CN109970970A - A kind of high-strength and high-toughness transparent nylon material and its preparation and application - Google Patents

Abstract

The invention relates to a high-strength and high-toughness transparent nylon material and its preparation and application. The raw materials include: short-carbon chain aliphatic nylon salt, semi-aromatic nylon salt, long-carbon chain aliphatic nylon salt, antioxidant, molecular weight regulator, Ionized water, etc. Preparation: The raw materials are put into the polymerization kettle, and the high-strength, high-toughness and transparent ternary copolymer nylon material can be obtained through the polymerization steps of heating up, maintaining pressure, releasing pressure, normal pressure, and discharging under pressure. It has better oil resistance, corrosion resistance, wear resistance and other properties than other transparent plastics, and can be widely used in automotive, electrical and electronic, machinery, optics, sports and other fields.

Description

A kind of high-strength and high-toughness transparent nylon material and its preparation and application

technical field

The invention belongs to the field of modified nylon material and its preparation and application, in particular to a high-strength and high-toughness transparent nylon material and its preparation and application.

Background technique

Transparent nylon is an amorphous or microcrystalline thermoplastic nylon with a light transmittance of 90%. Its transparency is better than polycarbonate (PC) and close to polymethyl methacrylate (PMMA). In addition, it has good thermal stability, impact toughness, electrical insulation, dimensional stability and aging resistance. The product has low shrinkage and low coefficient of linear expansion. It is resistant to dilute acids, alkalis, aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, oils and fats, but not alcohols. It can be dissolved in a mixture of 80% chloroform and 20% methanol. Superior to PC and PMMA in resistance to environmental stress cracking. Transparent nylon has better oil resistance, corrosion resistance, wear resistance, scratch resistance and other properties than other transparent plastics, and is widely used in automotive, electrical and electronic, machinery, optics, sports and other fields. At present, the preparation of transparent polyamides and related technologies are mastered in a few countries such as the United States, Japan, and France. The research and development of transparent polyamides in China started relatively late, and there are few types of new transparent polyamides developed, and the mastered synthesis and processing technologies And related patents are also relatively few. Most of the transparent polyamides used in my country are purchased from abroad. At the same time, the sales prices of transparent polyamides are very high, and some high-performance ones are even as high as more than ten thousand yuan per ton. In order to solve the objective fact that transparent polyamide products rely on imports for a long time, in order to meet domestic demand, the exploration of polyamide products with high light transmittance is of great practical significance.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a high-strength and high-toughness transparent nylon material and its preparation and application, and overcome the defects of the prior art such as complicated preparation process and limited source of raw materials. , pressure discharge and other polymerization steps to obtain high-strength and high-toughness transparent ternary copolymer nylon material.

A kind of ternary copolymerization nylon material of the present invention, by weight, the raw material components include:

Described short carbon chain aliphatic nylon salt is one or more of caprolactam, nylon 66 salt, nylon 46 salt, nylon 56 salt; semi-aromatic nylon salt is nylon 4T salt, nylon 6T salt, nylon 9T salt, nylon One or more of 5I salt and nylon 6I salt; Long carbon chain nylon salt is one or more of nylon 610 salt, nylon 1010 salt, nylon 612 salt, nylon 1012 salt; Molecular weight regulator is glacial acetic acid, One or more of dodecanedioic acid and adipic acid; antioxidant is one or more of dimethyl phthalate DMP, antioxidant 1098, antioxidant 1010, antioxidant SEED, phosphorous acid kind.

Said nylon 6I salt is synthesized by hexamethylenediamine and isophthalic acid.

Further preferably, the short carbon chain aliphatic nylon salt is caprolactam, nylon 66 salt; the semi-aromatic nylon salt is nylon 6T salt (by terephthalic acid and hexamethylene diamine, the molar mass ratio of 1.00:1.01 is controlled. Add deionized water to the polymerization kettle with the concentration of the salt solution at 40-60% by mass. After vacuuming and passing nitrogen to discharge the air, the heating device is turned on. The salt-forming temperature is 110-150°C, and the rotating speed of the stirring motor is 30-80 r/ min; reaction time 8～10h; after the salt-forming reaction is completed, the salt solution of nylon 6T is obtained, and nylon 6T salt is obtained by cooling, crystallization, filtration and vacuum drying); long carbon chain nylon salt is nylon 612; antioxidant is antioxidant 1098 .

A preparation method of a terpolymer nylon material of the present invention comprises:

(1) By weight, mix 40-60 parts of short carbon chain aliphatic nylon salts, 10-40 parts of semi-aromatic nylon salts, 10-40 parts of long carbon chain nylon salts, and 10-30 parts of deionized water , 0～1 part of molecular weight regulator and 0.05～0.2 part of antioxidant are added to the polymerization kettle;

(2) Seal the polymerization kettle, exhaust the air by vacuuming and pass nitrogen, start the heating device to heat up, the polymerization temperature is 190-280 ° C, and stir, and adjust the rotation speed in the range of 30-120 r/min in a timely manner. , normal pressure, vacuum polymerization reaction, and finally pass nitrogen to pressurize the material, that is, the ternary copolymer nylon material.

The preferred mode of above-mentioned preparation method is as follows:

In the step (1), the short carbon chain aliphatic nylon salt, the semi-aromatic nylon salt and the long carbon chain nylon salt are all subjected to drying treatment, specifically drying in a vacuum drying oven at 50-80° C. for 8-12 hours.

In the step (2), vacuuming and feeding nitrogen to discharge air is specifically: vacuuming to 60-90 kPa in the polymerization kettle, charging nitrogen to 0.3-0.5 Mpa in the polymerization kettle, and maintaining the pressure in the kettle at normal pressure after repeated 3 times.

In the step (2), start the heating device to heat up and stir, and the polymerization and pressure-holding process is specifically as follows: the initial setting of the heating device for polymerization is 200-270 ° C, and when the temperature in the kettle reaches 190-260 ° C, the pressure-holding reaction is performed for 1 to 3 hours, The holding pressure is 1.0～1.5Mpa, and the stirring speed is 100～120r/min.

The pressure relief in the step (2) is as follows: during the pressure holding process, the pressure is maintained within a certain voltage stabilization range by appropriate exhaust gas, and the temperature of the heating device is set at 220-300°C at the end of the pressure holding process while the pressure is relieved, and the pressure relief time is 0.5-1 h.

The normal pressure in the step (2) is specifically as follows: after the pressure relief is completed, the polymerization at normal pressure in the kettle is maintained for 2 to 5 hours, the temperature in the kettle is gradually raised to 240 to 280 ° C, and the stirring speed of the motor is adjusted to 50 to 70 r/min. .

In the step (2), vacuuming is: vacuuming by a vacuum pump, so that the vacuum degree in the kettle reaches 75～95kPa, the temperature in the kettle reaches 250～290℃, the whole process lasts for 0.5～1.5h, and the stirring speed of the motor is set to 15～ 30r/min.

In the step (2), before discharging, observe that the motor power or torque meets the requirements, stop stirring, pass nitrogen to normal pressure for reaction for 0.5h, and finally heat the discharge port and pressurize the discharge to obtain copolymerized nylon chips.

In the present invention, short carbon chain aliphatic nylon salt, semi-aromatic nylon salt, long carbon chain nylon salt, deionized water, molecular weight regulator and antioxidant are uniformly mixed into the polymerization kettle, heated to 190-260° C., Under the pressure of 1.0～1.5Mpa (gauge pressure), polymerize for 1～3h, then reduce the pressure to normal pressure for 2～5h; ; Finally, after passing nitrogen to normal pressure again for 10-30min, pressurized and discharged to obtain the product.

The invention provides an application of the ternary copolymerized nylon material, such as in the fields of automobiles, electrical and electronic, machinery, optics, sports, etc., and can be used as visual protective covers, isolation windows, optical protective glasses and various devices of various devices. Electronics, machinery and other fields.

beneficial effect

The present invention belongs to the modified preparation of nylon material, and obtained by melt copolymerization has the advantages of strong designability, stable and reliable quality of finished products (maintaining the same ratio of raw materials as the polymerization process to obtain stable product performance), high yield, and no production of A large amount of waste is discharged, and the material has the advantages of high strength, high impact toughness and high light transmittance.

It has better oil resistance, corrosion resistance, wear resistance and other properties than other transparent plastics, and can be widely used in automotive, electrical and electronic, machinery, optics, sports and other fields.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Caprolactam: Hunan Baling Petrochemical Co., Ltd.; Nylon 66 Salt: Germany BASF Co., Ltd.;

Nylon 612 salt: Jianhu Xinglong Nylon Co., Ltd.;

Antioxidant 1098: Tianjin Meishang Jiemei Technology Co., Ltd.

Nylon 6T salt: according to the molar mass ratio of terephthalic acid and hexamethylene diamine of 1.00:1.01, the control salt solution concentration is 40～60% mass ratio, add deionized water in the polymerization kettle, vacuumize and pass nitrogen to discharge air Then, turn on the heating device, the salt-forming temperature is 110-150°C, the stirring motor speed is 30-80r/min; the reaction time is 8-10h; after the salt-forming reaction is completed, a nylon 6T salt solution is obtained, which is cooled, crystallized and filtered. and vacuum drying to obtain nylon 6T salt.

Example 1

The vacuum-dried salts include: 1000g nylon 66 salt, 250g nylon 6T salt, 250g nylon 612 salt, 300ml deionized water, and 1.5g antioxidant 1098 into a 5L polymerization kettle. Firstly, the air in the kettle is discharged by vacuuming and passing nitrogen for 10min, and the heating is turned on to the pressure of 1.5Mpa in the kettle. At this time, the temperature is 200～230℃, and the motor speed is 120r/min; the pressure holding stage is started, and the time is 1h, and the pressure is maintained at 1.4 Between ～1.5Mpa; the time of exhausting to normal pressure at the end of pressure holding, time 0.5h, at this time, the temperature rises to 250～270℃; the normal pressure stage reaction is 2h, and the motor rotation speed is 50r/min; then reduced pressure polymerization 0.5h, Gradually evacuate to a negative pressure of 80-90kpa, the temperature is 260-290°C, and the number of motor revolutions is adjusted to 30r/min; finally, the stirring reaction is stopped for 10min and the pressure is discharged to obtain product slices.

Example 2

The vacuum-dried salts including: 1000g caprolactam, 250g nylon 6T salt, 250g nylon 612 salt, 500ml deionized water, 1.5g antioxidant 1098 were added to the 5L polymerization kettle. Firstly, the air in the kettle is discharged by vacuuming and passing nitrogen for 10min, and the heating is turned on to the pressure of 1.5Mpa in the kettle. At this time, the temperature is 200～230℃, and the motor speed is 120r/min; the pressure holding stage is started, and the time is 2h, and the pressure is maintained at 1.4 Between ～1.5Mpa; the time of exhausting to normal pressure at the end of pressure holding, time 0.5h, at this time the temperature rises to 240-260°C; normal pressure stage reaction for 4h, motor revolutions 50r/min; then reduced pressure polymerization for 1h, gradually Vacuum to a negative pressure of 80-90kpa, temperature at 250-270°C, and motor revolutions at 30r/min; finally, stop the stirring reaction for 10min and pressurize the material to obtain product slices.

Example 3

The vacuum-dried salts include: 800 g nylon 66 salt, 500 g nylon 6T salt, 200 g nylon 612 salt, 300 ml deionized water, and 1.5 g antioxidant 1098 into a 5L polymerization kettle. The polymerization process is the same as the implementation case 1.

Example 4

The vacuum-dried salts include: 800g nylon 66 salt, 200g nylon 6T salt, 500g nylon 612 salt, 300ml deionized water, and 1.5g antioxidant 1098 into a 5L polymerization kettle. The polymerization process is the same as the implementation case 1.

Example 5

The vacuum-dried salts include: 800 g caprolactam, 200 g nylon 6T salt, 500 g nylon 612 salt, 300 ml deionized water, and 1.5 g antioxidant 1098 into a 5L polymerization kettle. The polymerization process is the same as the implementation case 2.

Example 6

The vacuum-dried salts include: 800g caprolactam, 500g nylon 6T salt, 200g nylon 612 salt, 300ml deionized water, and 1.5g antioxidant 1098 into a 5L polymerization kettle. The polymerization process is the same as the implementation case 2.

Table 1: Performance table of copolymerized nylons of Examples 1 to 6

Claims (10)

1. a ternary copolymerization nylon material, is characterized in that, by weight, raw material component comprises: 2. nylon material according to claim 1, is characterized in that, described short carbon chain aliphatic nylon salt is one or more in caprolactam, nylon 66 salt, nylon 46 salt, nylon 56 salt; Semi-aromatic nylon The salt is one or more of nylon 4T salt, nylon 6T salt, nylon 9T salt and nylon 6I salt; long carbon chain nylon salt is one of nylon 610 salt, nylon 1010 salt, nylon 1012 salt, nylon 612 salt or several; molecular weight regulator is one or more of glacial acetic acid, dodecanedioic acid, adipic acid; antioxidant is dimethyl phthalate DMP, antioxidant 1098, antioxidant 1010, antioxidant One or more of oxidant SEED and phosphorous acid. 3. a preparation method of terpolymer nylon material, comprising: (1) By weight, mix 40-60 parts of short carbon chain aliphatic nylon salts, 10-40 parts of semi-aromatic nylon salts, 10-40 parts of long carbon chain nylon salts, and 10-30 parts of deionized water , 0～1 part of molecular weight regulator and 0.05～0.2 part of antioxidant are added to the polymerization kettle; (2) Seal the polymerization kettle, exhaust the air by vacuuming and pass nitrogen, start the heating device to heat up, stir, maintain pressure, release pressure, normal pressure, and vacuumize the polymerization reaction, and finally pass nitrogen to pressurize and discharge, that is, ternary Copolymer nylon material. 4. preparation method according to claim 3, is characterized in that, in described step (1), short carbon chain aliphatic nylon salt, semi-aromatic nylon salt, long carbon chain nylon salt are all processed through drying, specifically 50～ Dry in a vacuum drying oven at 80°C for 8 to 12 hours. 5. preparation method according to claim 3, is characterized in that, in the described step (2), evacuate and pass nitrogen to discharge air specifically: evacuate to 60～90kPa in the polymerization still, charge nitrogen to 0.3～0.5 in the polymerization still Mpa was repeated 3 times, and the pressure in the autoclave was maintained at normal pressure. 6. The preparation method according to claim 3, characterized in that in the step (2), the heating device is started to heat up and stir, and the pressure-holding is specifically: setting the heating device to be 200-270 °C, and when the temperature in the kettle reaches 190 °C ～260℃, hold pressure reaction for 1～3h, holding pressure is 1.0～1.5Mpa, and stirring speed is 100～120r/min. 7 . The preparation method according to claim 3 , wherein the pressure relief in the step (2) is as follows: after the pressure maintenance is completed, the temperature of the heating device is set at 220-300° C. and the pressure is released at the same time, and the pressure relief time is 0.5-1 h. 8 . 8. The preparation method according to claim 3, wherein the normal pressure in the step (2) is specifically: the normal pressure polymerization time is 2～5h, the temperature in the kettle is gradually raised to 240～280°C, and the motor stirring speed is adjusted It is 50～70r/min. 9. preparation method according to claim 3 is characterized in that, in the described step (2), vacuuming is: the final vacuum degree reaches 75～95kPa, the temperature in the kettle reaches 250～290 ℃, and the reaction time is 0.5～1.5h, The stirring speed is 15 to 30 r/min. 10. An application of the terpolymer nylon material of claim 1.