A polyamide composition, its preparation and use

Abstract

The application discloses a polyamide composition which comprises the following components in parts by weight: 80 parts of a polyamide resin, 10-35 parts of a polyether type antistatic agent, 0.05-1 part of a perfluorobutyl sulfonate and 0.05-1 part of aniline black. On the one hand, the application can significantly improve the technical defects of the polyether type antistatic agent under high temperature conditions by selecting the compound of the perfluorobutyl sulfonate and the 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 application relates to the technical field of high polymer materials, in particular to a polyamide composition and a preparation method and application thereof. BACKGROUND

[0002] Modified polyamides are widely used in internal force components or shell components of rail transportation, consumer appliances, power tools, shared bicycles and other industries due to their excellent comprehensive properties such as good mechanical properties, chemical resistance and heat resistance. In the field of machinery industry and power tools, dust accumulation and adhesion caused by static electricity accumulation often occur, and even explosion and fire caused by discharge and breakdown of IC components occur. The better the insulation of the material, the more likely it is to generate static electricity. Nylon has a very high insulation resistance, and its surface resistivity is 1x10 13 ~ 1x10 15 Ω. For the environment of severe friction during use, the accumulated charge on the surface of the nylon product cannot be discharged, which also limits the application of polyamide materials in the fields of electronics, chemical equipment, coal mines and other anti-static fields. In the above application fields, the environment temperature is high during long-term use, and in addition to the requirement of anti-static property, it also needs to have good anti-static durability.

[0003] According to different adding methods, the use of high polymer material antistatic agent can be divided into external coating type and internal adding type. The external coating type antistatic agent is coated on the surface of the product by brushing, spraying or dipping, but it is easy to be lost due to friction and washing, and can only provide short-term antistatic effect. The internal adding type antistatic agent is directly added and uniformly dispersed in the polymer, which can migrate from the inside of the high polymer material to the surface to form a uniform antistatic layer on the surface layer. Due to its resistance to friction and washing, the effect is durable, so it is the most widely used antistatic type in high polymer materials.

[0004] At present, polyether type antistatic agent is often used in polyamide antistatic materials due to its good antistatic property. However, the durability of polyether type antistatic agent is poor under high temperature working conditions, which limits its application. SUMMARY

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

[0006] The present application is realized by the following technical scheme:

[0007] A polyamide composition, by weight, comprises the following components:

[0008] Polyamide resin 80 parts;

[0009] Polyether type antistatic agent 10-35 parts;

[0010] Perfluorobutyl sulfonate 0.05-2 parts;

[0011] Aniline black 0.1-2 parts;

[0012] The weight ratio of perfluorobutyl sulfonate:aniline black ranges from (0.19-3):1.

[0013] The end amino group content of the polyamide resin ranges from 45-185 mmol / kg.

[0014] The polyamide composition of the present application has no particular limitation on the relative viscosity of the polyamide resin, and the technical effects of the present application can be achieved when the relative viscosity ranges from 0.8-4. The relative viscosity test method refers to GB 12006.1-89, polyamide viscosity determination method; the specific test method is as follows: the relative viscosity of the polyamide with a concentration of 0.01 g / L is measured in 96% concentrated sulfuric acid, and the NCY automatic viscometer is used for measurement.

[0015] Meanwhile, the content of the polyamide resin in the polyamide composition of the present application is not less than 60 wt%.

[0016] Preferably, the weight ratio of perfluorobutyl sulfonate:aniline black ranges from (0.8-1.2):1.

[0017] Preferably, the end amino group content of the polyamide resin ranges from 80-115 mmol / kg. The test method of the end amino group content of the polyamide resin is as follows: the polyamide resin is dissolved in a phenol-methanol mixed solution, so that the free amino groups at the end of the polyamide molecular chain are hydrolyzed out, and then a hydrochloric acid-ethanol mixed solution is used for titration of the free amino groups, and the amount of the hydrochloric acid-ethanol solution consumed is equivalent to the amount of the free amino groups, that is, the content of the end amino groups.

[0018] The polyether type antistatic agent is selected from at least one of polyethylene oxide, polyether amide, and methoxy polyethylene glycol acrylate.

[0019] Preferably, the polyether type antistatic agent is selected from polyether amide. The perfluorobutyl sulfonate is selected from at least one of potassium perfluorobutyl sulfonate and lithium perfluorobutyl sulfonate.

[0020] 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.

[0021] 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.

[0022] The carbon radical capturing agent, the antioxidant, etc. can be added or not according to the actual needs.

[0023] The polyamide composition is prepared by mixing the components according to the ratio, and then extruding and granulating through a double-screw extruder at a temperature of 180-320 DEG C and a rotating speed of 200-700 rpm.

[0024] The polyamide composition is applied to prepare an anti-static product, such as an electric appliance shell or a plastic part in an electric appliance.

[0025] The polyamide composition satisfying the present application has a surface resistivity of 10E+6-10E+10 before and after aging, and a resistance change rate of less than or equal to 1000% after aging. 6 ~10E+10 10 Ω (10E+6-10E+10 in the embodiment table of the present application), and a resistance change rate of less than or equal to 1000% after aging.

[0026] The present application has the following beneficial effects:

[0027] The present application can significantly improve the heat stability of the polyether type anti-static agent in the polyamide composition by selecting a specific content of perfluorobutyl sulfonate / aniline black compound and controlling the end amino group content of the polyamide resin, thereby improving the anti-static durability. Embodiment

[0028] The present application will be described in detail below in combination with specific embodiments. The following embodiments will help those skilled in the art to further understand the present application, but do not limit the present application in any form. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present application. These all belong to the protection scope of the present application.

[0029] The raw materials used in the present application are as follows:

[0030] The end amino group content of the following polyamide resin is obtained by actual measurement.

[0031] PA66-A: end amino group content 47 mmol / kg, EP-158, Zhejiang Huafeng;

[0032] PA66-B: end amino group content 85 mmol / kg, EP158NH, Zhejiang Huafeng;

[0033] PA66-C: end amino group content 110 mmol / kg, EP126NH, Zhejiang Huafeng;

[0034] PA66-D: end amino group content 180 mmol / kg, Zhejiang Huafeng;

[0035] PA66-E: end amino group content 24 mmol / kg, EPR32, Henan Shenma;

[0036] PA6: end amino group content 83 mmol / kg, HYEP-2500, Haiyang Chemical Fiber;

[0037] PA610: end amino group content 51 mmol / kg, PA610 F120, Shandong Guangyin;

[0038] Oil-soluble aniline black: NUBIAN® BLACK TN-870, Japan Oriental Chemical;

[0039] Alcohol-soluble aniline black: Solvent black 5, Hubei Jusheng Technology Co., Ltd.;

[0040] Water-soluble aniline black: Acid black 2, Hubei Jusheng Technology Co., Ltd.;

[0041] Polyethylene oxide: average Mv 200000, Aldrich;

[0042] Polyether amide: AS5502P, Xuyang Chemical Industry;

[0043] Methoxypolyethylene glycol acrylate: M.W. 1000, Aldrich;

[0044] Potassium perfluorobutylsulfonate: SC4, Shanghai Dofu New Material Technology Co., Ltd.

[0045] Preparation method of polyamide composition of examples and comparative examples: according to the ratio, mix each component uniformly, and extrude and granulate through a double-screw extruder, with a temperature range of 180-320°C and a rotation speed range of 350 revolutions / minute, to obtain a polyamide composition.

[0046] Test methods:

[0047] (1) Antistatic property: after baking the polyamide composition at 120°C in a blast oven for 4 h, injection-molded into a 100mm*100mm*3mm square plate, the surface resistivity of the material was tested using a surface resistivity meter, 5 pieces of each sample were tested and the average value was taken;

[0048] (2) Heat aging resistance: the surface resistivity aging retention rate of the material before and after aging at 140°C for 1000h was tested; after aging at 140°C for 1000h, the surface resistivity of the 100mm*100mm*3mm square plate was tested using a surface resistivity meter, 5 pieces of each sample were tested and the average value was taken to obtain the surface resistivity of the material after aging. The resistance change rate=(surface resistivity after aging-initial resistivity) / initial surface resistivity*100% (taking the absolute value of the calculated value).

[0049] Table 1: Weight parts of components and test results of polyamide compositions of Examples 1-6

[0050] 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 Polyether amide 15 15 15 15 15 15 Potassium perfluorobutylsulfonate 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%

[0051] From Examples 1 / 5-6, it is preferred that the oil-soluble nigrosine has a lower change in resistance after the aging test.

[0052] From Examples 1 / 5-6, it is preferred that the oil-soluble nigrosine has a lower change in resistance after the aging test.

[0053] Table 2: Weight parts of components and test results of polyamide compositions of Examples 7-10

[0054] Example 7 Example 8 Example 9 Example 10 PA66-A 80 80 80 80 Polyether amide 10 35 Polyethylene oxide 15 Methoxypolyethylene glycol acrylate 15 Potassium perfluorobutylsulfonate 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%

[0055] From Examples 1 / 9-10, it is preferred that the polyetheramide antistatic agent has better aging resistance in the formulation of the present application.

[0056] Table 3: Weight parts of components and test results of polyamide compositions of Examples 11-16

[0057] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 PA66-A 80 80 80 80 PA6 80 PA610 80 Polyether amide 15 15 15 15 15 15 Potassium perfluorobutylsulfonate 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%

[0058] From Examples 1 / 11-14, it is preferred that the weight ratio of perfluorobutyl sulfonate: nigrosine is in the range of (0.8-1.2): 1, which has better aging resistance.

[0059] Table 4: Weight parts of components and test results of polyamide compositions of Comparative Examples 1-4

[0060] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PA66-A 80 80 80 80 Polyether amide 15 15 15 15 Potassium perfluorobutylsulfonate 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%

[0061] From Comparative Examples 1-4, it is known that the aging resistance of antistatic property can be significantly improved only when the weight ratio of potassium perfluorobutyl sulfonate / nigrosine is in the limited range.

Claims

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

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

1.

3. The polyamide composition according to claim 1, characterized in that, The terminal amino content of polyamide resins ranges from 80 to 115 mmol / kg.

4. The polyamide composition according to claim 1, characterized in that, The polyether-type 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, characterized in that, The polyether-type antistatic agent is selected from polyether amide.

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

7. The polyamide composition according to claim 1, 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.

8. The polyamide composition according to claim 7, characterized in that, The aniline black mentioned is selected from oil-soluble aniline black.

9. The polyamide composition according to claim 1, 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.

10. A method for preparing the polyamide composition according to any one of claims 1-9, characterized in that, The process includes the following steps: mixing the components evenly according to the formula, granulating the mixture by extrusion through a twin-screw extruder at a temperature range of 180-320℃ and a rotation speed range of 200-700 rpm to obtain a polyamide composition.

11. The use of the polyamide composition according to any one of claims 1-9, characterized in that, Used to manufacture antistatic parts.