CN108329686B - Preparation method of high-performance nylon nano composite material - Google Patents
Preparation method of high-performance nylon nano composite material Download PDFInfo
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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Abstract
The invention discloses a preparation method of a high-performance nylon nano composite material, which comprises the following steps: self-made nano silicon dioxide is used as a filler, and is firstly designed on nano SiO through macromolecules2The surface of the sphere is grafted with polyamino acid molecular chains with similar chemical structure characteristics to nylon, and the double network structure function of a particle physical network and an entangled network of the grafted molecular chains and the matrix molecular chains is expected to be exerted simultaneously, so that the uniform dispersion of the nanoparticles in a polymer matrix and the good interface function of the nanoparticles and a matrix material are realized. Then modifying the macromolecule into SiO2Added into nylon for melt blending, thereby developing a novel high-performance nylon nano composite material with wide application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a high-performance nylon nano composite material.
Background
The nanometer material is applied to the polymer, and can perfectly combine the rigidity, dimensional stability and thermal stability of inorganic matters with the toughness, processability and dielectric property of the polymer, thereby obtaining the composite material with excellent performance. Although the nano material can comprehensively improve the comprehensive performance of the polymer, the nano material can also endow the polymer with unique physical and chemical properties. However, since the nanoparticles have a small particle size and a high surface energy, and are easily agglomerated to form secondary particles, the nanoparticles have poor dispersibility in polymers, and cannot exhibit a surface area effect, a volume effect, a quantum size effect, and the like, which are preferred, and thus the use effect thereof is seriously affected. In practical production and application, how to modify the surface of the nanoparticles, reduce agglomeration and caking, improve dispersibility, rheological property, photocatalytic effect and the like is one of the very important research subjects in the field of nano material science.
The surface chemical modification of the nano particle is to react active groups on the surface of the nano particle with chemical substances by a certain process method to eliminate or reduce the amount of the active groups on the surface of the nano particle so as to achieve the purpose of changing the surface property. The methods commonly used for nanoparticle surface modification include silane coupling agent modification, surfactant modification, inorganic coating, and the like. The surface of the nano particle has a large number of active groups, which is beneficial to reacting with one end of a coupling agent, and the other end of the coupling agent acts with a polymer matrix, so that the nano particle exists in a form of a cross-linking center in a polymer, the bonding force between molecules is improved, the structuring effect is basically eliminated, the wettability and the dispersity between the nano particle and the surface of the polymer are improved, the reinforcing dosage is increased, and the mechanical property can be improved.
After the surface micromolecule is organically modified, although the compatibility of the nanoparticles and a polymer matrix is improved, the micromolecules are small in molecular weight and cannot be wrapped too tightly, and a polar surface is easily exposed in the processing process, so that the dispersibility of the organically modified nanoparticles cannot meet the requirement for enhancing the performance of the matrix material, the application effect cannot reach the maximum, the price of the filler is high, and the price of the silica coupling agent is high, so that a novel modification method is developed and the action mechanism of the silica coupling agent is disclosed, and the key for improving the compatibility of the nanoparticles and the matrix is realized.
Besides the modification of the nanoparticles by small molecules such as silane coupling agents, another means for more effectively improving the dispersion of the nanoparticles and the acting force between the nanoparticles and the matrix is to graft molecular chains with the same property as the matrix polymer on the surfaces of the nanoparticles by a chemical grafting method. Currently, in such chemical modification, two methods are used, one is "Grafting from" in which the surface of the particles initiates Grafting, and the other is "Grafting to" in which prepared macromolecular chains are introduced into the surface of the particles. The two methods can improve the polarity of the particle surface well, and simultaneously, the chemical structure of the particles is completely consistent with that of the molecular chain of the matrix, so that the acting force between the particles and the matrix can be enhanced greatly. Both of these approaches are employed in polymer nanocomposites, but each has advantages and disadvantages: the "Grafting from" can precisely control the molecular weight and Grafting density of the polymer molecular chain grafted on the particle surface, for example, many groups of subjects adopt a living polymerization method, such as Atom Transfer Radical Polymerization (ATRP), and can precisely control the properties of the molecular chain grafted on the particle surface, and the "Grafting from" method also commonly adopts ring-opening polymerization, polycondensation and other methods to introduce the macromolecular chain on the particle surface, and can utilize bulk reaction or solution reaction. However, the modification by the "Grafting from" method is adopted, because there are many initiation points and the steric hindrance is large in the later stage of the reaction, the molecular weight of the prepared molecular chain is limited, but the Grafting density is relatively large, for example, Carrot and the like adopt the method to graft a PCL molecular chain on the CdS surface, and the maximum molecular weight can be 16000g/mol by controlling the ratio of the initiator and the monomer. Molecular chains are introduced to the surfaces of the nanoparticles by a 'Grafting to' method, so that molecular branches with high molecular weight can be obtained, but the Grafting density is relatively low due to the steric effect of the macromolecular chains, and meanwhile, the reaction conditions are harsh compared with 'Grafting from', and the nanoparticles are generally prepared by reactions such as nucleophilic addition, acyl chlorination or amidation.
As is well known, nylon is a common engineering plastic and is widely used in the fields of automobiles, machinery, buildings, electronic and electrical appliances, weaponry and the like. Especially applied in the field of automobile parts, for example, the intake manifold made of nylon can reduce the weight by 40-50 percent, reduce the intake resistance and improve the power of the engine. The demand for nylon in China increases by more than a dozen percent each year, and is expected to continue to increase in the coming years. Of course, nylon also has its drawbacks, such as chemical stability, poor resistance to strong acid and alkali; in the aspect of mechanical property, the dry state and low-temperature impact strength of the material are lower; in terms of weather resistance, it has a large water absorption rate, is easily burned, and is inferior in dimensional stability, heat resistance and light resistance, and the above-mentioned drawbacks limit its application range. Therefore, people improve the performance of nylon in a thousand ways, and common methods comprise filling, strengthening, copolymerization, blending, molecular compounding and the like.
The preparation methods of nylon nanocomposites are many, and CN102382452A discloses a preparation method of a nano-modified nylon composite, wherein the nano-modifier is polyhedral oligomeric silsesquioxane (POSS), and the prepared nano-material has high toughness and strength; however, the price of the nano modifier POSS is high, and the cost of the industrialized material is high. CN106009639A discloses a method for preparing a nano nylon composite material, wherein the nano material is nano sepiolite, and a nano nylon composite material with higher strength and insulating effect is developed; but the nano material is modified only by using silane as a coupling agent, and the modification effect is limited, so that the improvement of the mechanical property of the nano material is limited. CN106750271A discloses a preparation method of a nano-silica reinforced nylon 6 composite material, which comprises the steps of generating nano-silica by a sol-gel method, and preparing an in-situ nano-silica reinforced nylon material by a reactive extrusion method of a double-screw extruder.
In another aspect, the natural polymer having chemical structural similarity to nylon is a polyamino acid polymer. The constituent unit of nylon is also an amino acid, and the macromolecular chains are linked by peptide bonds (amido bonds). Amino acid is the most basic unit for forming biological protein, and the artificially synthesized polyamino acid has a structure similar to that of protein and has good biocompatibility and biodegradability; in addition, the side chain groups can be controlled to effectively react with various bioactive molecules, and the hydrophilicity, hydrophobicity and degradation performance of the material can be changed. The inherent intramolecular/intermolecular hydrogen bond action of the main chain of the polyamino acid polymer enables the polyamino acid polymer to form secondary structures such as alpha-helix, beta-fold and the like, and even tertiary and quaternary structures, so that the polyamino acid polymer can be self-assembled into a nano material with high precision and order and proper biological function, and the method has important significance for developing new functional biological materials. Considering the similarity of chemical structures of polyamino acid and nylon, but the diversity of monomers is more abundant, therefore, the polyamino group is utilized to modify the nano SiO2Grafting polyamino acid molecular chains with similar structure to nylon molecular chains on the surfaces of the nanoparticles, and realizing the nano SiO2The nano-particles are uniformly dispersed in a nylon matrix and strongly interact with a matrix material, so that a novel high-performance nylon nano composite material with wide application prospect is developed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a high-performance nylon nano composite material.
A preparation method of a high-performance nylon nano composite material comprises the following steps:
the method comprises the following steps: the preparation of nano silicon dioxide adopts
The method for preparing nano silicon dioxide particles is mainly characterized by that in alcohol phase medium, ammonia water is used to catalyze tetraethyl orthosilicate, and the experiment is carried out in hot water bath, and through hydrolysis-condensation the monodisperse spherical SiO is formed2Particles.
Step two: and (3) synthesizing NCA, weighing a certain amount of dry amino acid monomer, grinding, adding into a two-neck flask, vacuumizing for 30min, changing nitrogen for 3 times, adding anhydrous and oxygen-free Tetrahydrofuran (THF), and heating to 50 ℃. An amount of triphosgene was added with stirring. And after the reaction is carried out until the solution is clear, removing the solvent by rotary evaporation, then recrystallizing the solid product for three times by using anhydrous tetrahydrofuran and normal hexane, and fully drying to obtain the needle-shaped crystal product.
Step three: organically modifying the nanoparticles by using a coupling agent KH 550. Weighing a certain amount of nano SiO2And (3) carrying out ultrasonic dispersion on the powder in absolute ethyl alcohol uniformly. Respectively weighing absolute ethyl alcohol and deionized water, adding the absolute ethyl alcohol and the deionized water into a two-neck flask, and adding glacial acetic acid to adjust the pH value to 5. KH550 was then added dropwise to the flask and stirred to hydrolyze thoroughly. Then the nano SiO is put into2The suspension was added dropwise to the flask and stirred at room temperature for 12 h. And then centrifuging the reaction solution, washing and centrifuging the reaction solution by absolute ethyl alcohol, absolute THF and acetone respectively, and freeze-drying the reaction solution to obtain the organic silicon dioxide particles.
Step four: synthesis of nano particle surface grafted polyamino acid on SiO2Grafting long polyamino acid chains on the surfaces of the nanoparticles by a 'grafting from' method, and treating-NH on the surfaces of the nanoparticles with KH5502As an initiation center, the NCA monomer is initiated to gradually polymerize by a ring-opening polymerization method to grow a macromolecular chain on the surface of the nano particle. Mixing a certain amount of NCA monomer and aminated SiO2-NH2Mixing (the ratio of the two determines the length of a grafting molecular chain), adding anhydrous DMF, stirring in an ice bath, and reacting for 72 hours under the protection of nitrogen. Then the reaction solution is mixedCentrifuging, centrifuging and cleaning twice with DMF, and freeze drying to obtain solid product SiO2Grafting polyamino acid nano particles.
Step five: modified nano SiO2The particles and nylon are blended to prepare the nano composite material, and the nano particles and the nylon are blended and granulated by an extruder to prepare the high-performance nylon nano composite material.
The dosage of the ethanol in the first step is 100 parts, and the dosage of the ammonia water is 10-45 parts.
The dosage of the ethanol in the first step is 100 parts, and the dosage of the tetraethoxysilane is 10-35 parts.
The reaction temperature in the first step is 30-50 ℃.
The dosage of the ethanol in the first step is 100 parts, and the dosage of the water is 7-15 parts.
The size of the silica nano particles in the first step is between 20nm and 200 nm.
The amino acid monomer in the second step applicable to the invention can be glutamic acid, alanine and leucine.
NCA monomer and aminated SiO in step four applicable to the invention2-NH2From 0.5: 1 to 10: 1.
the nylon suitable for the invention can be PA6, PA66, PA610, PA8, PA12, PA1010 and PA 612.
The invention is suitable for the modified nanometer SiO2The addition amount of the particles is 1 to 20%.
Compared with the prior art, the invention has the following positive effects:
1) a controllable method for developing a nanoparticle surface graft polymer structure through macromolecular design realizes high-precision order of a polyamino acid modified nanoparticle surface structure through regulating and controlling a reaction method, reaction conditions, a monomer structure and property, molecular weight and secondary conformation of polyamino acid.
2) The polyamino acid modified nanoparticle modified nylon is a new nylon modification method, and the uniform dispersion of nanoparticles in a polymer matrix and good interface interaction between the nanoparticles and a matrix material can be realized by utilizing the similar molecular structure of polyamino acid and nylon. Meanwhile, the defects of nylon, such as mechanical property, dimensional stability and thermal stability, can be improved by depending on the special property and structure of the polyamino acid.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The described embodiments are merely a part, not all, of the invention. The tensile strength is tested according to GB/T1040.2-2006, the size of a tensile sample strip is 150mm multiplied by 10mm multiplied by 4mm, and the tensile speed is 50 mm/min; the bending strength is tested according to GB/T9341-2008, the bending spline size is 120mm multiplied by 10mm multiplied by 4mm, and the testing speed is 2 mm/min; the notched impact strength of the cantilever beam is tested according to GB/T1843.1-2008, the size of a sample strip is 80mm multiplied by 10mm multiplied by 4mm, the notch depth is 2mm, and the notch is V-shaped; the water absorption rate is 2mm, 23 ℃ and 24 h.
The preparation method of the nano-silica core-shell particles used in the following examples 1 to 4 is as follows:
(a) preparing nano silicon dioxide particles with adjustable particle size by a Stober method;
(b) performing surface modification on the nano-particles obtained in the step (a) by using silane coupling agent 3-aminopropyl triethoxysilane (KH550) for nano-silicon dioxide, and introducing amino groups (-NH) on the surfaces of the nano-particles2)；
(c) Adding dried benzyl glutamate (BLG) and triphosgene into a reaction bottle, vacuumizing and replacing nitrogen for 3 times, adding Tetrahydrofuran (THF) and reacting at 50 ℃. After the reaction is carried out until the solution is clear, the solvent in the reaction solution is evaporated in a rotating mode, and then the good solvent tetrahydrofuran and the poor solvent n-hexane are recrystallized for three times respectively to obtain a needle-shaped crystal product, namely BLG-NCA.
(d) Introducing the modified nano-silica particles obtained in the step (b) into a PBLG long chain by a 'grafting from' method, initiating by a ring-opening polymerization method, and gradually polymerizing the BLG-NCA monomer obtained in the step (c) on the surface of the nano-particles to grow into a macromolecular chain. The solvent is DMF, and the reaction is protected by nitrogen. Then settling, centrifuging at the speed of 7500r/min, and finally drying to obtain a solid product, namely the silicon dioxide grafted polyamino acid nano particle.
Example 1
A nylon composite material is prepared by blowing and drying nylon 6 and silicon dioxide grafted polyamino acid nano particles for 8 to 10 hours at a temperature of between 80 and 90 ℃; 100 parts of dried nylon 6, 3 parts of silicon dioxide grafted polyamino acid nano particles (NCA monomer and aminated SiO according to the weight ratio2-NH2In a ratio of 0.5: 1) 0.8 part of antioxidant and 0.5 part of processing aid Ethylene Bis Stearamide (EBS), fully and uniformly stirring to obtain a mixture, and mixing and granulating the nano particles and nylon 6 at the temperature of 250-270 ℃ by an extruder to obtain the high-performance nylon 6 nano composite material.
Example 2
A nylon composite material is prepared by blowing and drying nylon 6 and silicon dioxide grafted polyamino acid nano particles for 8 to 10 hours at a temperature of between 80 and 90 ℃; 100 parts of dried nylon 6, 3 parts of silicon dioxide grafted polyamino acid nano particles (NCA monomer and aminated SiO according to the weight ratio2-NH2In a ratio of 1: 1) 0.8 part of antioxidant and 0.5 part of processing aid Ethylene Bis Stearamide (EBS), fully and uniformly stirring to obtain a mixture, and mixing and granulating the nano particles and nylon 6 at the temperature of 250-270 ℃ by an extruder to obtain the high-performance nylon 6 nano composite material.
Example 3
A nylon composite material is prepared by blowing and drying nylon 6 and silicon dioxide grafted polyamino acid nano particles for 8 to 10 hours at a temperature of between 80 and 90 ℃; 100 parts of dried nylon 6, 3 parts of silicon dioxide grafted polyamino acid nano particles (NCA monomer and aminated SiO according to the weight ratio2-NH2The ratio of (A) to (B) is 2: 1) 0.8 part of antioxidant and 0.5 part of processing aid Ethylene Bis Stearamide (EBS), fully and uniformly stirring to obtain a mixture, and mixing and granulating the nano particles and nylon 6 at the temperature of 250-270 ℃ by an extruder to obtain the high-performance nylon 6 nano composite material.
Example 4
A nylon composite material is prepared by blowing and drying nylon 6 and silicon dioxide grafted polyamino acid nano particles for 8 to 10 hours at a temperature of between 80 and 90 ℃; 100 parts of dried nylon 6, 3 parts of silicon dioxide grafted polyamino acid nano particles (NCA monomer and aminated SiO according to the weight ratio2-NH2The ratio of (A) to (B) is 5: 1) 0.8 part of antioxidant and 0.5 part of processing aid Ethylene Bis Stearamide (EBS), fully and uniformly stirring to obtain a mixture, and mixing and granulating the nano particles and nylon 6 at the temperature of 250-270 ℃ by an extruder to obtain the high-performance nylon 6 nano composite material.
Comparative example 1 the nylon composition contained no silica. The control, which did not contain silica, was prepared by air-drying nylon 6 at 80-90 ℃ for 8-10 hours; according to the weight ratio, 100 parts of dried nylon 6, 0.8 part of antioxidant and 0.5 part of processing aid Ethylene Bis Stearamide (EBS) are fully and uniformly stirred to obtain a mixture, and the mixture is passed through an extruder to carry out blending granulation on the nano particles and the nylon 6 at the temperature of 250-270 ℃ to obtain the high-performance nylon 6 nano composite material.
Comparative example 2 the nylon composition contained pure silica. A nylon composite material is prepared by blowing and drying nylon 6 and pure silicon dioxide nano particles for 8-10 hours at the temperature of 80-90 ℃; according to the weight ratio, 100 parts of dried nylon 6, 4 parts of silicon dioxide nano particles, 0.8 part of antioxidant and 0.5 part of processing aid Ethylene Bis Stearamide (EBS) are fully and uniformly stirred to obtain a mixture, and the mixture is passed through an extruder to carry out blending granulation on the nano particles and the nylon 6 at the temperature of 250-270 ℃ to obtain the high-performance nylon 6 nano composite material.
Comparative example 3 the nylon composition contained pure silica. A nylon composite material is prepared by blowing and drying nylon 6 and pure silicon dioxide nano particles for 8-10 hours at the temperature of 80-90 ℃; according to the weight ratio, 100 parts of dried nylon 6, 12 parts of silicon dioxide nano particles, 0.8 part of antioxidant and 0.5 part of processing aid Ethylene Bis Stearamide (EBS) are fully and uniformly stirred to obtain a mixture, and the mixture is passed through an extruder to carry out blending granulation on the nano particles and the nylon 6 at the temperature of 250-270 ℃ to obtain the high-performance nylon 6 nano composite material.
The nylon composite materials obtained in examples 1 to 4 and comparative examples 1 to 3 were compared in water absorption and tensile properties, and the results are shown in Table 1.
TABLE 1 Properties of Nylon composite
As can be seen from Table 1, the nylon composite materials obtained in examples 1 to 4 of the present invention are superior to comparative examples 1 to 3 in tensile properties, bending properties and water absorption properties, which indicates that the nylon composite materials of the present invention can be modified by adding the silica grafted polyamino acid nanoparticles, the strength of the nylon can be enhanced, the nylon has good mechanical properties, and the tensile strength of the nylon composite materials is greatly increased; in addition, the nylon composite of the present invention also has low water absorption.
The applicant states that the process of the present invention is demonstrated by the above examples, but the present invention is not limited to the above steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (1)
1. A preparation method of a high-performance nylon nano composite material comprises the following steps:
the method comprises the following steps: the preparation of nano silicon dioxide adopts
The method for preparing nano silicon dioxide particles is mainly characterized in that ammonia water is used for catalyzing tetraethyl orthosilicate in an ethanol medium, experiments are carried out in a hot water bath, and monodisperse spherical nano SiO is formed by hydrolysis-condensation2Particles;
step two: the synthesis of NCA, weighing a certain amount of dry amino acid monomers, grinding and grinding the amino acid monomers, adding the amino acid monomers into a two-neck flask, vacuumizing for 30min, changing nitrogen for 3 times, adding anhydrous and oxygen-free Tetrahydrofuran (THF), heating to 50 ℃, adding a certain amount of triphosgene under stirring, performing rotary evaporation to remove a solvent after the reaction is performed until a solution is clear, then recrystallizing a solid product with anhydrous THF and n-hexane for three times, and fully drying to obtain an acicular crystal product;
step three: organically modifying nanoparticles by weighing a certain amount of nano SiO2The powder is evenly dispersed in absolute ethyl alcohol by ultrasonic, the absolute ethyl alcohol and deionized water are respectively weighed and added into a two-neck flask, glacial acetic acid is added to adjust the pH value to 5, then KH550 is added into the flask drop by drop, the mixture is stirred and fully hydrolyzed, and then nano SiO is added2The suspension is added into a flask drop by drop, stirred for 12 hours at room temperature, then the reaction liquid is centrifuged, washed and centrifuged by absolute ethyl alcohol, absolute THF and acetone respectively, and freeze-dried to obtain SiO2-NH2Nanoparticles;
step four: synthesis of nano particle surface grafted polyamino acid on SiO2-NH2Grafting polyamino acid long chain, SiO on the surface of the nanoparticle by a 'grafting from' method2-NH2-NH on the surface of nanoparticles2Initiating NCA monomer to gradually polymerize to grow macromolecular chain on the surface of the nano particle by ring-opening polymerization method as initiation center, and adding a certain amount of NCA monomer and SiO2-NH2Mixing the nanoparticles, adding anhydrous DMF, stirring in ice bath, reacting for 72h under the protection of nitrogen, centrifuging the reaction solution, centrifuging and cleaning twice with DMF, and freeze drying to obtain solid product SiO2Grafting polyamino acid nanoparticles;
step five: blowing and drying nylon 6 and the silicon dioxide grafted polyamino acid nano particles for 8-10 hours at the temperature of 80-90 ℃; 100 parts of dried nylon 6, 3 parts of silicon dioxide grafted polyamino acid nano particles according to the weight ratio, wherein NCA monomer and SiO2-NH2The proportion of the particles is 5: 1, 0.8 part of antioxidant and 0.5 part of processing aid ethylene distearamide, and fully and uniformly stirring to obtain a mixed materialBlending and granulating the mixture at the temperature of 250-270 ℃ through an extruder to prepare the high-performance nylon 6 nano composite material;
in the first step, the dosage of ethanol is 100 parts, and the dosage of ammonia water is 10-45 parts;
in the first step, the using amount of ethanol is 100 parts, and the using amount of tetraethyl orthosilicate is 10-35 parts;
the reaction temperature in the first step is 30-50 ℃;
in the first step, the size of the silicon dioxide nano particles is between 20nm and 200 nm;
and in the second step, the amino acid monomer is glutamic acid, alanine and leucine.
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| CN115651160A (en) * | 2022-11-11 | 2023-01-31 | 上海嘉均瑞科技有限公司 | Heat-preservation polyurethane sandwich template and preparation method thereof |
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