Polyamide composition as well as preparation method and application thereof

Abstract

The invention discloses a polyamide composition which comprises the following components in parts by weight: 80 parts of polyamide resin; 10 to 35 parts of a polyether type antistatic agent; 0.05 to 1 part of perfluorobutyl sulfonate; and 0.05 to 1 part of nigrosine. On one hand, the technical defect that a polyether type antistatic agent loses efficacy under a high-temperature condition can be remarkably overcome by selecting and compounding perfluorobutyl sulfonate and aniline black; on the other hand, the perfluorobutyl sulfonate can obviously reduce the addition amount of the antistatic agent.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, in particular to a polyamide composition and a preparation method and application thereof. Background Art

[0002] Modified polyamide is widely used in internal load-bearing parts or shell parts of industries such as rail transportation, consumer electronics, power tools, and shared bicycles due to its excellent comprehensive properties such as good mechanical properties, chemical resistance, and heat resistance. In the fields of mechanical industry and power tools, dust accumulation and adhesion caused by static electricity accumulation often occur. In severe cases, discharge may cause explosions and fires, and breakdown of IC components. The better the insulation of a material, the easier it is to generate static electricity. Nylon has a very high insulation resistance, and its surface resistivity level is 1×10 13 ~1×10 15 Ω, in the environment where severe friction is likely to occur during use, it is very easy to cause the charge accumulated on the surface of nylon products to be unable to be discharged and generate static electricity, which also limits the application of polyamide materials in electronic appliances, chemical equipment, coal mines and other fields that require antistatic. In the above application fields, some products are used in high ambient temperatures for a long time. In addition to requiring them to have antistatic properties, they are also required to have good antistatic durability.

[0003] According to different adding methods, the use of antistatic agents for polymer materials can be divided into external coating type and internal addition type. External coating antistatic agents are applied to the surface of products by brushing, spraying or dipping, but they are easily lost due to friction and washing, and can only provide short-term antistatic effects; internal antistatic agents are directly added and evenly dispersed in the polymer, and they can migrate from the inside of the polymer material to the surface, forming a uniform antistatic layer on the surface layer. Due to its resistance to friction and washing and long-lasting effectiveness, it is a widely used antistatic type in polymer materials.

[0004] At present, polyether antistatic agents have good antistatic properties and are often used in polyamide antistatic materials. However, the durability of polyether antistatic agents under high temperature conditions is poor, which limits their application. Summary of the invention

[0005] The object of the present invention is to provide an antistatic polyamide composition with good durability.

[0006] The present invention is achieved through the following technical solutions: A polyamide composition, comprising the following components in parts by weight: 80 parts of polyamide resin; 10-35 parts of polyether antistatic agent; Perfluorobutyl sulfonate 0.05-2 parts; Aniline black 0.1-2 parts; The weight ratio of perfluorobutyl sulfonate:aniline black is in the range of (0.19-3):1; The terminal amino group content of the polyamide resin is in the range of 45-185 mmol / kg.

[0007] The technical solution of the present invention has no particular limitation on the relative viscosity of the polyamide resin, and the technical effect of the present invention can be achieved when the relative viscosity is within the range of 0.8-4. The relative viscosity test method refers to GB 12006.1-89, polyamide viscosity number determination method; the specific test method is: the relative viscosity of polyamide with a concentration of 0.01 g / L is measured in 96% concentrated sulfuric acid, using an NCY automatic viscometer.

[0008] Meanwhile, in the polyamide composition of the present invention, the content of the polyamide resin is not less than 60 wt %.

[0009] Preferably, the weight ratio of perfluorobutyl sulfonate to aniline black is in the range of (0.8-1.2):1.

[0010] Preferably, the terminal amino group content of the polyamide resin is in the range of 80-115 mmol / kg. The test method for the terminal amino group content of the polyamide resin is as follows: the polyamide resin is dissolved in a phenol-methanol mixed solution to hydrolyze the free amino groups at the ends of the polyamide molecular chains, and then the free amino groups are titrated with a hydrochloric acid-ethanol mixed solution. The amount of hydrochloric acid-ethanol solution consumed is equal to the amount of free amino groups, that is, the content of the terminal amino groups.

[0011] The polyether antistatic agent is selected from at least one of polyethylene oxide, polyether amide and methoxy polyethylene glycol acrylate.

[0012] Preferably, the polyether antistatic agent is selected from polyether amide. The perfluorobutyl sulfonate is selected from at least one of potassium perfluorobutyl sulfonate and lithium perfluorobutyl sulfonate.

[0013] The aniline black is selected from at least one of oil-soluble aniline black, alcohol-soluble aniline black and water-soluble aniline black; preferably, the oil-soluble aniline black.

[0014] The polyamide is selected from at least one of PA56, PA510, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA6, PA7, PA11, PA12, PA6T, PA10T, PA MXD6, and PA MXD10.

[0015] Whether to add a specific amount of carbon free radical scavenger, antioxidant, etc. can be selected according to actual needs.

[0016] A method for preparing a polyamide composition, comprising the following steps: mixing each component evenly according to the ratio, and extruding and granulating through a twin-screw extruder at a temperature range of 180-320 °C and a rotation speed range of 200-700 revolutions per minute to obtain the polyamide composition.

[0017] The application of the polyamide composition is used for preparing antistatic articles, such as electrical appliance housings and plastic parts in electrical appliances.

[0018] The polyamide composition that meets the aging resistance and antistatic properties of the present invention has a surface resistivity range of 10^ 6 ~10^ 10 Ω (represented as 10E+6~10E+10 in the tables of the examples of the present invention), and the resistance change rate after aging is ≤1000%.

[0019] The present invention has the following beneficial effects: By selecting a specific content of the compound of perfluorobutyl sulfonate / aniline black and controlling the end amino group content of the polyamide resin, the present invention can significantly improve the heat resistance stability of the polyether-type antistatic agent in the polyamide composition, thereby improving the antistatic persistence. Embodiment

[0020] The present invention will be described in detail below in conjunction with specific examples. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0021] The sources of the raw materials used in the present invention are as follows: The following end amino group contents of the polyamide resins are obtained through actual measurement.

[0022] PA66-A: The end amino group content is 47 mmol / kg, EP-158, Huafeng, Zhejiang; PA66-B: The end amino group content is 85 mmol / kg, EP158NH, Huafeng, Zhejiang; PA66-C: The end amino group content is 110 mmol / kg, EP126NH, Huafeng, Zhejiang; PA66-D: The end amino group content is 180 mmol / kg, Huafeng, Zhejiang; PA66-E: The end amino group content is 24 mmol / kg, EPR32, Shenma, Henan; PA6: The end amino group content is 83 mmol / kg, HYEP-2500, Haiyang Chemical Fiber; PA610: The end amino group content is 51 mmol / kg, PA610 F120, Guangyin, Shandong; Oil-soluble aniline black: NUBIAN® BLACK TN-870, Oriental Chemical Co., Ltd., Japan; Alcohol-soluble aniline black: Solvent Black 5, Hubei Jusheng Technology Co., Ltd.; Water-soluble aniline black: Acid Black 2, Hubei Jusheng Technology Co., Ltd.; Polyethylene oxide: average Mv200000, Aladdin; Polyetheramide: AS5502P, Xuyang Chemical; Methoxy polyethylene glycol acrylate: MW1000, Aladdin; Potassium perfluorobutanesulfonate: SC4, Shanghai Polyfluoro New Material Technology Co., Ltd.

[0023] Preparation method of the polyamide composition of the embodiment and comparative example: according to the ratio, the components are mixed uniformly, and extruded into granules by a twin-screw extruder at a temperature range of 180-320° C. and a rotation speed range of 350 rpm to obtain a polyamide composition.

[0024] Various test methods: (1) Antistatic property: The polyamide composition was baked in a forced air oven at 120°C for 4 h, and then injection molded into a 100 mm*100 mm*3 mm square plate. The surface resistivity of the material was tested using a surface resistivity meter. Five samples were tested for each group and the average value was taken. (2) Heat aging resistance: Test the surface resistivity aging retention rate of the material before aging and after aging at 140°C for 1000h; after aging a 100mm*100mm*3mm square plate at 140°C for 1000h, use a surface resistivity meter to test the surface resistivity. Test 5 samples in each group and take the average value to obtain the surface resistivity of the material after aging. Calculate the resistance change rate = (surface resistivity after aging - initial resistivity) / initial surface resistivity * 100% (take the absolute value of the calculated value).

[0025] Table 1: Weight parts of each component of polyamide composition of Examples 1-6 and test results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PA66-A 80 80 80 PA66-B 80 PA66-C 80 PA66-D 80 Polyetheramide 15 15 15 15 15 15 Potassium perfluorobutanesulfonate 1 1 1 1 1 1 Oil soluble aniline black 0.4 0.4 0.4 0.4 Alcohol soluble aniline black 0.4 Water soluble aniline black 0.4 Initial surface resistivity, Ω 6.5E+09 6.2E+09 4.5E+09 7.2E+09 5.9E+09 4.2E+09 Surface resistivity after aging, Ω 4.5E+10 3.2E+10 2.2E+10 3.9E+10 4.3E+10 4.1E+10 Resistance change rate, % 592% 416% 389% 442% 629% 876% It can be seen from Examples 1-4 that the preferred range of the terminal amino group content of the polyamide resin is 80-115 mmol / kg, and the resistance change rate after the aging test is relatively low.

[0026] It can be seen from Examples 1 / 5-6 that the oil-soluble aniline black preferably has a lower resistance change rate after aging test.

[0027] Table 2: Weight parts of each component of the polyamide composition of Examples 7-10 and test results Example 7 Example 8 Example 9 Example 10 PA66-A 80 80 80 80 Polyetheramide 10 35 Polyethylene oxide 15 Methoxypolyethylene glycol acrylate 15 Potassium perfluorobutanesulfonate 0.05 2 1 1 Oil soluble aniline black 0.25 2 0.4 0.4 Initial surface resistivity, Ω 1.2E+10 9.6E+07 4.2E+09 8.2E+09 Surface resistivity after aging, Ω 9.5E+10 7.3E+08 3.9E+10 6.7E+10 Resistance change rate, % 692% 660% 829% 717% It can be seen from Examples 1 / 9-10 that the polyether amide antistatic agent has better aging resistance under the formulation of the present invention.

[0028] Table 3: Weight parts of each component of the polyamide composition of Examples 11-16 and test results Embodiment 11 Example 12 Example 13 Embodiment 14 Embodiment 15 Example 16 PA66-A 80 80 80 80 PA6 80 PA610 80 Polyetheramide 15 15 15 15 15 15 Potassium perfluorobutanesulfonate 0.23 0.63 0.76 0.35 1 1 Oil soluble aniline black 1.17 0.77 0.64 1.05 0.4 0.4 Initial surface resistivity, Ω 8.7E+09 7.7E+09 7.6E+09 7.1E+09 3.6E+09 7.1E+09 Surface resistivity after aging, Ω 6.8E+10 4.1E+10 3.9E+10 4.6E+10 2.1E+10 4.8E+10 Resistance change rate, % 682% 432% 413% 548% 483% 576% It can be seen from Examples 1 / 11-14 that when the weight ratio of perfluorobutyl sulfonate to aniline black is preferably in the range of (0.8-1.2):1, the aging resistance is better.

[0029] Table 4: Weight parts of each component of the comparative polyamide composition and test results Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PA66-A 80 80 80 80 Polyetheramide 15 15 15 15 Potassium perfluorobutanesulfonate 0.13 1.12 1 Oil soluble aniline black 1.27 0.28 0.4 Initial surface resistivity, Ω 8.9E+09 5.3E+09 8.9E+09 5.8E+09 Surface resistivity after aging, Ω 9.9E+10 6.4E+10 1.6E+11 8.8E+10 Resistance change rate, % 1012% 1108% 1698% 1417% It can be seen from Comparative Examples 1-4 that the present invention requires that the potassium perfluorobutylsulfonate / aniline black be mixed in a limited range in order to significantly improve the antistatic and aging resistance.

Claims

1. A polyamide composition, It is characterized in that By weight, it includes the following components: 80 parts of polyamide resin; 10-35 parts of polyether antistatic agent; Perfluorobutyl sulfonate 0.05-2 parts; Aniline black 0.1-2 parts; The weight ratio of perfluorobutyl sulfonate:aniline black is in the range of (0.19-3):1; The terminal amino group content of the polyamide resin is in the range of 45-185 mmol / kg.

2. The polyamide composition according to claim 1, It is characterized in that The weight ratio of perfluorobutyl sulfonate:aniline black is in the range of (0.8-1.2):

1.

3. The polyamide composition according to claim 1, It is characterized in that The terminal amino group content of the polyamide resin is in the range of 80-115 mmol / kg.

4. The polyamide composition according to claim 1, It is characterized in that The polyether antistatic agent is selected from at least one of polyethylene oxide, polyether amide and methoxy polyethylene glycol acrylate.

5. The polyamide composition according to claim 4, It is characterized in that The polyether antistatic agent is selected from polyether amide.

6. The polyamide composition according to claim 1, It is characterized in that The perfluorobutyl sulfonate is at least one selected from potassium perfluorobutyl sulfonate and lithium perfluorobutyl sulfonate.

7. The polyamide composition according to claim 1, It is characterized in that The aniline black is selected from at least one of oil-soluble aniline black, alcohol-soluble aniline black and water-soluble aniline black; preferably, the oil-soluble aniline black.

8. The polyamide composition according to claim 1, It is characterized in that The polyamide is selected from at least one of PA56, PA510, PA66, PA610, PA612, PA1010, PA1012, PA1212, PA6, PA7, PA11, PA12, PA6T, PA10T, PA MXD6, and PA MXD10.

9. A method for preparing a polyamide composition according to any one of claims 1 to 8, It is characterized in that The method comprises the following steps: mixing the components uniformly according to the proportion, extruding and granulating through a twin-screw extruder at a temperature range of 180-320 DEG C and a rotation speed range of 200-700 rpm to obtain a polyamide composition.

10. Use of the polyamide composition according to any one of claims 1 to 8, It is characterized in that Used to prepare antistatic parts.