TW201037011A - Method of preparing a heat-resistant polyamide - Google Patents

Abstract

The present invention relates to a method of preparing a heat-resistant polyamide including a repeating unit represented by Chemical Formula 3 by carrying out condensation polymerization with a monomer mixture including a diester compound and a diamine compound. The present invention can provide an economical method of preparing the heat-resistant polyamide in that a monomer, a raw material, is simply and chiefly prepared, and the polymerizing reaction time is short because it does not need a solvent separately.

Description

201037011 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing polyamide, and more particularly to a method for producing a relatively economical heat-resistant polyamide, wherein a single system as a raw material It can be prepared simply and inexpensively, and the present invention does not require a step of removing the solvent 'so that the polymerization reaction time is shortened. * [Prior Art] Polyamides represented by nylon 6 (nyl〇n 6) and nylon 66 (nylon®) are widely used in fibers, films, and sheets due to their superior mechanical properties and chemical resistance. Objects, injection molded articles and the like. ^ and 'Because the dissolution temperature of nylon 6 and nylon 66 are 23 〇ΐ: and 26 〇t ', therefore, the presence of domain 6 and nylon 66 is insufficient for ageing and makes it impossible. Used in semiconductor heating equipment, electricity, automobiles and the like. > In order to solve the problem of insufficient heat resistance, the domain 46 (nyk) n 46) prepared by reacting butanediamine with adipic acid has (4) The higher turning temperature is 9〇C. However, due to the high-density guanamine bond of nylon 46, it has a suction property because it is subjected to _ in the process, and because it replaces the aliphatic lanthanum or fat by using the dimethyl ketone. The monomer of the polyamine obtained from the amine is expensive, and thus the nylon 46 cannot be widely used. In addition, although polyimidate, polyether ketone, aromatic polyamine, polyphenylene sulfide and the like are highly heterogeneous resins, (4) they all have a high price of 201037011 and a complicated manufacturing method. In other words, since a conventional method for producing polyamines is to prepare a salt of a dicarboxylic acid and a diamine in diethanol, separate the salt from the aforementioned solution, and dissolve the separated salt in a large amount of solvent (for example, a large amount of water). ), the steps of removing water by the conditions of pressure and vacuum at high temperatures, so the conventional system is very cumbersome. In addition, because the conventional manufacturing method consumes a large amount of water and requires a large amount of energy to remove water, it is not economical. SUMMARY OF THE INVENTION In order to solve the above problems of the prior art, it is an object of the present invention to provide a heat-resistant poly-manufacturing method in which a single system as a raw material can be prepared simply and inexpensively. In order to attain the technical level, the present invention provides a method for producing a heat-resistant polyamine. The amine has a repeating unit as shown in Chemical Formula 3, which transmits a compound containing the second compound represented by the chemical formula i and a chemical formula. 2 (4) bisamine compound _ single compound is carried out by condensation polymerization: Chemical formula 1

Wherein 'Ri is an aromatic cigarette having a carbon number of 1 to 20 20; the fat is carbon number 6 to chemical formula 2 5 201037011 where 'I is an aliphatic hydrocarbon having a carbon number of 1 to 20 or a carbon number of 6 to 2 〇 Aromatic hydrocarbon; Chemical formula 3 Ο _ η ) - C - ΝΗ - Η ^ - ΝΗ - wherein '汉 2 is an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms. Here, the diamine compound represented by Chemical Formula 2 may be hexamethylene diamine (HMDA) or 2-methyl-i, 5-pentane diamine (MPDA). Furthermore, the monomer mixture may further comprise a diacid as represented by the following Chemical Formula 4: Chemical Formula 4 〇〇HO -c~R』-〇|| wherein 'R3 is an aliphatic hydrocarbon having 2 to 20 carbon atoms or Aromatic cigarettes with a carbon number of 6 to 20. [Embodiment] Hereinafter, the present invention will be described in more detail. 1 (4) A thermal polyamine prepared according to the present invention, which can be prepared by polymerizing a diester compound of the formula 1 and aminating cr (4) represented by the chemical formula 2 to prepare a The hydrogenation reaction is carried out to reduce the aryl hydrazine's aromatic ring to obtain the dimorphic compound. 201037011 Since the aromatic diester compound is inexpensive and it is also an intermediate product for the synthesis and production of a conventional polyamine, 1,4-cyclohexane dicarboxylic acW, In the prior art, the present invention has the advantage that the polyamine can be produced at a low cost via a reduction reaction step. ❹

In addition, since the diester compound represented by Chemical Formula 1 is extremely soluble in the diamine compound represented by Chemical Formula 2, and the present invention does not require a solvent removal step, the present invention also has a simple reaction and a fast reaction rate. Advantage. Therefore, the present invention does not require the steps of separating the salt from the reaction solution, dissolving the separated salt in a solvent including water, and removing water under vacuum conditions at a high temperature, so that the present invention can be reduced for solvent removal. The advantage of a large amount of energy consumed. In addition, since the equipment used for the process is simple, the remainder can be simplified, and the invention has the advantage of (4) greatly reducing the manufacturing cost of the final product, heat-resistant polyamide. In the method for producing Nylon according to the present invention, the calorific acid polyamine can be produced by a condensation polymerization reaction as shown by the tetraamine compound of the chemical formula 2 represented by Chemical Formula 1. Get: ~ Equation of Reaction 1

C 0Rl + n H2H-R2-MEl2

'2nRi〇H v

7 201037011 wherein R! and R2 may be an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms, and & R2 may preferably be an aliphatic hydrocarbon having a carbon number of 或者 or An aromatic hydrocarbon having 6 to 14 carbon atoms. More preferably, R! in Chemical Formula 1 may be a burning group having 1 to 6 carbon atoms. Most preferably, the compound represented by Chemical Formula 1 may be 1, 4-cyclohexane dicarboxylic acid dimethylester (or - methylcyclohexan-1, 4) - dimethyl cyclohexane-1 4-dicarboxylate), that is, Ri of the chemical formula 1 is a methyl group.

Further, & in Chemical Formula 2 is preferably a linear or branched olefin group having a carbon number of 丨 to 1〇. More preferably, the compound represented by Chemical Formula 2 may be hexamethylenediamine (HMDA) or 2-methyl-1,5-pentanediamine (MPDA). Further, the diester compound represented by Chemical Formula 1 can be obtained by a hydrogen reduction reaction of an aromatic diester compound represented by the following Reaction Scheme 2: Reaction Equation 2

Wherein Ri may be an aliphatic hydrocarbon having 1 to 2 carbon atoms or an aromatic hydrocarbon having a carbon number of 6 to 20' and preferably may be an aliphatic hydrocarbon having 1 to 14 carbon atoms or an aromatic having 6 to 14 carbon atoms. Family smoke. The aromatic diterpene compound may be a dialkyl group to a dibenzoic acid vinegar (dialkyl such as 叩 she also (6) or a diaryl terephthalic acid vinegar (diaryl (tetra) hthaiate). When the fang_二_compound is a two-recorded pair of stupid two Formic acid brewing 8 201037011 'Best heart can be the above-mentioned carbon number 丨 to 6 burning base. According to the conventional technology '1,4·cyclohexene saponin A) made in heat resistance = brewing amine manufacturing method The towel and the M_cyclohexanthene are prepared from the p-benzoic acid: acid, especially the di-diester compound used for the preparation of the dialkyl terephthalic acid vinegar. The product of the M• 环 烧 烧 贼 用于 用于 用于 用于 用于 用于 用于 用于 知 知 四 四 四 四.

The present invention can produce a heat-resistant polydecylamine more economically and rapidly by reducing the entire reaction step of producing polyamine. A yarn as shown in Chemical Formula 5 and the :=7 (four) ostomy are also provided. The total (4) represented by Chemical Formula 5 is a diamine compound represented by the chemical formula of the aliphatic or aromatic dinon and the formula 2 represented by the formula 2, and is subjected to condensation polymerization. The chemical formula 5 Ο 〇 〇 oil - R ^ - The aromatic hydrocarbon of NHV^-20 is =1 to 2 脂肪 of aliphatic hydrocarbons or carbon number 6 to carbon number 6 to _ lose TM to aliphatic smoke or R3 is carbon number 2 $ on n fragrant smoke, · The trace of the trace is either a natural number from 1 to 999 with a carbon number of 6 to 20; and a natural number up to 999. The latter may be a hydrocarbon having a carbon number of 丨 to 1 () or a branched chain of hydrocarbons 9 201037011, and R·3 may be a dilute hydrocarbon group having a carbon number of 2 to 6 or a stabilizing group. Specifically, the dicarboxylic acid represented by the chemical formula 4 may preferably be at least one compound selected from the group consisting of adipic acid, succinic acid, and stupid Formic acid (10) 叩 her. acid), isophthalic acid, phthalic acid, and phthalic anhydride. As shown in the following reaction formula 3, the copolymer of Chemical Formula 5 can be added to a diester compound represented by Chemical Formula 1 and a chemical formula by a monomer mixture containing an aliphatic or aromatic dicarboxylic acid represented by Chemical Formula 4. The mixture of the two diamine compounds is further prepared by a condensation polymerization reaction. As described above, when the condensation polymerization is carried out by adding the two oxic acid represented by Chemical Formula 4 to the compound of the formula 1 and the diamine compound represented by Chemical Formula 2, there is permeable. Appropriately control the addition of the diterpenic acid to the molar ratio to easily control the temperature of the heat-resistant polyamide. Reaction equation 3 [CHDR] 1〇_C V-V ^~〇Rl + H2N-R2->m2 + m h〇-LR3-L〇h

-2nRi〇H u-2mH2〇

Wherein 'Rl and R2 may be aroma of the aliphatic hydrocarbon 'w of carbon number i to 2〇' and Ri" preferably may be carbon number (1) 201037011 of the monthly fat _ or a carbon number of 6 to 14 Aromatic smoke: and two fat T or a base with a carbon number of 6 to 2 °. 彳 is a 2 to 6 achievable or stupid === prepared for the condensation polymerization of alanine The di- and di-pure complexes are introduced from a high-pressure reactor equipped with a mixture of ❹ 回流 and reflux. If the copolymer shown in Chemical Formula 5 is prepared, the aliphatic or aromatic _ Introduced into the aforementioned high-pressure reactor. After the introduction of the reactants, the high-pressure reactor is followed by a gradual increase in temperature. When the temperature inside the reactor rises to a higher level or higher, the alcohol is steamed. And collected in a condenser. Although the alcohol is collected to half of the theoretical collection, the air in the reactor is replaced with an inert gas such as nitrogen, argon, and the like, and the reactor is sealed. Increase the internal pressure of the reactor. The progress of the reaction is to increase the reaction temperature to 300 to 400 〇C. And the reaction of the reactor for 1 hour to 3 hours, preferably 1 hour 45 minutes to 2 hours 15 minutes, and more preferably 2 hours of stirring. At the same time 'control the reactor by using a valve The internal pressure does not exceed 20 kgf/cm2. After the internal pressure of the reactor is brought to atmospheric pressure by slowly opening the valve, the internal pressure of the reactor is further reduced to 1 torr or lower by using a vacuum pump. Stir for 2 to 4 hours, preferably 2 Π 201037011 hours 30 minutes to 3 hours 30 minutes, more preferably about 3 hours. When the torque of the stirring device or the instantaneous load is measured, the viscosity of the reactants is reached. When a value is required, an inert gas such as nitrogen, argon or the like is introduced into the reactor to release the vacuum, and an injection pressure of the inert gas is used to discharge the product. Additional solid state polymerization may be performed as needed. The solid state polymerization can be carried out by introducing a specific size of p〇lymerized chips into a reactor equipped with a stirring device to raise the temperature beyond the polymerization. The glass transition temperature of the slice, and the introduction of nitrogen or argon into the reactor or the vacuuming of the reactor are completed. As described above, the method for producing the heat-resistant polyamide of the present invention can be used as early as possible. An inexpensive monomer obtained by a hydrogenation reaction, without the need to separate the salt from the reaction valley liquid, using a large amount of water as a solvent to dissolve the separated salt, and cumbersome and complicated to consume a large amount of energy such as water removal Therefore, the present invention can provide a simple and cost-effective method for producing heat-resistant polyamide, because the steps of the polymerization reaction of the present invention are short and the energy consumption can be greatly reduced. The examples are compared to further understand the present invention. However, the following examples and comparative examples are merely illustrative of the invention, and the scope of the invention is not limited by the following. Example 1 200 g (1 equivalent) of 1,4-cyclohexane dicarboxylic acid dimethylester (Aldrich 12 201037011 company for sale 'cis structure and trans structure The mixture) and 233 g (2 mmol) of hexamethylene diamine (sold by Aldrich) were introduced into a high pressure reactor, stirred and mixed. After the temperature is raised to 75 ° C, the evaporated sterol can be collected by condensation through a condenser. When 32 g of sterol was distilled off, nitrogen was introduced into the reactor to remove oxygen' and the temperature was raised to 400 ° C after the valve was closed, after which the mixture was stirred for 2 hours. The internal pressure of the reactor was lowered to atmospheric pressure by slowly opening the valve and the mixture was polymerized for 3 hours by causing the reactor to become vacuum so that the internal pressure of the reactor became 1 torr or less. Thereafter, after the valve is opened, the nitrogen is introduced to release the vacuum, and the hot polyamide is discharged through the bottom discharge discharging device of the reactor and the polyamine is discharged. After cooling in water, it is cut into slices of a specific size using a cutting device. Example 2 Heat resistance was produced in substantially the same manner as in Example 1 except that 2-methyl-l, 5-pentane diamine was used instead of hexamethylenediamine. Polyamide. Example 3 except that 228 g (1 equivalent) of 1,4-cyclohexanedicarboxylic acid diethyl hydrazine was used (1,4-.}^1〇1^\&116<1^^1113〇乂}4 &(^(1(^1;11>^3161') (or diethyl cyclohexane-1, 4-dicarboxylate) instead of 200g ( In the same manner as the exemplified oxime, a heat-resistant polyamine is produced in the same manner as in the case of dimethyl carboxylic acid dimethyl ester of 1,4-cyclohexane hexene 13 201037011. / At this time, the 1,4-cyclohexane Dialkyl dicarboxylate is synthesized by transesterification reaction by the following method: 1 equivalent of dinonyl hexane dicarboxylate and 2 equivalents of ethanol are dissolved in xylene, and used The dean-stark device removes methanol while refluxing the above reactants. ~ Example 4 In addition to using 256 grams (1 equivalent) of iota, 4-cyclohexanedicarboxylic acid dipropylene vinegar (l , 4-cyclohexane dicarboxylic acid dipropylester) (or dipropyl cyclohexane 4-dicarboxylate) to replace 200 g (1 equivalent) of i, 4_cyclohexene Dimethyl dicarboxylate Further, the heat-resistant polyamide was produced in substantially the same manner as in Example 1. At this time, the dipropyl 1,4-cyclohexanedicarboxylate was subjected to a transesterification reaction as described below. To be synthesized: 1 equivalent of 1,4-cyclohexanedicarboxylic acid dinonyl ester and 2 equivalents of propanol were dissolved in xylene and refluxed using a dean-stark device. Simultaneous removal of methanol from the above reactants. Example 5 In addition to using 284 g (1 equivalent) of 1,4-cyclohexane dicarboxylic acid dibutylester (or 14 201037011 monobutyl) Dibutyl cyclohexane-l (4-dicarboxylate) is substituted for 200 g (1 equivalent) of hydrazine, 4_cyclohexanedicarboxylic acid dimethyl ester, and the rest The heat-resistant polyamide is produced in substantially the same manner as in Example •. At this time, the hydrazine, dibutyl 4-cyclohexanedicarboxylate is synthesized by transesterification as described below. : Dissolve 1 equivalent of hydrazine, 4 - cyclohexanedicarboxylic acid dimethyl ester and 2 equivalents of butanol in xylene, and The methanol was removed while refluxing the aforementioned reactants using a dean-stark device. Example 6 In addition to using 324 grams (1 equivalent) of 1,4,4-cyclohexanedicarboxylic acid diphenylester (or

A diphenyl cyclohexane-1 4-dicarboxylate is substituted for 200 g (1 equivalent) of decylcyclohexane didecanoate. The heat resistant polyamine was produced in the same manner as in the example. At this time, the 1,4-cyclohexanedicarboxylic acid diphenyl ester is synthesized by performing a transesterification reaction as described in the following method: 1 equivalent of hydrazine, 4_cyclohexanedicarboxylic acid dicarboxylic acid The ester was dissolved in dimethyl benzene with 2 equivalents of phenol, and the sterol was removed while refluxing the aforementioned reactants using a dean-stark device. The detailed reactant compositions of Examples 1 through 6 and the physical properties of the polyamines prepared therefrom are listed in Table 1 below. 15 201037011 [Table 1] ---______________ Diester-diamine viscosity (g/dl) Melting point Example 1 Dimethyl 1,4-cyclohexanedicarboxylate hexamethylenediamine 0.65 V 375 Example 2 1,4- Dimethyl cyclohexanedicarboxylate 2-methyl-1,5-penta 0.63 340 Example 3 Diethyl hexamethylenediamine hexanediamine 0.63 373 Example 4 Γ"U4-cyclohexanedicarboxylate Dipropyl hexyl diamine 0.61 Example 5 Dibutyl 1,4-cyclohexanedicarboxylate.~~~--------- Tr--- hexamethylenediamine 0.53 374 Example 6 1,4 - cyclohexanedicarboxylic acid di 4-ester ------ - one------ hexamethylenediamine 0.57 373 Comparative Examples 1 to 6 In addition to using the equivalent of two equivalents listed in Table 2 below The acid is substituted for 1 equivalent of dimethyl 1,4-cyclohexanedicarboxylate, and 2 equivalents of hexamethylenediamine are substituted for 2 equivalents of hexamethylenediamine listed in Table 2 below. Example 1 The same method was used to produce heat resistant polyamine. [Table 2] Dicarboxylic acid diamine viscosity (g/dl) Refining point (°c) Comparative Example 1 Ethylene diamine (ethylene diamine) 0.31 395 Comparative Example 2 Propylene diamine (propylene diamine) - 0.38 364 Comparative Example 3 Butylene diamine 0.35 385 Comparative Example 4 Octol diamine - 0.27 312 Comparative Example 5 Decane diamine 0.24 305 Comparative Example 6 Dodecane diamine 0.23 280 Examples 7 to 36 Except for the use of 1,4-cyclohexanedicarboxylic acid diterpenoid vinegar (CHDR) listed in Table 3 below The dicarboxylic acid was replaced by one molar equivalent of di-n-propyl 1,4-cyclohexanedicarboxylate according to Table 3, and the amount of hexamethylenediamine (as shown in Table 3 of Table 3) was used as 16 201037011 ( HMDA) or 2 equivalents of 2-methyl-1,5-pentanediamine (MPDA) to replace 2 equivalents of hexamethylenediamine, the heat resistant polyamine was produced in substantially the same manner as in Example 1. . [Table 3] CHDR (mol%) Copolymerization with dicarboxylic acid (mol%) Diamine viscosity (g/dl) Melting point (°C) Example 7 10 Adipic acid (90) HMDA 0.66 283 Example 8 50 Acid (50) HMDA 0.55 310 Example 9 90 Adipic acid (10) HMDA 0.54 355 Example 10 10 Adipic acid (90) MPDA 0.67 264 Example 11 50 Adipic acid (50) MPDA 0.65 290 Example 12 90 Adipic acid ( 10) MPDA 0.67 325 Example 13 10 Succinic acid (90) HMDA 0.55 301 Example 14 50 succinic acid (50) HMDA 0.48 345 Example 15 90 succinic acid (10) HMDA 0.45 358 Example 16 10 succinic acid (90) MPDA 0.57 293 Example 17 50 Succinic acid (50) MPDA 0.53 310 Example 18 90 Succinic acid (10) MPDA 0.53 334 Example 19 10 Terephthalic acid (90) HMDA 0.47 338 Example 20 50 Terephthalic acid (50) HMDA 0.44 359 Example 21 90 terephthalic acid (10) HMDA 0.54 Example 22 10 terephthalic acid (90) MPDA 0.47 325 Example 23 50 Terephthalic acid (50) MPDA 0.49 350 Example 24 90 Terephthalic acid (10) MPDA 0.44 Example 25 10 meta-phthalic acid (90) HMDA 0.51 318 Example 26 50-mesophthalic acid (50) HMDA 0.53 348 Example 27 90-dibenzoic acid (10) HMDA 0.58 - Example 2 8 10 stearic dicarboxylic acid (90) MPDA 0.47 328 Example 29 50 isophthalic acid (50) MPDA 0.55 360 Example 30 90 meta-phthalic acid (10) MPDA 0.52 - Example 31 10 Phthalic acid (90) HMDA 0.43 293 Example 32 50 o-Dibenzoic acid (50) HMDA 0.47 310 Example 33 90 Phthalic acid (10) HMDA 0.51 370 Example 34 10 phthalic acid (90) MPDA 0.47 286 Example 35 50 phthalic acid (50) MPDA 0.42 305 Example 36 90 phthalic acid (10) MPDA 0.44 317 Note: "-" indicates an example of thermal degradation before melting point. 17 201037011 [Experimental Example] The properties of the heat-resistant polyamide produced by the above examples and comparative examples were measured by the following methods' and the test results obtained are shown in Tables 1 to 3 above. Viscosity The heat-resistant polyamine produced by the above method was dissolved in m-toluene at 35. (: The viscosity of the heat-resistant polyamide is measured using an Ostwald Viscometer. The melting point is 1 Torr per minute using a differential scanning calorimeter (DSC). The melting speed was measured to measure the melting point of the thermal polyamine produced by the above method. As shown in Table 1, the polyamine produced by the methods of Examples 1 to 6 showed a melting point suitable for heat-resistant polyamide. However, it must be admitted that the polymers produced according to the simple method of the present invention also have good heat resistance by using the materials disclosed in Comparative Examples! to 6, but their degree of polymerization is substantial. More specifically In order to obtain a polymer having a high degree of polymerization, the polymer obtained by the comparative example must be subjected to, for example, an increase in the reaction time or a reaction of the ruthenium polymerization, so that the polymer obtained by the comparative example is not appropriate. However, it is necessary to obtain a polymer polymerized according to the example of the present invention only by the process of simple 18 201037011, but the polymer has good resistance. Further, the method for producing a polydecylamine of the present invention can be confirmed by the following examples 7 to 36, and it is possible to simply control the final by controlling the addition of a molar ratio of the introduced dicarboxylic acid and performing a condensation polymerization reaction. The melting temperature of the heat-resistant polyamide produced.

19

Claims (1)

201037011 VII. Patent application scope: 1. A method for producing a heat-resistant polyamine having a repeating unit represented by the following Chemical Formula 3 by a diester compound represented by the following Chemical Formula 1 and The monomer mixture of the diamine compound represented by the following Chemical Formula 2 is subjected to a condensation polymerization reaction. Chemical Formula 1 〇 - 〇 Rl ° - c - ( ) - C - ORi wherein Ri is a carbon number of 1 to 20 20 An aromatic hydrocarbon; an aliphatic hydrocarbon or an aromatic hydrocarbon having a carbon number of 6 to a chemical formula of 20; and an aromatic hydrocarbon of the formula 3 Ο II -ΤΊΗ-1^-oil 20 being an aliphatic hydrocarbon having 1 to 20 carbon atoms Or the manufacturing method described in the first item of the carbon number 6 chemical range, wherein, the chemical formula 2 3. "Please patent, the second item, wherein the 20 201037011 amine compound is hexamethylene diamine _DA) or 2 The method of the invention of claim 1, wherein the compound mixture further comprises a second oxic acid represented by the following Chemical Formula 4: Chemical Formula 4 vs. 〇|| Ο G 20 2 & An aliphatic cigarette having an inverse number of 2 to 2 Å or an aromatic hydrocarbon having a carbon number of 6 to 2 Å. 5 The manufacturing method according to claim 4, wherein the dibenzoic acid and the amber are the second At least one of the six heavy-duty heat-resistant polydecylamines in the group consisting of formic acid, isophthalic acid, and phthalic acid, comprising the following items of formula 3: To the manufacturer of the method of the fifth item - 34: Chemical formula 3 Ο II where 'R2 is an aromatic furnace having a carbon number of 1 to 20 of 20. The aliphatic hydrocarbons are either carbon number 6 to 7. As in the scope of the patent application, the sixth item, +, + contains a heat-resistant polyamine of the formula (4), which has a chemical formula of 5 疋. 201037011 Wherein R 2 is an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms, and R 2 is preferably an aliphatic hydrocarbon having 1 to 14 carbon atoms or an aromatic hydrocarbon having 6 to 14 carbon atoms; R3 is an aliphatic hydrocarbon having 2 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms; η is a natural number from 1 to 999; and m is a natural number from 1 to 999. 22 201037011 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: ❹ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇 wherein R2 is an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms. 3