WO2019210587A1

WO2019210587A1 - High-elasticity heat-resistant nylon 6 and preparation method

Info

Publication number: WO2019210587A1
Application number: PCT/CN2018/096473
Authority: WO
Inventors: 倪利锋; 刘国; 钱阳
Original assignee: 江苏弘盛新材料股份有限公司
Priority date: 2018-05-04
Filing date: 2018-07-20
Publication date: 2019-11-07
Also published as: CN108440956A

Abstract

The present invention relates to the technical field of fiber product related technologies, and provides a high-elasticity heat-resistant nylon 6 and a preparation method. The high-elasticity heat-resistant nylon 6 is prepared by preparing organic layered aluminum phosphonate and then adding same in caprolactam and plant fiber lignin. Due to the special lamellar structure of the organic layered aluminum phosphonate, the prepared high-elasticity heat-resistant nylon 6 is uniformly dispersed in a macromolecular matrix, caprolactam polymerization and uniform distribution can be implemented, the molecular skeleton is stable, and the stability of the nylon 6 for subsequent material preparation is facilitated, for example, uniform dyeing, high temperature resistance, low temperature resistance, difficult deformation, reduction of water content, difficult dampness, high elasticity, thermal stability and the like are facilitated.

Description

High elastic heat-resistant nylon 6 and preparation method thereof

Technical field

The invention relates to the technical field of textiles, in particular to the technical field of nylon preparation, and more particularly to a high elasticity heat resistant nylon 6 and a preparation method thereof.

Background technique

Nylon is the trade name of polyamide fiber, also known as nylon, nylon (Nylon), abbreviated as PA, the basic constituent material is an aliphatic polyamide linked by an amide bond - [NHCO] - which is a repeat of the molecular backbone. A general term for thermoplastic resins of the amide group - [NHCO] - including aliphatic PA, aliphatic-aromatic PA and aromatic PA. Among them, aliphatic PA has many varieties, large yield and wide application, and its name is determined by the specific carbon number of the synthetic monomer. Nylon 6 has the formula -[NH(CH2)5CO]-n, which is soluble in phenol and hot concentrated sulfuric acid. It has excellent electrical insulation properties, good alkali resistance and corrosion resistance, and is the best abrasion resistant fiber in synthetic fibers. .

The quality problems of the existing nylon 6 mainly include unstable molecular weight of the slice, high water content, high monomer content, yellowing of the slice, impurities, and the like. In the early production of nylon 6, there was a case where white spots were formed on the surface after slice extraction, and then in the subsequent drying process, most of the time, the white spots disappeared after the slices were dried, but the white spots still existed. . In the subsequent high-speed spinning process, the spunability of the slice with white spots is significantly reduced, which is easy to cause the yarn breakage, and the waste silk rate is significantly increased.

The main uses of nylon chips in China's domestic market are currently:

(1). Fiber-grade slicing, can be used for spinning civilian silk, underwear, socks, shirts, etc.; for spinning industrial yarn, tire cords, canvas lines, parachutes, insulation materials, fishing nets, safety belts, etc.

(2). Engineering plastic grade slicing, which can be used to produce gears, casings, hoses, oil resistant containers, cable sheathing, equipment parts of the textile industry, etc. of precision machines.

(3). Film-level slicing can be used in packaging industry, such as food packaging, medical packaging, etc.

(4). Nylon composite materials, including impact resistant nylon, reinforced high temperature resistant nylon, etc., used to make tools with special needs, such as enhanced high temperature resistant nylon can be used to manufacture impact drills, lawn mowers, etc.

Nylon can be modified to obtain more excellent properties, with better quality and better performance after modification.

In the prior art, for example, CN201510048786.9 discloses a photothermally stable nylon 6 and a preparation method thereof, and in the present invention, a hindered amine stabilizer and a hypophosphite stabilizer are added in the preparation process of the nylon 6, in both The synergistic effect of the product improves the dyeing properties and spinning properties of the product.

Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly elastic heat resistant nylon 6 and a preparation method thereof to solve the problems set forth in the above background art.

To achieve the above object, the present invention provides the following technical solutions:

The high elastic heat-resistant nylon 6 is composed of the following raw materials in parts by weight: 0.1-1.2 parts of microcrystalline cellulose, 0.5-1.7 parts of diethyl phthalate, 100-130 parts of caprolactam, expanded polytetrafluoroethylene 2-7 parts, 3-4 parts of sodium hypophosphite monohydrate, 2-3 parts of paraformaldehyde, 0.2-0.3 parts of 30-40% hydrochloric acid, 4-6 parts of bisphenol A type polycarbonate, chlorinated hexahydrate 5-7 parts of aluminum, 0.1-0.2 parts of triethylamine, 0.6-1 part of ammonium oxalate, 0.7-1 part of 2-thiol benzoimidazole, 2-3 parts of dodecyl mercaptan, and dodecyl three 1-2 parts of methyl ammonium chloride, 16-36 parts of plant fiber lignin, 1-2 parts of petroleum petroleum sulfonate, 0.1-0.2 parts of polysorbate 80, and 1.4-2 parts of potassium dihydrogen phosphate.

The above high-elastic heat-resistant nylon 6 preferably has the following raw materials in parts by weight: 0.6 parts of precipitated barium sulfate, 1.5 parts of diethyl phthalate, 130 parts of caprolactam, 4 parts of expanded polytetrafluoroethylene, sodium sodium hypophosphite 3 parts, 2 parts of paraformaldehyde, 0.2 parts of 35-37% hydrochloric acid, 4 parts of bisphenol A type polycarbonate, 5 parts of aluminum chloride hexahydrate, 0.15 parts of triethylamine, 0.6 parts of ammonium oxalate, 2-sulfur 0.8 parts of mercaptobenzimidazole, 2.5 parts of dodecyl mercaptan, 1.5 parts of dodecyltrimethylammonium chloride, 26 parts of plant fiber lignin, 2 parts of petroleum sulfonate, 0.2 parts of polysorbate 80 And potassium dihydrogen phosphate 1.4 parts.

The preparation method of the high elastic heat-resistant nylon 6 is as follows:

(1) weighing each raw material according to the above weight ratio;

(2) taking the above sodium hypophosphite monohydrate, adding it to deionized water having a weight of 5-7 times, stirring uniformly, feeding into a constant temperature water bath, slowly adding the above paraformaldehyde, and adding the above 30-40% under stirring conditions. Hydrochloric acid, under nitrogen protection and stirring for 8-9 hours, the output is cooled, suction filtration, and the precipitate is dried under vacuum at 80-85 ° C for 10-12 hours to obtain hydroxyalkylated phosphinic acid;

(3) The above hydroxyalkylated phosphinic acid is added to a weight of 2-5 times of tetrahydrofuran, and stirred uniformly to obtain a solution of organic phosphoric acid in furan;

(4) mixing the above bisphenol A type polycarbonate and triethylamine, adding to the mixture of 7-8 times the weight of tetrahydrofuran, raising the temperature, and stirring for 20-30 minutes with the above-mentioned organic phosphoric acid furan solution. Mixing, raising the temperature, stirring under nitrogen for 2-6 hours, removing the precipitate by filtration through a microporous membrane, and concentrating the filtrate under reduced pressure to remove tetrahydrofuran, thereby obtaining a polymerized organic phosphonic acid;

(5) adding the above potassium dihydrogen phosphate to deionized water having a weight of 1-6 times, stirring uniformly, adding ammonium oxalate and triethylamine, stirring at 3-4 minutes with heat to obtain a phosphoric acid dispersion;

(6) mixing the above aluminum chloride hexahydrate and lauryl trimethyl ammonium chloride, adding to the deionized water having a weight of 20-30 times of the mixture, and stirring uniformly to obtain an aluminum chloride dispersion;

(7) mixing the above petroleum calcium sulfonate and dodecyl mercaptan, raising the temperature, stirring for 4-5 minutes, adding 6-10 times of the weight of the above mixture to the toluene, stirring uniformly, adding polysorbate 80 , stirring at 100-200 rpm for 10-13 minutes to obtain a toluene emulsion;

(8) Take the above step 4 to polymerize the organic phosphonic acid, add it to the 7-10 times weight of the aqueous ethanol solution, stir evenly, add acetic acid or sodium hydroxide dropwise, adjust the pH, increase the temperature to 80-85 ° C, and then add The above aluminum chloride dispersion liquid and phosphoric acid dispersion liquid are kept under stirring for 6-7 hours, filtered by suction, and the filter cake is washed with water 3-4 times, and vacuum-dried at 50-60 ° C for 30-40 minutes to obtain an organic layered aluminum phosphonate. ;

(9) taking the above organic layered aluminum phosphonate, added to its weight 70-80 times the acetone solution, ultrasonic for 20-30 minutes, adding the above expanded polytetrafluoroethylene, continue to ultrasonic for 10-14 minutes, warming, adding The above 2-thiol benzoimidazole is stirred under heat for 1.5-2 hours, and dried under reduced pressure to obtain a highly elastic heat-resistant material;

(10) mixing the above high-elastic heat-resistant material with plant fiber lignin, caprolactam, microcrystalline cellulose, diethyl phthalate, stirring uniformly, feeding into an extruder, and extruding and extruding After the treatment, it is put into a twin-screw extruder for melt extrusion granulation to obtain a highly elastic heat-resistant nylon 6.

Further, the temperature of the constant temperature water bath in the step 1 is 75-85 °C.

Further, the elevated temperature in the step 4 is 60-65 ° C, and the pore size of the microporous membrane is 3.0-10.0 μm.

Further, the stirring is carried out in step 5, the temperature is 50-65 ° C, and the stirring speed is 800-1000 rpm / min.

Further, the temperature is raised in step 7, the temperature is kept at a temperature of 60-75 ° C, and the stirring speed is 600-1000 rpm / min.

Further, in the ethanol solution in the step 8, the ethanol concentration is 50-75%.

Further, the pH adjustment range in step 8 is: 6.5-8.0.

Further, in the step 8, the suction filtration is carried out, and the quantitative filtration paper is selected by suction filtration, and the quantitative filter paper has a pore size range of 30-50 μm.

Further, the concentration of the acetone solution in step 9 is 55-75%, the elevated temperature is 75-90 ° C, and the drying pressure under reduced pressure is 1.0-1.5 MPa.

Further, each of the mixture materials described in the step 10 is melt extruded and subjected to post treatment, which is a freeze treatment.

Further cold treatment is divided into the first freezing treatment, the second freezing treatment and the third freezing treatment. After the first freezing treatment, the material is returned to room temperature for 1 hour, and then the second freezing treatment is performed, and the second freezing is performed. After the treatment, the material was also returned to room temperature for 1 hour, and then subjected to a third freezing treatment.

Further, the first freezing process is continuous freezing for 2-3 hours in an environment of minus 5-10 ° C, and the second freezing process is continuous freezing for 3-5 hours in an environment of minus 10-20 ° C, second. The secondary freezing treatment is continuous freezing for 2-3 hours under an environment of minus 20-25 °C.

Further, the melt extrusion granulation condition in the step 10 is: divided into three stages, the first stage is 40-80 ° C, the pressure is 1.0-3.0 MPa, the second stage is 80-150 ° C, and the pressure is 3.0-4.5 MPa. The third stage is 150-220 ° C and the pressure is 4.5-5.5 MPa.

Further, the prepared high-elastic heat-resistant material is subjected to a curing treatment by spraying a high elastic heat-resistant material with a 0.05-0.1% glutaraldehyde-glycerin aqueous solution, and placing the high elastic heat-resistant material in an oven at 35-45 ° C. After being placed for 3-4 hours, the treated highly elastic heat-resistant material was placed in a ventilated box to remove glutaraldehyde.

The advantages of the invention are:

(1) The organic layered aluminum phosphonate of the present invention is added to caprolactam and plant fiber lignin to prepare a highly elastic heat-resistant nylon 6, which is in a polymer matrix due to a special lamellar structure of the layered organic phosphonic acid aluminum. Uniform dispersion can make the polymerization of caprolactam evenly distributed and the molecular skeleton is stable, which is beneficial to the stability of nylon 6 in the subsequent preparation of materials, such as uniform dyeing, high temperature resistance, low temperature resistance, and low deformation;

(2) The organic layered aluminum phosphonate in the preparation process effectively exerts a sheet barrier effect, prevents the entry of external flammable gases, water molecules, etc., inhibits the chain degradation process of the polymer matrix, and is generated when it is subjected to thermal pyrolysis. Some components, such as C02, CO, phosphorus-containing compounds, etc., can play a role in reducing the temperature of the zone. When wet, it can prevent the infiltration of water molecules into the nylon 6, thus reducing the water content and not being damp;

(3) Phosphorus radicals and the like can capture free radicals generated around the environment, improve the heat resistance temperature of the nylon 6 and improve the thermal stability of the material.

(4) The organic layered aluminum phosphonate stabilized dense carbon layer improves the toughness of the material. The high elastic heat resistant nylon 6 of the present invention has good resilience, strong drag resistance and is not easily damaged.

(5) After the curing process and post-treatment in the preparation process, the resilience of the high-elastic heat-resistant nylon 6 material can be strengthened, and the high-elastic heat-resistant nylon 6 has uniform texture and toughness.

detailed description

The technical solutions of the present patent are further described in detail below in conjunction with specific embodiments.

Example 1

A high elastic heat resistant nylon 6 and a preparation method thereof.

The high elastic heat-resistant nylon 6 is composed of the following raw materials in parts by weight: precipitated barium sulfate 0.6 parts, diethyl phthalate 1.5 parts, caprolactam 130 parts, expanded polytetrafluoroethylene 4 parts, monohydrate hypophosphorous acid 3 parts of sodium, 2 parts of paraformaldehyde, 0.2 parts of 35-37% hydrochloric acid, 4 parts of bisphenol A type polycarbonate, 5 parts of aluminum chloride hexahydrate, 0.15 parts of triethylamine, 0.6 parts of ammonium oxalate, 2- 0.8 parts of thiol benzoimidazole, 2.5 parts of dodecyl thiol, 1.5 parts of dodecyltrimethylammonium chloride, 26 parts of plant fiber lignin, 2 parts of petroleum sulfonate, and polysorbate 80 0.2 Parts, potassium dihydrogen phosphate 1.4 parts.

(1) weighing each raw material according to the above weight ratio;

(2) taking the above sodium hypophosphite monohydrate, adding it to deionized water having a weight of 5 times, stirring uniformly, feeding it into a constant temperature water bath of 75 ° C, slowly adding the above paraformaldehyde, and adding 30-40% of the above under stirring conditions. Hydrochloric acid, stirred under nitrogen for 8 hours, the output was cooled, suction filtered, and the precipitate was vacuum dried at 80 ° C for 10 hours to obtain hydroxyalkylated phosphinic acid;

(3) The above hydroxyalkylated phosphinic acid is added to the weight of 2.5 times of tetrahydrofuran, and stirred uniformly to obtain a solution of organic phosphoric acid in furan;

(4) The above bisphenol A type polycarbonate and triethylamine are mixed, added to the mixture of 7 times by weight of tetrahydrofuran, the temperature is raised to 60 ° C, and the mixture is kept warm for 20 minutes, and mixed with the above-mentioned organic phosphoric acid furan solution. Raising the temperature, stirring under nitrogen for 3 hours, removing the precipitate by filtration through a 10.0 μm microporous membrane, and concentrating the filtrate under reduced pressure to remove tetrahydrofuran to obtain a polymerized organic phosphonic acid;

(5) adding the above potassium dihydrogen phosphate to deionized water having a weight of 4 times, stirring uniformly, adding ammonium oxalate and triethylamine, and stirring at 55 ° C, 1000 rpm / min for 3 minutes to obtain a phosphoric acid dispersion;

(6) mixing the above aluminum chloride hexahydrate and dodecyltrimethylammonium chloride, adding to the deionized water having a weight of 20-30 times of the mixture, and stirring uniformly to obtain an aluminum chloride dispersion;

(7) mixing the above petroleum sulfonate and dodecyl mercaptan, raising the temperature at 60 ° C, stirring at 600 rpm / min for 4 minutes, adding 6 times the weight of the above mixture of toluene, stirring uniformly, adding polysorbate Stirring at 80,100 rpm for 10 minutes to obtain a toluene emulsion;

(8) Taking the above step 4 to polymerize the organic phosphonic acid, adding it to a 75% by weight aqueous solution of 55% ethanol, stirring uniformly, adding acetic acid or sodium hydroxide dropwise, adjusting the pH to 6.5, increasing the temperature to 80 ° C, and sequentially adding The aluminum chloride dispersion liquid and the phosphoric acid dispersion liquid were kept under stirring for 6 hours, and filtered by a 50 μm quantitative filter paper, and the filter cake was washed with water three times, and vacuum-dried at 50 ° C for 30 minutes to obtain an organic layered aluminum phosphonate;

(9) taking the above organic layered aluminum phosphonate, adding it to 70 times its weight of 55% acetone solution, sonicating for 20 minutes, adding the above expanded polytetrafluoroethylene, continuing ultrasonic for 10 minutes, heating 75 ° C, adding the above 2-thiol benzoimidazole, stirred under heat for 1.5 hours, and dried under reduced pressure at 1.0 MPa to obtain a highly elastic heat-resistant material;

Further, the first freezing treatment is continuous freezing for 2 hours in an environment of minus 10 ° C, the second freezing treatment is continuous freezing for 3 hours in an environment of minus 120 ° C, and the second freezing treatment is at minus 20 ° C. The environment was continuously frozen for 2 hours.

Further, the melt extrusion granulation condition in the step 10 is divided into three stages, a first stage of 50 ° C, a pressure of 2.0 MPa, a second stage of 120 ° C, a pressure of 3.0 MPa, a third stage of 200 ° C, and a pressure of 4.5. MPa.

Further, the prepared high-elastic heat-resistant material is subjected to a curing treatment by spraying a high-elastic heat-resistant material with a 0.05-0.1% glutaraldehyde-glycerin aqueous solution, and placing the high-elastic heat-resistant material in an oven at 35 ° C for 3 hours. After that, the treated highly elastic heat-resistant material is placed in a ventilating box to remove glutaraldehyde.

Example 2

The high elastic heat-resistant nylon 6 is composed of the following raw materials in parts by weight: 1.2 parts of microcrystalline cellulose, 0.5 part of diethyl phthalate, 120 parts of caprolactam, 2.5 parts of expanded polytetrafluoroethylene, one water 3 parts of sodium phosphate, 2 parts of paraformaldehyde, 0.2 parts of 30-40% hydrochloric acid, 4 parts of bisphenol A type polycarbonate, 5 parts of aluminum chloride hexahydrate, 0.1 parts of triethylamine, 0.6 parts of ammonium oxalate, 2 - thiol benzoimidazole 0.7 parts, dodecyl thiol 2.5 parts, dodecyltrimethylammonium chloride 2 parts, plant fiber lignin 16 parts, petroleum sulfonate 1 part, polysorbate 80 0.2 part and 1.4 parts of potassium dihydrogen phosphate.

The preparation method of the high elastic heat-resistant nylon 6 is as follows: the further cold treatment in the preparation process is divided into a first freezing treatment, a second freezing treatment, and a third freezing treatment, after the first freezing treatment After the material was returned to room temperature for 1 hour, the second freezing treatment was carried out. After the second freezing treatment, the material was also returned to room temperature for 1 hour, and then subjected to a third freezing treatment.

Further, the first freezing treatment is continuous freezing for 2 hours in an environment of minus 5 ° C, the second freezing treatment is continuous freezing for 3 hours in an environment of minus 10 ° C, and the second freezing treatment is at minus 20 ° C. The environment was continuously frozen for 3 hours.

The others were the same as in Example 1 and the curing treatment was not carried out.

Example 3

The high elastic heat-resistant nylon 6 is composed of the following raw materials in parts by weight: 1.0 part of microcrystalline cellulose, 1.2 parts of diethyl phthalate, 130 parts of caprolactam, 2 parts of expanded polytetrafluoroethylene, one water 3 parts of sodium phosphate, 2 parts of paraformaldehyde, 0.2 parts of 30-40% hydrochloric acid, 4 parts of bisphenol A type polycarbonate, 5 parts of aluminum chloride hexahydrate, 0.1 parts of triethylamine, 0.6 parts of ammonium oxalate, 2 - thiol benzoimidazole 0.7 parts, dodecyl thiol 2 parts, lauryl trimethyl ammonium chloride 1 part, plant fiber lignin 16 parts, petroleum sulfonate 1.5 parts, polysorbate 80 0.1 part and 1.4 parts of potassium dihydrogen phosphate.

The preparation method of the high elastic heat resistant nylon 6 is as follows: further, the melt extrusion granulation condition in the step 10 is: three stages, the first stage is 60 ° C, the pressure is 1.5. MPa, second stage 150 ° C, pressure 3.0 MPa, third stage 220 ° C, pressure 5.0 MPa.

Comparative Example 1

The control 1 nylon 6 was composed of the following raw materials in parts by weight: 1.2 parts of microcrystalline cellulose, 1.7 parts of diethyl phthalate, 100 parts of caprolactam, 2 parts of expanded polytetrafluoroethylene, and plant fiber lignin 16 Parts, 2-thiol benzoimidazole 0.7.

The preparation method of the control 1 nylon 6 is as follows:

(1) The above expanded polytetrafluoroethylene is added to the above 2-thiol benzoimidazole and 55-75% acetone solution, and the ultrasonication is continued for 14 minutes, the temperature is raised at 75 ° C, the temperature is stirred for 1.5 hours, and the vacuum is dried at 1.0 MPa. , that is, high elastic heat-resistant materials, high elastic heat-resistant materials and curing treatment.

(2) mixing the above high elastic heat-resistant material with plant fiber lignin, caprolactam, microcrystalline cellulose, diethyl phthalate raw materials, stirring uniformly, feeding into an extruder, after melt extrusion and carrying out After the treatment, it is put into a twin-screw extruder for melt extrusion granulation to obtain a highly elastic heat-resistant nylon 6.

Comparative Example 2

The control 2 nylon 6 is composed of the following raw materials in parts by weight: 1.0 part of microcrystalline cellulose, 0.8 part of diethyl phthalate, 100 parts of caprolactam, 2 parts of expanded polytetrafluoroethylene, and plant fiber lignin 20 Parts, 2-thiol benzoimidazole 0.7.

The preparation method of the control 2 nylon 6 is as follows:

(1) The above expanded polytetrafluoroethylene is added to the above 2-thiol benzoimidazole and 55-75% acetone solution, and the ultrasonication is continued for 14 minutes, the temperature is raised at 80 ° C, the temperature is stirred for 1.5 hours, and the pressure is dried at 1.5 MPa. , that is, high elastic heat-resistant materials;

The high elastic heat resistant material in Comparative Example 2 was not cured.

Comparative Example 3

The control 3 nylon 6 is composed of the following raw materials in parts by weight: 0.8 parts of microcrystalline cellulose, 1.7 parts of diethyl phthalate, 130 parts of caprolactam, 5 parts of expanded polytetrafluoroethylene, and plant fiber lignin 22 Parts, 2-thiol benzoimidazole 1.

The preparation method of the control 3 nylon 6 is as follows:

(1) The above expanded polytetrafluoroethylene is added to the above 2-thiol benzoimidazole and 55-75% acetone solution, and the ultrasonication is continued for 1 minute, the temperature is raised at 90 ° C, the temperature is stirred for 2 hours, and the pressure is dried at 1.5 MPa. , that is, high elastic heat-resistant materials;

(2) mixing the above-mentioned high-elastic heat-resistant material with plant fiber lignin, caprolactam, microcrystalline cellulose, diethyl phthalate raw materials, stirring uniformly, feeding into an extruder, and after being melt-extruded, put into double The melt extrusion granulation is carried out in a screw extruder to obtain a highly elastic heat-resistant nylon 6.

In the comparative example 3, the highly elastic heat-resistant material was subjected to a curing treatment, and the post-extrusion treatment was not performed.

Table 1 shows the performance test of nylon 6 produced in the examples of the present invention and the comparative examples. The results are as follows:

It is apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, and the present invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the invention is defined by the appended claims instead All changes in the meaning and scope of equivalent elements are included in the present invention.

In addition, it should be understood that although the description is described in terms of embodiments, not every embodiment includes only one independent technical solution. The description of the specification is merely for the sake of clarity, and those skilled in the art should regard the specification as a whole. The technical solutions in the respective embodiments may also be combined as appropriate to form other embodiments that can be understood by those skilled in the art.

Claims

A highly elastic heat-resistant nylon 6 characterized by comprising the following raw materials in parts by weight: 0.1-1.2 parts of microcrystalline cellulose, 0.5-1.7 parts of diethyl phthalate, 100-130 parts of caprolactam, and expanded body 2-7 parts of polytetrafluoroethylene, 3-4 parts of sodium hypophosphite monohydrate, 2-3 parts of paraformaldehyde, 0.2-0.3 parts of 30-40% hydrochloric acid, 4-6 parts of bisphenol A type polycarbonate, 5-7 parts of aluminum chloride hexahydrate, 0.1-0.2 parts of triethylamine, 0.6-1 part of ammonium oxalate, 0.7-1 part of 2-thiol benzoimidazole, 2-3 parts of dodecyl mercaptan, ten 1-2 parts of dialkyltrimethylammonium chloride, 16-36 parts of plant fiber lignin, 1-2 parts of petroleum petroleum sulfonate, 800.1-0.2 parts of polysorbate, and 1.4-2 parts of potassium dihydrogen phosphate.
The highly elastic heat-resistant nylon 6 according to claim 1, wherein the following raw materials are preferably composed by weight: 0.6 parts of precipitated barium sulfate, 1.5 parts of diethyl phthalate, 130 parts of caprolactam, and expanded polytetrathene. 4 parts of vinyl fluoride, 3 parts of sodium hypophosphite monohydrate, 2 parts of paraformaldehyde, 0.2 parts of 35-37% hydrochloric acid, 4 parts of bisphenol A type polycarbonate, 5 parts of aluminum chloride hexahydrate, and 0.15 of triethylamine Parts, 0.6 parts of ammonium oxalate, 0.8 parts of 2-thiol benzoimidazole, 2.5 parts of dodecyl mercaptan, 1.5 parts of dodecyl trimethyl ammonium chloride, 26 parts of plant fiber lignin, petroleum sulfonic acid 2 parts of calcium, 800.2 parts of polysorbate, and 1.4 parts of potassium dihydrogen phosphate.
A method for preparing a highly elastic heat-resistant nylon 6, characterized in that the steps are as follows:

(1) weighing each raw material according to the above weight ratio;

(2) taking the above sodium hypophosphite monohydrate, adding it to deionized water having a weight of 5-7 times, stirring uniformly, feeding into a constant temperature water bath, slowly adding the above paraformaldehyde, and adding the above 30-40% under stirring conditions. Hydrochloric acid, under nitrogen protection and stirring for 8-9 hours, the output is cooled, suction filtration, and the precipitate is dried under vacuum at 80-85 ° C for 10-12 hours to obtain hydroxyalkylated phosphinic acid;

(3) The above hydroxyalkylated phosphinic acid is added to a weight of 2-5 times of tetrahydrofuran, and stirred uniformly to obtain a solution of organic phosphoric acid in furan;

(4) mixing the above bisphenol A type polycarbonate and triethylamine, adding to the mixture of 7-8 times the weight of tetrahydrofuran, raising the temperature, and stirring for 20-30 minutes with the above-mentioned organic phosphoric acid furan solution. Mixing, raising the temperature, stirring under nitrogen for 2-6 hours, removing the precipitate by filtration through a microporous membrane, and concentrating the filtrate under reduced pressure to remove tetrahydrofuran, thereby obtaining a polymerized organic phosphonic acid;

(5) adding the above potassium dihydrogen phosphate to deionized water having a weight of 1-6 times, stirring uniformly, adding ammonium oxalate and triethylamine, stirring at 3-4 minutes with heat to obtain a phosphoric acid dispersion;

(6) mixing the above aluminum chloride hexahydrate and lauryl trimethyl ammonium chloride, adding to the deionized water having a weight of 20-30 times of the mixture, and stirring uniformly to obtain an aluminum chloride dispersion;

(7) mixing the above petroleum calcium sulfonate and dodecyl mercaptan, raising the temperature, stirring for 4-5 minutes, adding 6-10 times of the weight of the above mixture to the toluene, stirring uniformly, adding polysorbate 80 , stirring at 100-200 rpm for 10-13 minutes to obtain a toluene emulsion;

(8) Take the above step 4 to polymerize the organic phosphonic acid, add it to the 7-10 times weight of the aqueous ethanol solution, stir evenly, add acetic acid or sodium hydroxide dropwise, adjust the pH, increase the temperature to 80-85 ° C, and then add The above aluminum chloride dispersion liquid and phosphoric acid dispersion liquid are kept under stirring for 6-7 hours, filtered by suction, and the filter cake is washed with water 3-4 times, and vacuum-dried at 50-60 ° C for 30-40 minutes to obtain an organic layered aluminum phosphonate. ;

(9) taking the above organic layered aluminum phosphonate, added to its weight 70-80 times the acetone solution, ultrasonic for 20-30 minutes, adding the above expanded polytetrafluoroethylene, continue to ultrasonic for 10-14 minutes, warming, adding The above 2-thiol benzoimidazole is stirred under heat for 1.5-2 hours, and dried under reduced pressure to obtain a highly elastic heat-resistant material;

(10) mixing the above high-elastic heat-resistant material with plant fiber lignin, caprolactam, microcrystalline cellulose, diethyl phthalate, stirring uniformly, feeding into an extruder, and extruding and extruding After the treatment, it is put into a twin-screw extruder for melt extrusion granulation to obtain a highly elastic heat-resistant nylon 6.
The highly elastic heat resistant nylon 6 according to any one of claims 1 to 3, wherein the temperature of the constant temperature water bath in the step 1 is 75 to 85 °C.
The highly elastic heat-resistant nylon 6 according to any one of claims 1 to 3, wherein the elevated temperature in the step 4 is 60-65 ° C, and the pore size of the microporous filter is 3.0-10.0 μm.
A highly elastic heat-resistant nylon 6 according to any one of claims 1 to 3, characterized in that the temperature is stirred at a temperature of 50 to 65 ° C and a stirring speed of 800 to 1000 rpm / min.
A highly elastic heat-resistant nylon 6 according to any one of claims 1 to 3, characterized in that the temperature is raised in step 7, the temperature is kept at a temperature of 60 to 75 ° C, and the stirring speed is 600 to 1000 rpm / min.
The highly elastic heat-resistant nylon 6 according to any one of claims 1 to 3, wherein the aqueous ethanol solution in the step 8 has an ethanol concentration of 50 to 75%.
A highly elastic heat-resistant nylon 6 according to any one of claims 1 to 3, characterized in that the pH adjustment range in the step 8 is from 6.5 to 8.0.
The high-elastic heat-resistant nylon 6 according to any one of claims 1 to 3, characterized in that, in the step 8, the suction filtration is carried out, and the quantitative filtration paper is selected by suction filtration, and the quantitative filter paper has a pore diameter ranging from 30 to 50 μm.
The high elastic heat-resistant nylon 6 according to any one of claims 1 to 3, wherein the acetone solution has a concentration of 55-75% in step 9, an elevated temperature of 75-90 ° C, and a drying pressure of 1.0-pressure under reduced pressure. 1.5MPa.
The high elastic heat resistant nylon 6 according to any one of claims 1 to 3, wherein each of the mixture materials in the step 10 is melt extruded and subjected to post treatment, and the post treatment is a freezing treatment;

Further cold treatment is divided into the first freezing treatment, the second freezing treatment and the third freezing treatment. After the first freezing treatment, the material is returned to room temperature for 1 hour, and then the second freezing treatment is performed, and the second freezing is performed. After the treatment, the material was also returned to room temperature for 1 hour, and then subjected to a third freezing treatment.