transition temperature of the polymer can be determined by DSC
(Temperature increase rate 10℃/min, measurement range -150℃ to +60℃)
It was measured from In addition, the ends of the polymers in Examples and Comparative Examples were determined by ¹³ C-NMR (270MHz) measurement.
Substantially all were hydroxyl groups. Furthermore, the acid value in the polymer was measured by titration with KOH, and all polymers in Examples and Comparative Examples were 0.01.
It was below. Therefore, the number average molecular weight of the obtained polymer is determined by the following formula. Number average molecular weight = 2/(OH value x 10 ^-3 /56.11) Examples 1 to 6, Comparative Examples 1 to 3 A reactor equipped with a stirrer, a thermometer, and a fractionating tube was charged with the following materials as shown in Table 1. Add polyhydric alcohol, 70~
At 80°C sodium metal was added under stirring. After the sodium had completely reacted, diethyl carbonate was introduced in the amount shown in Table 1. When the reaction temperature was raised to 95-100°C under normal pressure, ethanol began to distill out. The temperature was gradually increased to 160°C for the time shown in Table 1. During this time, ethanol containing about 10% diethyl carbonate was distilled out. Thereafter, the pressure in the reactor was further reduced to 100 mmHg or less, and the reaction was carried out at 200° C. for the time shown in Table 1 with strong stirring while extracting ethanol. After cooling, the generated polymer was dissolved in dichloromethine, neutralized with dilute acid, washed with water several times, dehydrated with anhydrous sodium sulfate, the solvent was removed by distillation, and further heated at 2 to 3 mmHg at 140°C.
Let it dry for several hours. The properties of the obtained copolycarbonate diol are shown in Table 1.

【table】

[Table] Example 7 In a 1-volume separable flask equipped with a Wittmer fractionation tube, a reflux head, and a condenser at the top of the column,
1,6-hexanediol 236g (2 mol), 1,
Prepare 208 g (2 moles) of 5-pentanediol,
dimethyl carbonate under stirring at a temperature of 150-190℃.
It was added dropwise over 6.5 hours. At this time, from the top of the tower, 0~
Methanol containing 30% dimethyl carbonate was distilled out. Assuming that the reaction amount of dimethyl carbonate is equal to the added amount minus the distilled amount,
The amount of dimethyl carbonate added was adjusted so that the reaction amount of dimethyl carbonate was r=0.913 with respect to the number of moles of diol charged. The composition after distillation was analyzed by gas chromatography.
After finishing dimethyl carbonate dropping, 180-250℃
gradually increase the internal pressure of the system by 10mm from 700mmHg with a vacuum pump.
The pressure was reduced to about Hg and the reaction was allowed to proceed for 3.5 hours. Thereafter, the pressure was reduced from 10 mmHg to 0.05 mmHg and the reaction was carried out for 15 minutes. At this time, a small amount of distillate was obtained in the cooling trap. After the reaction was completed, about 500 g of an almost colorless transparent viscous liquid was obtained in the reactor. This product is ^13C
-NMR confirmed that it was a polycarbonate diol consisting of pentamethylene groups and hexamethylene groups. All polymer terminals were hydroxyl groups. Furthermore, its molecular weight was determined by GPC and was approximately 1300. Example 8 The same raw materials and the same method as in Example 7 were used. However, the reaction temperature should be adjusted to 170°C to 185°C when adding dimethyl carbonate, and 180°C to 200°C when reducing pressure.
The temperature was adjusted to ℃. Further, the amount of dimethyl carbonate added was adjusted so that r=0.947. After the reaction is complete, an almost colorless and transparent viscous liquid will be left in the reactor.
Got 500g. This product was determined by ¹³ C-NMR to be a polycarbonate diol consisting of pentamethylene and hexamethylene groups. All polymer terminals were hydroxyl groups. Further, its molecular weight was determined to be approximately 2200 by GPC. Comparative example 4 1,6-hexanediol 236 g (2.0 mol),
A copolycarbonate was obtained in the same manner as in Example 5, except that 320 g (2.0 mol) of 1,9-nonanediol was used. This copolycarbonate was a white solid at room temperature, showed a melting point peak at 28°C according to DSC, and was a crystalline polymer. ¹³ C−
NMR analysis confirmed that all polymer terminals were hydroxyl groups. The OH value was 46.8. This polycarbonate was evaluated as a polyurethane in a reference example. Example 9 In a 2 volume four neck round bottom flask equipped with a stirrer, thermometer, packed distillation column and feed funnel, 1.
500 parts of 6-hexanediol, 450 parts of 1,5-pentanediol, and 400 parts of ethylene carbonate were added. The mixture was heated and distilled under reduced pressure of approximately 120 mmHg. The distillate was collected at approximately 145-150°C. An additional 700 parts of ethylene carbonate was slowly added to the reaction mixture through the feed funnel, bringing the reaction temperature to about 200
The temperature was maintained at ~205°C. Approximately 570 parts of distillate were obtained. Then reduce the pressure to about 25mmHg,
Unreacted material was distilled off at an external temperature of about 200-250°C. Approximately 250 parts of distillate were recovered. Thereafter, the external temperature was raised to 220°C and a final distillation was carried out at 3 mmHg. Approximately 103 parts additional distillate was recovered. The residue had an OH value of 66.0 and had virtually no melting point. Example 10 A reactor equipped with a stirrer, a thermometer and a fractionating tube was
1,6-hexanediol 47.2g (0.4mol),
1,5-pentanediol 20.8g (0.2mol),
of 1,4-butanediol 18 g (0.2 mol), trimethylolpropane 11 g (0.08 mol), diallyl carbonate 100 g (0.7 mol) and sodium methoxide.
20 ml of 30% methanol solution was added. reaction temperature
The temperature was raised to 120°C, the degree of vacuum was set to 150 mmHg, and the mixture was stirred vigorously. The reaction was continued for 5 hours while allyl alcohol was distilled off. Next, 500 g (3.5 moles) of diallyl carbonate was added to the reactor, and the reaction was continued for another 2 hours under the same conditions. Next, the degree of vacuum was set to 2 mmHg, and a chain extension reaction of bisallyl carbonate was carried out while distilling off diallyl carbonate produced as a by-product during the reaction. The reaction was carried out for 25 hours while checking the viscosity and molecular weight. After cooling, the produced polymer was dissolved in dichloromethane, neutralized, washed with water, dried, and the solvent was distilled off under reduced pressure to obtain a liquid bisallyl copolycarbonate. The molecular weight is
It was 5500 on GPC. Polyurethane using copolycarbonate having hydroxyl group terminals The intrinsic viscosity [η] of the polyurethane in Examples and Comparative Examples was within the range of 0.8 to 1.2. In addition, the hydrolysis resistance of polyurethane in the examples is
A polyurethane film with a thickness of 100μ was treated in hot water at 100°C for 12 hours, and the film was evaluated based on the average molecular weight retention rate measured by GPC. Regarding light resistance, the same film was irradiated with 380 nm carbon arc ultraviolet rays for 25 hours using a fade meter, and the tensile strength retention rate after that was evaluated. Regarding oxidative deterioration resistance, TGA (in air, 10
Evaluation was made based on the thermal decomposition initiation temperature (temperature increase per minute). Regarding elastic recovery, after stretching a 100μ polyurethane film by 300% in about 90 seconds at room temperature,
After being held for about 90 seconds and suddenly contracted, the length was measured and evaluated based on its permanent elongation rate. Regarding chlorine resistance, the above film was treated in an aqueous solution of pH=7 containing 1773 ppm of sodium hypochlorite at 70° C. for 16 hours, and evaluated by the tensile strength retention rate of the film. For intrinsic viscosity, add 0.02g, 0.05g, 0.1g of polyurethane to 100ml of dimethylacetamide solution.
A dissolved polyurethane solution was prepared, the reduced viscosity was measured at 30°C, and the polyurethane concentration was extrapolated to zero. Examples 11 to 13 Comparative Examples 5 to 8 Aliphatic copolycarbonate was prepared in the same manner as in Example 1, except that 1,6-hexanediol and 1,5-pentanediol were used in the amounts shown in Table 2 as diols. Diol A~G (PC-A~PC
-G) was obtained. The OH values of each were as shown in Table 2.

[Table] Example 14 Aliphatic polycarbonate diol-H (abbreviated as PC-H) was obtained in the same manner as in Example 1 except that 440 parts of diethyl carbonate was used. The OH value was 75.0. Example 15 Aliphatic polycarbonate diol-I (abbreviated as PC-I) was obtained in the same manner as in Example 1 except that 490 parts of diethyl carbonate was used. The OH value is
It was 38.0. Example 16 496 parts (4.2 mol) of 1,6-hexanediol and 1,5-pentanediol were prepared in the same manner as in Example 5.
Copolycarbonate diol-J (abbreviated as PC-J) was obtained using 437 parts (4.2 mol) and 144 parts (1.6 mol) of 1,4-butanediol. The OH value was 53.3. Comparative Example 9 236 parts (2.0 mol) of 1,6-hexanediol and 320 parts of 1,9-nonanediol were prepared in the same manner as in Comparative Example 4.
(2.0 mol) was used to obtain copolycarbonate diol-K (abbreviated as PC-K). OH value is 46.8
It was hot. Comparative Example 10 Same as Comparative Example 3, 472 parts (4.0 mol) of 1,6-hexanediol, 360 parts of 1,4-butanediol
(4.0 mol) was used to obtain copolycarbonate diol-L (abbreviated as PC-L). OH value is 58.1
It was hot. Reference Examples 1 to 7 Comparative Reference Examples 1 to 8 PC-A to PC-G shown in Examples, polytetramethylene glycol (OH value 59.6, abbreviated as PTMG) synthesized by Asahi Kasei Corporation, polytetramethylene adipate (manufactured by Dic, OH value 58.3, abbreviated as PTA) (dehydrated under reduced pressure heating), mixed with toluene/MIBK (1/1wt/wt) in an amount four times the weight of the polyol. The mixture was dissolved in water and heated to 100°C (the weight of the preparation is shown in Table 3). Next, a predetermined amount of hexamethylene diisocyanate (abbreviated as HDI), 4,4'-methylenebis(cyclohexyl) diisocyanate (abbreviated as H-MDI), or diphenylmethane-4,4'-diisocyanate (abbreviated as MDI) is added. diisocyanate was dissolved in the same amount of toluene/MIBK (1/1wt/wt) as the weight of the diisocyanate, and added to the above polyol solution and mixed (the amount charged was
(shown in the table). Next, a 10% by weight toluene/MIBK (1/1wt/wt) solution of dibutyltin laurate was added to give a concentration of 100ppm based on the solids in the solution, and the solution was heated to 100°C.
A prepolymer was obtained by stirring for hours. Next, add a predetermined amount of a chain extender, either 1,4-butanediol or ethylene glycol, toluene/MIBK (1/1wt/wt) (the amount of solvent is such that the solid content in the solution is 25% by weight). The polyurethane solution was dissolved in a polyurethane solution (prepared as follows) and stirred vigorously at 100° C. for 1 hour (the amounts charged are shown in Table 3) to obtain a 25% by weight polyurethane solution. Next, the solvent was removed from this polymer solution under reduced pressure to obtain polyurethane. Table 3 shows the evaluation results of various performances of these polyurethanes.

[Table] Reference Examples 8 to 9 Comparative Reference Examples 9 to 12 PC-A, PC-J, PC-D, PC-L,
PTMG, 2 mol each of polyhexamethylene neopentylene adipate (manufactured by Hyel, OH value 56.0, abbreviated as PHNA) and diphenylmethane.
4 moles of 4,4'-diisocyanate under nitrogen stream
An isocyanate-terminated prepolymer was produced by reacting at 80° C. without solvent for 4 hours with stirring, and then cooled to room temperature, and sufficiently dehydrated dimethylacetamide was added thereto to dissolve it. A dimethylacetamide solution in which 2 moles of ethylenediamine had been dissolved was added all at once to this solution, and the mixture was stirred at room temperature for 30 minutes to obtain four types of 30% by weight polyurethane solutions. A part of the polyurethane solution is cast to obtain a 100μ film, which has hydrolysis resistance, light resistance, oxidation resistance, elastic recovery,
In addition to chlorine resistance data, room temperature tensile elongation and tensile strength data were obtained. The results are in Table 4 and 1.
Shown in the figure. Furthermore, an attempt was made to spin most of the polyurethane solution using a small spinning device to obtain polyurethane fibers. The results are shown in Table 4.

【table】

〔Effect of the invention〕

The copolycarbonate diol of the present invention is liquid at room temperature, has excellent workability, and has a good balance of hydrolysis resistance, light resistance, oxidative deterioration resistance, elastic recovery, etc. using the copolycarbonate diol of the present invention as a raw material. A smooth polyurethane resin is obtained.

[Brief explanation of drawings]

Figure 1 shows the polystyrene of the present invention (PC-A,
PC-J) and comparative examples (PC-D, PC-L,
This shows the tensile strength and tensile elongation of PTMG, PHNA).

Claims (1)

[Scope of Claims] 1 Consisting of the following repeating units A and B, the terminal group is a hydroxyl group, the ratio of A and B is 9:1 to 1:9
and an aliphatic copolycarbonate diol with an average molecular weight of 300 to 50,000. 2 A/B of copolycarbonate diol is
The aliphatic copolycarbonate diol of claim 1, which has a ratio of 75/25 to 15/85.