Polyether ester and method for producing the same

Abstract

To provide a polyether ester exhibiting a whitish color and a method for producing the polyether ester.SOLUTION: In the presence of an aluminum catalyst and a phosphorus compound, for example, by melt polycondensing methyl 4-(2-hydroxyethoxy)vanillate, a polyether ester having a structural unit represented by the following formula (1b) is produced. In this polyether ester, an L* value in an L*a*b* color system measured in accordance with JIS Z 8722 preferably satisfies 69≤L*.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyetherester and a method for producing the same. [Background technology]

[0002] For example, polyether esters having structural units represented by the following formula (1) have high heat resistance and high fluidity comparable to super engineering polymers, and are therefore expected to be used in electrical and electronic components, automobiles, fibers, and films. [ka] (In formula (1), R 0 is an aliphatic group having 2 to 8 carbon atoms, and R 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group.

[0003] Patent Document 1 describes a polyetherester composed of structural units of formula (1) above, which (i) has a reduced viscosity of 0.40 to 1.00 dL / g at 35°C when 0.12 g of the polymer is dissolved in 10 mL of a mixture of 1,1,2,2-tetrachloroethane and p-chlorophenol in an 8:5 mass ratio, (ii) has a melting point of 220°C to 300°C, a glass transition temperature (Tg) of 60°C to 100°C, and (iii) has a 5% mass loss temperature (Td) of 350°C or higher. Patent Document 1 also describes a method for producing a polyetherester, which comprises heating and reacting monomers for obtaining the polyetherester at normal pressure in the presence of a compound containing at least one element selected from the group consisting of titanium, molybdenum, manganese, cobalt, and germanium as a polymerization catalyst, followed by melt polycondensation while heating at 200°C to 300°C under reduced pressure.

[0004] Patent Document 2 describes a method for producing a polyether ester comprising structural units of the above formula (1), in which monomers for obtaining the polyether ester are reacted by heating at normal pressure in the presence of at least one compound selected from the group consisting of diisopropoxytitanium bis(triethanolaminate) and titanium diisopropoxybis(2,4-pentanedionate) as a polymerization catalyst, and then melt-polycondensed under reduced pressure while heating at a temperature of 200°C to 300°C. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-256646 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-52129 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the polyether esters produced by the methods described in Patent Documents 1 and 2 are colored dark, and are therefore of very low versatility as alternative materials to polyethylene terephthalate (PET).

[0007] Therefore, an object of the present invention is to provide a whitish polyetherester and a method for producing the same. [Means for solving the problem]

[0008] The present invention relates to a compound represented by the following formula (1): [ka] (In formula (1), R 0 is an aliphatic group having 2 to 8 carbon atoms, and R 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group. A method for producing a polyether ester having a structural unit represented by In the presence of an aluminum catalyst and a phosphorus compound, a reaction of the following formula (2): [ka] (In formula (2), R 0 is an aliphatic group having 2 to 8 carbon atoms, and R 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group, and R 3 is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a benzyloxy group, or a phenoxy group. A monomer represented by the formula: It is a method.

[0009] The present invention also provides a compound of the following formula (1): [ka] (In formula (1), R 0 is an aliphatic group having 2 to 8 carbon atoms, and R 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group. A polyether ester having a structural unit represented by L measured in accordance with JIS Z 8722 * a * b * L in color space * The value is 69≦L * fulfill It is a polyether ester. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a whitish polyetherester and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0011] In the present invention, a monomer represented by the following formula (2) is melt-polycondensed. [ka] (In formula (2), R 0 is an aliphatic group having 2 to 8 carbon atoms, and R 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group, and R 3 is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a benzyloxy group, or a phenoxy group.

[0012] R 0 is a divalent aliphatic group having 2 to 8 carbon atoms, and specific examples thereof include a 1,1-ethanediyl group, a 1,2-ethanediyl group (ethylene group), a 1,1-propanediyl group, a 1,2-propanediyl group (propylene group), a 1,3-propanediyl group, a 2,2-propanediyl group, a 1,1-butanediyl group, a 1,2-butanediyl group, a 1,3-butanediyl group, a 1,4-butanediyl group, a 2,2-butanediyl group, a 2,3-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 1,7-heptanediyl group, a 1,8-octanediyl group, and a 1,6-octanediyl group. Of these, a 1,2-ethanediyl group (ethylene group) is preferred. 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group, and are preferably each independently a hydrogen atom or a methoxy group. 3 is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a benzyloxy group, or a phenoxy group, and a methoxy group or an ethoxy group is preferred. The monomer represented by the above formula (2) may be used alone or in combination of two or more.

[0013] The monomer represented by the formula (2) is preferably one or more selected from the group consisting of 4-(2-hydroxyethoxy)benzoic acid ester represented by the following formula (2a), 4-(2-hydroxyethoxy)vanillic acid ester represented by the following formula (2b), and 4-(2-hydroxyethoxy)syringic acid ester represented by the following formula (2c). 3 is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a benzyloxy group, or a phenoxy group, and is preferably a methoxy group or an ethoxy group. [ka] [ka] [ka]

[0014] In the present invention, an aluminum catalyst is used as a catalyst for promoting melt polycondensation of the monomer represented by formula (2). This makes it possible to obtain a polyetherester having a high molecular weight and a whitish color. Examples of aluminum catalysts include metallic aluminum, aluminum oxide, aluminum hydroxide, aluminum halide, organic aluminum, aluminum alkoxide, aluminum phenoxide, aluminum chelate compounds, organic acid aluminum salts, and inorganic acid aluminum salts. Among these, it is preferable to use an aluminum alkoxide or an aluminum chelate compound as the aluminum catalyst, since this results in a polyetherester having a higher molecular weight and a whitish color. One aluminum catalyst may be used alone, or two or more aluminum catalysts may be used in combination.

[0015] Specific examples of aluminum alkoxides include aluminum methoxide, aluminum ethoxide, aluminum propoxide, aluminum isopropoxide, aluminum butoxide, aluminum sec-butoxide, aluminum isobutoxide, and aluminum tert-butoxide. Of these, aluminum ethoxide is preferred. Specific examples of aluminum chelate compounds include aluminum acetylacetonate, aluminum trifluoroacetylacetonate, aluminum hexafluoroacetylacetonate, aluminum acetylacetate, and aluminum ethylacetoacetate. Of these, aluminum acetylacetonate is preferred.

[0016] The amount of aluminum catalyst used is arbitrary as long as the desired polyether ester can be obtained by melt polycondensation of the monomer represented by formula (2). The amount of aluminum catalyst used per mole of monomer is preferably 0.001 to 0.100 mol, more preferably 0.002 to 0.050 mol, and even more preferably 0.003 to 0.010 mol.

[0017] In the present invention, a phosphorus compound is used as an additive to enhance the activity of the aluminum catalyst. This allows for the production of a polyetherester with a high molecular weight. Examples of phosphorus compounds include phosphoric acid (P(=O)(OH)3) or its ester or salt, phosphonic acid (RP(=O)(OH)2) or its ester or salt, phosphinic acid (R2-P(=O)(OH)) or its ester or salt, phosphine oxide (R3-P=O), and phosphine (R3-P) [each R independently represents an organic group]. Among these, phosphonic acid or its ester or salt is preferred, as it has a significant effect of enhancing the activity of the aluminum catalyst. A phosphonic acid ester (RP(=O)(OR)2) [each R independently represents an organic group] is more preferred. One phosphorus compound may be used alone, or two or more may be used in combination.

[0018] Specific examples of the phosphonate ester include methylphosphonic acid diesters such as dimethyl methylphosphonate, diethyl methylphosphonate, and diphenyl methylphosphonate; ethylphosphonic acid diesters such as dimethyl ethylphosphonate, diethyl ethylphosphonate, and diphenyl ethylphosphonate; phenylphosphonic acid diesters such as dimethyl phenylphosphonate, diethyl phenylphosphonate, and diphenyl phenylphosphonate; and benzylphosphonic acid diesters such as dimethyl benzylphosphonate, diethyl benzylphosphonate, and diphenyl benzylphosphonate.

[0019] Furthermore, it is more preferable to use a compound in which the phenyl group of a phenylphosphonic acid diester has a phenolic OH group and a bulky substituent as the phosphonic acid ester. Specific examples of such compounds include 3-tert-butyl-4-hydroxybenzylphosphonic acid diesters such as dimethyl 3-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3-tert-butyl-4-hydroxybenzylphosphonate, and diphenyl 3-tert-butyl-4-hydroxybenzylphosphonate; and 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diesters such as dimethyl 3-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. Of these, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diester is preferred, and 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl is more preferred.

[0020] The amount of the phosphorus compound used is arbitrary as long as it can enhance the activity of the aluminum catalyst and thereby allow the monomer represented by formula (2) to be melt polycondensed to obtain the desired polyether ester. However, the amount of the phosphorus compound used per 1 mol of the aluminum catalyst is preferably 0.5 to 10.0 mol, more preferably 0.002 to 0.05 mol, and even more preferably 0.003 to 0.01 mol.

[0021] In the present invention, a monomer represented by formula (2) is melt-polycondensed in the presence of an aluminum catalyst and a phosphorus compound. Any method for melt-polycondensation may be used as long as the desired polyether ester can be obtained by melt-polycondensing the monomer represented by formula (2). For example, the monomer represented by formula (2) may be heated at 180 to 300°C under normal pressure in the presence of an aluminum catalyst and a phosphorus compound, and then heated at 180 to 300°C under reduced pressure.

[0022] As described above, by melt polycondensing a monomer represented by formula (2) in the presence of an aluminum catalyst and a phosphorus compound, a polyether ester having a corresponding structural unit represented by formula (1) below can be produced. [ka] (In formula (1), R 0 is an aliphatic group having 2 to 8 carbon atoms, and R 1 and R 2 are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group.

[0023] In particular, by melt polycondensing a 4-(2-hydroxyethoxy)benzoate ester represented by formula (2a), a 4-(2-hydroxyethoxy)vanillate ester represented by formula (2b), and a 4-(2-hydroxyethoxy)syringate ester represented by formula (2c), it is possible to produce a polyetherester represented by formula (2a), a polyetherester represented by formula (2b), and a polyetherester represented by formula (2c), respectively. These polyetheresters may be homopolymers or copolymers. [ka] [ka] [ka]

[0024] The polyether ester having the structural unit represented by formula (1) produced in the present invention exhibits a whitish color. Here, "whitish color" means a color with high brightness. Specifically, the L measured in accordance with JIS Z 8722, which is an index of the color brightness of the polyether ester having the structural unit represented by formula (1), * a * b * L in color space * The value is 69≦L * It is preferable that the above L * The value is 72≦L * It is more preferable that 75≦L * It is more preferable that 78≦L * It is particularly preferable that the above L * The larger the value, the brighter the white color, so it is preferable. * It may be ≦90.

[0025] Furthermore, the above L * a * b * a in color system * value and b * The value is -2.0≦a * ≦2.0 -2.0≦b * ≦22.0 It is more preferable to satisfy the following. * value and b * The value is an index of hue and saturation, and a * If the value is positive, the color is red. * A negative value means more green, and b * If the value is positive, the color is yellow. * A negative value means that the color is bluer, and the larger the value, the more vivid the color. * The value is -1.7≦a * ≦1.7 is more preferable, and -1.4≦a *It is more preferable that the above b * The value is -1.7≦b * ≦17.0, and it is more preferable that −1.4≦b * It is more preferable that L≦12.0. * a * b * L in color space * value, a * value, and b * The value can be measured by the method shown in the examples below.

[0026] The polyetherester having a structural unit represented by formula (1) produced by the present invention preferably has a large molecular weight. Specifically, the number average molecular weight (Mn) of the polyetherester having a structural unit represented by formula (1) is preferably 10,000 or more, more preferably 12,000 or more, even more preferably 14,000 or more, and particularly preferably 16,000 or more. The number average molecular weight (Mn) of the polyetherester having a structural unit represented by formula (1) may be, for example, 100,000 or less. The number average molecular weight (Mn) of the polyetherester having a structural unit represented by formula (1) can be measured by the method shown in the examples described below.

[0027] According to the present invention as described above, it is possible to provide a whitish polyetherester and a method for producing the same. [Example]

[0028] Example 1 A 50 mL recovery flask was charged with methyl 4-(2-hydroxyethoxy)vanillate (0.5326 g, 2.0 mmol) as the monomer, aluminum ethoxide (Al(OEt)3, 0.0016 g, 0.010 mmol) as the catalyst, and diethyl 3,5-di-tert-butyl-4-hydroxybenzenephosphonate (DPBHT, 0.0071 g, 0.020 mmol) as the additive. The resulting mixture was heated to 190 °C under a nitrogen stream and stirred for 20 min. The temperature was then increased to 280 °C in 10 °C increments every 10 min. The temperature was maintained at 280 °C for 30 min, and the reaction was continued at 280 °C for 3 h while reducing the pressure with a vacuum pump. The reaction mixture was then cooled to room temperature, dissolved in chloroform and trifluoroacetic acid, and the resulting solution was poured into methanol. The insoluble portion was filtered to recover the polyetherester (yield: 0.2506 g).

[0029] The number average molecular weight (Mn) and coloration state (L * a * b * L in color space * value, a * value, and b * The number average molecular weight (Mn) was measured by GPC using a mixture of chloroform and 4-chlorophenol (1 / 1 (v / v)) as the eluent. * a * b * L in color space * value, a * value, and b * The values ​​were measured using a Color Reader colorimeter (manufactured by Konica Minolta, product name: CR-20) in accordance with JIS Z 8722. The results are shown in Table 1.

[0030] <Example 2> The procedure was the same as in Example 1, except that aluminum isopropoxide (Al(OiPr)3) was used as the catalyst. The results are shown in Table 1.

[0031] Example 3 The procedure was the same as in Example 1, except that aluminum sec-butoxide (Al(OsBu)3) was used as the catalyst. The results are shown in Table 1.

[0032] Example 4 The procedure was the same as in Example 1, except that aluminum tert-butoxide (Al(OtBu)3) was used as the catalyst. The results are shown in Table 1.

[0033] <Example 5> The procedure was the same as in Example 1, except that aluminum acetylacetonate (Al(acac)3) was used as the catalyst. The results are shown in Table 1.

[0034] Example 6 Except for using 1.5 times the amount (0.030 mmol) of additive, the same method as in Example 5 was carried out. The results are shown in Table 1.

[0035] Example 7 Except for using 2.0 times the amount (0.040 mmol) of additive, the same method as in Example 5 was used. The results are shown in Table 1.

[0036] Example 8 Except for using 2.5 times the amount (0.050 mmol) of additive, the same method as in Example 5 was carried out. The results are shown in Table 1.

[0037] Example 9 The procedure was the same as in Example 1, except that aluminum ethylacetoacetate (Al(EAA)3) was used as the catalyst. The results are shown in Table 1.

[0038] Example 10 The procedure was the same as in Example 1, except that aluminum trifluoroacetylacetonate (Al(acacF3)3) was used as the catalyst. The results are shown in Table 1.

[0039] <Comparative Example 1> The same procedure as in Example 1 was carried out except that titanium isopropoxide (Ti(OiPr)4) was used as the catalyst. However, the resulting polyether ester had low solubility in the eluent, and it was not possible to measure the number average molecular weight (Mn). The results are shown in Table 1.

[0040] <Comparative Example 2> The procedure was the same as in Example 1, except that iron acetylacetonate (Fe(acac)3) was used as the catalyst. The results are shown in Table 1.

[0041] <Comparative Example 3> The procedure was the same as in Example 1, except that zinc acetylacetonate (Zn(acac)2) was used as the catalyst. The results are shown in Table 1.

[0042] <Comparative Example 4> Except for using 2,4,6-tri-tert-butylphenol (tBu3PhOH) as the additive, the same procedure as in Example 5 was carried out. The results are shown in Table 1.

[0043] <Comparative Example 5> The procedure was the same as in Example 5, except that methyl 4-hydroxy-3,5-di-tert-butylbenzenepropionate (MPBHT) was used as the additive. The results are shown in Table 1.

[0044] <Comparative Example 6> The experiment was carried out in the same manner as in Example 5, except that 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenol (MBP) was used as the additive. The results are shown in Table 1.

[0045] <Comparative Example 7> Except for not using any additive, the same procedure as in Example 5 was carried out. The results are shown in Table 1.

[0046] [Table 1]

[0047] As described above, the polyether esters obtained in Examples 1 to 10 using an aluminum catalyst and a phosphorus compound have a large number average molecular weight (Mn) and a large L * On the other hand, the polyether esters obtained in Comparative Examples 1 to 3, which used a catalyst other than an aluminum catalyst, Comparative Examples 4 to 6, which added an additive other than a phosphorus compound, and Comparative Example 7, which did not use an additive, had small number average molecular weights (Mn) and L * The small value indicates a blackish color.

[0048] Example 11 The same procedure as in Example 7 was carried out, except that 4-(2-hydroxyethoxy)methyl vanillate (vanilate, 1.6 mmol) and 4-(2-hydroxyethoxy)methyl syringate (syringate, 0.4 mmol) were used as monomers. The results are shown in Table 2.

[0049] Example 12 The same procedure as in Example 7 was carried out, except that 4-(2-hydroxyethoxy)methyl vanillate (vanilate, 1.2 mmol) and 4-(2-hydroxyethoxy)methyl syringate (syringate, 0.8 mmol) were used as monomers. The results are shown in Table 2.

[0050] Example 13 The procedure was the same as in Example 7, except that 4-(2-hydroxyethoxy)methyl syringate (syringate, 2.0 mmol) was used as the monomer. The results are shown in Table 2.

[0051] [Table 2]

[0052] The copolymer polyether ester of methyl 4-(2-hydroxyethoxy)vanillate and methyl 4-(2-hydroxyethoxy)syringate (Examples 11 and 12) and the homopolymer polyether ester of methyl 4-(2-hydroxyethoxy)syringate (Example 13) obtained using an aluminum catalyst and a phosphorus compound have a large number average molecular weight (Mn) and a low L * The large value indicates a whitish color.

[0053] Example 14 The same procedure as in Example 7 was carried out, except that methyl 4-(2-hydroxyethoxy)vanillate (vanilate, 1.6 mmol) and methyl 4-(2-hydroxyethoxy)benzoate (benzoate, 0.4 mmol) were used as monomers. The results are shown in Table 3.

[0054] Example 15 The same procedure as in Example 7 was carried out, except that methyl 4-(2-hydroxyethoxy)vanillate (vanilate, 1.2 mmol) and methyl 4-(2-hydroxyethoxy)benzoate (benzoate, 0.8 mmol) were used as monomers. The results are shown in Table 3.

[0055] Example 16 The procedure was the same as in Example 7, except that methyl 4-(2-hydroxyethoxy)benzoate (Benzoate, 2.0 mmol) was used as the monomer. The results are shown in Table 3.

[0056] [Table 3]

[0057] The copolymer polyether ester of methyl 4-(2-hydroxyethoxy)vanillate and methyl 4-(2-hydroxyethoxy)benzoate (Examples 14-15) and the homopolymer polyether ester of methyl 4-(2-hydroxyethoxy)benzoate (Example 16) obtained using an aluminum catalyst and a phosphorus compound have a large number average molecular weight (Mn) and a low L* The large value indicates a whitish color.

Claims

1. The following formula (1): 【Chemistry 1】 (In formula (1), R ０ is an aliphatic group having 2 to 8 carbon atoms, and R １ and R ２ are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group. A method for producing a polyether ester having a structural unit represented by In the presence of an aluminum catalyst and a phosphorus compound, a reaction product of the following formula (2): 【Chemistry 2】 (In formula (2), R ０ is an aliphatic group having 2 to 8 carbon atoms, and R １ and R ２ are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group, and R ３ is a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a benzyloxy group, or a phenoxy group. A monomer represented by the formula: method.

2. The compound represented by formula (2) is one or more compounds selected from the group consisting of 4-(2-hydroxyethoxy)benzoic acid ester, 4-(2-hydroxyethoxy)vanillic acid ester, and 4-(2-hydroxyethoxy)syringic acid ester. The method of claim 1.

3. The aluminum catalyst is an aluminum alkoxide or an aluminum chelate compound. The method of claim 1.

4. The aluminum catalyst is aluminum ethoxide or aluminum acetylacetonate. The method of claim 3.

5. The phosphorus compound is a phosphonic acid or an ester or salt thereof. The method of claim 1.

6. The phosphorus compound is 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ester. The method of claim 5.

7. In the presence of the aluminum catalyst and the phosphorus compound, the monomer represented by formula (2) is heated at 180 to 300°C under normal pressure, and then heated at 180 to 300°C under reduced pressure, thereby melt-polycondensing the monomer represented by formula (2). The method of claim 1.

8. The L of the polyether ester having the structural unit represented by the formula (1) measured in accordance with JIS Z 8722 ＊ a ＊ b ＊ L in color system ＊ The value is 69≦L ＊ fulfill The method of claim 1.

9. The L of the polyether ester having the structural unit represented by the formula (1) measured in accordance with JIS Z 8722 ＊ a ＊ b ＊ a in the color system ＊ value and b ＊ The value is -2.0≦a ＊ ≦2.0 -2.0≦b ＊ ≦22.0 fulfill The method of claim 8.

10. The number average molecular weight (Mn) of the polyether ester having the structural unit represented by the formula (1) is 10,000 or more. The method of claim 1.

11. The following formula (1): 【Transformation 3】 (In formula (1), R ０ is an aliphatic group having 2 to 8 carbon atoms, and R １ and R ２ are each independently a hydrogen atom, a hydroxy group, a methoxy group, or an ethoxy group. A polyether ester having a structural unit represented by L measured in accordance with JIS Z 8722 ＊ a ＊ b ＊ L in color system ＊ The value is 69≦L ＊ fulfill Polyetherester.

12. L measured in accordance with JIS Z 8722 ＊ a ＊ b ＊ a in the color system ＊ value and b ＊ The value is -2.0≦a ＊ ≦2.0 -2.0≦b ＊ ≦22.0 fulfill The polyetherester of claim 11.

13. The number average molecular weight (Mn) is 10,000 or more. The polyetherester of claim 11.

Images