TW314529B - Meta wholly aromatic polyamide copolymers - Google Patents

Abstract

A meta wholly aromatic polyamide copolymers, including the following polycondensation: (a) m-phenylene diamine; (b) isophthaloyl chloride; (c) have the formula of at least one comonomer; and components exceeding no 15 mole%. Of them, W=halogenated atom, COOH, CnH2n+1(n=1~2) X=halogenated atom, CH3, H; Y=CnH2n(n=1,2), O, or no; Z=halogenated atom, COOH, CnH2n=1(n=1~2).

Description

314529 A7 B7 Printed by the Employee Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs i. Description of the invention (1) This article is based on fully aromatic polyamides with improved flame resistance, especially regarding the inclusion of at least 85% The gold-aromatic polyamidoamine of the repeating unit of m-phenylene isophthalasiide (-phenylene isophthalasiide) and the selected repeating unit of aromatic diamine and dinitrogen. Quanfangfan Polyamide was synthesized in the 1950s. [SLKwolek and Η.H. Yang, " History of Araiid FibersMin Haniade Fiber · Their Origin and Deve1opent ", ed. By RB S o yi〇ur and R. S. Porter, Elsevier Applied Science (1993)]. During the period of I960, due to the improvement of polymerization technology and the invention of low-temperature solution polycondensation method, the synthesis of para-type wholly aromatic polyamide was successful. [S.L. Kwolek, US Patent No. 3,600,350 (1971)]. These technologies have developed several types of fully aromatic polyamides, such as poly (m-phenyl-isophenyl glycol amine) (Po 1 y (B-pheny lene i sophtha 1 aB i de)) (MPD -I), Poly (p-benzaaide) (PBA) (Poly (p-phenylene ter * ephthalaBide) (PPD- T)). Among them, two fiber products, MPD-I and PPD-T, were commercialized in 1962 and 1972 respectively, and are now widely used in industrial applications. It is generally known that fully aromatic enzyme products have excellent characteristics, such as thermal Stability, chemical resistance, dimensional stability, flame resistance and other properties. Among these characteristics, flame resistance is the most noticed in industrial thermal protective clothing. In addition to the above properties, MPD-I fiber combines the characteristics of the fabric, and is especially suitable for the above-mentioned applications.

nn «si mV (please read the precautions on the back before filling in this page) A Packing — Order ί. ------- This paper standard uses the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) A7 B7 Fifth, the description of the invention (2) The measurement of the flame resistance of the polymer is to test the limit gas concentration index of the polymer [liiiting oxygen index (.LOI)], which is defined at room temperature, the test product in the gas radon Μ combined The lowest gas concentration in the gas that can be burned. From the literature [HHYang, "Aromatic High-strength Fibers", Wiley Interscience, New York (1989)], it can be understood that general fully aromatic polyamide fibers have a more distant LOI value; in other words, such polymers are more fatty Aromatic or semi-aromatic polymers have better flame resistance properties. Among fully aromatic polymers, aromatic heterocycles and aromatic polyimide amines have a higher L0I value than aromatic polyamides. That is, the flame resistance is better. For improving the flame resistance of Nylon and polyester, industrially tried methods include polymer modification, addition of additives, or polymer blending. As for aromatic polyamides, Fujie is in the United States Patent 4, 196,118 (1980) suggests the use of organic compounds containing phosphorus and halogen atoms as a flammable agent to increase the flame resistance of MPD-I fiber lozenges. Although this fiber containing additives improves flame resistance, it also decreases Printed and printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs (read the precautions on the back and then fill out this page). Therefore, the purpose of the present invention is to improve the flame resistance of the gold aromatic polyimide, and Maintain its excellent thermal stability. In detail, the purpose of the present invention is to improve the flame resistance of poly (m-phenyl-isophenylenediamide) (MPD-I) by modifying the polymer. In the course of the present invention, it was found that fully aromatic polyamines, especially MPD-I, can be added with an aromatic group of formula (IV) below 15 mol% to improve its flame resistance. The paper scale is free of Chinese national standards (CNS) Μ specification (210 X 297mm) 314529 A7 B7 5. Description of the invention (3)

X X

Z

(Please read the note $ item on the back and then fill out this page) -f. 装 _ 定 資 資 資 資 體 銆 銆 € 銆 € 銆 € 銆 € 銆 € 鈥 鈥 鈥 W = S elementary atom, COOH, C »H2« + i ( n = l ~ 2) X = halogen atom, CH3 Y = C n Η 2 (η = 1 ～ 2), 0, S, S Ο Λ, or no Z dibinsu atom, COOH, (% Η2η “(η = 1 ~ 2) According to the so-called wholly aromatic polyamide according to the present invention, it is defined as a linear polymer containing at least 85 mol% repeating units as shown below .; __NRl -Ar1-NR2-C〇-Ar2 -C〇-'! --- NK-^-Ar 3-CO-- 1-(where Ari, Arz and Ar3 are aromatic groups, and Ari and Arz can be heard or different, 1? 2 and 1 ? 3 is a lower alkyl or gas atom, and 5 ^ and 1 can be the same or different). An example of such a fully aromatic polyamide is poly (m-phenyl-isophthalamide) and contains at least 85 mol% below the formula between one -5-This paper scale is easy to use Chinese National Standard (CMS) A4 specifications (210X297 mm) 314529 V. Description of invention (4 A7 B7 phenyl-isobenzene monobromoamine repeat unit Copolymer-ΝΗ

Issue d (V) The polymer of the present invention is prepared by low-temperature solution polycondensation, polycondensation of meta-aromatic diamine 'meta-aromatic dibromochloride and the following formula ι_ν ingredients: -nh- ^ Q ^- nh (I) __ co-^^ co — (Π) w (Please read the precautions on the back before filling this page)

T outfit-«-Printed by Beigong Consumer Cooperation of China National Standards Bureau, Ministry of Economic Affairs

NH-(HI) OV) (V) w The polymerization reaction is carried out in amide solvent. It is necessary to add alkaline salts to promote the reaction. Commonly used amide-based solvents include nitrogen, N-l-methylmetacrylamine (NJlST-dimetliyl acetamide, DMAc) — 6 — (correction page). This paper scale uses the Chinese standard rate (CNS) A4 as standard ( 210 χ 297 mm) A7 B7 printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs 5. Description of the invention (5), dimethyl for Ba * ide (DMF), and N-methyl-2 -1 {± rr _ / ({| 161; 1171-2-? 71 ^ 〇1 丨 € 1〇116, {1.1 | 11)). The test ^ 4 bond includes 0 chloride, lithium chloride, lithium phosphate and so on. The polymer concentration in the polymerization reaction is at least higher than 10 wt%. The salt content can be added according to the solubility and concentration of the polymer, and the addition of Dong varies from zero to excess. The polymerization temperature is initially -101 to 10 * 0, and finally it is lower than 70. The reaction time depends on the polymerization composition. Generally, the reaction time of high molecular weight polymers is about 1 to 2 hours. The present invention is further illustrated by the following non-limiting examples. Example 1 Preparation of poly (m-phenylphenyl-isophthalamide) (MPD-I) A 5-liter jacketed cylindrical glass reactor was equipped with a double-helical stir bar, and 409.0 g (3.7.8 mole) of N-phenylene diaiine (MPD), 3605g (3500 · 1) of anhydrous nitrogen-methyl-2-tt ketone (NMP), and ventilation of radon gas. After cooling the MPD / HMP solution to 0, after about 15 minutes, 767.9 g (3.78 mole) of isophthaioyl chloride (Icl) was added. The temperature of the reactant gradually rises, and the viscosity of the reactant rises sharply, and the low temperature is maintained by cooling. After reacting for 20 minutes, raise the temperature of the cooling water to 60 and maintain it for 10 to 15 minutes. After the reaction, the polymer was poured into the storage tank. When the temperature drops to room temperature, the reaction mixture will form a light amber high-viscosity condensate. This polymerization mixture contains about 20 MPD-I polymers. The obtained gold aromatic polyamidoamine solution was precipitated and dried with 97% concentrated sulfuric acid as the solvent, the polymer concentration was 0.5g / 100Bl, and the relative viscosity of the polymer was tested at 30 ° C (relativeviscosity η > ·· ι). Then calculate the intrinsic viscosity value according to the following formula: This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 Gongmai) --- 7 ---- Γ ^ --.---- τι order .-- ---- C (Please read the precautions on the back before filling in this page) A7 B7 5. Description of the invention (〇IV = In (n, ..) / CC: Concentration This polymer has an inherent viscosity of 1.1 dL / s Value. The polymer solution is obtained by dip casting on the glass plate according to the traditional method to make a polymer film of about 2g. If the film is dried under vacuum at 150 * 0, 76BBHg for 6 hours, then L0I and thermogravimetric analysis (TGA) test. The measured 5% weight loss temperature (Ts) is about 444.5t. The LOI of the polymer in film form is about 27% according to ASTM D2863-87. The results are shown in Table 10. Examples 2 to 10 These examples discuss the properties of the copolymer of m-phenyl-iso-phenylenediamide. Example 1 during the experimental procedure, the raw materials for the polymerization were added in addition to MPD and 1C 10 * ole% of aromatic diamine or difermented chlorine, for copolymerization. The results obtained are listed in Table 1. These copolymers have a 5% reset loss temperature range of 388 .51 ^ 449.410, L0I value is between 2 7.4% ~ 3 3.6%. It can be seen that its flame resistance is improved, and there is no major change in thermal stability. Read the precautions on the back and fill in this page) This comparative example is based on the method shown in Fujie et al. (US Patent 4,196,118), by which a 90/10 ratio MPD-I / tris (chloroethyl) phosphate (TCP) mixture is prepared Compare. Take 3g of the MPD-ϊ prepared in the dried example, dissolve it in 151g of NMP at 70T, and add 0.3g of TCP to the MPD-I / NMP solution, mix well. Then prepare MPD- I / TCP film, and the above test. The test result 5% weight loss temperature is about 260 < 〇, its dagger 〇1 according to the US Patent 4,196, the paper size is used in the Chinese National Standard (CNS) A4 specification (210X297 mm ) 314529 A7 B7 Fifth, the description of the invention (7), reported in 11 8 is 36%, it can be seen that although the flame resistance is improved, but the thermal stability is greatly reduced. Table

* Tma -nn ^^^ 1 «VI comonomer repeat unit real family> 1 (10 mol%) intrinsic viscosity value (dL / g) T5.TGA 5% wt weight loss temperature (.〇LOI (% ) No comonomer

—CO

ΝΠ

Ml IIjC Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy 9 ΙΟ Comparative examples

1.12 444.5 27.2 1,05 431.6 30.9 1.24 438.2 29.6 1.48 417.5 30.1 1.10 436.5 28.1 1.20 417.1 30.5 0.80 441.4 33.6 1.60 418.2 27.4 1.40 388.5 30.9 2.14 436.6 27.4 1.1 260.1 36 (Please read the precautions on the back before filling in this page) Order * Λ The standard speed of this paper is China National Standard (CNS) Α4 specification (210Χ297mm)

Claims (1)

6. Patent application scope (revised version):-* &lt;:… 1. A meta-type wholly aromatic polyamide copolymer, which is polycondensed by the following components 7- ... ⑻ Inter-aromatic; ^ 2 ^ &quot; (b) m-aromatic diacid; and (c) one or more comonomers having the following structure; and the content shall not exceed 15 mol%. W-n I WH .......... In I _ I-(please read the notes on the back before filling in this 1) Order --- f 碅 工 consumer cooperative printed by the Central Standards Bureau of the Ministry of Economic Affairs (Wherein W dihalogen atom, COOH, CJi2n + 1 (n = l ~ 2) X = halogenogen, CH3, HY diCnH2n (n = l ~ 2), 0, or Z-free dihalogen atom, COOH, CnHUi (n = l ~ 2). _ 10 — (correction page) The paper size is used in China National Standard (CN§) A4 specification (210X297 public daughter) VI. Patent application scope 'A8 B8 C8 D8 2. If applied The copolymer described in item 1 of the patent scope, where (a) is m-diamine benzene (b) is m-phenylenedichlorine and (c) is C0 C0 3. The copolymer as described in item 1 of the patent application scope, where (a) is m-diamine benzene (b) is m-phenylenedichlorine, ⑻ is NH——Li C1 4. if patent scope is applied The copolymer according to item 1, wherein (a) is m-diamine benzene (b) is m-phenylenedichloride, (c) is · NH- -NH C1 I:-; ----- f —installed ^ ----:-ordered ----- f line (please read the note $ item on the back and then fill in this page) Printed bag of the Ministry of Economic Affairs Central Bureau of Industry and Consumer Cooperatives 5. If applying The copolymer described in item 1 of the patent scope, wherein (a) is m-diaminobenzene (b) is m-phthalic acid gas "(c) is 11— (Amendment page) This paper standard uses the Chinese National Standard (CNS) 4 specifications (210X297 gong) 314529 -A8 B8 C8 D8 VI. Patent application scope 6. Copolymer as described in item 1 of patent application scope , Where (a) is m-diaminebenzene (b) is m-phenylenedichloride, (c) is · NH-COOH 7. The copolymer as described in item 1 of the patent application scope, where (a) is M-diamine benzene (b) is m-phenylenedi gas, (c) is NH 8. The copolymer as described in item 1 of the patent application scope, where ⑻ is m-diaminobenzene (b) is m-phenylenedichlorine, (c) is nnnn I in ^ —I nn n (please first Read the note $ item on the back and fill in this page) Order NH General. -&lt; 〇 &gt;-NH Ministry of Economic Affairs, Central Bureau of Standardization, Zhengong Consumer Cooperative Printed ►- 9. The copolymer as described in item 1 of the patent application, where (a) is m-diamine benzene (b) It is m-phenylenediamide gas, (c) is NH -CH2- Shun — 12 — (revised page) C line ------- this paper ruler A Xiao Zhongzhong National Standard (CNS) Λ4 specification (210X297 Xian) 314529 Shenjing patent scope Ά8 B8 C8 D8 10 === copolymer, of which diamine benzene NH U_ ^ 神 簡 _ Ershu ’s common secret, its core consists of at least% mol% <Wei unit between phenyl-m-phenylenediamine represented by the following formula: '^ m ~ NH-CO CO- (V) 11.1 ^ ----- f -installed-- (please read the precautions before filling out this page) Central Department of the Ministry of Carriage and Economy 65 ^ *: Industrial and Consumer Cooperatives _!?-H 12- The copolymer as described in item 1 of the scope of the patent application, the molded article prepared is a fiber having a linear density greater than 0.25 denier / filament. One 13 — (correction page)-order ·. · * Line · ------- This paper standard uses the Chinese National Standard (CNS) (210X297 mm)