TW401393B - The carboxyl derivatives containing a naphthene and ether chain - Google Patents

Abstract

This is a method of producing carboxyl derivatives containing naphthene and ther chain. The carboxyl derivatives containing naphthene and ether chain in this invention together with the reaction of the aromatic diamine are prepared to produce the novel total aromatic polyamides. The acquired polyamides consist of excellent thermal stability, and is soluble in the suitable organic solvents. From this solution, a polymer film with the transparent, weathering and strong tenacious properties can be produced. The series of the total aromatic polyamides can become a high performance polymer material with easy processing.

Description

Attachment 2 The reviewer stated clearly that this e; 401303 V. Description of the invention (A7 B7 amendment supplement <: 4 (:-whether to change the original congratulatory content of the Ministry of Economic Affairs Central Standard Bureau staff consumer cooperatives printed this invention is related to the use It is used as a raw material for the production of fully aromatic polyamidoamines with good processability, thermal stability, and organic solubility, and a carboxyl derivative containing a naphthalene ring and an ether chain, and a preparation method thereof. The present invention is particularly related to the preparation of organic solubility 1,4-bis (para-carboxyphenoxy) naphthalene and 2,6_bis (para-carboxyphenoxy) naphthalene of wholly aromatic polyamines and methods for making same. Fully aromatic polyamines (wholly Aromatic polyamides) have excellent thermal stability and balanced physical and chemical properties. However, due to their high melting point and low solubility in organic solvents, poor processability is not easy to process into desired shapes such as films or fibers. For example, the following structures Aromatic polyfluorene and polyfluorene: 〇NH-

Tm = 500eC

Kevlar --N

v 〇Kepton x \ X: O (polybenzoxazole) X: S (polybenzothiazole) X: NH (polybenzimidazole) 3 (correction page) This paper is applicable to China Standard (CNS) A4 (210X297 mm) —-------- f ------ IT ------ ^.... _ (Please read the notes on the back first 4. Write this page again) Attachment 2 4 The commentator stated clearly, this e; 401303 V. Description of the invention (A7 B7 amendment supplement <: 4 (:-whether to change the original congratulatory content of the Central Standards Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs) The present invention relates to a carboxyl derivative containing a naphthalene ring and an ether chain, which is used as a raw material for the production of fully aromatic polyamines with good processability, thermal stability, and organic solubility, and a preparation method thereof. The present invention is particularly The invention relates to 1,4-bis (para-carboxyphenoxy) naphthalene and 2,6_bis (para-carboxyphenoxy) naphthalene, which are used to prepare organic soluble fully aromatic polyamines, and a preparation method thereof. Fully aromatic polyamides have excellent thermal stability and balanced physical and chemical properties. However, because of their high melting point and low solubility in organic solvents, they are processable. Good easily processed into a desired shape such as a film or fiber, for example, the following configuration of an aromatic polyamide, polyimide: square NH-

Tm = 500eC

Kevlar --N

v 〇Kepton x \ X: O (polybenzoxazole) X: S (polybenzothiazole) X: NH (polybenzimidazole) 3 (correction page) This paper is applicable to China Standard (CNS) A4 (210X297 mm) —-------- f ------ IT ------ ^.... _ (Please read the notes on the back first Write this page again.) I 401393 V. Description of the invention (4 out: amendments and supplements "" Order 1, 4 or 2 ^ -naphthalenediol and para-fluorobenzonitrile or para-chlorobenzonitrile The nuclear-fluorine substitution reaction yields a compound pepper of the formula (K): NC-M-0— < 〇) -CN (Π) (b) The compound of formula (I) is hydrolyzed or gasified or esterified. Examples of the preparation of the naphthyl ring and ether chain-containing tether derivatives of the present invention are shown below. fPlease read the precautions on the back before writing this page) • 1 ^ J ---- Install ·

F-CN-®2 * ·

The present invention will be described in detail by the following examples, which are not intended to limit the scope of the present invention. Example 1: Inventory of 1,4-bis (para-carboxy-phenylphenyl) naphthalene (MNCA) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A three-necked flask of a condenser was charged with 16.02 g (100 millimoles) of 1,4-naphthalenediol and 27.64 g (20 millimoles, 100 cc) of toluene and 200 ml of NMP to obtain a mixture. It was heated under stirring at 140 ° C for 6 hours under nitrogen to accelerate the dehydration reaction. After the toluene was removed, the mixture was cooled and 24.22 g (200 mmol) of para-fluorobenzonitrile was added. Let 6 (correction page) This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) A7 B7 V. Description of the invention (

N Π 〇 Ν '

N- PI 2080 CH-

Ultem polyquinoxaline has extremely high TgTm and is not easy to be processed into fibers and films. Therefore, the following linear polyimide with lower Tg which is suitable for melt processing has been developed.

(80%)

Tg: 310 ° C

Tg: 216 ° CI— 7: ----- I equipment-^ --- >-Order ------ Dream (Please read the notes on the back before filling this page) Central Standard of the Ministry of Economy Printed by Bureau Shellfish Consumer Cooperative

Tg: 222 ° q This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)

40iS〇S A7-I supplement bundle light year ^ > a '-_ \ The reaction was cooled at 470ec for 10 hours and poured into 3% cold water. Passing through and recrystallizing from acetonitrile, 21-75 g (yield 60%) of white needle-like 1,4-bis (p-cyanophenoxy) fluorene (1,4-NCN) was obtained. Melting point 197-198 ° C. IR spectrum (KBr) showed absorption at 2228 cm1 (on) and absorption at 1108 and 1236 cm · 1 (C-0-C). 〇241114 > Calculated by 1202: C 79 54%, H, 3 89%, N 7 73% Found: C, 79.26%, H, 4.08%, N / 7.61% Then it was hydrolyzed in an aqueous potassium hydroxide solution to recognize the double (P-Cyanophenoxy) Tea (1,4_NCN) until ammonia is not produced. The solution was cooled and the pH was adjusted to 3 by adding hydrochloric acid. The white precipitate formed was collected by filtration and dried in the air to obtain M-bis (para-tertylphenoxy) naphthalene (14NCA). The yield was 100%. No purification is needed 'melting point 353-3551. The IR spectrum (KBr) showed absorption at 1680 (^ (0 = 0). The rest of the case 2: 2,6_bis (para-carboxyl benzene gas 臬 silly Q 6NCA) is equipped with a nitrogen inlet, Ding -16.02 g (100 mmol) of 2,6-naphthalene glycol, 27.64 g (20 mmol, 100 cc) of toluene and 200 ml of toluene were added to the three-necked flask of the Duck dehydrator and condenser. NMP to obtain a mixture. The mixture was heated under nitrogen at 1401 ° C for 6 hours to accelerate the dehydration reaction. After the toluene was removed, the mixture was cooled and 24.22 g (200 mmol) of para-fluorobenzonitrile was added. This reaction was allowed to proceed for 10 hours at 4701, and then cooled and poured into 3% of cold water. The reaction mixture was recrystallized from acetonitrile to obtain 21,75 g (yield 60%) of white needle-like 2,6-bis ( Para-cyanophenoxy) naphthalene (2,6-NCN). Melting point 252.2eC. IR spectrum (KBr) shows absorption at 2228cm1 (C ^ N) and absorption at 1108, 1236cm · 1 (C-0- C). 7 — (88.8.24 revised page) This paper size is in accordance with Chinese standards (CNS) Α4 size (210 X 297 mm) (Please read the notes on the back before filling this page} Central Standards of the Ministry of Economy Printed by Bureau Shellfish Consumer Cooperative

_ _ I, I equipment. Order Μ ----------- I

A7 ___ B7 0 0 II II

LARC-TPI Tg: 264. ° Q V. Description of Invention (3) '' n

Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics Good electrical and electrical properties, but because of its low solubility in organic solvents, it is not easy to process into fibers or films. Therefore, the purpose of the present invention is to provide a raw material compound that can be used to react with an aromatic diamine to make an organic soluble fully aromatic polyamidoamine which has good thermal stability and is soluble in a suitable solvent The inventors have found that the purpose of the present invention can be achieved by reacting a carboxyl derivative containing a ring-receiving ring and an ether chain having the following structure with an aromatic diamine. x- Office "〇-⑴ where X is C / or OH or OR and ^^^ or the compound of the formula (I) of the present invention can be prepared by the following steps I-^ ------ -| Install-^ ---.-- order ------ line (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210X297) (%) Five and six results, calculated as "丨"-C24H14N2 02: C 79 54%, Η 3 89%, Ν 7 73〇 / 〇 measured: C / 79.26%, Η, 4.08%, N, 7.61% followed by hydrolysis of 2,6-bis (p-cyanophenoxy) in a hydroxide-aqueous solution and steaming (2,6-NCN)-until ammonia is not produced. The solution was cooled and HCl was adjusted to 3 by adding hydrochloric acid. The white precipitate formed was collected by filtration and dried in the air to obtain 2,6-bis (p-carboxyphenoxy) naphthalene (26NCA). The yield was 100%. No purification is required, and the melting point is 352.3 C. IR spectrum (KBr) showed absorption at 1680011-1 (€ = 0). The 1,4-NCA and 2,6-NCA prepared in the above Examples 1 and 2 are reacted with an aromatic diamine to obtain a fully aromatic polyfluorene having good thermal stability and organic solubility. The aromatic diamine used in the following application examples is an aromatic diamine having the structure of the formula: Ν2Ν-Αγ2-ΝΗ2 (I) where Ar # 普普普普 (a) (b) (c) (« 0 (e) —CHj-, ^-.-(Please read the notes on the back before filling this page)

* 1T Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs («(g)

8 (correction page) This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇 > < 297 mm) i 401393 V. Description of the invention (4 out: amendment and supplement "" Order 1, 4 or 2 ^ -Naphthol is subjected to a nucleophilic-fluorine substitution reaction with para-fluorobenzonitrile or para-chlorobenzonitrile to obtain a compound pepper of the formula (K): NC-M-0 — < 〇) -CN (Π ) (b) Hydrolyzing or gasifying or esterifying a compound of formula (I). Examples of the preparation of the naphthyl ring and ether chain-containing tether derivatives of the present invention are shown below. fPlease read the precautions on the back before writing this page) • 1 ^ J ---- Install ·

F-CN-®2 * ·

The present invention will be described in detail by the following examples, which are not intended to limit the scope of the present invention. Example 1: Inventory of 1,4-bis (para-carboxy-phenylphenyl) naphthalene (MNCA) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A three-necked flask of a condenser was charged with 16.02 g (100 millimoles) of 1,4-naphthalenediol and 27.64 g (20 millimoles, 100 cc) of toluene and 200 ml of NMP to obtain a mixture. It was heated under stirring at 140 ° C for 6 hours under nitrogen to accelerate the dehydration reaction. After the toluene was removed, the mixture was cooled and 24.22 g (200 mmol) of para-fluorobenzonitrile was added. Let 6 (correction page) This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm)

40iS〇S A7-I supplement bundle light year ^ > a '-_ \ The reaction was cooled at 470ec for 10 hours and poured into 3% cold water. Passing through and recrystallizing from acetonitrile, 21-75 g (yield 60%) of white needle-like 1,4-bis (p-cyanophenoxy) fluorene (1,4-NCN) was obtained. Melting point 197-198 ° C. IR spectrum (KBr) showed absorption at 2228 cm1 (on) and absorption at 1108 and 1236 cm · 1 (C-0-C). 〇241114 > Calculated by 1202: C 79 54%, H, 3 89%, N 7 73% Found: C, 79.26%, H, 4.08%, N / 7.61% Then it was hydrolyzed in an aqueous potassium hydroxide solution to recognize the double (P-Cyanophenoxy) Tea (1,4_NCN) until ammonia is not produced. The solution was cooled and the pH was adjusted to 3 by adding hydrochloric acid. The white precipitate formed was collected by filtration and dried in the air to obtain M-bis (para-tertylphenoxy) naphthalene (14NCA). The yield was 100%. No purification is needed 'melting point 353-3551. The IR spectrum (KBr) showed absorption at 1680 (^ (0 = 0). The rest of the case 2: 2,6_bis (para-carboxyl benzene gas 臬 silly Q 6NCA) is equipped with a nitrogen inlet, Ding -16.02 g (100 mmol) of 2,6-naphthalene glycol, 27.64 g (20 mmol, 100 cc) of toluene and 200 ml of toluene were added to the three-necked flask of the Duck dehydrator and condenser. NMP to obtain a mixture. The mixture was heated under nitrogen at 1401 ° C for 6 hours to accelerate the dehydration reaction. After the toluene was removed, the mixture was cooled and 24.22 g (200 mmol) of para-fluorobenzonitrile was added. This reaction was allowed to proceed for 10 hours at 4701, and then cooled and poured into 3% of cold water. The reaction mixture was recrystallized from acetonitrile to obtain 21,75 g (yield 60%) of white needle-like 2,6-bis ( Para-cyanophenoxy) naphthalene (2,6-NCN). Melting point 252.2eC. IR spectrum (KBr) shows absorption at 2228cm1 (C ^ N) and absorption at 1108, 1236cm · 1 (C-0- C). 7 — (88.8.24 revised page) This paper size is in accordance with Chinese standards (CNS) Α4 size (210 X 297 mm) (Please read the notes on the back before filling this page} Central Standards of the Ministry of Economy Printed by Bureau Shellfish Consumer Cooperative

_ _ I, I equipment. Order M ----------- I Fifth, six follow-up, for the calculation of "丨 丨-C24H14N2〇2": C 79 54%, Η 3 89%, Ν 7 73〇 / 〇 measured 値: C / 79.26%, Η, 4.08%, Ν, 7.61% followed by hydrolysis of 2,6-bis (para-cyanophenoxy) in a hydrogen hydroxide solution, steaming (2, 6-NCN) —until no ammonia is produced. Cool the solution and add hydrochloric acid to adjust ρΗ 3 to 3. Collect the white precipitate formed by filtration and dry in the air to obtain 2,6-bis (para-carboxyphenoxy ) Naphthalene (2 6NCA). Yield 100%. No purification is required. Refining point 352.3 C. IR spectrum (KBr) shows absorption at 1680001-1 (€ = 0). From Example 1 and above The 1,4-NCA and 2,6-NCA produced in 2 can be reacted with an aromatic diamine to obtain a fully aromatic polyfluorene having good thermal stability and organic solubility. In the following application examples, The aromatic diamine used is an aromatic diamine having the following structure: Ν2Ν-Αγ2-ΝΗ2 (I) where Ar # 普普普普 (a) (b) (c) («0 (e) —CHj- , ^-.-(Please read the notes on the back before filling this page)

* 1T Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs («(g)

8 (correction page) This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇 < 297 mm) 5. Description of the invention (7) A7 B7

Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs, that is, the aromatic diamine of the former type is para-phenylenediamine (4a), meta-phenylenediamine (4b), benzidine (4c), 4,4 -Oxydiphenylamine (4d), 3,4, monooxydiphenylamine (4e) '4,4'-diaminodiphenylmethane (40,1,4-bis (para-aminophenoxy) ) Benzene (4g), α, α'-bis (p-aminophenyl) -1,4-diisopropylbenzene (4h), 4,4'bis (p-aminophenoxy) Diphenyl (4i), 2,2'-bis [para- (para- (amino-phenoxy) phenyl] propane (4j), 1,1'-bis [para-para-amino-benzene (Oxy) phenyl] -1-phenylethane (4k), 2,2'-bis [p- (p-aminoaminophenoxy) phenyl] hexafluoropropane (41), bis [p- -(Para-phenoxy) phenyl] (4m), and 2,2'-bis [para- (para-aminophenoxy) _1,4-diisopropylbenzene (4n) 〇 Application Example 1: Preparation of Fully Aromatic Polyamide (5d) 0.25 g (1.25 mmol) of 4,4'-oxydianiline (4d), 0.50 g ( 1.2 millimoles) of the diacid (1, 4NCA) prepared in Example 1, 0.5 g of calcium chloride, 5 ml of NMP; 1 ml of pyridine and 0.9 ml of triphenyl phosphite It was 1〇〇. . Heat for three hours. The resulting mixture was slowly poured into 300 ml of methanol, collected by filtration, and applied to the Chinese paper standard (CNS) A4 specification (210 × 297 mm) at the paper size. 0¾ (Please read the note on the back ^ κ before filling this page ), Νβ

4013 ^ 3 A7 B7 V. Description of the invention (8) Dry in air at 100 ° C. The inherent viscosity of the obtained wholly aromatic polyamidoamine (5d) of the present invention is (Tlinh) 2.22 (U / g (measured in 30 ° C containing 5wt% LiCl, concentration 0.5g / d £ 2 DMAc), Tg 240 ° C (measured by DSC in N2 at a heating rate of TC / min). Please refer to Table 1. Application Example 2-14: Preparation of fully aromatic polyamines 5a-5c, 5e-5ii In the same manner as in Application Example 1, but using aromatic diamines 4a-4c, 5e-5n), a series of fully aromatic polyamidoamines (5a-5c, 5e-5n) of the present invention were prepared and the same The method measured the intrinsic viscosity (iinh) and Tg. The results are shown in Table 1. I --- 1-: ------ fitting-- (Please read the precautions on the back before filling in this card) The Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperation, Du Printed Table 1 Polyurethane No. Shirt (_) Tg (° C) 5a 1.40-5b 1.34 204 5c 1.68-5d 2.22 240 5e 1.42 233 5d 1.40 220 5g 1.52 220 5h 1.28 145 51 1.30 213 5j 1.86 213 5k 1.32 227 51 1.58 216 5m 1.27 220 5n 1.70 213 In addition, the solubility and tension properties of the organic solvents of the fully aromatic polyamidoamines 5a-5n prepared in Examples 1-14 were tested and reported in Table 2 °

• 1T This paper size is in accordance with Chinese national standard (CNS > 8 4 specifications (210X297 cm) 401393 A7 V. Description of the invention (9) Table 2 _ Solubility a) _ Tension properties b) Polyamide tension breaking elongation tension NO. _ Strength Length Modulus NMPIMAcaviFaVSOm · Duck THF (MPa) (%) (GPa) 5a _c)-5b + + + + +-84 10 1.91 5c -C) 5d + + + + + _c) 5e + + + + + 82 8 1.72 5d + + + + + _ 64 8 1.38 5g + soil-• 86 8 1.90 5h + + soil s + s 83 9 1.61 5i + +-73 7 1.64 5j + + shitu + s 104 9 2.14 5k + + ss + + h 70 7 1.64 51 + + + + + + 71 8 1.52 5m + + ss + + 74 8 1.66 5n + + + h + h + s 65 6 1.54 a). +: soluble, + h: Heat soluble, ±: Partially soluble, S: Swell,-: Insoluble. b). Slowly evaporate, the polymer solution in DMAc forms a thin film c). The thin film cannot be formed — IU-^ ----- pack --.--.-- order:-: ---- New (Please read the notes on the back before filling this page) Application Example 15 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: Preparation of Fully Aromatic Polyamide (4d) 0.25 g (1.25 mmol) 4,4'-oxydianiline. (4d), 0.50 g (1.2 mmol) of the diacid (2,6NCA) prepared in Example 2, 0.5 g of calcium chloride, 5 ml of NMP; 1 ml of pyridine and 0.9 ml of triphenyl phosphite The mixture was heated at 100 ° C for two hours. The resulting mixture was slowly poured into 300 ml of methanol, collected by filtration, and dried at 100 ° C in the air. The obtained full aromatic polymer paper of the present invention is sized for the Chinese National Standard (CNS) A4 (210X297 mm) «01393 A7 B7 V. Description of the invention (1) The inherent viscosity of the amine (4d) is ( ηίηΙι) 2.19 < 1 ^ (measured in DMAc containing 5wt% LiCl 'at a concentration of 0.5 g / W at 30 ° C), Tg is 230 ° C (measured by DSC in N2 at a heating rate of 20 ° C / min) Please refer to Table 3. Application Examples 16-29: The production of fully aromatic polyamine 4a.-4c '4e-4n is the same as that of Application Example 15, but using aromatic diamine ( 4a-4c, 5e-5n) prepared a series of fully aromatic polyamines (Zhichi, 4e-4n) and measured the inherent viscosity (TWO 'Tg, tensile properties and organic solvent properties) in the same way and recorded in the following Table 3 and Table 4 ° Table 3 ___. Used riMd) (di / g) Number NMP (m〇iym〇CaCl2 (g) in DMAc-50 / 〇LiCl in concentrated n2S〇4 1) Central Ministry of Economic Affairs Printed by Tifeng Bureau Shellfish Consumer Cooperative \ ly \ J, \ J, b VI / VJ \ — ^ / —N ccccccc 1050 + 5 + 44 + 2 + 25 + 155 + 2 + 4 + 2 + 4 104 45 5 5 5 5 4a4b4c4d4e4f4g4h4i · Seven 4k414m4n 2.5 0.6〇H). 6glicl) 1.431 1.3 0.6 0.3 1 2.5 0.9 -c) 1.0 0.5 2.19 1.0 0.5 1.50 1.0 0.5 1.47 1.3 0.6 1.56 1.3 0.6 1.30 1.3 0.6 (+ 0.5 # ia) _c) 1.3 0.6 1.64 1.3 0.6 1.39 1.3 0.6 1.72 1.3 0.6 1.39 1.3 0.6 1.71

4 7 4 0 3 2 3 3 · 2 · 68 · 7 2 · 4 li 11 lx 1X 7 4 6 0 13 6 Ό 3 · ο · 1 · 7 · 5 o · Au 11 Αν -1 lx Au (a) each The amount of the diacid and the diamine monomer = 1.25 millitorles' TPP = 0.9ml (2.5 millimoles), the reaction temperature = 110 ° C, and the reaction time = 3 hours. (b) The polymer precipitates during the reaction, and it no longer dissolves when NMP is added. (c) Add a certain amount of NMP first. If it cannot be dissolved, then add another amount. The paper size is applicable to China National Standard (CNS) A4 scale (210X297 mm) I 丨 I ~~: -------- Packing. — ^ — Order; —; ---- i (Please read the notes on the back before filling out this page) A7 B7 V. NMP of Invention Description (11). Rhenium was measured at a concentration of 0.5 g / dl at 30 ° C. (e) Insoluble. (f) After the complete dissolution, it is determined in Table 4. Tensile properties of the poly-No. poly-earth film a) DSC difficult tensile strength breaking elongation tensile modulus Tg ^ C) TmfC) (MPa) (%) (GPa) __ 4a4b4c4d4e4f4g4h4i · Seven 4k4i4m4n 91d) d) _8890d), 80d) 7474707282 28 17 16 0 1M 1 * 11 11 3 06 2 3 5 5 8 3 I · 2 * 1 ^^ 1 I · 0 · 7 · 7 · 9 · 2 2. 2 2 11111 22 8505725568357 1939420610039 65643067202338 J 丨 ^^ ----- install --.-- J-- order:-: ---- k (please read the note $ on the back before filling in this Page) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (a) Films were slowly evaporated from the polymer solution of DMAc. (b) A temperature rise rate of 20 ° C / min midpoint temperature in nitrogen. (c) Significant exotherm occurred on the first DSC heating. (d) No film formation. From Table 1, Table 2, Table 3 and Table 4 above, it can be known that the inherent viscosity of the obtained wholly aromatic polyamines is between 1.27-2.22 d € / g and the molecular weight is very high, so it can be made into Tough and flexible film. In addition, these full aromatic paper sizes are in accordance with Chinese National Standards (CNS) A4 (210X297 mm) A7 B7 V. Description of the invention (12) Aromatic polyamines are easily soluble in polar solvents such as DMAc, NMP, m -Cresol, even in less polar pyridine. In addition, the Tg of the above-mentioned wholly aromatic polyamide of the present invention is between 195-240 ° C. When the temperature reaches 400 ° C, it is stable in air or nitrogen, and the temperature of 10% weight loss is above 480 ° C. In addition, tensile properties such as tensile strength, tensile modulus and elongation at break are all good. J 丨 ^^ ---- Packing-- · --J--Order:-: ---- i (Please read the notes on the back before filling out this page) The paper size of the paper is applicable to China Gujia Standard (CNS) M specification (210X 297 mm)

Claims (1)

4〇1393 Announcement 丨 Patent Application No. 07751 I. Application for a revised version of the patent application, a carboxyl derivative of serapene ring and ether chain with the following structure (I): Φ c-X (I) Refill the items where X is OH; Atj is The size of the paper is in accordance with the Chinese National Standard (CNS) 8 1 2 3 (21 ×: 297 mm). Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. CN (I) —15 — (88.8.24 revised page) 1 As the carboxy derivative of item 1 in the scope of patent application, it is 14 bis (para-tertylphenoxy) naphthalene. 2 As the quinyl derivative of item 1 of the patent application park, it is 2,6-bis (para-carboxyphenoxy) naphthalene. 3 A compound having the structure (E): 4〇1393 Announcement 丨 Patent Application No. 07751 I. Application for a revised version of the patent application, a carboxyl derivative of serapene ring and ether chain with the following structure (I): Φ c-X (I) Refill the items where X is OH; Atj is The size of the paper is in accordance with the Chinese National Standard (CNS) 8 1 2 3 (21 ×: 297 mm). Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. CN (I) —15 — (88.8.24 revised page) 1 As the carboxy derivative of item 1 in the scope of patent application, it is 14 bis (para-tertylphenoxy) naphthalene. 2 As the quinyl derivative of item 1 of the patent application park, it is 2,6-bis (para-carboxyphenoxy) naphthalene. 3 A compound having the structure (E) of the following formula: Patent application scope A8 Bδ C8 D8 5. The compound according to item 4 of the patent application scope, which is 1,4-bis (para-cyanobenzeneamino) naphthalene. 6. The compound as claimed in item 4 of the patent application, which is 2,6-bis (para-aminophenoxy) naphthalene. 7. —A method for preparing a carboxyl derivative containing a naphthalene ring and an ether bond structure of formula (I), 0 0x ~ c ~~ ^ 〇y ~ ° -Ari-Q— ^ 〇y ~ c —x (I ) l · — aj ^ ii ^ — ^^ 1 In ^ i ^ ii (Please read the notes on the back before filling out this page) where X is OH; Ar ^ The consumption cooperation for employees of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China includes the following steps: (a) Order 1,4-naphthalenediol with para-fluorobenzonitrile or para-fluorobenzonitrile for nucleophilic fluorine substitution The compound of formula (Π;) is obtained: Nc ~ ^ 5y ~ ο-αγ, -ο— (where Ar > Or ^^) CN (I) (b) The compound of formula (Π) is hydrolyzed to obtain the compound of formula (I). 1 16-(88.8.24 revised page) This paper size applies to Chinese national standards (CNS > M size (210X 297 mm)