阅读说明：本技术 一种利用纳米粒子协同增强mc尼龙复合材料的方法 (Method for synergistically enhancing MC nylon composite material by using nano particles ) 是由 姜波 张春华 张爱臣 于 2021-07-29 设计创作，主要内容包括：本发明公开了一种利用纳米粒子协同增强MC尼龙复合材料的方法,属于工程塑料改性领域,包括如下步骤：S1、采用γ-氨丙基三乙氧基硅烷(APTES)对云母进行改性,制备氨基修饰云母粒子；S2、采用γ-缩水甘油醚基丙基三乙氧基硅烷(γ-GPS)对玻璃纤维粒子进行改性,制备环氧基修饰玻璃纤维粒子。本发明提供的协同增强MC尼龙的方法具有工艺过程简单易行、生产周期短等优点,通过该方法所制备MC尼龙/SiC@SiO2复合材料与纯MC尼龙相比,具有力学强度高、耐热性好以及良好的耐磨性能等,可满足在较高载荷下的耐热性和摩擦磨损性能的需求,在高新技术领域具有广阔的应用前景。(The invention discloses a method for synergistically enhancing an MC nylon composite material by utilizing nano particles, which belongs to the field of engineering plastic modification and comprises the following steps: s1, modifying mica with gamma-Aminopropyltriethoxysilane (APTES) to prepare amino modified mica particles; s2, modifying the glass fiber particles by adopting gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) to prepare the epoxy group modified glass fiber particles. Compared with pure MC nylon, the MC nylon/SiC @ SiO2 composite material prepared by the method has the advantages of high mechanical strength, good heat resistance, good wear resistance and the like, can meet the requirements of heat resistance and frictional wear resistance under higher load, and has wide application prospect in the high and new technology field.)

1. A method for cooperatively enhancing an MC nylon composite material by utilizing nano particles is characterized by comprising the following steps:

s1, modifying mica with gamma-Aminopropyltriethoxysilane (APTES) to prepare amino modified mica particles;

s2, modifying the glass fiber particles by adopting gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) to prepare epoxy group modified glass fiber particles;

s3, compounding the MC nylon with the amino-modified mica particles and the epoxy-modified glass fiber particles through an in-situ polymerization method to construct a reinforcing network, and preparing the nano particle synergetic reinforced MC nylon composite material.

2. The method for the synergistic enhancement of the MC nylon composite material by the nano particles as claimed in claim 1, wherein in step S1, the method comprises the following steps:

s11, placing the mica particles in a drying oven at 150 ℃ for constant temperature for 4h, cooling to room temperature, dispersing the mica particles in absolute ethyl alcohol, and carrying out ultrasonic treatment for 20-90 min;

s12, mixing the mica particles with the gamma-aminopropyl triethoxysilane (APTES) according to the mass ratio of 100: (2-7), adding 3-aminopropyl trimethoxy silane (APTMS) for reaction, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 4-8h to obtain a product;

s13, performing centrifugal separation on the product, washing the product for 3 to 5 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at 70 ℃ for 8 to 16 hours to prepare the amino modified mica particles.

3. The method for the synergistic enhancement of the MC nylon composite material by the nano particles as claimed in claim 1, wherein in step S2, the method comprises the following steps:

s21, placing the glass fiber particles in a drying oven at 150 ℃ and keeping the temperature for 4 hours, cooling to room temperature, dispersing the glass fiber particles in absolute ethyl alcohol, and carrying out ultrasonic treatment for 20-90 min;

s22, mixing the glass fiber particles and the gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) according to the mass ratio of 100: (2-7), adding a silane coupling agent (gamma-GPS) for reaction, adjusting the pH to 5-6, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 4-8 hours;

and S23, centrifugally separating the product, washing the product for 3 to 5 times by using absolute ethyl alcohol, and drying the product for 8 to 16 hours in a vacuum drying oven at the temperature of 70 ℃ to obtain the epoxy group modified glass fiber particles.

4. The method for the synergistic enhancement of the MC nylon composite material by the nano particles as claimed in claim 1, wherein in step S3, the method comprises the following steps:

s31, adding caprolactam monomer into a reactor, heating to 75-95 ℃ to melt all caprolactam, the amino-modified mica particles and the epoxy-modified glass fiber particles according to the mass ratio of 100: (0.1-6): (0.1-6), stirring strongly to disperse uniformly, heating to 115 ℃ and 135 ℃, and dehydrating in vacuum for 20-60 min;

s32, first-stage vacuum relief, and mixing caprolactam and sodium hydroxide according to a molar ratio of 100: (0.1-1.0), then adding sodium hydroxide, and dehydrating in vacuum at 135-145 ℃ for 20-60 min;

s33, secondary vacuum relief, and mixing caprolactam and toluene diisocyanate according to a molar ratio of 100: (0.1-0.8), then adding toluene diisocyanate, quickly shaking up, quickly pouring into a mold preheated to 160-180 ℃, preserving heat for 20-30 min, cooling to room temperature, and demolding to obtain the nano particle synergistic reinforced MC nylon composite material.

Technical Field

The invention relates to the field of engineering plastic modification, in particular to a method for synergistically enhancing an MC nylon composite material by using nanoparticles.

Background

Monomer casting nylon (MC nylon, MC PA6 for short) is a nylon product obtained by anion ring-opening polymerization reaction of caprolactam monomer under the conditions of activating agent, initiating agent and specific temperature, because MC nylon has the advantages of simple forming process, high mechanical strength, good chemical stability and light weight, etc., it can replace steel, copper, aluminum, etc. to be used for manufacturing parts such as bush, shaft sleeve, gear, rack, worm gear, pulley, loom shuttle, propeller and various sealing rings, etc., and has the functions of reducing weight and cost, therefore, MC nylon is widely used in the fields of textile machinery, national defense, chemical industry, etc., with the development of science and technology, MC nylon has certain defects, which leads to the application of nylon products to be limited, for example, because of poor heat resistance, the MC nylon has limited application in the high-temperature field, and relatively low mechanical strength and toughness compared with metal materials, making their use in mechanical load-bearing articles limited.

The inorganic nano particles are adopted to modify the polymer material, so that the material performance can be effectively improved, the cost is low, and the inorganic nano particles become one of novel materials with the most development potential.

The invention provides a method for synergistically enhancing MC nylon engineering plastics by using nano particles, which takes massive mica powder and glass fiber powder with high length-diameter ratio as raw materials, adopts gamma-Aminopropyltriethoxysilane (APTES) to modify mica particles, adopts gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) to modify glass fiber particles, improves the compatibility of the glass fiber particles in MC nylon and monomers, and improves the intermolecular interaction force of a filler and a nylon molecular main chain and the interaction force between the fillers; the MC nylon modification method provided by the invention has the advantages of rich raw materials, short production period, simple and easy technological process and the like, and the synergistically enhanced MC nylon composite material prepared by the method has the characteristics of high hardness, good thermal stability, excellent mechanical properties and the like.

Disclosure of Invention

1. Technical problem to be solved

Aiming at the problems in the prior art, the invention aims to provide a method for synergistically enhancing an MC nylon composite material by utilizing nano particles.

2. Technical scheme

In order to solve the problems, the invention adopts the following technical scheme:

a method for synergistically enhancing an MC nylon composite material by utilizing nanoparticles comprises the following steps:

s1, modifying mica with gamma-Aminopropyltriethoxysilane (APTES) to prepare amino modified mica particles;

s2, modifying the glass fiber particles by adopting gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) to prepare epoxy group modified glass fiber particles;

s3, compounding the MC nylon with the amino-modified mica particles and the epoxy-modified glass fiber particles through an in-situ polymerization method to construct a reinforcing network, and preparing the nano particle synergetic reinforced MC nylon composite material. Compared with pure MC nylon, the MC nylon/SiC @ SiO2 composite material prepared by the method has the advantages of high mechanical strength, good heat resistance, good wear resistance and the like, can meet the requirements of heat resistance and frictional wear resistance under higher load, and has wide application prospect in the high and new technology field.

As a preferable embodiment of the present invention, in step S1, the method specifically includes the following steps:

s11, placing the mica particles in a drying oven at 150 ℃ for constant temperature for 4h, cooling to room temperature, dispersing the mica particles in absolute ethyl alcohol, and carrying out ultrasonic treatment for 20-90 min;

s12, mixing the mica particles with the gamma-aminopropyl triethoxysilane (APTES) according to the mass ratio of 100: (2-7), adding 3-aminopropyl trimethoxy silane (APTMS) for reaction, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 4-8h to obtain a product;

s13, performing centrifugal separation on the product, washing the product for 3 to 5 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at 70 ℃ for 8 to 16 hours to prepare the amino modified mica particles.

As a preferable embodiment of the present invention, in step S2, the method specifically includes the following steps:

s21, placing the glass fiber particles in a drying oven at 150 ℃ and keeping the temperature for 4 hours, cooling to room temperature, dispersing the glass fiber particles in absolute ethyl alcohol, and carrying out ultrasonic treatment for 20-90 min;

s22, mixing the glass fiber particles and the gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) according to the mass ratio of 100: (2-7), adding a silane coupling agent (gamma-GPS) for reaction, adjusting the pH to 5-6, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 4-8 hours;

and S23, centrifugally separating the product, washing the product for 3 to 5 times by using absolute ethyl alcohol, and drying the product for 8 to 16 hours in a vacuum drying oven at the temperature of 70 ℃ to obtain the epoxy group modified glass fiber particles.

As a preferable embodiment of the present invention, in step S3, the method specifically includes the following steps:

s31, adding caprolactam monomer into a reactor, heating to 75-95 ℃ to melt all caprolactam, the amino-modified mica particles and the epoxy-modified glass fiber particles according to the mass ratio of 100: (0.1-6): (0.1-6), stirring strongly to disperse uniformly, heating to 115 ℃ and 135 ℃, and dehydrating in vacuum for 20-60 min;

s32, first-stage vacuum relief, and mixing caprolactam and sodium hydroxide according to a molar ratio of 100: (0.1-1.0), then adding sodium hydroxide, and dehydrating in vacuum at 135-145 ℃ for 20-60 min;

s33, secondary vacuum relief, and mixing caprolactam and toluene diisocyanate according to a molar ratio of 100: (0.1-0.8), then adding toluene diisocyanate, quickly shaking up, quickly pouring into a mold preheated to 160-180 ℃, preserving heat for 20-30 min, cooling to room temperature, and demolding to obtain the nano particle synergistic reinforced MC nylon composite material.

3. Advantageous effects

Compared with the prior art, the invention has the advantages that:

compared with pure MC nylon, the MC nylon/SiC @ SiO2 composite material prepared by the method has the advantages of high mechanical strength, good heat resistance, good wear resistance and the like, can meet the requirements of heat resistance and frictional wear resistance under higher load, and has wide application prospect in the high and new technology field.

Drawings

FIG. 1 is a flow chart of a method for synergistically enhancing MC nylon composite material by using nanoparticles according to the present invention.

Detailed Description

The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.

Example 1:

referring to fig. 1, a method for synergistically enhancing an MC nylon composite material by using nanoparticles includes the following steps:

s1, modifying mica with gamma-Aminopropyltriethoxysilane (APTES) to prepare amino modified mica particles:

s11, placing the mica particles in a drying oven at 150 ℃ for constant temperature for 4h, cooling to room temperature, dispersing the mica particles in absolute ethyl alcohol, and carrying out ultrasonic treatment for 20-90 min;

s12, mixing the mica particles with gamma-aminopropyl triethoxysilane (APTES) according to the mass ratio of 100: (2-7), adding 3-aminopropyl trimethoxy silane (APTMS) for reaction, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 4-8h to obtain a product;

s13, performing centrifugal separation on the product, washing the product for 3-5 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at 70 ℃ for 8-16 h to obtain amino modified mica particles;

s2, modifying the glass fiber particles by adopting gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) to prepare the epoxy group modified glass fiber particles:

s21, placing the glass fiber particles in an oven at 150 ℃ and keeping the temperature for 4 hours, dispersing the glass fiber particles in absolute ethyl alcohol after cooling to room temperature, and carrying out ultrasonic treatment for 20-90 min;

s22, mixing the glass fiber particles with gamma-glycidyl ether propyl triethoxysilane (gamma-GPS) according to the mass ratio of 100: (2-7), adding a silane coupling agent (gamma-GPS) for reaction, adjusting the pH to 5-6, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 4-8 hours;

s23, centrifugally separating the product, washing the product for 3-5 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at 70 ℃ for 8-16 h to obtain epoxy group modified glass fiber particles;

s3, compounding MC nylon, amino-modified mica particles and epoxy-modified glass fiber particles through an in-situ polymerization method, constructing a reinforcing network, and preparing the nano particle synergetic reinforced MC nylon composite material:

s31, adding caprolactam monomer into a reactor, heating to 75-95 ℃ to melt the caprolactam monomer completely, and mixing the caprolactam monomer, the amino-modified mica particles and the epoxy-modified glass fiber particles according to a mass ratio of 100: (0.1-6): (0.1-6), stirring strongly to disperse uniformly, heating to 115 ℃ and 135 ℃, and dehydrating in vacuum for 20-60 min;

s32, first-stage vacuum relief, and mixing caprolactam and sodium hydroxide according to a molar ratio of 100: (0.1-1.0), then adding sodium hydroxide, and dehydrating in vacuum at 135-145 ℃ for 20-60 min;

s33, secondary vacuum relief, and mixing caprolactam and toluene diisocyanate according to a molar ratio of 100: (0.1-0.8), then adding toluene diisocyanate, quickly shaking up, quickly pouring into a mold preheated to 160-180 ℃, preserving heat for 20-30 min, cooling to room temperature, and demolding to obtain the nano particle synergistic reinforced MC nylon composite material.

Example 2:

1. preparation of amino-modified mica particles: placing 4 g of mica particles in a drying oven at 150 ℃ for constant temperature for 4h, cooling to room temperature, dispersing in 250 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 40 min; adding 0.15 g of APTMS, raising the reaction temperature to 60 ℃, carrying out reflux condensation reaction for 6 h, carrying out centrifugal separation on the product, washing the product for 5 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at 70 ℃ for 8h to obtain amino modified mica particles;

2. preparation of epoxy group modified glass fiber particles: placing 4 g of glass fiber particles in a drying oven with the temperature of 150 ℃ for constant temperature for 4h, cooling to room temperature, dispersing in 250 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 40 min; adding 0.15 g of gamma-GPS, adjusting the Ph to 5.5 by using acetic acid, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 6 hours; centrifugally separating the product, washing the product for 5 times by using absolute ethyl alcohol, and drying the product for 8 hours in a vacuum drying oven at 70 ℃ to obtain epoxy group modified glass fiber particles;

3. preparing a composite material by an in-situ polymerization method: weighing 100g of caprolactam monomer, adding the caprolactam monomer into a reactor, heating to 85 ℃ to melt the caprolactam monomer, weighing 1g of amino-modified mica particles and 1g of epoxy-modified glass fiber particles, adding the amino-modified mica particles and the epoxy-modified glass fiber particles into the reactor, uniformly dispersing, heating to 130 ℃, and performing vacuum dehydration for 20 min; removing vacuum, adding 0.5 g of sodium hydroxide, and vacuum dehydrating at 140 deg.C for 20 min; and (3) removing vacuum, adding 0.5 g of toluene diisocyanate, quickly shaking up, quickly pouring into a mold preheated to 165 ℃ in advance, preserving heat for 20min, cooling to room temperature, and demolding to obtain the MC nylon/SiC @ SiO2 composite material product.

Example 3:

1. preparation of amino-modified mica particles: placing 20 g of mica particles in a drying oven at 150 ℃ for constant temperature for 4h, cooling to room temperature, dispersing in 4000 mL of absolute ethanol, and performing ultrasonic treatment for 60 min; adding 0.8 g of APTMS, raising the reaction temperature to 60 ℃, carrying out reflux condensation reaction for 6 h, carrying out centrifugal separation on the product, washing the product for 5 times by using absolute ethyl alcohol, and drying the product in a vacuum drying oven at 70 ℃ for 8h to obtain amino modified mica particles;

2. preparation of epoxy group modified glass fiber particles: placing 20 g of glass fiber particles in a drying oven with the temperature of 150 ℃ for 4h, cooling to room temperature, dispersing in 4000 mL of absolute ethyl alcohol, and performing ultrasonic treatment for 60 min; adding 0.8 g of gamma-GPS, adjusting the pH value to 5.5 by using acetic acid, raising the reaction temperature to 60 ℃, and carrying out reflux condensation reaction for 6 hours; and (3) centrifugally separating the product, washing the product for 5 times by using absolute ethyl alcohol, and drying the product for 8 hours in a vacuum drying oven at 70 ℃ to obtain the epoxy group modified glass fiber particles.

3. Preparing a composite material by an in-situ polymerization method: weighing 200g of caprolactam monomer, adding the caprolactam monomer into a reactor, heating to 85 ℃ to melt the caprolactam monomer, weighing 1.8g of amino-modified mica particles and 1.8g of epoxy-modified glass fiber particles, adding the amino-modified mica particles and the epoxy-modified glass fiber particles into the reactor, uniformly dispersing, heating to 130 ℃, and performing vacuum dehydration for 20 min; removing vacuum, adding 0.95 g of sodium hydroxide, and vacuum dehydrating at 140 deg.C for 20 min; and (3) removing vacuum, adding 1g of toluene diisocyanate, quickly shaking up, quickly pouring into a mold preheated to 170 ℃, preserving heat for 20min, cooling to room temperature, and demolding to obtain the synergistic reinforced MC nylon composite material product.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the equivalent replacement or change according to the technical solution and the modified concept of the present invention should be covered by the scope of the present invention.