Polyamide composite material as well as preparation method and application thereof

Abstract

The invention discloses a polyamide composite material as well as a preparation method and application thereof, and relates to the technical field of engineering plastics. The invention provides a polyamide composite material. The polyamide composite material is prepared from the following components in parts by weight: 20 to 80 parts of polyamide resin, 5 to 60 parts of syndiotactic polystyrene, 0.1 to 3 parts of stannous mono-sulphate, 0 to 35 parts of reinforcing filler and 0.05 to 6 parts of compatilizer. According to the polyamide composite material provided by the invention, the syndiotactic polystyrene and the stannous mono-sulphate are cooperated, so that the mechanical property and the heat-resistant stability of the polyamide composite material are further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and in particular to a polyamide composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Nylon materials, also known as polyamides, are commonly used in many industries such as textiles, automobiles, household appliances, tools, etc. The processing methods include injection molding, extrusion, die casting, rotational molding, etc. Among them, extrusion has long been one of the most widely used scenarios for nylon materials. However, in a high-temperature environment, polyamide materials face a series of challenges, such as decreased thermal stability, reduced strength, color change, poor dimensional stability, etc., which seriously affect the service life and reliability of products. In a high-temperature environment, the main challenges are as follows: ① Decreased thermal stability: High temperature causes polyamide materials to be prone to thermal decomposition, and the performance decreases significantly. ② Color change: In a high-temperature environment, polyamide materials may undergo oxidation reactions, resulting in color changes.

[0003] Therefore, a polyamide composite material with a high mechanical property retention rate and good heat resistance stability has broad application prospects. Summary of the Invention

[0004] Based on this, the purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a polyamide composite material with a high mechanical property retention rate and good heat resistance stability, a preparation method thereof, and an application thereof.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is: A polyamide composite material, comprising the following components in parts by weight: 20 - 80 parts of polyamide resin, 5 - 60 parts of syndiotactic polystyrene, 0.1 - 3 parts of stannous sulfate, 0 - 35 parts of reinforcing filler, and 0.05 - 6 parts of compatibilizer.

[0006] The present invention provides a polyamide composite material, wherein stannous sulfate can play a better role in the syndiotactic polystyrene system, and syndiotactic polystyrene and stannous sulfate cooperate to further improve the mechanical properties and heat resistance stability of the polyamide composite material.

[0007] Preferably, the weight percentage of the polyamide resin in the polyamide composite material is not less than 20%.

[0008] More preferably, the weight percentage of the polyamide resin in the polyamide composite material is not less than 35%.

[0009] Preferably, it comprises the following components in parts by weight: 40 - 60 parts of polyamide resin, 20 - 30 parts of syndiotactic polystyrene, and 0.4 - 1.5 parts of stannous sulfate.

[0010] During the actual experiment, the inventor found that when the parts by weight are within the above range, the mechanical properties and heat resistance stability of the prepared polyamide composite material are better.

[0011] Optionally, the parts by weight of the polyamide resin are one of 20 parts, 30 parts, 40 parts, 45 parts, 50 parts, 55 parts, 58 parts, 60 parts, 61 parts, 63 parts, 65 parts, 70 parts, 80 parts or the range value of any two of them; the syndiotactic polystyrene is one of 5 parts, 10 parts, 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, 40 parts, 45 parts, 50 parts, 55 parts, 58 parts, 60 parts or the range value of any two of them; the stannous sulfate is one of 0.1 part, 0.2 part, 0.5 part, 0.7 part, 0.9 part, 1.0 part, 1.2 part, 1.5 part, 2.0 part, 2.5 part, 3.0 part or the range value of any two of them; the reinforcing filler is one of 0 part, 1 part, 5 parts, 8 parts, 10 parts, 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts, 28 parts, 30 parts, 35 parts or the range value of any two of them; the compatibilizer is one of 0.05 part, 0.1 part, 0.2 part, 0.5 part, 0.7 part, 0.9 part, 1.0 part, 1.2 part, 1.5 part, 2.0 part, 2.2 parts, 2.5 part, 3.0 part, 3.2 parts, 3.5 part, 4.0 part, 4.5 parts, 5 parts, 5.5 parts, 6 parts or the range value of any two of them.

[0012] Preferably, the melt flow rate of the syndiotactic polystyrene at 300 °C / 1.2 kg according to ISO 1133-1:2011 is 8-30 g / 10 min. Further preferably, the melt flow rate of the syndiotactic polystyrene at 300 °C / 1.2 kg according to ISO 1133-1:2011 is 10-15 g / 10 min.

[0013] Preferably, the viscosity of the polyamide resin is 120-180 mL / g.

[0014] The viscosity of the above polyamide resin can be obtained by testing according to the ISO 307-2019 standard. The solvent is H2SO4 with a mass fraction of 96%. The flow times of the solvent and the flow times of the polyamide solution in the solvent with a concentration of 0.005 g / mL are measured at 25 °C using the same viscometer, and the viscosity value of the polyamide resin is calculated based on these measured values and the known solution concentration.

[0015] Optionally, the syndiotactic polystyrene has a melt flow rate of 8 g / 10 min, 9 g / 10 min, 12 g / 10 min, 15 g / 10 min, 18 g / 10 min, 20 g / 10 min, 25 g / 10 min, 28 g / 10 min, 30 g / 10 min, or a range value of any two of them according to ISO 1133-1:2011 at 300 °C / 1.2 kg.

[0016] Optionally, the viscosity of the polyamide resin is a range value of 120 mL / g, 130 mL / g, 135 mL / g, 140 mL / g, 145 mL / g, 150 mL / g, 155 mL / g, 160 mL / g, 165 mL / g, 170 mL / g, 180 mL / g, or any two of them.

[0017] Preferably, the polyamide resin is at least one of aliphatic polyamide, aliphatic-aromatic polyamide, and aromatic polyamide; More preferably, the aliphatic polyamide is at least one of PA6, PA7, PA11, PA12, PA66, PA46, PA56, PA510, PA610, PA612, PA1010, PA1012; and / or, the aliphatic-aromatic polyamide is at least one of PA4T, PA5T, PA6T, PA9T, PA10T, MXD6; and / or, the aromatic polyamide is at least one of poly(p-phenyleneterephthalamide) and poly(m-phenylenediamine isophthalamide).

[0018] The inventors found in actual experiments that when the melt flow rate of syndiotactic polystyrene is 8-30 g / 10 min, and / or the viscosity of the polyamide resin is 120-180 mL / g, the two-phase distribution in the alloy system is reasonable, and the mechanical properties and heat resistance stability of the prepared polyamide composite material are better.

[0019] Preferably, the reinforcing material is inorganic fiber or organic fiber, wherein the inorganic fiber is one of carbon fiber, metal carbide fiber, glass fiber, ceramic fiber, metal solidified fiber, asbestos fiber, and boron fiber, and the organic fiber is aramid fiber.

[0020] Preferably, the compatibilizer is at least one of maleic anhydride graft copolymer and fumarated 2,6-dimethylphenol homopolymer; wherein, the maleic anhydride graft copolymer is one of maleic anhydride grafted PP, maleic anhydride grafted PE, and maleic anhydride grafted POE.

[0021] More preferably, the compatibilizer is fumarated 2,6-dimethylphenol homopolymer.

[0022] Preferably, the polyamide composite further comprises 0.1-5 parts of processing aids, and the aids are at least one of antioxidants and lubricants. For example, 0.2-2 parts of antioxidants and 0.3-3 parts of lubricants.

[0023] Preferably, the antioxidant is at least one of hindered phenol antioxidants, hindered amine antioxidants, and phosphite antioxidants. Specifically, the antioxidant includes but is not limited to N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (Antioxidant 1098), tris[2,4-di-tert-butylphenyl] phosphite (Antioxidant 168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Antioxidant 1010), and at least one of phosphite antioxidants;

[0024] Preferably, the lubricant is at least one of stearic acid, metal stearates, modified ethylene bis-fatty acid amides, hyperbranched polyesters, aliphatic fatty acid esters, and ethylene-acrylic acid copolymers.

[0025] In addition, the present invention provides a method for preparing the polyamide composite, comprising the following steps:

[0026] (1) Weigh each component by weight parts;

[0027] (2) After mixing the above components, add them to an extruder for melt dispersion, and extrude and pelletize to obtain the polyamide composite.

[0028] Preferably, the conditions for melt extrusion by the extruder are: extrusion temperature 190-300 °C, screw length-diameter ratio (32-48):1, and screw rotation speed 250-500 rpm.

[0029] Furthermore, the present invention provides the application of the polyamide composite in the field of electronic and electrical engineering. The present invention provides the application of the polyamide composite in the modules related to heat storage and heat release in electronic and electrical engineering.

[0030] Compared with the prior art, the beneficial effects of the present invention are: The present invention provides a polyamide composite, which further improves the mechanical properties and heat resistance stability of the polyamide composite through the synergy of syndiotactic polystyrene and stannous sulfate. Specific embodiments

[0031] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. The purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. The experimental reagents and instruments designed in the embodiments and comparative examples of the present invention are all common ordinary reagents and instruments unless otherwise specified, and can be obtained from commercial channels. In the embodiments and comparative examples, the experimental methods used are all conventional methods unless otherwise specified; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch of raw materials.

[0032] The raw materials used in the examples and comparative examples are described as follows, but are not limited to these materials:

[0033] Polyamide resin - 1: M2400, viscosity 130 mL / g, XinHui Meida;

[0034] Polyamide resin - 2: 6T - 120, viscosity 145 mL / g, Shanghai YingGu Gu;

[0035] Polyamide resin - 3: M2800, viscosity 170 mL / g, XinHui Meida;

[0036] Syndiotactic polystyrene - 1: XAREC TM 90ZC, Idemitsu, melt flow rate 9 g / 10 min (300 °C / 1.2 kg);

[0037] Syndiotactic polystyrene - 2: 130ZC, Idemitsu, melt flow rate 13.0 g / 10 min (300 °C / 1.2 kg);

[0038] Syndiotactic polystyrene - 3: 142ZC, Idemitsu, melt flow rate 14.2 g / 10 min (300 °C / 1.2 kg);

[0039] Syndiotactic polystyrene - 4: XAREC TM 300ZC, Idemitsu, melt flow rate 30 g / 10 min (300 °C / 1.2 kg);

[0040] Atactic polystyrene - 5: GPPS123P, Shanghai Secco, melt flow rate 8 g / 10 min (200 °C / 5 kg);

[0041] Compatibilizer - 1: CAS No.: 171885 - 12 - 4, CX - 1, fumarated 2,6 - dimethylphenol homopolymer, Idemitsu;

[0042] Compatibilizer - 2: PC - 1, maleic anhydride grafted PP, Nanhai Baichen;

[0043] Compatibilizer - 3: N493, maleic anhydride grafted POE, DuPont;

[0044] Tin(II) sulfate, Shanghai Aladdin Biochemical Technology Co., Ltd;

[0045] Tin(IV) hydroxide, Shanghai Aladdin Biochemical Technology Co., Ltd;

[0046] Glass fiber: ECS10 - 03 - 568H, Jushi Group;

[0047] Antioxidant: IRGANOX 1098, BASF;

[0048] Lubricant: A - C540A, Honeywell.

[0049] Examples and Comparative Examples

[0050] The present invention provides a polyamide composite material. The components and their weight parts of the polyamide composite material are selected as shown in Table 1 - 2. The preparation method of the polyamide composite material includes the following steps: (1) Weigh each component according to the weight parts; (2) After mixing the above components, add them to an extruder for melting and dispersion, and then extrude and pelletize to obtain the polyamide composite material. The conditions for melt extrusion of the extruder are: extrusion temperature 190 - 230 - 230 - 230 - 240 - 240 - 240 - 240 - 240 - 220 °C, the screw length - diameter ratio is 40:1, and the screw speed is 300 rpm.

[0051] Performance Testing

[0052] Injection molding stability test: Place the sample material in a dehumidifying dryer and dry it at 110 °C for more than 4 h. Inject tensile specimens and color plates respectively under the following conditions: ① 270 °C, injection molding cycle 30 s; ② 290 °C, injection molding cycle 5 min.

[0053] (1) Tensile strength retention rate

[0054] Test the tensile strength according to ISO 527 - 2 - 2012, with a tensile speed of 10 mm / min. Test the tensile strength of the specimens obtained under condition ① and condition ② respectively, and calculate according to the following formula: Tensile strength retention rate = tensile strength under condition ② ÷ tensile strength under condition ① × 100%.

[0055] (2) Color change amplitude (△E)

[0056] Use an X - rite Color Eye 7000A colorimeter. According to the GB / T 7921 - 2008 standard, continuously measure the color plate 3 times under a D65 - 10° light source, and take the average value as the L, a, b value results under the corresponding conditions. Calculate the color change amplitude between condition ① and condition ②. The calculation formula is as follows:

[0057] ΔE = [(ΔL) 2 +(Δa) 2 +(Δb) 2 1 / 2 。

[0058] The test results are shown in Table 1-2.

[0059] Table 1

[0060]

[0061]

[0062]

[0063] Table 2

[0064]

[0065] As can be seen from the above table, for the polyamide composite material prepared in the embodiment of the present invention, the tensile strength retention rate is above 80%, the color change range ΔE < 7.5, and it has good mechanical property retention rate and heat resistance stability in a high-temperature environment.

[0066] By comparing Examples 1-3, it can be known that when the viscosity of the polyamide resin is 120-180 mL / g, the prepared polyamide composite material has good mechanical property retention rate and heat resistance stability in a high-temperature environment.

[0067] By comparing Example 1 with Examples 4-6, it can be known that when the melt flow rate of syndiotactic polystyrene is 10-15 g / 10 min at 300 °C / 1.2 kg according to ISO 1133-1:2011, the prepared polyamide composite material has better mechanical property retention rate and heat resistance stability in a high-temperature environment.

[0068] By comparing Example 1 with Examples 7-9, it can be known that when there are 40-60 parts of polyamide resin, 20-30 parts of syndiotactic polystyrene, and 0.4-1.5 parts of stannous sulfate, the prepared polyamide composite material has better mechanical property retention rate and heat resistance stability in a high-temperature environment.

[0069] By comparing Example 1 with Examples 10-11, it can be known that when the compatibilizer is a homopolymer of fumaric acid-modified 2,6-dimethylphenol, the mechanical properties and heat resistance stability of the polyamide composite material are better improved, and the effect is better.

[0070] ​It can be seen from the comparison between Example 1 and Comparative Examples 1-5 that syndiotactic polystyrene and stannous sulfate cooperate to further improve the mechanical properties and heat resistance stability of the polyamide composite material. When the addition amount of stannous sulfate is too high, it has a negative effect on the retention rate of mechanical properties. When the addition amount of stannous sulfate is too low, the improvement of the properties of the prepared polyamide composite material is not obvious. It can be seen from the comparison between Example 1 and Comparative Example 6 that stannous sulfate can play a better role in the syndiotactic polystyrene system. Syndiotactic polystyrene and stannous sulfate cooperate to further improve the mechanical properties and heat resistance stability of the polyamide composite material.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polyamide composite material, characterized in that, It comprises the following components in parts by weight: 20 - 80 parts of polyamide resin, 5 - 60 parts of syndiotactic polystyrene, 0.1 - 3 parts of stannous sulfate, 0 - 35 parts of reinforcing filler, and 0.05 - 6 parts of compatibilizer.

2. The polyamide composite material according to claim 1, characterized in that, It comprises the following components in parts by weight: 40 - 60 parts of polyamide resin, 20 - 30 parts of syndiotactic polystyrene, and 0.4 - 1.5 parts of stannous sulfate.

3. The polyamide composite material according to claim 1, wherein The melt flow rate of the syndiotactic polystyrene is 8 - 30 g / 10 min at 300 °C / 1.2 kg according to ISO1133 - 1:2011.

4. The polyamide composite material according to claim 1, wherein The viscosity of the polyamide resin is 120 - 180 mL / g.

5. The polyamide composite material according to claim 1, characterized in that, The polyamide resin is at least one of aliphatic polyamide, aliphatic - aromatic polyamide, and aromatic polyamide; preferably, The aliphatic polyamide is at least one of PA6, PA7, PA11, PA12, PA66, PA46, PA56, PA510, PA610, PA612, PA1010, PA1012; and / or, the aliphatic - aromatic polyamide is at least one of PA4T, PA5T, PA6T, PA9T, PA10T, MXD6; and / or, the aromatic polyamide is at least one of poly(p - phenylene terephthalamide) and poly(m - phenylene isophthalamide).

6. The polyamide composite material according to claim 1, characterized in that, The reinforcing material is inorganic fiber or organic fiber.

7. The polyamide composite material according to claim 1, characterized in that, The compatibilizer is at least one of maleic anhydride graft copolymer and fumarated 2,6 - dimethylphenol homopolymer; preferably, the compatibilizer is fumarated 2,6 - dimethylphenol homopolymer.

8. The polyamide composite material according to claim 1, wherein It further comprises 0.1 - 5 parts of processing aids, and the aids are at least one of antioxidant and lubricant.

9. A method for preparing a polyamide composite material according to any one of claims 1-8, characterized in that, It comprises the following steps: (1) Weigh each component according to parts by weight; (2) After mixing the above components, add them into an extruder for melting and dispersion, and then extrude and pelletize to obtain the polyamide composite material.

10. Use of a polyamide composite material as described in any one of claims 1 - 8 in the field of electronic and electrical engineering.

Images