JP3466379B2 - polyester - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester, and more particularly, to a polyester suitable for applications such as paints, adhesives, polyurethanes and polyamide elastomers and polyester elastomers. [0002] In the field of paints, adhesives, polyurethanes and the like, polyesters having a hydroxyl group at the molecular terminal have been used. Such polyesters include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6
Polyesters obtained from polyhydric alcohols such as hexanediol, trimethylolpropane and glycerin and polybasic acids or anhydrides or ester derivatives thereof are known. Among these polyesters, an aromatic dicarboxylic acid such as phthalic anhydride, isophthalic acid and terephthalic acid is used in combination with an aliphatic dicarboxylic acid such as adipic acid as a polybasic acid, and a dihydric or trihydric or higher polyhydric alcohol and an ester are used. Hydroxyl-terminated polyesters obtained by the chemical reaction are widely used in the fields of paints and adhesives. A hydroxyl-terminated polyester obtained by subjecting an aliphatic dicarboxylic acid such as adipic acid to an esterification reaction with a dihydric or trihydric or higher polyhydric alcohol is a 2-terminal polyester.
Polyurethane can be made by reacting with isocyanate compounds having functionalities or higher, and is used for a wide range of applications such as elastomers, paints, adhesives, coating agents, and foams. [0004] Further, polyesters having a carboxyl group at the molecular end can be converted into a polyester polyamide having excellent heat resistance by reacting with a difunctional or more isocyanate compound, and are used for applications such as elastomers. [0005] Conventional polyesters having a hydroxyl group or a carboxyl group at the molecular end generally have poor hydrolysis resistance. For this reason, the products obtained from these conventional polyesters have a problem that the surface tends to become tacky or crack easily in a relatively short time. In order to improve the hydrolysis resistance of the polyester, it is generally effective to reduce the ester group concentration of the polyester. In order to reduce the ester group concentration in the polyester, it is preferable to form the polyester from a glycol having a large number of carbon atoms and a dicarboxylic acid having a large number of carbon atoms.However, the obtained polyester has a high tendency to crystallize and generally has a high viscosity liquid or There is a problem that it becomes solid and is inferior in workability. In addition, paints, adhesives, polyurethanes, and polyamide elastomers and polyester elastomers obtained from polyesters formed from glycols having a large number of carbon atoms and dicarboxylic acids having a large number of carbon atoms have improved hydrolysis resistance, but are not crystallized. When left in a low-temperature atmosphere such as −20 ° C., for example, the low-temperature characteristics represented by bending resistance, flexibility (flexibility), low-temperature adhesion, and the like are significantly reduced. The inventors of the present invention have conducted various studies to provide polyesters having excellent hydrolysis resistance and no tendency to crystallize using industrially available raw materials. 8-octanediol and / or 1,9-
A polyester containing nonanediol has been found and a patent application has already been filed (see JP-A-63-182330). However, even in the case of this polyester, a slight tendency to crystallize may be observed at a temperature in a range where it is usually used, and there is room for improvement in flexibility when a polyurethane or polyamide elastomer is used. . Thus, the present invention has excellent hydrolysis resistance,
Polyester that does not have a tendency to crystallize and has excellent flexibility (flexibility), hydrolysis resistance and low-temperature properties when used in applications such as paints, adhesives, polyurethanes, polyamide elastomers and polyester elastomers. It is an object of the present invention to provide a novel polyester which gives a product having the same. According to the present invention, the above object is achieved by the following formula (1) and / or the following formula (2): -CO-R-CO-O-CH _{2- CH (CH 3) - (CH} 2) 4 -CH (CH 3)
_{-CH 2 -O- (1) -CO-} R-CO-O-CH 2 -CH (CH 3) - (CH 2) 5 -CH (CH 3)
-CH ₂ -O- ₍₂₎ [wherein, R is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group, Ali alkarylene group or -C ₆ H ₄ -X,
—C ₆ H ₄ — (X represents at least one group selected from the group consisting of O, S, SO ₂ , an alkylidene group having 2 to 8 carbon atoms or an alkylene group having 1 to 2 carbon atoms)] This is solved by providing a polyester characterized by having a repeating unit represented by the formula (1) as a main component and having a number average molecular weight of 300 to 30,000. In the present invention, "mainly composed of the repeating unit represented by the formula (1) and / or the formula (2)" means that at least 20 mol% or more of the repeating units constituting the polyester have the formula (1) And / or equation (2)
Means a repeating unit represented by When the content of the repeating unit represented by the formula (1) and / or the formula (2) in the repeating unit constituting the polyester is less than 20 mol%, the flexibility (flexibility) of the obtained polyester is reduced. And physical properties such as hydrolysis resistance are reduced. The content of the repeating unit represented by the formula (1) and / or the formula (2) in the repeating unit constituting the polyester is more preferably 50 mol% or more. In the above formula (1) and / or formula (2), examples of the alkylene group having 2 to 20 carbon atoms represented by R include a methylene group, an ethylene group, a propylene group, a hexamethylene group, heptamethylene group, octamethylene group, and examples of the cycloalkylene group include, for example, such as 1,4-cyclohexylene group, the ants alkarylene group include phenylene group, naphthylene group . The alkylidene group having 2 to 8 carbon atoms represented by X includes, for example, an ethylidene group and an isopropylidene group, and the alkylene group having 1 to 2 carbon atoms includes a methylene group and an ethylene group. . The repeating unit represented by the formula (1) comprises a diol unit represented by the following formula (3) and a dicarboxylic acid unit represented by the following formula (4). _{-O-CH 2 -CH (CH 3} ) - (CH 2) 4 -CH (CH 3) -CH 2 -O- (3) -CO-R-CO- (4) ( wherein, R defined The repeating unit represented by the formula (2) is composed of a diol unit represented by the following formula (5) and a dicarboxylic acid unit represented by the above formula (4). _{-O-CH 2 -CH (CH 3} ) - (CH 2) 5 -CH (CH 3) -CH 2 -O- (5) [0016] Here, the diol unit represented by the formula (3) is 2 , 7-Dimethyl-1,8-octanediol, and the diol unit represented by the formula (5) is derived from 2,8-dimethyl-1,9-nonanediol. 2,
3,7-dimethyl-1,8-O-click butanediol, for example,
Manufactured industrially by hydrogenating the product obtained by reacting 2-methyl-1,8-octanedial, derived from 2,7-octadien-1-ol, which is mass-produced and readily available, with formaldehyde can do. In addition, 2,8-dithimer-1,9-nonanediol is obtained, for example, by reacting 1,9-nonandial, derived from 2,7-octadien-1-ol, which is mass-produced and easily available, with formaldehyde. It can be produced industrially by hydrogenating the product. The polyester provided by the present invention is:
It can contain other polyol units other than 2,7-dimethyl-1,8-octanediol unit and 2,8-dimethyl-1,9-nonanediol unit. As such another polyol unit, a low molecular weight polyol unit is suitably used. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-
1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-
Nonanediol, 1,10-decanediol, 2,2-
Low molecular weight diol units such as diethyl-1,3-propanediol, 1,4-cyclohexanediol, and cyclohexanedimethanol are exemplified. These low molecular polyol units may be used alone or in combination of two or more. In addition, trimethylolpropane, trimethylolethane, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol and the like.
You may make it contain the unit which consists of low molecular polyols of functional or higher. The content of these low molecular polyol units is as follows:
Desirably, the content is less than 20 mol% based on the total amount of the polyol units constituting the polyester. The dicarboxylic acid unit represented by the formula (4) includes an aliphatic dicarboxylic acid unit such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; and an alicyclic ring such as cyclohexanedicarboxylic acid. formula di <br/> acid unit phthalic acid, terephthalic acid, isophthalic acid, and aromatic dicarboxylic acid units, such as naphthalene dicarboxylic acid, among others aliphatic dicarboxylic acid units are preferred. These dicarboxylic acid units derived from the corresponding dicarboxylate <br/> phosphate or its ester derivative. [0020] These dicarboxylic acid unit is used by being appropriately selected depending on the resulting polyester applications.
For example, in order to obtain a polyester that gives a polyurethane having excellent flexibility (flexibility), hydrolysis resistance, and low-temperature properties, it is preferable to use adipic acid, azelaic acid, and sebacic acid among the aliphatic dicarboxylic acid units. It may be used these di mosquito <br/> carboxylic acid units alone or may be used by mixing two or more kinds. Further, a polycarboxylic acid unit having three or more functionalities may be contained. The polyester provided by the present invention needs to have a number average molecular weight of 300 to 30,000. When the number average molecular weight is smaller than 300, the low-temperature properties and flexibility are poor, while the number average molecular weight is less than 300.
If it is larger than 00, mechanical properties such as strength and flexibility become poor. Number average molecular weight of polyester is 700 to 200
More preferably, it is within the range of 00. When the polyester of the present invention is used for applications such as production of polyurethane, it is necessary that the polyester has a hydroxyl group at a molecular terminal. When used for applications such as production of polyamide elastomers, it is necessary to have a carboxyl group at the molecular terminal. Terminal structure of the polyester can be appropriately adjusted by varying the molar ratio of the di-ol component and dicarboxylic acid component as a raw material. The number of hydroxyl groups or carboxyl groups present in the polyester varies depending on the intended use, but the number of hydroxyl groups or carboxyl groups is generally 2 or more per molecule, and preferably 2 to 3 per molecule. If
Polyester can be used for most applications and has versatility. The method for producing the polyester of the present invention is not particularly limited, and a known polyester polycondensation method can be applied. For example, 2,7-dimethyl-1,8-octanediol, or 2,8-dimethyl-1,9-nonanediol, or 2,7-dimethyl-1,8-octanediol and 2,8-dimethyl-1 , 9 mixture of nonanediol, or 2,7-dimethyl-1,8-octanediol and / or 2,8-dimethyl-1,9-low molecular weight diol mixture containing nonanediol and dicarboxylic acid component or The ester derivative is charged at a predetermined ratio, an esterification or transesterification reaction is performed, and the resulting reaction product is further subjected to a polycondensation reaction at a high temperature and in the presence of a polycondensation catalyst to obtain a desired molecular weight. Polyester can be manufactured. A wide range of polycondensation catalysts can be used for the production of polyester. Such polycondensation catalysts include, for example, tetramethoxytitanium, tetraethoxytitanium,
Titanium compounds such as tetra-n-propoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium ;
Examples include tin compounds such as n-butyltin oxide, di-n-butyltin dilaurate, and dibutyltin diacetate ; combinations of acetates such as magnesium, calcium, and zinc with antimony oxide or the above titanium compounds. These polycondensation catalysts are preferably used in the range of 5 to 500 ppm based on the total polyester produced. The polyester obtained according to the present invention has excellent hydrolysis resistance and does not have a tendency to crystallize, and exhibits excellent flexibility when used in paints, adhesives, polyurethanes and polyamide elastomers and polyester elastomers. To provide products having properties (flexibility), hydrolysis resistance and low-temperature properties. Further, the polyester obtained by the present invention is a novel high-performance material applicable to various other uses. EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the number average molecular weight of the polyester was determined by calculation based on the hydroxyl value and the acid value of the polyester. Example 1 480 g of 2,7-dimethyl-1,8-octanediol
And 292 g of adipic acid were charged into a reactor, heated to 200 ° C. in a nitrogen atmosphere under normal pressure, and an esterification reaction was carried out while distilling off generated water out of the system. At the time when the amount of generated water was reduced, 20 mg of tetraisopropoxy titanium was added, and 150 to 100 mmH
The reaction was continued while the pressure was reduced to g. Acid value is 1.0 KOHm
At the time of g / g, the degree of vacuum was further gradually increased by a vacuum pump to complete the reaction. As a result, a hydroxyl value of 5
Polyester having 6.1 KOH mg / g, acid value of 0.20 KOH mg / g and number average molecular weight of 2,000 and having hydroxyl groups at both ends (hereinafter abbreviated as polyester A)
I got Examples 2 to 5, Comparative Examples 1 to 3 An esterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 except that the diol component and the dicarboxylic acid component shown in Table 1 were used. (Hereinafter, the polyesters obtained in Examples 2 to 5 are respectively referred to as polyesters B to E, and the polyesters obtained in Comparative Examples 1 to 3 are respectively referred to as polyesters F to H). Table 1 shows the physical properties of the polyesters B to H.
Among the polyesters A to H, the polyesters A to E have 20
At 20 ° C., and polyesters FH were waxy or solid at 20 ° C. [Table 1] In Table 1, the diol component and dicarboxylic acid are indicated by the following abbreviations, respectively. DMOD: 2,7-dimethyl-1,8-octanediol DMND: 2,8-dimethyl-1,9-nonanediol MOD: 2-methyl-1,8-octanediol ND: 1,9-nonanediol AD: Adipic acid AZ: Azelaic acid Example 6 337 g of adipic acid, 296 g of 2,7-dimethyl-1,8-octanediol and 2,8-dimethyl-1,9
57 g of nonanediol was charged into a reactor and heated to 200 to 210 ° C. in a nitrogen atmosphere under normal pressure to carry out an esterification reaction while distilling off generated water out of the system. When the amount of generated water distills low, tetraisopropoxy
25 mg of titanium was added, and the reaction was driven while gradually reducing the pressure with a vacuum pump, and the reaction was completed when the terminal hydroxyl groups were almost eliminated. As a result, the hydroxyl value is 0.15 KO
A polyester having carboxyl groups at both ends (hereinafter abbreviated as polyester I) having Hmg / g, acid value of 56.5 KOHmg / g and number average molecular weight of 1986 was obtained. Examples 7 to 8 and Comparative Example 4 An esterification reaction and a polycondensation reaction were carried out in the same manner as in Example 6 except that the diol component and dicarboxylic acid shown in Table 2 were used. (Hereinafter, the polyesters obtained in Examples 7 and 8 are referred to as polyesters J and K, respectively, and the polyester obtained in Comparative Example 4 is referred to as polyester L). Table 2 shows the physical properties of the polyesters J to L. Among the polyesters I to L, the polyesters I to K were liquid at 20 ° C, and the polyester L was solid at 20 ° C. [Table 2] The abbreviations in Table 2 mean the same compounds as the abbreviations in Table 1. Reference Examples 1 to 8 Using the polyesters A to H obtained in Examples 1 to 5 and Comparative Examples 1 to 3, polyurethanes were produced in the following manner. That is, 0.05 mol (100 g) of each of polyesters A to H, 0.1 mol of 1,4-butanediol (9 mol)
g) and 0.15 mol (37.5 g) of 4,4′-diphenylmethane diisocyanate were reacted in dimethylformamide (DMF) at 80 ° C. for 5 to 8 hours under a nitrogen atmosphere to obtain a DMF solution of polyurethane (nonvolatile content 30%). ) Got. The DMF solution of polyurethane thus obtained was cast on a glass plate and dried to obtain a dry film having a thickness of 100 μm. Using this film, mechanical performance [stress against 400% strain (400%
Modulus: M ₄₀₀ ) Breaking strength and breaking elongation], and hydrolysis resistance were evaluated. The results are shown in Table 3 below. Evaluation of mechanical performance Evaluation was made according to the method specified in JIS K7311. That is, a polyurethane film having a thickness of 100 μm was formed, and a dumbbell-shaped test piece was prepared from the film. Using the obtained test piece, M ₄₀₀ , breaking strength and breaking elongation were measured at a tensile speed of 50 cm / min using an Instron universal testing machine (manufactured by Instron). Evaluation of hydrolysis resistance A polyurethane film having a thickness of 100 μm was formed, and the film was allowed to stand in hot water at 100 ° C. for 7 days. The retention rate (%) of the breaking strength was determined according to the following formula, and was used as an index of hydrolysis resistance. ## EQU1 ## ◎ A piece of polyurethane film having a low temperature characteristic of about 10 mg was formed, and this film was subjected to -1 using a differential scanning calorimeter (DSC).
The temperature was raised at a rate of 10 ° C./min from 50 ° C., and the glass transition temperature (° C.) was obtained and used as an index of low-temperature characteristics. [Table 3] From the results in Table 3, it can be seen that the polyesters A to E containing the repeating units represented by the formulas (1) and / or (2) were used (Reference Examples 1 to 5),
Or, when the polyesters F to H containing no repeating unit represented by the formula (2) are used (Comparative Examples 6 to 8), it is clear that the physical properties of the obtained polyurethane are different as follows. . That is, the polyurethanes obtained in Reference Examples 1 to 5 have smaller values of stress (M ₄₀₀ ) for 400% strain than the polyurethanes obtained in Reference Examples 6 to 8,
The value of the elongation at break is larger than that of the polyurethanes obtained in Reference Examples 6 to 8, and is excellent in flexibility. further,
Mechanical strength, hydrolysis resistance, low temperature properties, etc. are also 2-methyl-
It is the same as polyester containing 1,8-octanediol and 1,9-nonanediol, and is comparable to polyester. Reference Examples 9 to 12 Polyamide elastomers were produced by the following method using the polyesters (I to L) having carboxyl groups at both ends obtained in Examples 6 to 8 and Comparative Example 4. That is, each of the polyesters I to L was 0.1 mol (200 mol).
g), 0.25 mol (47 g) of azelaic acid and 4,
0.35 mol (87.5 g) of 4'-diphenylmethane diisocyanate was added to 1-methyl-2-phospholene-1-oxide as a catalyst in sulfolane under a nitrogen atmosphere and reacted at 180 ° C. for 7 to 10 hours. Thus, a sulfolane solution of polyamide elastomer (nonvolatile content: 30%) was obtained. The polyamide elastomer sulfolane solution thus obtained was cast on a glass plate and dried to a thickness of 0.1 mm.
2 mm and 100 μm dry films were obtained. Using this film, low-temperature flexibility and hydrolysis resistance were evaluated by the following methods. The results are shown in Table 4 below. ◎ Low-temperature flexibility (low-temperature flexibility) A polyamide elastomer film piece having a thickness of 0.2 mm was formed, and this film was measured for dynamic viscoelasticity (Vibron).
Using an apparatus, the glass transition temperature (° C.) was determined under the condition of 110 Hz. Further, a molded article obtained by applying a sulfolane solution of a polyamide elastomer on an artificial leather substrate and drying was evaluated at −20 ° C. for bending resistance according to the following criteria. That is, the longest is 3 cm and the shortest is 1 cm
Under the bending test conditions of 8600 bending times / hour with a stroke width of, when there is no change at the number of bending times of 100,000 times or more, the bending resistance is “○”. When it was so damaged that it could be seen, the bending resistance was evaluated as "x". Table 4 shows the results. Polyamide elastomers having a low glass transition temperature and good flexibility at low temperatures have no tendency to crystallize and are excellent in low-temperature flexibility (low-temperature flexibility). Evaluation of hydrolysis resistance A film of a polyamide elastomer having a thickness of 100 μm was formed, and the film was left in hot water at 100 ° C. for 7 days.
The retention (%) of the logarithmic viscosity measured at ° C. was determined according to the following formula, and was used as an index of hydrolysis resistance. The results are shown in Table 4 below. ## EQU2 ## [Table 4] From the results in Table 4, it can be seen that the polyesters I to K containing the repeating units represented by the formulas (1) and / or (2) were used (Reference Examples 9 to 11) and the formulas (1) and (2). Or, when compared with the case where the polyester L containing no repeating unit represented by the formula (2) is used (Reference Example 12), it is clear that the physical properties of the obtained polyamide elastomer are different as follows. That is, the polyamide elastomers obtained in Reference Examples 9 to 11 have a lower glass transition temperature, are superior in bending resistance, and are excellent in low-temperature flexibility than the polyamide elastomers obtained in Reference Example 12. Further, the hydrolysis resistance is the same as that of the polyester containing 2-methyl-1,8-octanediol and 1,9-nonanediol, and there is no inferiority. According to the present invention, excellent hydrolysis resistance is obtained.
Polyester that does not have a tendency to crystallize and has excellent flexibility (flexibility), hydrolysis resistance and low-temperature properties when used in applications such as paints, adhesives, polyurethanes, polyamide elastomers and polyester elastomers. Novel polyesters are provided that provide a product having the same.

Claims (1)

(57) Patent Claims 1. A following formula (1) and / or the following formula (2) -CO-R-CO -O-CH 2 -CH (CH 3) - (CH 2 ) ₄ -CH (CH ₃ )
_{-CH 2 -O- (1) -CO-} R-CO-O-CH 2 -CH (CH 3) - (CH 2) 5 -CH (CH 3)
-CH ₂ -O- ₍₂₎ [wherein, R is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group, Ali alkarylene group or -C ₆ H ₄ -X,
—C ₆ H ₄ — (X represents at least one group selected from the group consisting of O, S, SO ₂ , an alkylidene group having 2 to 8 carbon atoms or an alkylene group having 1 to 2 carbon atoms)] And a number average molecular weight of from 300 to 30,000.