SEMIAROMATIC COPOLYAMIDE RESIN AND POLYAMIDE MOLDING COMPOSITION CONSISTING OF THE SAME

Abstract

The present invention discloses a semiaromatic copolyamide resin and a polyamide molding composition consisting of the same, consisting of following repeat units: (A) 26-80 mol % of units derived from para-amino benzoic acid; (B) 4-70 mol % of units derived from 11-aminoundecanoic acid or undecanolactam, and 0-70 mol % of units derived from another amino acids having 6 to 36 carbon atoms or units consisting of a lactam having 6-36 carbon atoms; (C) 0-37 mol % of units derived from a diamine unit having 4 to 36 carbon atoms; and (D) 0-37 mol % of units derived from a diacid unit having 6 to 36 carbon atoms; wherein, (A)+(B)+(C)+(D)=100 mol %; and molar contents of the units derived from para-amino benzoic acid and those derived from 11-aminoundecanoic acid or undecanolactam are not equal to 50 mol % simultaneously.

Claims

1-12. (canceled)

13. A semiaromatic copolyamide resin consisting of following repeat units by molar percentage: (A) based on an amount of all monomeric units, 26-80 mol % of units derived from para-amino benzoic acid; (B) based on the amount of all monomeric units, 4-70 mol % of units derived from 11-aminoundecanoic acid or undecanolactam, and 0-70 mol % of units derived from another amino acids having 6-36 carbon atoms or units consisting of a lactam having 6-36 carbon atoms; (C) based on the amount of all monomeric units, 0-37 mol % of units derived from a diamine unit having 4-36 carbon atoms; and (D) based on the amount of all monomeric units, 0-37 mol % of units derived from a diacid unit having 6-36 carbon atoms; wherein, (A)+(B)+(C)+(D)=100 mol %; and molar contents of the units derived from para-amino benzoic acid and the units derived from 11-aminoundecanoic acid or undecanolactam are not equal to 50 mol % simultaneously.

14. The semiaromatic copolyamide resin according to claim 13, wherein the semiaromatic copolyamide resin consists of the following repeat units by molar percentage: (A) based on the amount of all monomeric units, 26-80 mol % of the units derived from para-amino benzoic acid; and (B) based on the amount of all monomeric units, 4-70 mol % of the units derived from 11-aminoundecanoic acid or undecanolactam, and 4-70mol % of the units derived from the amino acids having 6-36 carbon atoms or the units consisting of the lactam having 6-36 carbon atoms; wherein, (A)+(B)=100 mol %; and the molar contents of the units derived from para-amino benzoic acid and those derived from 11-aminoundecanoic acid or undecanolactam are not equal to 50 mol % simultaneously.

15. The semiaromatic copolyamide resin according to claim 13, wherein the semiaromatic copolyamide resin consists of the following repeat units by molar percentage: (A) based on the amount of all monomeric units, 40-60 mol % of the units derived from para-amino benzoic acid; (B) based on the amount of all monomeric units, 10-40 mol % of the units derived from 11-aminoundecanoic acid or undecanolactam, and 10-40 mol % of the units derived from the amino acids having 6-36 carbon atoms or the units consisting of the lactam having 6-36 carbon atoms; (C) based on the amount of all monomeric units, 5-25 mol % of the units derived from the diamine unit having 4-36 carbon atoms; and (D) based on the amount of all monomeric units, 5-25 mol % of the units derived from the diacid unit having 6-36 carbon atoms; wherein, (A)+(B)+(C)+(D)=100 mol %; and the molar contents of the units derived from para-amino benzoic acid and those derived from 11-aminoundecanoic acid or undecanolactam are not equal to 50 mol % simultaneously.

16. The semiaromatic copolyamide resin according to claim 13, wherein the molar content of the units derived from para-amino benzoic acid is not equal to the molar content of the units derived from 11-aminoundecanoic acid or undecanolactam.

17. The semiaromatic copolyamide resin according to claim 14, wherein the molar content of the units derived from para-amino benzoic acid is not equal to the molar content of the units derived from 11-aminoundecanoic acid or undecanolactam.

18. The semiaromatic copolyamide resin according to claim 15, wherein the molar content of the units derived from para-amino benzoic acid is not equal to the molar content of the units derived from 11-aminoundecanoic acid or undecanolactam.

19. The semiaromatic copolyamide resin according to claim 13, wherein with reference to ASTM D3418-2003, a melting point of the semiaromatic copolyamide resin is 270-360 C.; with reference to GB12006.1-89, an intrinsic viscosity is 0.80-1.0 dl/g; a water absorption is equal to or less than 2.0%; a b-value is equal to or less than 1.0; wherein a test method for the water absorption is as follows: injection molding a sample into a 20 mm20 mm2 mm part, with a weight recorded as a0, after placing the part into water at a temperature of 95 C. for 240 hours, weighing the part with a weight recorded as al, and the water absorption=(a1-a0)/a0*100%; and a test method for the b-value is as follows: obtaining a smooth panel after injection molding 3000 g of sample particles with a 50*30*2 mm panel mold, and placing the panel on a Color-Eye-7000A computer color photometer of Libero to obtain the b-value.

20. The semiaromatic copolyamide resin according to claim 14, wherein with reference to ASTM D3418-2003, a melting point of the semiaromatic copolyamide resin is 270-360 C.; with reference to GB12006.1-89, an intrinsic viscosity is 0.80-1.0 dl/g; a water absorption is equal to or less than 2.0%; a b-value is equal to or less than 1.0; wherein a test method for the water absorption is as follows: injection molding a sample into a 20 mm20 mm2 mm part, with a weight recorded as a0, after placing the part into water at a temperature of 95 C. for 240 hours, weighing the part with a weight recorded as a1, and the water absorption=(a1a0)/a0*100%; and a test method for the b-value is as follows: obtaining a smooth panel after injection molding 3000 g of sample particles with a 50*30*2 mm panel mold, and placing the panel on a Color-Eye-7000A computer color photometer of Libero to obtain the b-value.

21. The semiaromatic copolyamide resin according to claim 15, wherein with reference to ASTM D3418-2003, a melting point of the semiaromatic copolyamide resin is 270-360 C.; with reference to GB12006.1-89, an intrinsic viscosity is 0.80-1.0 dl/g; a water absorption is equal to or less than 2.0%; a b-value is equal to or less than 1.0; wherein a test method for the water absorption is as follows: injection molding a sample into a 20 mm20 mm2 mm part, with a weight recorded as a0, after placing the part into water at a temperature of 95 C. for 240 hours, weighing the part with a weight recorded as a1, and the water absorption=(a1a0)/a0*100%; and a test method for the b-value is as follows: obtaining a smooth panel after injection molding 3000 g of sample particles with a 50*30*2 mm panel mold, and placing the panel on a Color-Eye-7000A computer color photometer of Libero to obtain the b-value.

22. The semiaromatic copolyamide resin according to claim 13, wherein the diamine unit having 4 to 36 carbon atoms is selected from one or more of a linear or branched aliphatic diamine, a cycloaliphatic diamine and an aromatic diamine; the linear or branched aliphatic diamine is selected from one or more of 1,4-butylenediamine, 1,5-pentanediamine, 2-methylpentamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-6-hexanediamine, 2,4,4-trimethyl-6-hexanediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine; the cycloaliphatic diamine is selected from one or more of cyclohexanediamine, 1,3-bis(amino-methyl)-cyclohexane, isophoronediamine, norbomane dimethylamine, 4,4-diaminodicyclohexylmethane, 2,2-(4,4-diaminodicyclohexyl)propane and 3,3-dimethyl-4,4-diaminodicyclohexylmethane; and the aromatic diamine is selected from m-xylylenediamine.

23. The semiaromatic copolyamide resin according to claim 14, wherein the diamine unit having 4 to 36 carbon atoms is selected from one or more of a linear or branched aliphatic diamine, a cycloaliphatic diamine and an aromatic diamine; the linear or branched aliphatic diamine is selected from one or more of 1,4-butylenediamine, 1,5-pentanediamine, 2-methylpentamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-6-hexanediamine, 2,4,4-trimethyl-6-hexanediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine; the cycloaliphatic diamine is selected from one or more of cyclohexanediamine, 1,3-bis(amino-methyl)-cyclohexane, isophoronediamine, norbornane dimethylamine, 4,4-diaminodicyclohexylmethane, 2,2-(4,4-diaminodicyclohexyl)propane and 3,3-dimethyl-4,4-diaminodicyclohexylmethane; and the aromatic diamine is selected from m-xylylenediamine.

24. The semiaromatic copolyamide resin according to claim 15, wherein the diamine unit having 4 to 36 carbon atoms is selected from one or more of a linear or branched aliphatic diamine, a cycloaliphatic diamine and an aromatic diamine; the linear or branched aliphatic diamine is selected from one or more of 1,4-butylenediamine, 1,5-pentanediamine, 2-methylpentamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-6-hexanediamine, 2,4,4-trimethyl-6-hexanediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine; the cycloaliphatic diamine is selected from one or more of cyclohexanediamine, 1,3-bis(amino-methyl)-cyclohexane, isophoronediamine, norbornane dimethylamine, 4,4-diaminodicyclohexylmethane, 2,2-(4,4-diaminodicyclohexyl)propane and 3,3-dimethyl-4,4-diaminodicyclohexylmethane; and the aromatic diamine is selected from m-xylylenediamine.

25. The semiaromatic copolyamide resin according to claim 13, wherein the diacid unit having 6-36 carbon atoms is selected from one or more of naphthalenedicarboxylic acid, isophthalic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecandioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, dimer acid, cis- and/or trans-cyclohexane-1,4-dicarboxylic acid and cis- and/or trans-cyclohexane-1,3-dicarboxylic acid.

26. The semiaromatic copolyamide resin according to claim 14, wherein the diacid unit having 6-36 carbon atoms is selected from one or more of naphthalenedicarboxylic acid, isophthalic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecandioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, dimer acid, cis- and/or trans-cyclohexane-1,4-dicarboxylic acid and cis- and/or trans-cyclohexane-1,3-dicarboxylic acid.

27. The semiaromatic copolyamide resin according to claim 15, wherein the diacid unit having 6-36 carbon atoms is selected from one or more of naphthalenedicarboxylic acid, isophthalic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecandioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, dimer acid, cis- and/or trans-cyclohexane-1,4-dicarboxylic acid and cis- and/or trans-cyclohexane-1,3-dicarboxylic acid.

28. A polyamide molding composition containing the semiaromatic copolyamide resin according to claim 13, comprising following components in parts by weight: the semiaromatic copolyamide resin 30-100 parts; a reinforcing filler 0-70 parts; and an additive 0-50 parts.

29. The polyamide molding composition according to claim 28, wherein the reinforcing filler has a shape of a fibrous shape, with an average length of 0.01 mm to 20 mm, preferably 0.1 mm to 6 mm; the reinforcing filler has a draw ratio of 5:1 to 2000:1, preferably 30:1 to 600:1; based on a total weight of the polyamide molding composition, an amount of the reinforcing filler is 10 to 50 parts, preferably 15 to 40 parts; the reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler, the inorganic reinforcing filler being selected from one or more of a glass fiber, a potassium titanate fiber, a metal-cladded glass fiber, a ceramic fiber, a wollastonite fiber, a metallic carbide fiber, a metal-solidified fiber, an asbestos fiber, an alumina fiber, a silicon carbide fiber, a gypsum fiber and a boron fiber, preferably the glass fiber; and the organic reinforcing filler is selected from an aromatic polyamide fiber and/or a carbon fiber.

30. The polyamide molding composition according to claim 28, wherein the reinforcing filler has a shape of a non-fibrous shape, with an average particle size of 0.001 m to 100 m, preferably 0.01 m to 50 m, and is selected from one or more of a potassium titanate whisker, a zinc oxide whisker, an aluminum borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophyllite, bentonite, montmorillonite, lithium montmorillonite, synthetic mica, asbestos, an aluminosilicate, aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, ferric oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide.

31. The polyamide molding composition according to claim 28, wherein the additive is selected from one or more of a flame retardant, an impact modifier, an additional polymer and a processing agent; the flame retardant is a halogen flame retardant or a halogen-free flame retardant, preferably the halogen-free flame retardant; and said additional polymer is selected from one or more of an aliphatic polyamide, a polyolefin homopolymer, an ethylene--olefin copolymer or an ethylene-acrylate copolymer.

32. The polyamide molding composition according to claim 28, wherein the polyamide molding composition has a water absorption equal to or less than 1.0%, and according to the national standard GB/T 1634.2-2004, a heat deflection temperature is tested as 280 C. to 320 C.; a b-value is equal to or less than 3.0; wherein a test method for the water absorption is as follows: injection molding a sample into a 20 mm20 mm2 mm part, with a weight recorded as a0, after placing the part into water at a temperature of 95 C. for 240 hours, weighing the part with a weight recorded as a1, and the water absorption=(a1a0)/a0*100%; and a test method for the b-value is as follows: obtaining a smooth panel after injection molding 3000 g of sample particles with a 50*30*2 mm panel mold, and placing the panel on a Color-Eye-7000A computer color photometer of Libero to obtain the b-value.

Description

DESCRIPTION OF THE EMBODIMENTS

[0121] The present invention will be further described by specific implementations below, and embodiments below are the preferred implementations of the present invention, but the implementations of the present invention are not limited by the following embodiments.

[0122] Raw materials used in the present invention are all commercially available.

Performance Test Methods:

[0123] A test method of melting point of the semiaromatic copolyamide resin: in accordance with ASTM D3418-2003; the specific test method is as follows: Perkin Elmer Dimond DSC Analyzer was used for testing the melting point of a sample; a nitrogen atmosphere with a flow rate of 40 mL/min; the sample was heated to 340 C. at a rate of 10 C./min, held at 340 C. for 2 minutes, then cooled to 50 C. at a rate of 10 C./min, and heated to 340 C. at a rate of 10 C./min again, and an endothermic peak temperature at this moment was set as the melting point T.sub.m.

[0124] A test method of intrinsic viscosity of the semiaromatic copolyamide resin: polyamide intrinsic viscosity test method in accordance with GB12006.1-89; the specific test method is as follows: the intrinsic viscosity of the polyamide was measured in 98% concentrated sulfuric acid at 25 C.0.01 C.

[0125] A test method of water absorption: injection molding a sample into a 20 mm20 mm2 mm part, with a weight recorded as a0; after placing the part into water at a temperature of 95 C. for 240 hours, weighing the part with a weight recorded as a1. And the water absorption=(a1a0)/a0*100%.

[0126] A test method of a product color (b-value) of the semiaromatic copolyamide resin (molding composition): obtaining a smooth panel after injection molding 3000 g of sample particles with a 50*30*2 mm panel mold, and placing the panel on the Color-Eye-7000A computer color photometer of Libero to obtain a b-value. The value reflects the color of the semiaromatic copolyamide resin (molding composition) product, and the higher the value, the worse the product color.

[0127] A test of a heat deflection temperature: testing according to the national standard GB/T 1634.2-2004.

Synthesis of Semiaromatic Copolyamide Resin A-J and A-F

[0128] Reaction raw materials were added into a pressure reactor equipped with a magnetic coupling stir, a condenser tube, a gas-phase mouth, a feeding mouth and a pressure anti-explosion mouth. Then benzoic acid, sodium hypophosphite and deionized water were added. The amount of benzoic acid accounted for 2.5% of a molar content of all monomers, the weight of sodium hypophosphite accounted for 0.1% of the weight of other materials except for deionized water, and the weight of the deionized water accounted for 30% of the weight of all materials. The pressure reactor was vacuumized and high purity nitrogen was charged as protection air, and a reaction mixture was heated to 220 C. within 2 hours under stirring and was stirred for another hour at 220 C., followed by being heated to 230 C. under stirring. The reaction was carried on for 2 hours at a constant temperature of 230 C. and under a constant pressure of 2.2 MPa, and the pressure was kept constant by removing water formed. Discharging was carried out after the reaction was finished, a prepolymer was vacuum dried for 24 hours at 80 C. to obtain a prepolymerized product. The prepolymerized product was solid-phase tackified in a condition of 30-60 C. below the melting point and 50 Pa vacuum, and the semiaromatic copolyamide resin was obtained. Property indices such as the intrinsic viscosity, melting point, water absorption and color of the obtained semiaromatic copolyamide resin are listed in Table 1.

TABLE-US-00002 TABLE 1 Resin Resin Resin Resin Resin Resin Resin Resin Resin Resin A B C D E F G H I J Para-amino benzoic 30 35 40 50 60 50 50 40 40 80 acid/mol 11-aminoundecanoic 70 65 60 40 40 40 20 40 4 acid/mol Undecanolactam/ 60 mol 1,6-hexanediamine/ 5 10 10 4 mol Adipic acid/mol 5 10 10 4 Caprolactam/mol 10 10 8 Melting point/ C. 271 290 301 315 328 311 320 325 303 343 Intrinsic viscosity/ 0.87 0.88 0.85 0.83 0.89 0.86 0.84 0.92 0.88 0.90 dl/g Water absorption/% 1.3 1.3 1.2 1.0 1.2 1.2 1.0 1.7 1.1 1.6 b 1.5 1.7 1.6 1.8 1.5 1.7 1.8 0.9 1.5 0.5 Resin Resin Resin Resin Resin Resin A B C D E F Para-amino benzoic 10 90 40 40 50 50 acid/mol 1,6-hexanediamine/ 30 mol Adipic acid/mol 30 Caprolactam/mol 60 11-aminoundecanoic 90 10 50 acid/mol Undecanolactam/mol 50 Melting point/ C. 210 The melting 322 318 307 308 Intrinsic viscosity/ 0.88 point was higher than 0.87 0.91 2.35 2.46 dl/g a decomposition Water absorption/% 1.4 temperature, and it 1.7 1.8 1.6 1.7 b 1.4 was difficult to 2.5 2.0 1.8 1.9 perform the experiment.

[0129] It can be seen from Table 1 that in the resins A-J, by replacing terephthalic acid with the para-amino benzoic acid monomer and controlling the molar contents of the para-amino benzoic acid unit and the 11-aminoundecanoic acid unit or the undecanolactam unit, the prepared semiaromatic copolyamide resin had advantages such as high heat resistance, improved color property, excellent flowability and low water absorption. In the resin A, the content of para-amino benzoic acid was too low that the melting point of the resin was relatively low and the heat resistance was very poor; in the resin B, the content of para-amino benzoic acid was too high that the melting point of the resin was higher than the decomposition temperature, leading to none application value; in the resins C and D, 11-aminoundecanoic acid was not used as a comonomer, resulting in poor color of the resin, while in the resins E and F, the contents of para-amino benzoic acid and 11-aminoundecanoic acid or undecanolactam were 50 mol % simultaneously, i.e. molar ratios of those two were the same, resulting in that a molecular weight of the resin was hard to control, with quite high intrinsic viscosity and poor flowability, which is bad for the injection molding in later stage.

EMBODIMENTS 1-8 AND COMPARATIVE EXAMPLES 1-6

Preparation of the Polyamide Molding Composition

[0130] The semiaromatic copolyamide resin, a reinforcing filler, a flame retardant and other aids were mixed uniformly in a high-speed mixer according to formulas in Table 2, followed by being added into a double-screw extruder through a main feed port, while the reinforcing filler was side-fed through a side-feed scales. After extruding, cooling by means of water, pelletizing and drying, the polyamide composition was obtained. Particularly, an extrusion temperature was set 20 C. above the melting point and results of each property are shown as Table 2.

TABLE-US-00003 TABLE 2 Components of the polyamide molding composition and test results of properties (parts by weight) Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 1 2 3 4 5 6 7 8 Type of the C C F F G H I J semiaromatic copolyamide resin Weight of the 30 60 30 60 50 30 75 50 semiaromatic copolyamide resin Glass fiber 60 20 60 20 30 60 15 30 OCV995 Phosphinate 10 10 10 10 OP 1230 Wollastonite 5 5 5 5 5 5 5 5 Polybutylene-1 5 5 5 5 5 5 5 5 Water 0.4 0.7 0.5 0.9 0.7 0.6 0.8 0.8 absorption/% Heat deflection 287 282 293 281 288 290 280 311 temperature (1.8 MPa)/ C. b 0.8 2.2 0.5 2.0 1.9 3.0 0.7 3.0 Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Type of the A C D E F semiaromatic copolyamide resin Weight of the 60 60 50 60 60 semiaromatic copolyamide resin Glass fiber 20 20 30 20 20 OCV995 Phosphinate 10 10 10 10 10 OP 1230 Wollastonite 5 5 5 5 5 Polybutylene-1 5 5 5 5 5 Water 1.1 1.1 1.2 1.2 1.1 absorption/% Heat deflection 177 278 275 271 273 temperature (1.8 MPa)/ C. b 3.4 6.7 6.5 5.8 6.2

[0131] It can be seen from Table 2 that in the same formula of the molding composition, the polyamide molding composition comprising the semiaromatic copolyamide resin of the present invention possessed obvious advantage in the properties, such as heat resistance, water absorption and color.