CN113265046A - High-strength heat-insulation nylon material - Google Patents
High-strength heat-insulation nylon material Download PDFInfo
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The invention discloses a high-strength heat-insulating nylon material, which belongs to the technical field of composite materials and comprises the following raw materials, by weight, 40-85 parts of modified polyamide/nylon 66 block copolymer, 15-35 parts of modified glass fiber and 0.5-2.5 parts of antioxidant. The invention takes p-hydroxy methyl benzaldehyde, heptafluoropropionic acid and adipic acid as reactants to gradually synthesize an intermediate 5, and then the intermediate 5 and nylon 66 monomer salt are utilized to carry out solution polymerization to form the modified polyamide/nylon 66 block copolymer, and the block copolymer has the structure of semi-aromatic polyamide, contains a large amount of phenyl and fluorine-containing chains, and has the characteristics of excellent mechanical property and low moisture absorption performance. Therefore, the high-strength heat-insulating damping material provided by the invention has low moisture absorption performance, excellent mechanical performance and small change of the size and physical properties of a product caused by moisture absorption.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a high-strength heat-insulation nylon material.
Background
Nylon is commonly known as polyamide, is the first synthetic fiber appearing in the world, has good comprehensive properties including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricity, has low friction coefficient, certain flame retardance, is easy to process and has wide application. Among them, nylon is commonly used in the modification preparation of raw materials of the heat insulating strip to increase the heat resistance and mechanical properties of the heat insulating strip.
Chinese patent with application number CN201911314262.4 discloses a high-strength heat-insulating nylon material and a preparation method and application thereof, and the high-strength heat-insulating nylon material comprises the following components of nylon 6650-75 parts, compatilizer 3-15 parts, coupling agent 0.1-1 part, lubricant 0.2-1.2 parts, antioxidant 0.1-1.5 parts and glass fiber 22-28 parts; the heat-insulating nylon material has good tensile strength at the temperature of-30-90 ℃, but the highest use temperature is not high, and nylon 66 used as a raw material inevitably has strong water absorption, and the absorbed water can weaken the acting force among molecular chains, has a plasticizing effect on the material, reduces the glass transition temperature, increases the product size and the like, and the influences inevitably reduce the mechanical property of the heat-insulating strip, thereby influencing the use of the heat-insulating strip.
Therefore, the present invention provides a high-strength heat insulation nylon material to solve the above problems.
Disclosure of Invention
The invention aims to provide a high-strength heat-insulating nylon material, which solves the technical problem that the product size and physical properties of the heat-insulating nylon material are changed due to the hygroscopicity of raw materials.
The purpose of the invention can be realized by the following technical scheme:
the high-strength heat-insulating nylon material comprises, by weight, 40-85 parts of modified polyamide/nylon 66 block copolymer, 15-35 parts of modified glass fiber, and 0.5-2.5 parts of antioxidant.
The modified polyamide/nylon 66 block copolymer is prepared by the following steps:
step A, adding p-hydroxy methyl benzaldehyde, toluene, petroleum ether, ethanol and p-toluenesulfonic acid into a three-neck flask with a condensation reflux pipe and a stirring magneton, uniformly stirring, heating the reaction system to 93 ℃ by using an oil bath kettle, stirring at the stirring speed of 350 r/min, carrying out reflux reaction for 4-8h, and then carrying out column separation on the reaction liquid (the volume ratio of ethyl acetate to petroleum ether is 2:1) to obtain an intermediate 1; adding the intermediate 1, benzene and p-toluenesulfonic acid into a three-neck flask with a condensation reflux pipe and a stirring magneton, uniformly stirring, heating the temperature of a reaction system to 63 ℃ by using an oil bath pot, dropwise adding heptafluoropropionic acid by using a dropping funnel under the stirring state at the dropping speed of 1 drop/second, carrying out reflux reaction for 6-12h, and separating the reaction liquid by using a column (the volume ratio of methanol to chloroform is 2:5) to obtain an intermediate 2; adding the intermediate 2, deionized water and formic acid into a three-neck flask with a condensation reflux pipe and a stirring magneton, uniformly stirring, heating the temperature of a reaction system to 82 ℃ by using an oil bath kettle, carrying out reflux reaction for 10 hours, and carrying out rotary evaporation for 1-2 hours at 110 ℃ to obtain an intermediate 3, wherein the reaction formula is shown as follows;
step B, adding the intermediate 3, aniline and aniline hydrochloride obtained in the step A into a four-neck flask with a stirring magneton and nitrogen introducing device, uniformly stirring, heating a reaction system to 113 ℃ by using an oil bath pot, reacting at a constant temperature for 2 hours, heating the reaction system to 152 ℃, continuing to react at the constant temperature for 1.5 hours, distilling under reduced pressure for 30 min after the reaction is finished, cooling the system to 55 ℃, adding 2 mol/L diluted hydrochloric acid to dissolve the rest substances, filtering, neutralizing the filtrate with 2 mol/L diluted sodium hydroxide solution until the pH is 7-8, generating a precipitate, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 3-5 times, recrystallizing a crude product with ethanol/water for two times, and finally drying at 60 ℃ in vacuum for 24 hours to obtain an intermediate 4; adding the intermediate 4, triethylamine and toluene into a three-neck flask with a stirrer, uniformly stirring, then adding adipic acid, heating a reaction system to 55 ℃ by using a water bath kettle, and reacting for 2-4 hours with stirring to obtain an intermediate 5, wherein the reaction formula is shown as follows;
step C, adding hexamethylene diamine and deionized water into a three-neck flask, stirring uniformly, adding adipic acid under a stirring state, adding sodium hypophosphite, heating a reaction system to 52 ℃ by using a water bath kettle, stirring for reaction for 3 hours, adjusting the pH of the reaction solution after the reaction is finished until the reaction solution is clear and transparent, cooling the reaction solution in air, distilling under reduced pressure to remove water, filtering, and drying a filter cake in a vacuum oven at 80 ℃ for 12 hours to obtain a nylon 66 salt monomer, wherein the reaction formula is shown as follows;
and D, dissolving the nylon 66 salt monomer obtained in the step C in deionized water, uniformly stirring to form a nylon 66 salt monomer solution, dissolving the intermediate 5 obtained in the step B in dimethyl sulfoxide, uniformly stirring to form a solution A, uniformly mixing the nylon 66 salt monomer solution and the solution A, pouring into an autoclave, vacuumizing the autoclave, introducing nitrogen to discharge air in the autoclave, stirring at 70RPM, gradually heating to 235 ℃, setting the pressure in the autoclave to be 3MPa, carrying out heat preservation and pressure maintenance reaction for 3 hours, then carrying out air discharge and pressure reduction, discharging air to normal pressure in 1 hour, introducing nitrogen for 1 hour to discharge a small molecular product, taking out a reactant under the protection of nitrogen after the reaction is finished, cooling, crushing the reactant, and placing the crushed reactant in a vacuum oven at 210 ℃ for 8 hours to obtain the modified polyamide/nylon 66 block copolymer, wherein the reaction formula is shown below.
Further, the dosage ratio of p-hydroxy methyl benzaldehyde, toluene, petroleum ether, ethanol and p-toluenesulfonic acid in the step A is 0.1mol:30-50mL:1-3mL:0.3-0.4mol:0.4-0.7 mL; the dosage ratio of the intermediate 1, the benzene, the p-toluenesulfonic acid and the heptafluoropropionic acid is 0.1mol to 40-70mL to 0.4-0.7mL to 0.15-0.18 mol; the dosage ratio of the intermediate 2, the deionized water and the formic acid is 0.1mol:20-30mL:0.5-0.8 mL.
Further, in the step B, the dosage ratio of the intermediate 3 to the aniline hydrochloride is 0.1mol to 0.11-0.13mol to 4-6 mL; the dosage ratio of the intermediate 4, triethylamine, toluene and adipic acid is 0.1mol to 0.15-0.2mol to 60-80mL to 0.11-0.13 mol.
Furthermore, the using amount ratio of the hexamethylene diamine, the deionized water, the adipic acid and the sodium hypophosphite in the step C is 0.1mol:30-50mL:0.11-0.13mol:0.032 mol.
Further, the mass ratio of the nylon 66 salt monomer solution to the solution A in the step D is 7.5-9.2: 1.8-2.5; the mass ratio of the nylon 66 salt monomer to the deionized water in the nylon 66 salt monomer solution is 0.8-1.4: 0.6-1.2; the mass ratio of the intermediate 5 to the dimethyl sulfoxide in the solution A is 0.4-0.8: 1.2-1.6.
Further, the modified glass fiber is acid-etched glass fiber, and the specific acid etching method refers to journal, journal of "journal of composite Material", volume 28, No. 4, year 2011, pages 8, month 34-39.
Further, the antioxidant is at least one of hindered phenol, thioester or phosphite antioxidant.
The high-strength heat-insulating nylon material is prepared by the following steps:
step one, adding the dried modified polyamide/nylon 66 block copolymer and an antioxidant into a high-speed blender, and stirring and mixing for 20-40 min by 900-1200 r/min to obtain a premix;
and step two, adding the premix and the modified glass fiber obtained in the step one into an extrusion device, and performing melt extrusion and cooling to obtain the high-strength heat-insulating nylon material.
Further, the temperature of the extrusion device in the second step is 275-.
The invention has the beneficial effects that:
1. the invention firstly protects the aldehyde group of p-hydroxymethyl benzaldehyde to form an intermediate 1, then uses the alcoholic hydroxyl group in the molecule of the intermediate 1 to react with the carboxyl group in heptafluoropropionic acid to obtain an intermediate 2, then carries out deprotection on the intermediate 2 to form an intermediate 3, then uses the reaction of aniline and the intermediate 3 to form an intermediate 4, and the intermediate 4 contains two terminal amino groups and a fluorine-containing chain, therefore, the intermediate 4 and adipic acid are used as the monomers of polyamide to carry out polycondensation reaction to form a polyamide polymer containing the fluorine chain, namely an intermediate 5, and then uses the intermediate 5 and nylon 66 monomer salt to carry out solution polymerization to form a modified polyamide/nylon 66 block copolymer, and the block copolymer comprises:
the semi-aromatic polyamide has a structure of semi-aromatic polyamide formed by polycondensation of aromatic diamine and aliphatic dicarboxylic acid, has friction wear resistance, fatigue resistance and creep resistance, greatly improves the glass transition temperature and the melting temperature due to the large number of phenyl groups contained in the molecule, has small influence of temperature change on strength and rigidity, greatly reduces the hygroscopicity compared with aliphatic polyamide, and has small change of the size and physical properties of products caused by moisture absorption;
contains a large amount of fluorine-containing chains, further reduces the surface energy of the polymer, further reduces the moisture absorption performance of the polymer, and has certain stain resistance;
contains alkyl chains and nylon 66 molecular chains, so that the polymer has better processing performance than aromatic polyamide.
2. According to the invention, the glass fiber is subjected to acid etching, so that a plurality of hydroxyl groups are formed on the surface of the glass fiber, the glass fiber has better compatibility with the modified polyamide/nylon 66 segmented copolymer in the blending and extrusion process, hydrogen bonds formed among molecular chains are promoted to be uniformly distributed in a composite material system, and the mechanical property of the obtained composite material is enhanced.
In conclusion, the high-strength heat-insulating nylon material provided by the invention has excellent mechanical properties and processability, low moisture absorption performance and small change of the size and physical properties of a product caused by moisture absorption.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the modified polyamide/nylon 66 block copolymer is prepared by the following steps:
step A, adding p-hydroxy methyl benzaldehyde, toluene, petroleum ether, ethanol and p-toluenesulfonic acid into a three-neck flask with a condensation reflux pipe and a stirring magneton, uniformly stirring, heating the reaction system to 93 ℃ by using an oil bath kettle, stirring at the stirring speed of 350 r/min, carrying out reflux reaction for 6 hours, and then carrying out column separation on the reaction liquid (the volume ratio of ethyl acetate to petroleum ether is 2:1) to obtain an intermediate 1; adding the intermediate 1, benzene and p-toluenesulfonic acid into a three-neck flask with a condensation reflux pipe and a stirring magneton, uniformly stirring, heating the temperature of a reaction system to 63 ℃ by using an oil bath pot, dropwise adding heptafluoropropionic acid by using a dropping funnel under the stirring state at the dropping speed of 1 drop/second, performing reflux reaction for 10 hours, and separating the reaction liquid by using a column (the volume ratio of methanol to chloroform is 2:5) to obtain an intermediate 2; adding the intermediate 2, deionized water and formic acid into a three-neck flask with a condensation reflux pipe and a stirring magneton, uniformly stirring, heating the temperature of a reaction system to 82 ℃ by using an oil bath kettle, carrying out reflux reaction for 10 hours, and carrying out rotary evaporation for 2 hours at 110 ℃ to obtain an intermediate 3;
step B, adding the intermediate 3, aniline and aniline hydrochloride obtained in the step A into a four-neck flask with a stirring magneton and nitrogen introducing device, uniformly stirring, heating a reaction system to 113 ℃ by using an oil bath pot, reacting at a constant temperature for 2 hours, heating the reaction system to 152 ℃, continuing to react at the constant temperature for 1.5 hours, distilling under reduced pressure for 30 min after the reaction is finished, cooling the system to 55 ℃, adding 2 mol/L diluted hydrochloric acid to dissolve the rest substances, filtering, neutralizing the filtrate with 2 mol/L diluted sodium hydroxide solution until the pH is 7, generating a precipitate, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 3 times, recrystallizing a crude product with ethanol/water for two times, and finally drying at 60 ℃ in vacuum for 24 hours to obtain an intermediate 4; adding the intermediate 4, triethylamine and toluene into a three-neck flask with a stirrer, uniformly stirring, then adding adipic acid, heating a reaction system to 55 ℃ by using a water bath kettle, and stirring for reacting for 4 hours to obtain an intermediate 5;
step C, adding hexamethylene diamine and deionized water into a three-neck flask, stirring uniformly, adding adipic acid under a stirring state, adding sodium hypophosphite, heating a reaction system to 52 ℃ by using a water bath kettle, stirring for reaction for 3 hours, adjusting the pH of a reaction solution after the reaction is finished until the reaction solution is clear and transparent, cooling the reaction solution in air, distilling under reduced pressure to remove water, filtering, and drying a filter cake in a vacuum oven at 80 ℃ for 12 hours to obtain a nylon 66 salt monomer;
and D, dissolving the nylon 66 salt monomer obtained in the step C in deionized water, uniformly stirring to form a nylon 66 salt monomer solution, dissolving the intermediate 5 obtained in the step B in dimethyl sulfoxide, uniformly stirring to form a solution A, uniformly mixing the nylon 66 salt monomer solution and the solution A, pouring into an autoclave, vacuumizing the autoclave, introducing nitrogen to discharge air in the autoclave, stirring at 70RPM, gradually heating to 235 ℃, setting the pressure in the autoclave to be 3MPa, carrying out heat preservation and pressure maintenance reaction for 3 hours, then carrying out air discharge and pressure reduction, discharging air to normal pressure in 1 hour, introducing nitrogen for 1 hour to discharge a small molecular product, taking out a reactant under the protection of nitrogen after the reaction is finished, cooling, crushing the reactant, and placing the crushed reactant in a vacuum oven at 210 ℃ for 8 hours to obtain the modified polyamide/nylon 66 block copolymer.
The ratio of the amounts of the raw materials used in the respective steps is shown in Table 1.
TABLE 1
Example 2:
the modified polyamide/nylon 66 block copolymer is prepared by the following steps:
prepared according to the procedure of example 1;
the ratio of the amounts of the raw materials used in the respective steps is shown in Table 2.
TABLE 2
Example 3:
the modified polyamide/nylon 66 block copolymer is prepared by the following steps:
prepared according to the procedure of example 1;
the ratio of the amounts of the raw materials used in the respective steps is shown in Table 3.
TABLE 3
Example 4:
the high-strength heat-insulating nylon material comprises the following raw materials, by weight, 40 parts of a modified polyamide/nylon 66 block copolymer, 15 parts of modified glass fibers and 0.5 part of an antioxidant. The modified polyamide/nylon 66 block copolymer is prepared in example 1, the modified glass fiber is acid-etched glass fiber, and the antioxidant is hindered phenol antioxidant 1010.
The high-strength heat-insulating nylon material is prepared by the following steps:
step one, adding the dried modified polyamide/nylon 66 block copolymer and an antioxidant into a high-speed blender, and stirring and mixing 35 min at 900 r/min to obtain a premix;
and step two, adding the premix and the modified glass fiber obtained in the step one into an extruder, performing melt extrusion, wherein the temperature of the extruder is 275 ℃, the extrusion rate is 195 r/min, and then cooling to obtain the high-strength heat-insulating nylon material.
Example 5:
the high-strength heat-insulating nylon material comprises the following raw materials, by weight, 65 parts of a modified polyamide/nylon 66 block copolymer, 20 parts of modified glass fibers and 1 part of an antioxidant. The modified polyamide/nylon 66 block copolymer is prepared in example 2, the modified glass fiber is acid-etched glass fiber, and the antioxidant is a thioester antioxidant DLTP.
The high-strength heat-insulating nylon material is prepared by the following steps:
step one, adding the dried modified polyamide/nylon 66 segmented copolymer and an antioxidant into a high-speed blender, and stirring and mixing 35 min at 1000 r/min to obtain a premix;
and step two, adding the premix and the modified glass fiber obtained in the step one into an extrusion device, performing melt extrusion, wherein the temperature of the mixture discharged from the extrusion device is 295 ℃, the extrusion rate is 200 r/min, and then cooling to obtain the high-strength heat-insulating nylon material.
Example 6:
a high-strength heat-insulating nylon material comprises the following raw materials, by weight, 85 parts of a modified polyamide/nylon 66 block copolymer, 35 parts of modified glass fibers and 2.5 parts of an antioxidant. The modified polyamide/nylon 66 block copolymer is prepared in example 3, the modified glass fiber is acid-etched glass fiber, and the antioxidant is phosphite antioxidant 168.
The high-strength heat-insulating nylon material is prepared by the following steps:
step one, adding the dried modified polyamide/nylon 66 block copolymer and an antioxidant into a high-speed blender, and stirring and mixing at 1200 r/min for 35 min to obtain a premix;
and step two, adding the premix and the modified glass fiber obtained in the step one into an extrusion device, performing melt extrusion, wherein the temperature of the mixture discharged from the machine is 330 ℃, the extrusion rate is 260 r/min, and then cooling to obtain the high-strength heat-insulating nylon material.
Example 7:
the polyamide/nylon 66 block copolymer is prepared by the following steps:
step A, adding p-hydroxy methyl benzaldehyde, aniline and aniline hydrochloride into a four-neck flask with a stirring magneton and nitrogen introducing device, uniformly stirring, heating a reaction system to 113 ℃ by using an oil bath pot, reacting at a constant temperature for 2 hours, heating the reaction system to 152 ℃, continuing to react at the constant temperature for 1.5 hours, distilling under reduced pressure for 30 min after the reaction is finished, cooling the system to 55 ℃, adding 2 mol/L diluted hydrochloric acid to dissolve the rest substances, filtering, neutralizing the filtrate with 2 mol/L diluted sodium hydroxide solution until the pH is 8.5, generating a precipitate, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 3 times, recrystallizing a crude product with ethanol/water for two times, and finally drying at 60 ℃ in vacuum for 24 hours to obtain an intermediate 6; adding the intermediate 6, triethylamine and toluene into a three-neck flask with a stirrer, uniformly stirring, then adding adipic acid, heating a reaction system to 55 ℃ by using a water bath kettle, and stirring for reacting for 4 hours to obtain an intermediate 7, wherein the reaction formula is shown as follows;
step B, adding hexamethylene diamine and deionized water into a three-neck flask, stirring uniformly, adding adipic acid under a stirring state, adding sodium hypophosphite, heating a reaction system to 52 ℃ by using a water bath kettle, stirring for reaction for 3 hours, adjusting the pH of a reaction solution after the reaction is finished until the reaction solution is clear and transparent, cooling the reaction solution in air, distilling under reduced pressure to remove water, filtering, and drying a filter cake in a vacuum oven at 80 ℃ for 12 hours to obtain a nylon 66 salt monomer;
and step C, dissolving the nylon 66 salt monomer obtained in the step B in deionized water, uniformly stirring to form a nylon 66 salt monomer solution, dissolving the intermediate 7 obtained in the step A in dimethyl sulfoxide, uniformly stirring to form a solution A, uniformly mixing the nylon 66 salt monomer solution and the solution A, pouring into an autoclave, vacuumizing the autoclave, introducing nitrogen to discharge air in the autoclave, stirring at 70RPM, gradually heating to 235 ℃, setting the pressure in the autoclave to be 3MPa, carrying out heat preservation and pressure maintenance reaction for 3 hours, then carrying out air discharge and pressure reduction, discharging air to normal pressure in 1 hour, introducing nitrogen for 1 hour to discharge a small molecular product, taking out a reactant under the protection of nitrogen after the reaction is finished, cooling, crushing the reactant, and placing the crushed reactant in a vacuum oven at 210 ℃ for 8 hours to obtain the polyamide/nylon 66 block copolymer, wherein the reaction formula is shown below.
Comparative example 1:
a high-strength heat-insulating nylon material comprises, by weight, 6640 parts of nylon, 15 parts of modified glass fiber, and 0.5 part of antioxidant. The modified glass fiber is acid etched glass fiber, and the antioxidant is hindered phenol antioxidant 1010.
The preparation steps of the high-strength heat-insulating nylon material refer to the preparation steps of example 4.
Comparative example 2:
a high-strength heat-insulating nylon material comprises the following raw materials, by weight, 65 parts of a modified polyamide/nylon 66 block copolymer and 1 part of an antioxidant. The modified polyamide/nylon 66 block copolymer is prepared in example 2, the modified glass fiber is acid-etched glass fiber, and the antioxidant is a thioester antioxidant DLTP.
The preparation steps of the high-strength heat-insulating nylon material refer to the preparation steps of example 5.
Comparative example 3:
a high-strength heat-insulating nylon material comprises, by weight, 85 parts of a polyamide/nylon 66 block copolymer, 35 parts of modified glass fibers and 2.5 parts of an antioxidant. The modified polyamide is prepared in example 7, the modified glass fiber is acid-etched glass fiber, and the antioxidant is phosphite antioxidant 168.
The preparation steps of the high-strength heat-insulating nylon material refer to the preparation steps of example 5.
The high-strength heat-insulating nylon materials obtained in examples 4 to 6 and comparative examples 1 to 3 were subjected to a tensile strength test in accordance with the tensile property measurement of GB/T1040 plastic;
the bending strength is tested according to the measurement of the bending performance of GB/T9341 plastics;
the impact strength of the gap of the simply supported beam is tested according to the impact performance of the GB/T1043 plastic simply supported beam;
testing the thermal deformation temperature according to the measurement of the GB/T1634 plastic load deformation temperature;
water absorption, namely placing a test sample strip into water at normal temperature for soaking for 72 hours, and then measuring the water absorption;
the water resistance is tested according to the GB/T6682 normal temperature soaking test (method B), the sample is placed in three-level water (the temperature is 23 ℃ plus or minus 2 ℃) specified by GB/T6682 to be soaked for 1000 hours, then the sample is placed at room temperature for 48 hours, and then the room temperature tensile characteristic value is measured.
The measured data are shown in Table 4.
TABLE 4
In the above table, it can be seen from the tensile strength, flexural strength, impact strength and heat distortion temperature that the mechanical properties and heat resistance of the high-strength thermal insulation damping materials obtained in examples 4 to 6 are good in correspondence to those of comparative examples 1 to 3, that the water absorption of the high-strength thermal insulation damping materials obtained in examples 4 to 6 is smaller than those of comparative examples 1 to 3 as seen from the water absorption, and that the water resistance of the high-strength thermal insulation damping materials obtained in examples 4 to 6 is better than those of comparative examples 1 to 3 as seen from the transverse tensile characteristic values.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. The high-strength heat-insulating nylon material is characterized by comprising the following raw materials, by weight, 40-85 parts of modified polyamide/nylon 66 block copolymer, 15-35 parts of modified glass fiber and 0.5-2.5 parts of antioxidant;
the modified polyamide/nylon 66 block copolymer is prepared by the following steps:
step A, uniformly stirring p-hydroxymethylbenzaldehyde, methylbenzene, petroleum ether, ethanol and p-toluenesulfonic acid, heating a reaction system to 93 ℃, carrying out reflux reaction for 4-8 hours under stirring, and then separating reaction liquid through a column to obtain an intermediate 1; uniformly stirring the intermediate 1, benzene and p-toluenesulfonic acid, heating the reaction system to 63 ℃, dropwise adding heptafluoropropionic acid at a dropping speed of 1 drop/second under a stirring state, performing reflux reaction for 6-12h, and separating the reaction liquid through a column to obtain an intermediate 2; uniformly stirring the intermediate 2, deionized water and formic acid, heating the temperature of a reaction system to 82 ℃, carrying out reflux reaction for 10 hours, and then carrying out rotary evaporation to obtain an intermediate 3;
step B, after the intermediate 3, aniline and aniline hydrochloride obtained in the step A are uniformly stirred, heating a reaction system to 113 ℃, carrying out constant-temperature reaction for 2 hours, then heating the reaction system to 152 ℃, continuing to carry out constant-temperature reaction for 1.5 hours, after the reaction is finished, reducing the temperature of the system to 55 ℃, carrying out reduced-pressure distillation, then adding dilute hydrochloric acid to dissolve the rest substances, filtering, neutralizing the filtrate with dilute sodium hydroxide solution until the pH value is 7-8, filtering after complete precipitation, repeatedly washing a filter cake for 3-5 times, recrystallizing the obtained crude product with ethanol/water twice, and finally carrying out vacuum drying to obtain an intermediate 4; uniformly stirring the intermediate 4, triethylamine and toluene, then adding adipic acid, heating the reaction system to 55 ℃, and stirring for reacting for 2-4h to obtain an intermediate 5;
step C, uniformly stirring hexamethylenediamine and deionized water, adding adipic acid under a stirring state, adding sodium hypophosphite, heating the reaction system to 52 ℃, stirring for reaction for 3 hours, adjusting the pH of the reaction solution after the reaction is finished until the reaction solution is clear and transparent, cooling the reaction solution, distilling under reduced pressure, filtering, and placing a filter cake in a vacuum oven for drying to obtain a nylon 66 salt monomer;
and D, dissolving the nylon 66 salt monomer obtained in the step C in deionized water, uniformly stirring to form a nylon 66 salt monomer solution, dissolving the intermediate 5 obtained in the step B in dimethyl sulfoxide, uniformly stirring to form a solution A, uniformly mixing the nylon 66 salt monomer solution and the solution A, pouring into an autoclave, vacuumizing the autoclave, introducing nitrogen, gradually heating to 235 ℃, setting the pressure in the autoclave to be 3MPa, carrying out heat preservation and pressure maintenance reaction for 3 hours, then carrying out air release and pressure reduction, releasing air to the normal pressure in 1 hour, then introducing nitrogen for 1 hour, taking out the reactant under the protection of nitrogen after the reaction is finished, cooling, crushing the reactant, and drying the crushed reactant in a vacuum oven to obtain the modified polyamide/nylon 66 block copolymer.
2. The high-strength thermal insulation nylon material as claimed in claim 1, wherein the amount ratio of p-hydroxymethylbenzaldehyde, toluene, petroleum ether, ethanol and p-toluenesulfonic acid in step A is 0.1mol:30-50mL:1-3mL:0.3-0.4mol:0.4-0.7 mL; the dosage ratio of the intermediate 1, the benzene, the p-toluenesulfonic acid and the heptafluoropropionic acid is 0.1mol to 40-70mL to 0.4-0.7mL to 0.15-0.18 mol; the dosage ratio of the intermediate 2, the deionized water and the formic acid is 0.1mol:20-30mL:0.5-0.8 mL.
3. The high-strength heat insulation nylon material as claimed in claim 1, wherein in the step B, the amount ratio of the intermediate 3 to the aniline hydrochloride is 0.1mol:0.11-0.13mol:4-6 mL; the dosage ratio of the intermediate 4, triethylamine, toluene and adipic acid is 0.1mol:0.15-0.2mol:60-80mL:0.11-0.13 mol.
4. The high-strength heat-insulating nylon material as claimed in claim 1, wherein the amount ratio of hexamethylenediamine, deionized water, adipic acid and sodium hypophosphite in step C is 0.1mol:30-50mL:0.11-0.13mol:0.032 mol.
5. The high-strength heat insulation nylon material as claimed in claim 1, wherein the mass ratio of the nylon 66 salt monomer solution to the solution A in the step D is 7.5-9.2: 1.8-2.5; the mass ratio of the nylon 66 salt monomer to the deionized water in the nylon 66 salt monomer solution is 0.8-1.4: 0.6-1.2; the mass ratio of the intermediate 5 to the dimethyl sulfoxide in the solution A is 0.4-0.8: 1.2-1.6.
6. The high-strength heat insulation nylon material as claimed in claim 1, wherein the modified glass fiber is an acid etched glass fiber.
7. The high-strength thermal insulation nylon material as claimed in claim 1, which is prepared by the following steps:
step one, mixing the dried modified polyamide/nylon 66 segmented copolymer with an antioxidant to obtain a premix;
and step two, melting, extruding and cooling the premix and the modified glass fiber obtained in the step one to obtain the high-strength heat-insulating nylon material.
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| CN202110661250.XA CN113265046A (en) | 2021-06-15 | 2021-06-15 | High-strength heat-insulation nylon material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940741A (en) * | 2022-07-11 | 2022-08-26 | 安徽冠泓塑业有限公司 | High-toughness anti-aging fire-fighting boot and production method thereof |
| CN115536538A (en) * | 2022-09-23 | 2022-12-30 | 濮阳市盛通聚源新材料有限公司 | Fluorine-containing diamine, fluorine-containing high-temperature-resistant nylon and preparation method thereof |
| CN115651399A (en) * | 2022-12-12 | 2023-01-31 | 平顶山学院 | High-strength anti-fatigue flame-retardant heat-insulating strip nylon composite material and synthesis method thereof |
-
2021
- 2021-06-15 CN CN202110661250.XA patent/CN113265046A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114940741A (en) * | 2022-07-11 | 2022-08-26 | 安徽冠泓塑业有限公司 | High-toughness anti-aging fire-fighting boot and production method thereof |
| CN115536538A (en) * | 2022-09-23 | 2022-12-30 | 濮阳市盛通聚源新材料有限公司 | Fluorine-containing diamine, fluorine-containing high-temperature-resistant nylon and preparation method thereof |
| CN115536538B (en) * | 2022-09-23 | 2023-09-26 | 濮阳市盛通聚源新材料有限公司 | Fluorine-containing diamine, fluorine-containing high-temperature-resistant nylon and preparation method thereof |
| CN115651399A (en) * | 2022-12-12 | 2023-01-31 | 平顶山学院 | High-strength anti-fatigue flame-retardant heat-insulating strip nylon composite material and synthesis method thereof |
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