A conductive and friction-resistant bio-based PA46 composite material and a preparation method thereof

Abstract

The invention discloses a conductive and friction-resistant bio-based PA46 composite material and a preparation method thereof. The composite material is prepared from the following components by weight: 80 to 100 parts of PA46, 10 to 16 parts of modified fullerene, and 0.1 to 0.5 parts of antioxidant; wherein the synthesis mechanism of the modified fullerene is as follows: firstly, hydroxylated fullerene is synthesized, and then the hydroxyl group of the hydroxylated fullerene can react with the amino group on dopamine to generate dopamine functionalized fullerene. The catechol group on the dopamine functionalized fullerene can react with the epoxy group of the epoxy resin and the amino group in the amine curing agent trishydroxymethylaminomethane to generate modified fullerene grafted with dopamine and epoxy resin. The present invention prepares a composite material with excellent conductive performance and good friction resistance by applying the modified fullerene to the PA46 material.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to a conductive and friction-resistant bio-based PA46 composite material and a preparation method thereof. Background Art

[0002] Polybutylene adipamide (PA46) is a common bio-based polyamide resin with a wide range of applications. PA46 has the characteristics of high strength, high chemical stability and easy processing and molding. In order to improve the safety and reliability of equipment such as oil and gas exploration and mining and avoid the accumulation of friction static electricity, in addition to requiring the material to have a low friction coefficient, it is often also required that the material has good electrical conductivity, which limits the application of PA46 composite materials in these specific fields. At present, there is no public report on conductive and friction-resistant bio-based PA46 composite materials. Summary of the invention

[0003] In view of the deficiencies in the prior art, the present invention innovatively synthesizes a conductive and friction-resistant bio-based PA46 composite material, which greatly expands the application scope of the PA46 composite material and has very practical significance.

[0004] The objective of the present invention is achieved through the following technical solutions:

[0005] A conductive and friction-resistant bio-based PA46 composite material is prepared from the following components in parts by weight:

[0006] PA46 80-100 parts,

[0007] 10-16 parts of modified fullerene,

[0008] Antioxidant 0.1-0.5 parts;

[0009] The preparation method of the modified fullerene is as follows:

[0010] (1) placing fullerene, hydrogen peroxide, deionized water and Fenton's catalyst in a reaction vessel, reacting at 50-60° C. for 6-8 hours to obtain a mixture; filtering the mixture to separate solid matter therein, filtering, washing and drying the solid matter in sequence to obtain hydroxylated fullerene; preferably, the mass ratio of fullerene, hydrogen peroxide, deionized water and Fenton's catalyst is (30-40): (20-40): (100-120): (1-3).

[0011] (2) placing hydroxylated fullerene, dopamine powder and deionized water in a reaction vessel, reacting at 30-40° C. for 8-10 hours to obtain a mixture; filtering the mixture to separate the solid matter therein, filtering, washing and drying the solid matter in sequence to obtain dopamine functionalized fullerene; preferably, the mass ratio of hydroxylated fullerene, dopamine powder and deionized water is (30-40): (16-18): (120-160).

[0012] (3) Place dopamine functionalized fullerene, amine curing agent, epoxy resin, and deionized water in a reaction vessel, stir and react at 50-70°C for 10-12 hours to obtain a mixture; filter the mixture to separate the solid matter therein, filter, wash, and dry the solid matter in sequence to obtain the modified fullerene. Preferably, the amine curing agent is trishydroxymethylaminomethane; the mass ratio of dopamine functionalized fullerene, amine curing agent, epoxy resin, and deionized water is (30-40): (8-12): (12-16): (80-100).

[0013] In a further embodiment, the antioxidant is at least one of tris(2,4-di-tert-butyl)phenyl phosphite (referred to as Irganox 168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (referred to as Irganox 1010) and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (referred to as Irganox 1330).

[0014] The present invention also discloses a method for preparing the conductive and friction-resistant bio-based PA46 composite material, comprising the following steps:

[0015] (1) Weigh 80-100 parts of PA46, 10-16 parts of modified fullerene, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0016] (2) Extruding and granulating the mixed material obtained in step (1) from a twin-screw extruder to obtain a PA46 composite material. Preferably, the twin-screw extruder comprises six temperature zones arranged in sequence, and the temperatures of the zones are: zone 1 temperature 260-280°C, zone 2 temperature 280-300°C, zone 3 temperature 310-330°C, zone 4 temperature 310-330°C, zone 5 temperature 310-330°C, zone 6 temperature 310-330°C; the head temperature of the twin-screw extruder is 310-330°C, and the screw speed is 200-280r / min.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] 1. The mechanism of synthesizing modified fullerene in this patent is as follows: first, hydroxylated fullerene is synthesized, and then the hydroxyl group of hydroxylated fullerene can react with the amino group on dopamine to generate dopamine functionalized fullerene. The catechol group on dopamine functionalized fullerene can react with the epoxy group of epoxy resin and the amino group in the amine curing agent trishydroxymethylaminomethane to generate modified fullerene grafted with dopamine and epoxy resin.

[0019] 2. The covalent bond of dopamine significantly enhances the interfacial effect between fullerene, epoxy resin and PA46 matrix, which not only limits the movement of the main molecular chain of PA46 matrix but also protects fullerene from falling off during friction, thus enhancing the interfacial effect. During the friction process, the fullerene-dopamine peeled off from the continuous network structure gradually forms a fullerene-dopamine film under the action of mechanical force. This film can not only play a lubricating role but also prevent further wear of the wear surface, which also improves the friction resistance of PA46 matrix. Fullerene itself has certain conductivity, and using it to modify PA46 also improves the conductivity of PA46 composite materials.

[0020] 3. Compared with general PA materials, the PA46 composite material synthesized by this patent has excellent conductivity and good friction resistance, and can be widely used in various conductive and friction-resistant material fields. DETAILED DESCRIPTION

[0021] The present invention is further described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] The raw materials used in the following examples and comparative examples are as follows:

[0023] PA46 (model D1306PBK), Nanjing Hongrui; fullerene, Puyang Yongxin Fullerene Technology Co., Ltd.; hydrogen peroxide, Jinan Kunfeng Chemical Co., Ltd.; deionized water, Shanghai Lianshi Chemical Reagent Co., Ltd.; Fenton catalyst, Jiangxi Huihua Technology Co., Ltd.; dopamine powder, Hubei Guangao Biotechnology Co., Ltd.; tris(hydroxymethylaminomethane), Shandong Polychemical Co., Ltd.; epoxy resin (model EP-12), Jinan Linhai Chemical Co., Ltd.; antioxidants (models Irganox168, Irganox1010, Irganox1330), BASF, Germany.

[0024] The models and suppliers of the above raw materials are only for illustrating the sources and components of the reagents used in the experiments of the present invention so as to fully disclose the information, and do not mean that the present invention cannot be realized by using other similar reagents or reagents provided by other suppliers.

[0025] Preparation Example 1

[0026] (1) 300 g of fullerene, 200 g of oxidant hydrogen peroxide, 1.0 kg of deionized water, and 10 g of Fenton's catalyst were weighed and placed in a reaction vessel, and reacted at 50° C. for 6 h to obtain a mixture; the mixture was filtered to separate the solid matter therein, and the solid matter was filtered, washed, and dried in sequence to obtain hydroxylated fullerene.

[0027] (2) Weigh 300 g of hydroxylated fullerene, 160 g of dopamine powder, and 1.2 kg of deionized water, place them in a reaction vessel, and react at 30° C. for 8 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain dopamine-functionalized fullerene.

[0028] (3) Weigh 300 g of dopamine-functionalized fullerene, 80 g of amine curing agent tris(hydroxymethyl)aminomethane), 120 g of epoxy resin, and 800 g of deionized water, put them into a reaction vessel, and react them at 50° C. with stirring for 10 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain modified fullerene M1.

[0029] Example 1

[0030] (1) Weigh 80 parts of PA46, 10 parts of modified fullerene M1, and 0.1 parts of Irganox 168, mix and stir evenly to obtain a mixture;

[0031] (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder to form pellets, thereby obtaining a PA46 composite material P1. The temperatures of the zones of the twin-screw extruder are: zone 1 temperature 260°C, zone 2 temperature 280°C, zone 3 temperature 310°C, zone 4 temperature 310°C, zone 5 temperature 310°C, zone 6 temperature 310°C; the head temperature of the twin-screw extruder is 310°C, and the screw speed is 200 r / min.

[0032] Preparation Example 2

[0033] (1) Weigh 400 g of fullerene, 400 g of oxidant hydrogen peroxide, 1.2 kg of deionized water, and 30 g of Fenton's catalyst, place them in a reaction vessel, and react them at 60° C. for 8 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in sequence to obtain hydroxylated fullerene.

[0034] (2) Weigh 400 g of hydroxylated fullerene, 180 g of dopamine powder, and 1.6 kg of deionized water, place them in a reaction vessel, and react them at 40° C. for 10 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain dopamine-functionalized fullerene.

[0035] (3) Weigh 400 g of dopamine-functionalized fullerene, 120 g of amine curing agent tris(hydroxymethyl)aminomethane), 160 g of epoxy resin, and 1.0 kg of deionized water, put them into a reaction vessel, and react them at 70° C. with stirring for 12 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain the modified fullerene M2.

[0036] Example 2

[0037] (1) Weigh 100 parts of PA46, 16 parts of modified fullerene M2, 0.1 parts of Irganox168, 0.2 parts of Irganox1330, and 0.2 parts of Irganox1010, mix and stir to obtain a mixture;

[0038] (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder to form pellets, thereby obtaining a PA46 composite material P2. The temperatures of the zones of the twin-screw extruder are: zone 1 temperature 280°C, zone 2 temperature 300°C, zone 3 temperature 330°C, zone 4 temperature 330°C, zone 5 temperature 330°C, zone 6 temperature 330°C; the head temperature of the twin-screw extruder is 330°C, and the screw speed is 280 r / min.

[0039] Preparation Example 3

[0040] (1) Weigh 350 g of fullerene, 300 g of oxidant hydrogen peroxide, 1.1 kg of deionized water, and 20 g of Fenton's catalyst, place them in a reaction vessel, and react at 55° C. for 7 h to obtain a mixture; filter the mixture to separate solid matter, and filter, wash, and dry the solid matter in turn to obtain hydroxylated fullerene.

[0041] (2) Weigh 350 g of hydroxylated fullerene, 170 g of dopamine powder, and 1.4 kg of deionized water, place them in a reaction vessel, and react at 35° C. for 9 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain dopamine-functionalized fullerene.

[0042] (3) Weigh 350 g of dopamine-functionalized fullerene, 100 g of amine curing agent tris(hydroxymethyl)aminomethane), 140 g of epoxy resin, and 900 g of deionized water, put them into a reaction vessel, and react them at 60° C. with stirring for 11 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain modified fullerene M3.

[0043] Example 3

[0044] (1) Weigh 90 parts of PA46, 13 parts of modified fullerene M3, 0.1 parts of Irganox168, and 0.2 parts of Irganox1010, mix and stir to obtain a mixture;

[0045] (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder to form pellets, thereby obtaining a PA46 composite material P3. The temperatures of the zones of the twin-screw extruder are: zone 1 temperature 270°C, zone 2 temperature 290°C, zone 3 temperature 320°C, zone 4 temperature 320°C, zone 5 temperature 320°C, zone 6 temperature 320°C; the head temperature of the twin-screw extruder is 320°C, and the screw speed is 240 r / min.

[0046] Preparation Example 4

[0047] (1) Weigh 320 g of fullerene, 325 g of oxidant hydrogen peroxide, 1.15 kg of deionized water, and 28 g of Fenton's catalyst, place them in a reaction vessel, and react at 56° C. for 6 h to obtain a mixture; filter the mixture to separate solid matter, and filter, wash, and dry the solid matter in turn to obtain hydroxylated fullerene.

[0048] (2) Weigh 335 g of hydroxylated fullerene, 175 g of dopamine powder, and 1.45 kg of deionized water, place them in a reaction vessel, and react at 38° C. for 9 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain dopamine-functionalized fullerene.

[0049] (3) Weigh 335 g of dopamine-functionalized fullerene, 115 g of amine curing agent tris(hydroxymethyl)aminomethane), 135 g of epoxy resin, and 835 g of deionized water, put them into a reaction vessel, and react them at 55° C. with stirring for 11 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain modified fullerene M4.

[0050] Example 4

[0051] (1) Weigh 95 parts of PA46, 15 parts of modified fullerene M4, 0.1 parts of Irganox1010, and 0.2 parts of Irganox1330, mix and stir to obtain a mixture;

[0052] (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder to form pellets, thus obtaining a PA46 composite material P4. The temperatures of the zones of the twin-screw extruder are: zone 1 temperature 265°C, zone 2 temperature 285°C, zone 3 temperature 315°C, zone 4 temperature 315°C, zone 5 temperature 315°C, zone 6 temperature 315°C; the head temperature of the twin-screw extruder is 315°C, and the screw speed is 250r / min.

[0053] Preparation Example 5

[0054] (1) Weigh 315 g of fullerene, 295 g of oxidant hydrogen peroxide, 1.05 kg of deionized water, and 29 g of Fenton's catalyst, place them in a reaction vessel, and react at 55° C. for 7 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain hydroxylated fullerene.

[0055] (2) Weigh 360 g of hydroxylated fullerene, 175 g of dopamine powder, and 1.45 kg of deionized water, place them in a reaction vessel, and react at 38° C. for 9 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain dopamine-functionalized fullerene.

[0056] (3) Weigh 345 g of dopamine-functionalized fullerene, 95 g of amine curing agent tris(hydroxymethyl)aminomethane), 145 g of epoxy resin, and 955 g of deionized water, put them into a reaction vessel, and react them at 65° C. with stirring for 12 h to obtain a mixture; filter the mixture to separate the solid matter therein, and filter, wash, and dry the solid matter in turn to obtain modified fullerene M5.

[0057] Example 5

[0058] (1) Weigh 82 parts of PA46, 12 parts of modified fullerene M5, 0.1 parts of Irganox 1010, and 0.2 parts of Irganox 168, mix and stir to obtain a mixture;

[0059] (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder to form pellets, thereby obtaining a PA46 composite material P5. The temperatures of the zones of the twin-screw extruder are: zone 1 temperature 275°C, zone 2 temperature 295°C, zone 3 temperature 325°C, zone 4 temperature 325°C, zone 5 temperature 325°C, zone 6 temperature 325°C; the head temperature of the twin-screw extruder is 325°C, and the screw speed is 255 r / min.

[0060] Comparative Example 1

[0061] (1) Weigh 82 parts of PA46, 0.1 parts of Irganox1010, and 0.2 parts of Irganox168, mix and stir evenly to obtain a mixture;

[0062] (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder to form pellets, thereby obtaining a PA46 composite material D1. The temperatures of the zones of the twin-screw extruder are: zone 1 temperature 275°C, zone 2 temperature 295°C, zone 3 temperature 325°C, zone 4 temperature 325°C, zone 5 temperature 325°C, zone 6 temperature 325°C; the head temperature of the twin-screw extruder is 325°C, and the screw speed is 255 r / min.

[0063] Comparative Example 2

[0064] (1) Weigh 82 parts of PA46, 12 parts of fullerene, 0.1 parts of Irganox1010, and 0.2 parts of Irganox168, mix and stir to obtain a mixture;

[0065] (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder to form pellets, thereby obtaining a PA46 composite material D2. The temperatures of the zones of the twin-screw extruder are: zone 1 temperature 275°C, zone 2 temperature 295°C, zone 3 temperature 325°C, zone 4 temperature 325°C, zone 5 temperature 325°C, zone 6 temperature 325°C; the head temperature of the twin-screw extruder is 325°C, and the screw speed is 255 r / min.

[0066] Performance Test:

[0067] The PA46 composite materials prepared in the above Examples 1-5 and Comparative Examples 1-2 were made into test strips by injection molding, wherein: the test standard for surface resistivity is ASTM D257, and the unit is Ω; the test standard for friction coefficient (dry grinding) is ASTM D1894; the test results are shown in Table 1 below:

[0068] Table 1 Test results

[0069] Test items X1 X2 X3 X4 X5 D1 D2 Surface resistivity <![CDATA[5.8×10 6 ]]> <![CDATA[4.9×10 6 ]]> <![CDATA[5.1×10 6 ]]> <![CDATA[8.2×10 6 ]]> <![CDATA[6.9×10 6 ]]> <![CDATA[5.3×10 14 ]]> <![CDATA[5.3×10 6 ]]> Friction coefficient (dry grinding) 0.46 0.44 0.47 0.48 0.46 0.58 0.50

[0070] It can be seen from Table 1 that the conductivity and friction resistance of the composite materials prepared in Examples 1-5 are better than those in Comparative Example 1, and the friction resistance is better than that in Comparative Example 2. In general, the conductivity and friction resistance of the materials prepared in the present invention are more excellent, which expands the application field of PA46 composite materials.

[0071] The above disclosures are only a few specific embodiments of the present application, but the present application is not limited thereto, and any changes that can be conceived by those skilled in the art should fall within the protection scope of the present application.

Claims

1. A conductive and friction-resistant bio-based PA46 composite material, characterized by: It is prepared from the following components by weight: PA46 80-100 parts, 10-16 parts of modified fullerene, Antioxidant 0.1-0.5 parts; The preparation method of the modified fullerene is as follows: (1) placing fullerene, hydrogen peroxide, water, and Fenton's catalyst in a reaction vessel, reacting at 50-60° C. for 6-8 hours to obtain a mixture; filtering the mixture to separate solid matter therein, and filtering, washing, and drying the solid matter in sequence to obtain hydroxylated fullerene; (2) placing hydroxylated fullerene, dopamine powder, and water in a reaction vessel, reacting at 30-40° C. for 8-10 hours to obtain a mixture; filtering the mixture to separate solid matter therein, and filtering, washing, and drying the solid matter in sequence to obtain dopamine-functionalized fullerene; (3) placing dopamine-functionalized fullerene, amine curing agent, epoxy resin, and water into a reaction vessel, stirring and reacting at 50-70° C. for 10-12 hours to obtain a mixture; filtering the mixture to separate solid matter therein, and filtering, washing, and drying the solid matter in sequence to obtain a modified fullerene.

2. The conductive and friction-resistant bio-based PA46 composite material according to claim 1, characterized in that: In step (1), the mass ratio of fullerene, hydrogen peroxide, water and Fenton catalyst is (30-40): (20-40): (100-120): (1-3).

3. The conductive and friction-resistant bio-based PA46 composite material according to claim 1, characterized in that: In step (2), the mass ratio of hydroxylated fullerene, dopamine powder and water is (30-40):(16-18):(120-160).

4. The conductive and friction-resistant bio-based PA46 composite material according to claim 1, characterized in that: In step (3), the amine curing agent is tris(hydroxymethyl)aminomethane; the mass ratio of dopamine functionalized fullerene, amine curing agent, epoxy resin and water is (30-40):(8-12):(12-16):(80-100).

5. The conductive and friction-resistant bio-based PA46 composite material according to any one of claims 1 to 4, characterized in that: The antioxidant is at least one of tris(2,4-di-tert-butyl)phenyl phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

6. The method for preparing the conductive and friction-resistant bio-based PA46 composite material according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Weigh 80-100 parts of PA46, 10-16 parts of modified fullerene, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) Extruding the mixed material obtained in step (1) through a twin-screw extruder and granulating it to obtain a PA46 composite material.

7. The method for preparing the conductive and friction-resistant bio-based PA46 composite material according to claim 6, characterized in that: In step (2), the twin-screw extruder includes six temperature zones arranged in sequence, and the temperatures of each zone are: zone one temperature 260-280°C, zone two temperature 280-300°C, zone three temperature 310-330°C, zone four temperature 310-330°C, zone five temperature 310-330°C, zone six temperature 310-330°C; the head temperature of the twin-screw extruder is 310-330°C, and the screw speed is 200-280r / min.