SEMIAROMATIC POLYAMIDE RESIN AND PREPARATION METHOD THEREOF AND POLYAMIDE MOLDING COMPOSITION CONSISTING OF THE SAME

Abstract

The present invention discloses a semiaromatic polyamide resin, a preparation method thereof, and a polyamide molding composition consisting of the same, which consists of following components: (A) 20 to 95 wt % of a PA10T homopolymer derived from 1,10-decanediamine and terephthalic acid; and (B) 5 to 80 wt % of a PA6T homopolymer derived from 1,6-hexanediamine and terephthalic acid.

Particularly, (A)+(B)=100 wt %.

In the present invention, by adding a certain amount of the PA10T homopolymer into the PA6T homopolymer, a melting point of the PA6T homopolymer can be significantly decreased to be below a decomposition temperature thereof, and thereby a processability of the PA6T homopolymer is improved. The prepared semiaromatic polyamide resin has a decreased melting point, and may be processed normally. The polyamide molding composition consisting of the semiaromatic polyamide resin has a good processability, and has excellent surface properties.

Claims

1-9. (canceled)

10. A semiaromatic polyamide resin consisting of following components in percentage by weight: (A) 20-95 wt % of a PA10T homopolymer derived from 1,10-decanediamine and terephthalic acid; and (B) 5-80 wt % of a PA6T homopolymer derived from 1,6-hexanediamine and terephthalic acid; wherein (A)+(B)=100 wt %.

11. The semiaromatic polyamide resin according to claim 10, wherein the semiaromatic polyamide resin consists of following components in percentage by weight: (A) 30-85 wt % of the PA10T homopolymer derived from 1,10-decanediamine and terephthalic acid; and (B) 15-70 wt % of the PA6T homopolymer derived from 1,6-hexanediamine and terephthalic acid; wherein (A)+(B)=100 wt %.

12. The semiaromatic polyamide resin according to claim 11, wherein the semiaromatic polyamide resin consists of following components in percentage by weight: (A) 40-70 wt % of the PA10T homopolymer derived from 1,10-decanediamine and terephthalic acid; and (B) 30-60 wt % of the PA6T homopolymer derived from 1,6-hexanediamine and terephthalic acid; wherein (A)+(B)=100 wt %.

13. The semiaromatic polyamide resin according to claim 10, wherein with reference to ASTM D3418-2003, a melting point of the semiaromatic polyamide resin is 280 C.-340 C., preferably 285 C.-320 C., more preferably 290 C.-310 C.

14. The semiaromatic polyamide resin according to claim 11, wherein with reference to ASTM D3418-2003, a melting point of the semiaromatic polyamide resin is 280 C.-340 C., preferably 285 C.-320 C., more preferably 290 C.-310 C.

15. The semiaromatic polyamide resin according to claim 12, wherein with reference to ASTM D3418-2003, a melting point of the semiaromatic polyamide resin is 280 C.-340 C., preferably 285 C.-320 C., more preferably 290 C.-310 C.

16. A preparation method of the semiaromatic polyamide resin according to claim 10, the preparation method comprising following steps: after uniformly mixing a PA6T homopolymer derived from 1,6-hexanediamine and terephthalic acid and a PA10T homopolymer derived from 1,10-decanediamine and terephthalic acid in a high-speed mixer in proportion, putting a mixture into a pulverizer to be pulverized into powders of 5-10 pm; adding the powders into a double-screw extruder through a main feed port, obtaining the semiaromatic polyamide resin after extruding, cooling by means of water, pelletizing and drying.

17. A polyamide molding composition containing the semiaromatic polyamide resin according to claim 10, the composition comprising following components in parts by weight: TABLE-US-00004 the semiaromatic polyamide resin 30-100 parts; a reinforcing filler 0-70 parts; and an additive 0-50 parts.

18. A polyamide molding composition containing the semiaromatic polyamide resin according to claim 11, the composition comprising following components in parts by weight: TABLE-US-00005 the semiaromatic polyamide resin 30-100 parts; a reinforcing filler 0-70 parts; and an additive 0-50 parts.

19. A polyamide molding composition containing the semiaromatic polyamide resin according to claim 12, the composition comprising following components in parts by weight: TABLE-US-00006 the semiaromatic polyamide resin 30-100 parts; a reinforcing filler 0-70 parts; and an additive 0-50 parts.

20. The polyamide molding composition according to claim 17, wherein the reinforcing filler has a shape of a fibrous shape, with an average length of 0.01-20 mm, preferably 0.1-6 mm; the reinforcing filler has an aspect 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 10-50 parts, preferably 15-40 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 or a boron fiber, preferably the glass fiber; and the organic reinforcing filler is selected from an aromatic polyamide fiber and/or a carbon fiber.

21. The polyamide molding composition according to claim 18, wherein the reinforcing filler has a shape of a fibrous shape, with an average length of 0.01-20 mm, preferably 0.1-6 mm; the reinforcing filler has an aspect 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 10-50 parts, preferably 15-40 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 or a boron fiber, preferably the glass fiber; and the organic reinforcing filler is selected from an aromatic polyamide fiber and/or a carbon fiber.

22. The polyamide molding composition according to claim 19, wherein the reinforcing filler has a shape of a fibrous shape, with an average length of 0.01-20 mm, preferably 0.1-6 mm; the reinforcing filler has an aspect 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 10-50 parts, preferably 15-40 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 or a boron fiber, preferably the glass fiber; and the organic reinforcing filler is selected from an aromatic polyamide fiber and/or a carbon fiber.

23. The polyamide molding composition according to claim 17, wherein the reinforcing filler has a shape of a non-fibrous shape, with an average particle size of 0.001-100 m, preferably 0.01-50 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.

24. The polyamide molding composition according to claim 18, wherein the reinforcing filler has a shape of a non-fibrous shape, with an average particle size of 0.001-100 m, preferably 0.01-50 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.

25. The polyamide molding composition according to claim 19, wherein the reinforcing filler has a shape of a non-fibrous shape, with an average particle size of 0.001-100 m, preferably 0.01-50 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.

26. The polyamide molding composition according to claim 17, 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 one or more of an aliphatic polyamide, a polyolefin homopolymer, an ethylene--olefin copolymer or an ethylene-acrylate copolymer.

27. The polyamide molding composition according to claim 18, 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 one or more of an aliphatic polyamide, a polyolefin homopolymer, an ethylene--olefin copolymer or an ethylene-acrylate copolymer.

28. The polyamide molding composition according to claim 19, 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 one or more of an aliphatic polyamide, a polyolefin homopolymer, an ethylene--olefin copolymer or an ethylene-acrylate copolymer.

Description

DESCRIPTION OF THE EMBODIMENTS

[0114] The present invention is further described below by specific implementations, 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.

Synthesis of a PA6T Homopolymer:

[0115] 400 g (3.44 mol) of hexanediamine, 548 g (3.30 mol) of terephthalic acid, 11.3 g (0.09 mol) of benzoic acid, 1.0 g of sodium hypophosphite and 410 g of water 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. The pressure reactor was vacuumized and filled with high purity nitrogen as protection gas, and was heated to 220 C. within 2 hours under stirring, the reaction mixture was stirred at 220 C. for 1 hour, and then the temperature of the reactants was heated to 250 C. under stirring. The reaction was carried on at a constant temperature of 250 C. and under a constant pressure of 3.6 MPa for 2 hours, and the pressure was kept constant by removing water formed. A discharging was carried out after the reaction was finished, and a prepolymer was vacuum dried at 80 C. for 24 hours to obtain a prepolymerized product. The prepolymerized product was solid-phase tackified under a vacuum condition of 290 C. and 50 Pa to obtain the PA6T homopolymer. The PA6T homopolymer has a melting point of 370 C., and a relative viscosity of 2.33.

Synthesis of a PA10T Homopolymer:

[0116] 400 g (2.32 mol) of decanediamine, 370.5 g (2.23 mol) of terephthalic acid, 10.3 g (0.08 mol) of benzoic acid, 1.0 g of sodium hypophosphite and 340 g of water were added into the pressure reactor equipped with the magnetic coupling stir, the condenser tube, the gas-phase mouth, the feeding mouth and the pressure anti-explosion mouth. The pressure reactor was vacuumized and filled with high purity nitrogen as the protection air, and was heated to 220 C. within 2 hours under stirring, a reaction mixture was stirred at 220 C. for 1 hour, and then a temperature of a reactant was heated to 240 C. under stirring. A reaction was carried on at a constant temperature of 240 C. and under a constant pressure of 3.0 MPa for 2 hours, and the pressure was kept constant by removing water formed. A discharging was carried out after the reaction was finished, and a prepolymer was vacuum dried at 80 C. for 24 hours to obtain a prepolymerized product. The prepolymerized product was solid-phase tackified under a vacuum condition of 250 C. and 50 Pa to obtain the PA10T homopolymer. The PA10T homopolymer has a melting point of 316 C., and a relative viscosity of 2.35.

[0117] Other raw materials used in the present invention are all commercially available.

Performance Test Methods:

[0118] A test method of a melting point of a semiaromatic polyamide 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 Tm.

[0119] Surface properties of polyamide molding composition moldings are characterized by a surface roughness Ra, a test of which was carried out in accordance with GB10610-89 Rules and Procedures for the Measurement of Surface Roughness Using Stylus Instrument of the State Standard of the People's Republic of China. Specific steps are as follows: injection molding a sample into a 100 mm100 mm2 mm part; measuring a surface roughness value Ra using a JB-6C stylus roughness meter manufactured by Guangzhou Guangzhuo Metering Instrument Co., Ltd. The bigger the Ra is, the rougher the surface is.

[0120] 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=(a1-a0)/a1*100%.

Preparation of Semiaromatic Polyamide Resins A-G and A

[0121] After the PA10T homopolymer and the PA6T homopolymer were uniformly mixed in proportion of Table 1 in a high-speed mixer, a mixture was put into an AB10 type airflow pulverizer manufactured by Weifang Jinghua Powder Engineering Equipment Co., Ltd to be pulverized into powders of 5-10 m; the powders were added into a double-screw extruder through a main feed port; after extruding, cooling by means of water, pelletizing and drying, the semiaromatic polyamide resin was obtained. Melting points of the obtained semiaromatic polyamide resins are listed in Table 1.

TABLE-US-00002 TABLE 1 Resin Resin Resin Resin Resin Resin Resin Resin A B C D E F G A PA6T 5 30 50 60 70 80 15 95 homo- polymer/wt % PA10T 95 70 50 40 30 20 85 5 homo- polymer/wt % melting 325 290 293 307 320 335 312 348 point/ C.

[0122] It can be seen from Table 1 that, in the resins A-G, by adding a certain amount of the PA10T homopolymer into the PA6T homopolymer, a melting point of the PA6T homopolymer can be significantly decreased to be below a decomposition temperature, and the prepared semiaromatic polyamide resin has a decreased melting point, and may be processed normally.

Embodiments 1-8 and Comparative Examples 1-2: Preparation of Polyamide Molding Composition

[0123] After a semiaromatic polyamide resin, a reinforcing filler, and additives were uniformly mixed according to formulas in Table 2 in a high-speed mixer, a mixture was added into a double-screw extruder through a main feed port, and 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. Respective performance results are shown as Table 2.

TABLE-US-00003 TABLE 2 Components and test results of performance of the polyamide molding compositions (parts by weight) Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- Comparative Comparative ment 1 ment 2 ment 3 ment 4 ment 5 ment 6 ment 7 ment 8 Example 1 Example 2 Type of the A B D E F G C E PA6T A semiaromatic polyamide resin parts by 50 50 50 50 75 30 60 60 50 50 weight of the semiaromatic polyamide resin glass fiber 30 30 30 30 15 60 40 40 30 30 OCV995 Phosphinate 15 15 15 15 15 15 OP 1230 wollastonite 3 3 3 3 5 5 3 3 poly- 2 2 2 2 5 5 2 2 butylene-1 water 1.0 1.2 1.3 1.4 2.3 0.7 1.3 1.5 The melting 1.6 absorp- point was too tion/% high, and it Ra/m 2.10 1.51 1.88 1.99 2.13 1.76 1.72 2.38 was unable to 4.76 be processed.

[0124] It can be seen from Table 2 that, in the same formula of the molding composition, the polyamide molding composition containing the semiaromatic polyamide resin of the present invention has a good processability, and has excellent surface properties. The melting point of the pure PA6T is higher than the decomposition temperature, and it is unable to be processed. The resin A, due to a too high amount of PA6T, is close to the decomposition temperature, and there is a large number of small molecules of gas escape when melting, resulting in very rough product surface, and poor surface properties.