TW387917B - Copolyamide composition with a high glass transition temperature and a low melting point - Google Patents

Abstract

A copolyamide composition perared from hexamethylene diamine and mixture of adipic acid, terephthalic acid and isophthalic acid, has a melting point below 300 DEG C, a glass transition temperature between 100 DEG C and 130 DEG C and physical properties similar to nylon 66.

Description

Seal A7 of Zhengong Consumer Cooperative of the Central Bureau of Plant Planning, Ministry of Economic Affairs " ------------------- V. Description of Invention (l) ----- A polykanamine copolymer prepared from a mixture of hexamethylene diamine and adipic acid, terephthalic acid, and isophthalic acid. Especially about Gu. It has a melting point (Tm) of less than 300 and c and a glass transition temperature (Tg) of 100. . Polycollamine copolymer with mechanical properties similar to 130 eC and nylon 66. 100/0 octamethylene p-phenylenediamine donkey amine (Bu Xia 6 also 16116 terephthaiamide (6T)) polymer has a high Tg, but at the same time has a too high Tm (greater than 37 (rc) is not suitable Melt processing. Although replacing a part of "terephthalic acid with isophthalic acid can reduce the Tg while maintaining high Tg ', the 6T / 6I (hexamethylene terephthalate / hexamethylene methane Butylamine isophthalate) copolymer has lower crystallinity. Therefore, polyamine copolymers composed of 66 (xylylene hexamethylene diamine), 6T and 61 have been developed and applied. In different fields, for example, in Japanese Patent Publication Sho 46-18809 (71018809), 66 = —NH — (-CH2) 6—NH—C — (-CH2) 4—C-

Synthetic polyamine copolymer for monomers, the amount of 66 / 6T / 6Ι = 1〇 ～ 50/10 This paper size is fast-moving China National Standard (CNS) A4 specification (210X297 mm) (Please read the back Please fill in this page for the matters needing attention) Order A7 B7 V. Description of the invention (2) Printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) ~ 50/10 ~ 55, using fibers as the purpose. "Japanese Laid-open Patent Publication Sho 52-85516 (77085516) synthesizes polyamide copolymer polymer fibers with a weight ratio of 66/61761 = 20 to 70/15 to 45A5 to 35. Japanese Patent Gazette Sho 46-28218 (71028218) synthesizes a polyamide copolymer polymer with 66/61761 = 10 to 80/10 to 50/10 to 55. U.S. Patent U.S.P. 4,238,603 (1980) synthesizes a polyamide copolymer polymer with 66 / 6T / 6I = 2 ~ 15/45 ~ 68/30 ~ 40. Japanese Patent Gazette 68-067801 Synthesize 66/61761 = 10 ~ 80/10 ~ 65/10 ~ 55 Synthetic Polyamide Fiber. US Patent U.S.P. 4,218,509 synthesizes polyamide copolymer polymer fibers. At least 66 units must have 50%, 6T is 20 ~ 40%, and 61 is 2 ~ 20%. US Patent U.S.P. 4,521,484 Synthetic Polyamide Copolymer Monofilament "of which at least 66 units must be 60%, 61 = 15 to 30%, and 6T = 5 to 10%. US patent USP 4,603,166 and reissued US 4,603,166 with a molar ratio of HMDA / AA / TPA / IPA = 100/5 to 35/65 to 95/0 to 25 are synthesized with high heat deflection temperature and Crystalline poly (vinyl alcohol) copolymer. U.S. Patent No. 4,246,395 synthesizes a polyamine copolymer with 66 / 6T / 6I = 5 ～ 20/40 ～ 75/20 ～ 40. It has a melting point (Tm) of less than 320 ° C, good thermal stability, and glass transition temperature ( Tg) is higher than 115 ΐ. US patent U.S.P. 4,268,661 66 / 6T / 6Ι = 0 ～ 15/0 ～ 50/50 ～ 100 mol ratio synthetic engineering plastic, its glass transition temperature is 140 ～ 170 t. Japanese Patent Gazette JP 60-32980 (9432980) and JP 60-32979 (9432979) are composed of 66/61761 = 30 ~ 95/0 ~ 40/5 ~ 30 to synthesize crystalline polyamine copolymers, mainly injection molding grade Mainly. Japanese Patent Gazette JP 31-26725 (9126725) uses hexamethylene diamine, terephthalic acid, isophthalic acid paper standard Chinese national hazel standard (CNS > M specification (210X297) A A 7 B7 V. Invention Explanation (3) and hexamethylene diamine as reactants, in the presence of sodium hypoporous acid (Sodiumhypophosphite), a polyamine copolymer is synthesized. Japanese Patent Publication JP 30-07761 (9007761) Isophthalic acid = 〇 ~ 70/30 ~ 100/0 ~ 40 ratio and hexamethylenediamine-synthesized polyamidoamine copolymer, which has the characteristics of heat resistance, water, chemical properties and high mechanical strength. German patent DE 3506656 (1986) with adipic acid / terephthalic acid and isophthalic acid = 30 ~ 51 / 48.5 ~ 70, of which terephthalic acid / isophthalic acid = 48.5 ~ 60/40 ~ 51.5 and hexamethylene diamine Synthetic polyamide copolymer with high Tg and low hygroscopicity. European Patent Publication EPA121,984 (1984) with adipic acid / terephthalic acid / isophthalic acid = 5 ~ 35/5 ~ 35 / 60 ~ 90 and hexamethylene diamine synthetic polyamine copolymer, with 10 ~ 60% glass fiber or glass beads and mineral or carbon fiber ingredients, with high Folding temperature (240 ~ 305 ° C). Japanese Patent Laid-Open Publication No. 06-287299 [94287299] uses a continuous process to synthesize a polyamine copolymer having heat resistance and low water absorption. Its composition is (please first (Read the notes on the back and fill out this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs

ΠΙ = NH (-CH2) 6—NH—d; — (~ CH2) 4 IV = NH —fCH2) 5

This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) B7 V. Description of the invention (4) I / 11 = 55 ~ 80/20 ~ 45, I dll = 20 ~ 80/20 ~ 80, or I / IV = 55. ~ 90/10 ~ 45. Japanese Patent Laid-Open Publication No. 06,287,300 [94,287,300] Synthesize a polyamine copolymer of heat resistance and crystallinity. Its composition is:

-(CH2) 6—NH-C

0 II -c Π = NH—fCH2) 6—NH- DI = NH—eCH2) 6—NH-H-4CH2) 5 -C-

-f € H2) 4 — ((Please read the precautions on the back before filling this page)

IV j Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

CH2 synthesizes a polyamine copolymer with a weight ratio of I / 11 = 55 ~ 80/20 ~ 45, I / ΙΠ = 20 ~ 80/20 ~ 80, or I dV = 55 ~ 90/10 ~ 45. European Patent Publication E.P.A. 0,409,666 consists of:

B

The A / B / C ratio is 0.5 ~ 49.5 / 0 ~ 20 / 0.5 ~ 49.5, and R is -H2C \ (I) and one eat) factory one (π), and the ratio is I / π -6. Applicable to Chinese National Standard (CNS) A4 (210X29? Mm)

Ο

〇 II A7 _B7___ V. Description of the invention (5) = 0.5 ~ 50/0 ~ 49.5 Synthetic polyamidoamine copolymer with Tg greater than 90 ° C, and oxygen permeability is about 2.0CC-mil / 100in2day-atm or more less. European Special Case Bulletin E.P.A. 0,291,096 Synthesis of a polyamine copolymer having a high flexural temperature, the composition is: A = NH (CH2) 6—NH —— (〇 Β

C = —ΝΗ— (CH2) 6 —ΝΗ —c — (CH2) 4—C where the A / B / C ratio is 60 ~ 90/5 ~ 35/5 ~ 35. The object of the present invention is to provide a polyamide copolymer having a melting point (Tm) of less than 300 ° C, a glass transition temperature of 100-130 ° C, and mechanical properties similar to nylon 66. The purpose of the present invention can be achieved by providing a polymer consisting of the following repeating units (please read the notes on the back before filling this page): β

NH— (CH2) n1 —NH —C— (〇Η2) 4_) --- C (A)

o II Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -NH- (CH2) n2 —NH —C— ~ C_

NH ™ (CH2) n3 ——NH —C (B) (C) where the molar ratio of the dicarboxylic acid moiety in the units (A) (B) and (C) is 0-30: 30-60: 30-65, and n2 and n3 are integers of 2-14 respectively. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) printed by Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs «-A7 _________ B7__ V. Description of the invention (ό) Amine copolymers can be used as engineering plastics. For example, plastic processing machines such as injection molding machines and extrusion machines can be used to form plastic products or laminated boards for automotive components, gears, bearings, electronic and electrical parts (supplies), electrical and wire jackets, and money boxes. , ㈣ use chair 〇 casters and so on. The polymagnetic amine copolymer of the present invention is also suitable for use as residual fiber and filament fiber for fishnet wire, industrial fiber, and tire reinforcement. The present invention < polydonylamine copolymer, preparation method, characteristics and advantages are described in detail by the following examples. The preparation of the amidine copolymerized mosquito according to the present invention can be carried out in three stages. In the first step, a polymeric prepolymer is prepared in a Lin reaction tank suitable for processing high-deficiency materials. Firstly, each reactant, including specific dicarboxylic acid terephthalic acid, adipic acid and isophthalic acid, diamine (usually an aqueous solution of hexamethylene diamine) and additives are added to the reaction tank at an external temperature of 15 (rcT) The amount of water added is usually 5 to 25 weight percent of the reactant b. Then the reaction tank is purged with nitrogen or its secret gas and the reaction mixture is heated to about 240 C to 310 X :. During the entire reaction The pressure, mainly the vapor pressure, is maintained at 4_5Kg / em2 »When the water output in the pre-polymerization process reaches about 3G% of the total water output, the pressure is then discharged to 1Kg / cm2. The prepolymer is discharged The second step is the final polycondensation step and can use a conventional stirred reaction tank or double screw-like extruder reactor (the so-called reaction extrusion method). This final polycondensation step should use a stirred reactor Shi Nao was carried out at about 36 ° β (: outside temperature, emptyness of about 70Cm-Hg. If this final polycondensation step is a double screw-like extruder, due to its high area and volume ratio, the heat transfer effect is good, } — ^ ------ T-^ — r (Please read the back first Please fill in this page again for attention) # " ". — ----- 「线 ---; __ 1 .I -1! M -8-Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Note (7) The powerful stirring effect is good, and it can provide various stages of heating, different stages of exhaust, and multiple stages of the same or different degrees of emptying and air extraction devices, so the polycondensation reaction can be continuously performed from the inside in a short reaction, the unit capacity In addition, the reaction extruding equipment is simple, unlike the general commercial reaction tank, the process is complicated, the monomer extruded by the reaction, the co-monomer adjustment flexibility is large, so it is easy to handle high-melt resin. When using this reaction extrusion method, about 240 -280 ° C and about 60 cm-Hg in the air. The following examples illustrate the present invention, these examples are a general illustration of the present invention and do not limit the scope of the present invention. Example 1 (A) prepolymerization Synthesis of the body Clean a 2-liter reaction tank equipped with a stirrer and blow dry with nitrogen. After dissolving 120 g of hexamethylene diamine in a 70 ° C hot water bath, add distilled water to the dissolved hexamethylene diamine. The amount of distilled water is dissolved 17% by weight of diamine. The mixture is then poured into a reaction tank and an appropriate amount of adipic acid (the molar ratio of which is to hexamethylenediamine is 1: 1.03) and 0.1% by weight of sodium diphosphonium hypophosphite is added. The air in the reaction tank was purged with nitrogen for more than 5 times. Then the external temperature of the reactor was set to 230 ° C. After 10 minutes, the temperature was raised to 250 ° C. After 30 minutes at constant temperature, the temperature was increased to 280 ° C. After 30 minutes, Raise the temperature to 310 ° C, continue to maintain for 30 minutes, and finally increase the external temperature to 340 ° C. During the heating process, the pressure is maintained at 4-5kg / cm2. When the water output reaches 60mf (about 30% water output rate), increase the pressure Reduced to lKg / cm2. At this time, the total water output is about 75m / (water output rate is about 70%). Then this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ^^ 1- ..... I =--> ^^ 1 ΙΓ =, 1. (Please read the note on the back first Please fill in this page again) Order 387917 Printed by Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ------------ B7 __: __ V. Description of Invention (8) " ~~~ — — The formed prepolymer was discharged into ice water under a pressure of IKg / cm2. (B) Samples of the final product, polyamine. In this step, a steel pipe immersed in 360. Reactor: Put 0.5 ~ lg dried prepolymer into steel pipe, and when the internal temperature reaches below 70cm-Hg when the internal temperature reaches 20 ° C lower than the melting point of the sample, remove the steel pipe and place it in ice water to cool it. Below 100 ° C, remove the sample for analysis. PP (C) Polyamide The relative viscosity of the polyamide is obtained by measuring the viscosity in a Cannon HO three-port viscosity tube immersed in a constant temperature bath. The temperature of the water tank was maintained at 30 ° C and 0.1 ° C, and the solvent used was phenol / tetramethane (6/4, w / w), and the concentration of polyamine was 0.5 g / d. The relative viscosity (R v) is 1.0 to 1.5. (D) The first sample is heated from room temperature to 300 ° C at a ripple rate of 20 eC / min by DSC analysis and measurement in a DSC. After 300 ° C, it is quickly cooled to room temperature, and then heated from room temperature to 350 ° C at a rate of 20 ° C / min. #Tm and Tg (based on the second temperature rise and Tg) The results are shown in Table 1. Example 2 Except that adipic acid was replaced with a mixture of adipic acid, terephthalic acid, and isophthalic acid, the other conditions and the molar ratio (the molar ratio of diamine and diacid) were all The polymer analysis data is as follows. The relative viscosities of the synthesized co-polymers are greater than RV = 1.6, and Tg and Tm are shown in Table 1. -10-This paper size applies to China National Standard (CNS) A4 specifications (210X297mm) (Please read the notes on the back before filling out this page) h-binding-binding · h4.

»I— II 387917_B7__ V. Explanation of the invention (9) Table 1. Effect of polyamidoamine copolymers composed of different bisacids and hexamethylene diamine on 1 ^ and Tm. Molar ratio Tg (° C) Tm of bisacid composition (° C) adipic acid / terephthalic acid / isophthalic acid 5/40/55 123 245 adipic acid / terephthalic acid / isophthalic acid 5/50/45 124 268 adipic acid / terephthalic acid Dicarboxylic acid / isophthalic acid 5/60/35 120 306 Adipic acid / terephthalic acid / isophthalic acid 10/30/60 113-* Adipic acid / terephthalic acid / isophthalic acid 10 / 40/50 120 245 adipic acid / terephthalic acid / isophthalic acid 10/50/40 121 265 adipic acid / terephthalic acid / isophthalic acid 10/60/30 118 312 adipic acid / Terephthalic acid / isophthalic acid 15/35/50 112 231 adipic acid / terephthalic acid / isophthalic acid 15/40/45 115 259 adipic acid / terephthalic acid / m Phthalic acid 15/50/35 111 144 Adipic acid / terephthalic acid / isophthalic acid 20/40/40 107 246 Adipic acid / terephthalic acid / isophthalic acid 30/30/40 91 225 Adipic acid / terephthalic acid / isophthalic acid 30/40/30 98 252 Adipic acid 100 45 265 (Please read the Please fill in this page for the matters needing attention) -Λ · * 装 l · Note: * indicates that no obvious Tm can be measured. Example 3 (A) The synthesis of the prepolymer was used except that the reaction tank was changed from 2 liters to 50 liters. Two pre-polymers were prepared by the methods of Examples 1 and 2. One was prepared from hexamethylene diamine (HMDA) and adipic acid (AA), and the other was prepared from hexamethylene diamine and mixed ratio AA / TA / IA. = 10/50/40 mixture as raw material. (B) Synthesis of final product polyamide copolymer In this example, a twin screw extruder reactor was used to prepare the final product polyamide copolymer. The prepolymer is dried and powdered and then fed to a twin-screw extruder (Zeki 45mm Φ) for reaction extrusion polymerization. The reaction conditions are shown in Table 2. 0 -11-Paper size: Chinese National Standard (CNS) A4 specification (210X297 mm)-Order-Γ Line Ministry of Economic Affairs, Central Standards Bureau, Consumer Consumption Du printed 387917 V. Description of the invention (10) Rotating ripple of table screw (rpm) Temperature of reaction zone (° C) Hollow degree of reaction zone (c-Hg) Die temperature (° C) 180 1 2 3 4 5 6 7 8 120 240 265 273 290 280 278 270 12 3 60 60 60 270 (C) DSC analysis The Tm and Tg of the final polyamine copolymer were determined according to the method of Example 1. The results are shown in Table III. (D) Measurement of physical properties A single screw injection molding machine (Niigata Stubba) is used to prepare test samples. The preparation conditions are as follows: — ..―.----- * (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Injection screw: diameter 30mm Φ barrel temperature setting: 256 ~ 255 ℃ nozzle setting temperature: 274 ° C mold temperature: 110 ° c injection pressure: 3 kg / cm2 injection Holding time: 10 sec Cooling time: 50 sec Mold opening time: 1.2 sec Screw speed: 100 rpm The tensile strength, tensile strength, and flexural modulus of the test sample produced are tested according to ASTM-D638 and measured The results are shown in Table III: -12-Order. Γ line. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 cm) 387917 V. Description of the invention (11)

Table III. Composition of adipic acid Adipic acid (AA) / terephthalic acid (TA) / isophthalic acid (ΙΑ) Molar ratio 100 10/50/40 Tensile strength; kg / cm2 (Tensile strength ) 750 900 flexural strength; kg / cm2 (Flexural strength) 1200 1500 flexural modulus of elasticity; kg / cm2 (Flexural Modulus) 27000 33000 Tg (° C) 45 121 Tm (° C) 265 266 As shown in Table III, The polyamide copolymer of the present invention has a Tm below 300 ° C ^ ------ L ^-l · —.— (Please read the note on the back before filling this page) at 100-130 ° Tg between C and mechanical properties equal to or better than nylon 66. _ &Quot; " Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -13-This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

IB patent scope B8 ν- · ρο ΊΟ D8 ν 387917 A polyamine copolymer having a melting point below 300 * 〇 and a glass transition temperature of 100-130eC, including the following repeating units: 0 -NH-f CH ^ NH —C— (CH2) 4—C— -nh- ^ ch ^ nh- oo ㈧ o (B) —NH-fCH ^ NH—C ' (C) The Central Fengfeng Bureau of the Ministry of Lijin, Λ Gongxiao #Cooperatives, 5- «. Where the molar ratio of the diacid units in units (A), (B), and (C) is" ο: 3〇 ~ 60: 30 to 65, and ni, u2, and n3 are integers between 2 and 14. 2. The polyamine copolymer of item 1 of the patent application, wherein (A), (2) and (c) The molar ratio of the diacid unit in the unit is 1 ~ 15: 35-60: 30-60. 3. For example, the polyamine copolymer of the patent application Fangu No. 1, wherein (A), fluorene and (C) The molar ratio of the diacid unit in the unit is 1 ~ 10: 40 ~ 60: 50 ~ 60. Let the polyamine amine co-polymer of item 1 of the patent application park, where nl and weepy are 6. ^ 5 · For example, the patented polyamide copolymer of item 1 can be made into an engineering plastic. Main 6. The patented patent copolymer of item 1 can be made into a fiber. 7. If the polyamine copolymer is applied for item 1 of the patent scope, it can be made into a laminate. Μ- (88.9.15 revised page) (Please read the notes ^ | ^ on the back before filling the book 1) Pack. Order IB patent scope B8 ν- · ρο ΊΟ D8 ν 387917 A polyamine copolymer having a melting point below 300 * 〇 and a glass transition temperature of 100-130eC, including the following repeating units: 0 -NH-f CH ^ NH —C— (CH2) 4—C— -nh- ^ ch ^ nh- oo ㈧ o (B) —NH-fCH ^ NH—C ' (C) The Central Fengfeng Bureau of the Ministry of Lijin, Λ Gongxiao #Cooperatives, 5- «. Where the molar ratio of the diacid units in units (A), (B), and (C) is" ο: 3〇 ~ 60: 30 to 65, and ni, u2, and n3 are integers between 2 and 14. 2. The polyamine copolymer of item 1 of the patent application, wherein (A), (2) and (c) The molar ratio of the diacid unit in the unit is 1 ~ 15: 35-60: 30-60. 3. For example, the polyamine copolymer of the patent application Fangu No. 1, wherein (A), fluorene and (C) The molar ratio of the diacid unit in the unit is 1 ~ 10: 40 ~ 60: 50 ~ 60. Let the polyamine amine co-polymer of item 1 of the patent application park, where nl and weepy are 6. ^ 5 · For example, the patented polyamide copolymer of item 1 can be made into an engineering plastic. Main 6. The patented patent copolymer of item 1 can be made into a fiber. 7. If the polyamine copolymer is applied for item 1 of the patent scope, it can be made into a laminate. Μ- (88.9.15 revised page) (Please read the notes ^ | ^ on the back before filling the book 1) Pack. Order