CN114806149A - Super-tough high-temperature-resistant nylon material and preparation method thereof - Google Patents
Super-tough high-temperature-resistant nylon material and preparation method thereof Download PDFInfo
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- CN114806149A CN114806149A CN202210652061.0A CN202210652061A CN114806149A CN 114806149 A CN114806149 A CN 114806149A CN 202210652061 A CN202210652061 A CN 202210652061A CN 114806149 A CN114806149 A CN 114806149A
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- BBJZBUKUEUXKDJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[1-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]hexyl]propanamide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1CCC(=O)NC(CCCCC)NC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BBJZBUKUEUXKDJ-UHFFFAOYSA-N 0.000 claims description 3
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
Abstract
The invention provides a super-tough high-temperature-resistant nylon material and a preparation method thereof, belongs to the field of high polymer materials, and can solve the technical problems of complex process, low solid-phase polycondensation efficiency, more byproducts, difficulty in quality control, irregular appearance and the like of the conventional high-temperature nylon preparation method. The preparation method comprises the following steps: the preparation method of the super-tough high-temperature-resistant nylon material comprises the following steps: drying and pretreating a nylon raw material; adding the pretreated raw materials into a frequency modulation rotary vacuum kettle, adding a solid phase tackifier and a toughening agent into the kettle body to carry out solid phase polycondensation, controlling the solid phase polycondensation time, temperature, vacuum degree and nitrogen purging amount, and cooling to obtain a solid phase polycondensate; and adding an antioxidant and a lubricant into the solid-phase polycondensate, and extruding and granulating by an extruder to obtain the super-tough high-temperature-resistant nylon material. The nylon material obtained by the invention has the characteristics of regular and compact appearance, low volatile content, excellent mechanical property, stable quality and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a super-tough high-temperature-resistant nylon material and a preparation method thereof.
Background
The temperature-resistant nylon materials prepared by the solid phase polycondensation method are various, mainly comprise PA5T, PA6T/6, PA6T/6I, PA6T/66, PA9T, PA10T and the like, and have good heat resistance, high temperature resistance, relatively low water absorption and excellent machining performance, so that the nylon materials are widely used in the industries of automobiles, electronic appliances, LEDs and the like.
The existing solid phase polycondensation for preparing high temperature nylon mostly adopts a 'two-step method' of 'prepolymerization-polycondensation', for example, Chinese patent applications CN101759853A, CN103923313A and the like adopt the method, but the method has more problems, for example, prepolymer residue can cause batch-to-batch mixing to influence the quality of solid phase polycondensate; in addition, the chinese patent application CN103539934A discloses a method for preparing high temperature resistant nylon by continuous copolymerization, which utilizes the problems of multiple process, high energy consumption, difficult control of the final product quality, etc. in the method, the dibasic acid, diamine and chain extender are prepolymerized into salt and then subjected to solid phase polycondensation, and the solid phase polycondensate is subjected to extrusion granulation and then subjected to solid phase tackifying.
In order to solve the above problems, a new preparation method has been proposed in recent years, and solid phase batch polycondensation is used to prepare high temperature nylon, for example, chinese patent applications CN101768266A, CN104817693A, CN104327265A, etc. all describe solid phase polycondensation to prepare high temperature nylon.
Therefore, the key point for solving the problems is to develop a preparation method which can reduce the preparation process, reduce the defective rate of solid-phase tackifying, improve the solid-phase polycondensation efficiency, reduce the generation amount of byproducts and ensure the regular appearance and quality of finished products.
Disclosure of Invention
Aiming at the technical problems of complex working procedures, low solid-phase polycondensation efficiency, more byproducts, difficult quality control, irregular appearance and the like of the conventional high-temperature nylon preparation method, the invention provides the super-tough high-temperature-resistant nylon material with simple preparation process, high solid-phase polycondensation efficiency, less byproducts and high finished product quality and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the preparation method of the super-tough high-temperature-resistant nylon material comprises the following steps:
drying the nylon raw material to obtain a pretreated raw material;
adding the pretreated raw materials into a frequency modulation rotary vacuum kettle, adding a solid-phase tackifier and a toughening agent into the kettle body to perform solid-phase polycondensation reaction, controlling the solid-phase polycondensation time, temperature, vacuum degree and nitrogen purging amount, and cooling to obtain a solid-phase polycondensate;
and adding an antioxidant and a lubricant into the solid-phase polycondensate, and extruding and granulating by an extruder to obtain the super-tough high-temperature-resistant nylon material.
In one embodiment, the nylon raw material is a high temperature resistant nylon raw material selected from polyterephthalamide or poly-m-phthalamide;
the solid phase adhesion promoter is selected from one or a combination of two of 4370-20, GY-0609, F-36, ADR4468, ADR4370, Zemac-L65, Zemac-L68, E60P and HK 8850;
the toughening agent is selected from any one or the combination of two of ethylene acrylic acid copolymer, maleic anhydride grafted ethylene octene copolymer MAH-g-POE, maleic anhydride functionalized ethylene octene copolymer MAH-g-POE or polyolefin elastomer grafted maleic anhydride POE-g-MAH;
the antioxidant is selected from any one or the combination of two of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, PW-9225B, BRUGGOLEN H10, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, H3337 and H161;
the lubricant is selected from HW-800P,
691. One or the combination of two of the materials of HyperC181, WE60, PETS-3 and PTFE-0141.
In one embodiment, the ethylene acrylic acid copolymer is A560, the maleic anhydride grafted ethylene octene copolymer MAH-g-POE is W1B, the maleic anhydride functionalized ethylene octene copolymer MAH-g-POE is FB521A, and the polyolefin elastomer grafted maleic anhydride POE-g-MAH is selected from any one or a combination of CM5805, N216, ST-1 or FZ-07.
In one embodiment, the addition amount of the toughening agent is 1-5% of the mass of the pretreatment raw material, and the mass ratio of the pretreatment raw material to the solid-phase tackifier is 1: (0.5-2), the addition amount of the antioxidant is 0.01-1% of the mass of the solid-phase polycondensation, and the addition amount of the lubricant is 0.05-1% of the mass of the solid-phase polycondensation.
In one embodiment, the drying treatment temperature is 100-120 ℃, the drying time is 6-8h, and the drying treatment device is selected from any one of an electric heating vacuum oven, an electric heating blast oven, a steam oven and a high-temperature oven.
In one embodiment, the solid phase polycondensation time is 1-3h, the temperature is 200-220 ℃, the vacuum degree is 1-3MPa, and the nitrogen purging amount is 1-5L/min.
In one embodiment, the pH of the solid phase polycondensate is controlled to be 8.0 to 9.5.
In one embodiment, the extrusion temperature of the extruder is 280-320 ℃, the vacuum degree is 0.05-0.08MPa, and the extrusion rotation speed is 4-6 HZ.
In one embodiment, the extruder is selected from any one of a single screw combination extruder or a twin screw combination extruder.
The invention also provides a super-tough high-temperature-resistant nylon material which is prepared by the preparation method of the super-tough high-temperature-resistant nylon material in any embodiment, and the intrinsic viscosity of the material is greater than 0.9dL/g after drying at the temperature of 100-120 ℃ for 4-6 h.
Compared with the prior art, the invention has the advantages and positive effects that:
1. according to the super-tough high-temperature-resistant nylon material and the preparation method thereof, provided by the invention, the preparation process can be reduced, the defective solid-phase tackifying rate can be reduced, the solid-phase polycondensation efficiency can be improved, meanwhile, the reaction temperature can be reduced by adding a proper toughening agent, the by-product generation amount can be reduced, and finally, the super-tough high-temperature-resistant nylon material obtained by extrusion and particle extraction is regular and compact in appearance, low in volatile content, excellent in mechanical property and stable in quality;
2. the super-tough high-temperature-resistant nylon material and the preparation method thereof provided by the invention solve the problems of more solid-phase polycondensation byproducts, difficulty in quality control, irregular appearance and the like;
3. the super-tough high-temperature-resistant nylon material provided by the invention is dried at the temperature of 100 ℃ and 120 ℃ for 4-6h, and then the test intrinsic viscosity is more than 0.9 dL/g.
Drawings
Fig. 1 is a drawing illustrating an extrusion granulation of a super-tough high temperature resistant nylon material according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, 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 obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The embodiment of the invention provides a preparation method of a super-tough high-temperature-resistant nylon material, which comprises the following steps:
s1, drying the nylon raw material to obtain a pretreated raw material;
s2, adding the pretreated raw materials into a frequency modulation rotary vacuum kettle, adding a solid-phase tackifier and a flexibilizer into the kettle body to perform solid-phase polycondensation, controlling the solid-phase polycondensation time, temperature, vacuum degree and nitrogen purging amount, and cooling to obtain a solid-phase polycondensate;
and S3, adding an antioxidant and a lubricant into the solid-phase polycondensate, and extruding and granulating through an extruder to obtain the super-tough high-temperature-resistant nylon material.
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, wherein the toughening agent and the tackifier added in the method are key materials for a toughening test, the toughening agent and the tackifier are key materials for the toughening test, functional groups of the toughening agent and the high-temperature-resistant nylon have polycondensation activity at a certain temperature and under a certain pressure, and the flexible toughening agent is connected to a chain segment of the high-temperature-resistant nylon through a condensation reaction. The tackifier (or chain extender) connects active groups at the grafting ends when condensation is carried out, so that the length and molecular weight of a molecular chain are increased, the viscosity of a system is increased, meanwhile, the antioxidant mainly prevents high-temperature active groups from being oxidized in the polycondensation process, and the lubricant mainly reduces the problems of local overheating and dispersion of the polycondensate due to the increase of the viscosity.
Further, the above examples define that the order of addition of raw materials is: the nylon material, the solid phase toughening agent, the antioxidant, the lubricant and the tackifier, wherein the antioxidant and the lubricant have a certain synergistic effect, the antioxidant prevents oxidation of active groups of materials from influencing the condensation rate, and the lubricant reduces friction of the materials from influencing the condensation rate by local overheating.
In a specific embodiment, the nylon raw material is a high-temperature resistant nylon raw material selected from polyterephthalamide or polymetaphenylene diamide, and specifically selected from any one or a combination of 501, TKR4350, N200, SLPPA1252, SLPPA M21, A1000 and A6000;
the solid phase tackifier is selected from any one or the combination of two of 4370-20 (a functional copolymer with ultrahigh epoxy content), GY-0609 (nylon and chemical fiber tackifier), F-36 (nylon chain extender and nylon tackifier), ADR4468 (Joncry ADR4468 as a German Basff chain extender), ADR4370 (polyester chain extender), Zemac-L65, Zemac-L68, Zemac-E60P (Zemac: ethylene maleic anhydride syndiotactic copolymer-chain extender) and HK8850 (chain extender),
the toughening agent is selected from any one or a combination of two of ethylene acrylic acid copolymer, maleic anhydride grafted ethylene octene copolymer MAH-g-POE, maleic anhydride functionalized ethylene octene copolymer MAH-g-POE or polyolefin elastomer grafted maleic anhydride POE-g-MAH;
the antioxidant is selected from any one or the combination of two of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, PW-9225B, BRUGGOLEN H10, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, H3337 and H161;
among the above antioxidants: n, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine as an antioxidant 1098, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] type 1010, N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate type 1076, PW-9225B as a main antioxidant AT-10, an auxiliary antioxidant AT-626 and a third component stabilizing chelating agent, the novel efficient antioxidant is prepared by fine processing, BRUGGOLEN H10 is powdered inorganic phosphate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene as an antioxidant AT-330, a hindered phenol antioxidant, H3337 is a mixture of organic copper salt and organic halogen, and H161 is a mixture of phenol antioxidant and auxiliary antioxidant.
The lubricant is selected from HW-800P (high temperature resistant wax with special molecular weight),
691(
691 is a modified synthetic polyester wax with properties similar to montan wax), HyperC181 (hyperbranched polyester polymeric domain), WE60 (Kelaien nylon lubricant WE60 synthetic wax), PETS-3 (pentaerythritol), PTFE-0141 (polytetrafluoroethylene), or a combination of two thereof
In a specific embodiment, the ethylene acrylic acid copolymer is A560, the maleic anhydride grafted ethylene octene copolymer MAH-g-POE is W1B, the maleic anhydride functionalized ethylene octene copolymer MAH-g-POE is FB521A, and the polyolefin elastomer grafted maleic anhydride POE-g-MAH is selected from any one or a combination of CM5805, N216, ST-1 or FZ-07.
In a specific embodiment, the addition amount of the toughening agent is 1% -5% of the mass of the pretreatment raw material, and the mass ratio of the pretreatment raw material to the solid-phase tackifier is 1: (0.5-2), the addition amount of the antioxidant is 0.01-1% of the mass of the solid-phase polycondensation, and the addition amount of the lubricant is 0.05-1% of the mass of the solid-phase polycondensation.
In a specific embodiment, the drying treatment temperature is 100-120 ℃, the drying time is 6-8h, and the drying treatment device is selected from any one of an electric heating vacuum oven, an electric heating blast oven, a steam oven and a high-temperature oven.
In a specific embodiment, the solid phase polycondensation time is 1-3h, the temperature is 200-220 ℃, the vacuum degree is 1-3MPa, and the nitrogen purging amount is 1-5L/min.
In one embodiment, the pH of the solid phase polycondensate is controlled to be from 8.0 to 9.5.
In a specific embodiment, the extrusion temperature of the extruder is 280-320 ℃, the vacuum degree is 0.05-0.08MPa, and the extrusion rotating speed is 4-6 HZ.
In a specific embodiment, the extruder is selected from any one of a single-screw combination extruder or a twin-screw combination extruder.
The invention also provides a super-tough high-temperature-resistant nylon material which is prepared by using the preparation method of the super-tough high-temperature-resistant nylon material in any embodiment, and the intrinsic viscosity is greater than 0.9dL/g after drying at the temperature of 100-120 ℃ for 4-6 h.
In order to more clearly and specifically describe the super tough high temperature resistant nylon material and the preparation method thereof provided by the embodiments of the present invention, the following description will be made with reference to specific embodiments.
Example 1
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes dupont 501 resin as a nylon raw material for illustration, and specifically comprises the following steps:
(1) a pretreatment stage: weighing 5Kg 501 resin, putting into a high-temperature oven, and drying at 105 ℃ for 4 h;
(2) solid phase polycondensation stage: weighing 4Kg of the dried 501 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 4370-20 Kg of solid phase tackifier, adding 40g of toughener A560, uniformly shaking a closed kettle cover, introducing 1L/min of nitrogen for purging for 3 times, adjusting the vacuum energy degree of a polycondensation kettle to 1MPa after the replacement is finished, carrying out polycondensation at the temperature of 200 ℃ for 6 hours, stopping the reaction, discharging the reaction product from the bottom of the polycondensation kettle, and controlling the pH to be 8.7;
(3) and (3) an extrusion granulation stage: 5Kg of the cooled polymer was weighed and added to 5g of 1098 antioxidant and 5g of PETS-3 lubricant by the following extrusion process using a single screw extruder:
table 1 example 1 single screw extruder extrusion process
(4) And (3) performance testing: drying the prepared extruded particles at 110 ℃ for 4h, and testing the intrinsic viscosity to be: 0.95 dL/g.
Example 2
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes an a1000 resin as a nylon raw material for illustration, and specifically comprises the following steps:
(1) a pretreatment stage: weighing 5Kg of A1000 resin, putting the A1000 resin into an electric heating blast oven, and drying the A1000 resin for 5 hours at 105 ℃;
(2) solid phase polycondensation stage: weighing 4Kg of the dried A1000 resin, adding the weighed 4Kg of the dried A1000 resin into a frequency modulation rotary vacuum kettle, sequentially adding 2Kg of solid phase tackifier E60P, adding 40g of toughening agent W1B, uniformly shaking a closed kettle cover, introducing 1.5L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of a polycondensation kettle to 1.5MPa after the replacement is finished, keeping the polycondensation temperature at 205 ℃, stopping the reaction after the polycondensation lasts for 8 hours, then discharging the reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 8.9;
(3) and (3) an extrusion granulation stage: 5.5Kg of the cooled condensate was weighed, 5.5g of an antioxidant H10 was added,
691 lubricant 5.5g, by twin screw extruder extrusion process according to the following table:
table 2 example 2 twin-screw extruder extrusion process
| Two regions/. degree.C | Three region/. degree.C | Four regions/. degree.C | Five regions/. degree.C | Six regions/. degree.C | Seven regions/. degree.C |
| / | 280 | 300 | 300 | 295 | 290 |
| Seven regions/. degree.C | Octal/. degree C | Nine regions/. degree.C | Head/. degree C | Rotational speed/HZ | Vacuum degree/MPa |
| 285 | 280 | 295 | 300 | 4.5 | 0.06 |
(4) And (3) performance testing: the prepared extruded granules were dried at 105 ℃ for 6h, and the test intrinsic viscosity was: 0.98 dL/g.
Example 3
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes TKR4350 resin as a nylon raw material as an example to explain, and specifically includes:
(1) a pretreatment stage: weighing 5Kg of TKR4350 resin, putting into an electric heating vacuum oven, and drying at 115 ℃ for 6 h;
(2) solid phase polycondensation stage: weighing 4.5Kg of the dried TKR4350 resin, adding the weighed dried TKR4350 resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.25Kg of solid-phase tackifier E60P, adding 45g of flexibilizer N216, shaking the closed kettle cover uniformly, introducing 2L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 2MPa after the replacement is finished, keeping the polycondensation temperature at 200 ℃, stopping the reaction after the polycondensation time is 8 hours, then discharging the reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 9.2;
(3) and (3) an extrusion granulation stage: weighing 8Kg of the cooled condensate, adding 8g of H3337 antioxidant and 8g of HW-800P lubricant, and performing the following extrusion process by a double-screw extruder according to the following table:
table 3 example 3 twin screw extruder extrusion process
| Two regions/. degree.C | Three region/. degree.C | Four regions/. degree.C | Five regions/. degree.C | Six regions/. degree.C | Seven regions/. degree.C |
| / | 280 | 285 | 305 | 305 | 295 |
| Region seven/. degree.C | Octal/. degree C | Nine regions/. degree.C | Head/. degree C | Rotational speed/HZ | Vacuum degree/MPa |
| 280 | 280 | 290 | 305 | 5.5 | 0.07 |
(4) And (3) performance testing: drying the prepared extruded particles for 3h at 120 ℃, and testing the intrinsic viscosity to be: 1.10 dL/g.
Example 4
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes SLPPA M21 resin as a nylon raw material for illustration, and specifically includes:
(1) a pretreatment stage: weighing 5.5Kg of SLPPA M21 resin, putting into an electric heating air-blowing oven, and drying at 120 ℃ for 4 h;
(2) solid phase polycondensation stage: weighing 5.5Kg of the dried SLPPA M21 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.75Kg of solid phase tackifier E60P, adding 55g of toughening agent FB521A, shaking the closed kettle cover uniformly, introducing 1.5L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 3MPa after the displacement is finished, keeping the polycondensation temperature at 200 ℃, stopping the reaction after the polycondensation time is 6 hours, then discharging the reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 9.3;
(3) and (3) an extrusion granulation stage: 9Kg of the cooled condensate was weighed into 9g of H161 antioxidant and 9g of HyperC181 lubricant, and extruded using a twin screw extruder as follows:
table 4 example 4 twin screw extruder extrusion process
| Two regions/. degree.C | Three region/. degree.C | Four regions/. degree.C | Five regions/. degree.C | Sixth zone/. deg.C | Seven regions/. degree.C |
| / | 280 | 295 | 300 | 300 | 295 |
| Seven regions/. degree.C | Octal/. degree C | Nine regions/. degree.C | Head/. degree C | Rotational speed/HZ | Vacuum degree/MPa |
| 280 | 280 | 295 | 300 | 5.0 | 0.07 |
(4) And (3) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h and tested to have an intrinsic viscosity of 1.30 dL/g.
Example 5
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes N200 resin as a nylon raw material as an example for explanation, and specifically includes:
(1) a pretreatment stage: weighing 5Kg of N200 resin, putting the N200 resin into an electric heating vacuum oven, and drying the N200 resin for 4 hours at 110 ℃;
(2) solid phase polycondensation stage: weighing 4.5Kg of the dried N200 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.25Kg of solid phase tackifier ADR4468, adding 45g of toughening agent CM5805, shaking the closed kettle cover uniformly, introducing 2L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 2MPa after the replacement is finished, keeping the polycondensation temperature at 200 ℃, stopping the reaction after the polycondensation time is 8 hours, then discharging the reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 9.5;
(3) and (3) an extrusion granulation stage: 8Kg of the cooled polymer was weighed and added with 8g of 9225B antioxidant and 8g of HW-800P lubricant, according to the following extrusion process of a single screw extruder:
table 5 example 5 single screw extruder extrusion process
(4) And (3) performance testing: drying the prepared extruded particles at 120 ℃ for 3h, and testing the intrinsic viscosity to be: 1.42 dL/g.
Comparative example 1
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes N200 resin as a nylon raw material as an example for explanation, and specifically includes:
(1) a pretreatment stage: weighing 5Kg of N200 resin, putting the N200 resin into an electric heating vacuum oven, and drying the N200 resin for 4 hours at 110 ℃;
(2) solid phase polycondensation stage: weighing 4.5Kg of the dried N200 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.25Kg of solid phase tackifier ADR4468, adding 90g of toughening agent CM5805, shaking the closed kettle cover uniformly, introducing 2L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 2MPa after the replacement is finished, stopping the reaction after the polycondensation temperature is 200 ℃ and the polycondensation time is 8 hours, and then discharging the reaction product from the bottom of the polycondensation kettle, wherein the pH value is controlled at 9.5;
(3) and (3) an extrusion granulation stage: weighing 5Kg of the cooled condensate, adding 10g of 1098 antioxidant and 10g of PETS-3 lubricant according to the extrusion process of a single screw extruder shown in the following table:
TABLE 6 COMPARATIVE EXAMPLE 1 Single screw extruder extrusion Process
(4) And (3) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h and had an intrinsic viscosity of 1.31 dL/g.
Comparative example 2
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes N200 resin as a nylon raw material as an example for explanation, and specifically includes:
(1) a pretreatment stage: weighing 5Kg of N200 resin, putting the N200 resin into an electric heating vacuum oven, and drying the N200 resin for 4 hours at 110 ℃;
(2) solid phase polycondensation stage: weighing 4.5Kg of the dried N200 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.25Kg of solid phase tackifier ADR4468, adding 135g of toughening agent CM5805, shaking the closed kettle cover uniformly, introducing 2L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 2MPa after the replacement is finished, stopping the reaction after the polycondensation temperature is 200 ℃ and the polycondensation time is 8 hours, and then discharging the reaction product from the bottom of the polycondensation kettle, wherein the pH value is controlled at 9.5;
(3) and (3) an extrusion granulation stage: weighing 5Kg of the cooled condensate, adding 10g of 1098 antioxidant and 10g of PETS-3 lubricant according to the extrusion process of a single screw extruder shown in the following table:
TABLE 7 COMPARATIVE EXAMPLE 2 Single screw extruder extrusion Process
(4) And (3) performance testing: the prepared extruded particles are dried at 110 ℃ for 4h, and the intrinsic viscosity is 1.21 dL/g.
Comparative example 3
The embodiment provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes N200 resin as a nylon raw material as an example for explanation, and specifically includes:
(1) a pretreatment stage: weighing 5Kg of N200 resin, putting the N200 resin into an electric heating vacuum oven, and drying the N200 resin for 4 hours at 110 ℃;
(2) solid phase polycondensation stage: weighing 4.5Kg of the dried N200 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.25Kg of solid phase tackifier ADR4468, adding 180g of toughening agent CM5805, shaking the closed kettle cover uniformly, introducing 2L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 2MPa after the replacement is finished, stopping the reaction after the polycondensation temperature is 200 ℃ and the polycondensation time is 8 hours, and then discharging the reaction product from the bottom of the polycondensation kettle, wherein the pH value is controlled at 9.5;
(3) and (3) an extrusion granulation stage: weighing 5Kg of the cooled condensate, adding 10g of 1098 antioxidant and 10g of PETS-3 lubricant according to the extrusion process of a single screw extruder shown in the following table:
TABLE 8 COMPARATIVE EXAMPLE 3 Single screw extruder extrusion Process
(4) And (3) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h with an intrinsic viscosity of 0.98 dL/g.
Comparative example 4
The comparative example provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes N200 resin as a nylon raw material as an example for explanation, and specifically comprises the following steps:
(1) a pretreatment stage: weighing 5Kg of N200 resin, putting the N200 resin into an electric heating vacuum oven, and drying the N200 resin for 4 hours at 110 ℃;
(2) solid phase polycondensation stage: weighing 4.5Kg of the dried N200 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.25Kg of solid phase tackifier ADR4468, adding 225g of toughening agent CM5805, shaking the closed kettle cover uniformly, introducing 2L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 2MPa after the replacement is finished, stopping the reaction after the polycondensation temperature is 200 ℃ and the polycondensation time is 8 hours, and then discharging the reaction product from the bottom of the polycondensation kettle, wherein the pH value is controlled at 9.5;
(3) and (3) an extrusion granulation stage: weighing 5Kg of the cooled condensate, adding 10g of 1098 antioxidant and 10g of PETS-3 lubricant according to the extrusion process of a single screw extruder shown in the following table:
TABLE 9 COMPARATIVE EXAMPLE 4 Single screw extruder extrusion Process
(4) And (3) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h with an intrinsic viscosity of 0.83 dL/g.
Comparative example 5
The comparative example provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes the SLPPA M21 resin as a nylon raw material for illustration, and specifically comprises the following steps:
(1) a pretreatment stage: weighing 5.5Kg of SLPPA M21 resin, putting into an electric heating air-blowing oven, and drying at 120 ℃ for 4 h;
(2) solid phase polycondensation stage: weighing 5.5Kg of the dried SLPPA M21 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.75Kg of solid phase tackifier E60P, adding 110g of toughening agent FB521A, uniformly shaking a closed kettle cover, introducing 1.5L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of a polycondensation kettle to 3MPa after the displacement is finished, keeping the polycondensation temperature at 200 ℃, stopping the reaction after the polycondensation time is 6 hours, then discharging a reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 9.3;
(3) and (3) an extrusion granulation stage: 9Kg of the cooled condensate was weighed into 9g of H161 antioxidant and 9g of HyperC181 lubricant, and extruded using a twin screw extruder as follows:
TABLE 10 COMPARATIVE EXAMPLE 5 twin-screw extruder extrusion Process
| Two regions/. degree.C | Three region/. degree.C | Four regions/. degree.C | Five regions/. degree.C | Six regions/. degree.C | Seven regions/. degree.C |
| / | 280 | 295 | 300 | 300 | 295 |
| Seven regions/. degree.C | Octal/. degree C | Nine regions/. degree.C | Head/. degree C | Rotational speed/HZ | Vacuum degree/MPa |
| 280 | 280 | 295 | 300 | 5.0 | 0.07 |
(4) And (3) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h and tested to have an intrinsic viscosity of 1.25 dL/g.
Comparative example 6
The comparative example provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes the SLPPA M21 resin as a nylon raw material for illustration, and specifically comprises the following steps:
(1) a pretreatment stage: weighing 5.5Kg of SLPPA M21 resin, putting into an electric heating air-blowing oven, and drying at 120 ℃ for 4 h;
(2) solid phase polycondensation stage: weighing 5.5Kg of the dried SLPPA M21 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.75Kg of solid phase tackifier E60P, adding 165g of toughening agent FB521A, shaking the closed kettle cover uniformly, introducing 1.5L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 3MPa after the displacement is finished, keeping the polycondensation temperature at 200 ℃, stopping the reaction after the polycondensation time is 6 hours, then discharging the reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 9.3;
(3) and (3) an extrusion granulation stage: 9Kg of the cooled condensate was weighed into 9g of H161 antioxidant and 9g of HyperC181 lubricant, and extruded using a twin screw extruder as follows:
TABLE 11 comparative example 6 twin-screw extruder extrusion Process
| Two regions/. degree.C | Three region/. degree.C | Four regions/. degree.C | Five regions/. degree.C | Six regions/. degree.C | Seven regions/. degree.C |
| / | 280 | 295 | 300 | 300 | 295 |
| Seven regions/. degree.C | Octal/. degree C | Nine blocks/. degree C | Head/. degree C | Rotational speed/HZ | Vacuum degree/MPa |
| 280 | 280 | 295 | 300 | 5.0 | 0.07 |
(4) And (3) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h and tested to have an intrinsic viscosity of 1.1 dL/g.
Comparative example 7
The comparative example provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes the SLPPA M21 resin as a nylon raw material for illustration, and specifically comprises the following steps:
(1) a pretreatment stage: weighing 5.5Kg of SLPPAM21 resin, putting the resin into an electric heating air-blowing oven, and drying for 4h at 120 ℃;
(2) solid phase polycondensation stage: weighing 5.5Kg of the dried SLPPA M21 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.75Kg of solid phase tackifier E60P, adding 220g of toughening agent FB521A, shaking the closed kettle cover uniformly, introducing 1.5L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of the polycondensation kettle to 3MPa after the displacement is finished, keeping the polycondensation temperature at 200 ℃, stopping the reaction after the polycondensation time is 6 hours, then discharging the reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 9.3;
(3) and (3) an extrusion granulation stage: 9Kg of the cooled condensate was weighed into 9g of H161 antioxidant and 9g of HyperC181 lubricant, and extruded using a twin screw extruder as follows:
TABLE 12 COMPARATIVE EXAMPLE 7 twin-screw extruder extrusion Process
| Two regions/. degree.C | Three region/. degree.C | Four regions/. degree.C | Five regions/. degree.C | Six regions/. degree.C | Seven regions/. degree.C |
| / | 280 | 295 | 300 | 300 | 295 |
| Seven regions/. degree.C | Eight regions/℃ | Nine regions/. degree.C | Head/. degree C | Rotational speed/HZ | Vacuum degree/MPa |
| 280 | 280 | 295 | 300 | 5.0 | 0.07 |
(4) And (3) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h and tested to have an intrinsic viscosity of 0.86 dL/g.
Comparative example 8
The comparative example provides a preparation method of a super-tough high-temperature-resistant nylon material, which takes SLPPA M21 resin as a nylon raw material for illustration, and specifically comprises the following steps:
(1) a pretreatment stage: weighing 5.5Kg of SLPPA M21 resin, putting into an electric heating air-blowing oven, and drying at 120 ℃ for 4 h;
(2) solid phase polycondensation stage: weighing 5.5Kg of the dried SLPPA M21 resin, adding the weighed resin into a frequency modulation rotary vacuum kettle, sequentially adding 2.75Kg of solid phase tackifier E60P, adding 275g of toughening agent FB521A, uniformly shaking a closed kettle cover, introducing 1.5L/min of nitrogen for purging for 3 times, adjusting the vacuum degree of a polycondensation kettle to 3MPa after the displacement is finished, keeping the polycondensation temperature at 200 ℃, stopping the reaction after the polycondensation time is 6 hours, then discharging a reaction product from the bottom of the polycondensation kettle, and controlling the pH value to be 9.3;
(3) and (3) an extrusion granulation stage: 9Kg of the cooled condensate was weighed into 9g of H161 antioxidant and 9g of HyperC181 lubricant, and extruded using a twin screw extruder as follows:
TABLE 13 comparative example 8 twin-screw extruder extrusion Process
| Two regions/. degree.C | Three region/. degree.C | Four regions/. degree.C | Five regions/. degree.C | Six regions/. degree.C | Seven regions/. degree.C |
| / | 280 | 295 | 300 | 300 | 295 |
| Seven regions/. degree.C | Octal/. degree C | Nine regions/. degree.C | Head/. degree C | Rotational speed/HZ | Vacuum degree/MPa |
| 280 | 280 | 295 | 300 | 5.0 | 0.07 |
(4) And (4) performance testing: the prepared extruded particles were dried at 110 ℃ for 4h and tested to have an intrinsic viscosity of 0.79 dL/g.
Performance testing
The invention performs physical property characterization and performance test on the super-tough high-temperature-resistant nylon material samples prepared in the above embodiments and comparative examples, and the characterization equipment and test standards are shown in the following table:
TABLE 14 test items, test equipment, and test standards
TABLE 15 results of performance test of examples and comparative examples
Table 16 comparative example performance test results
As can be seen from the data in the above table, the comprehensive index of the polycondensate subjected to extrusion granulation after solid phase polycondensation is superior to the index of the polycondensate not subjected to solid phase polycondensation in the comparative example, and the intrinsic viscosity of the nylon material obtained by the preparation method provided by the invention can reach 1.30dL/g at most. Therefore, the super-tough high-resistant nylon material and the preparation method thereof have the characteristics of simple treatment process, easy control of process parameters, simple process operation and the like, and the material has the characteristics of regular and compact appearance, low volatile content, excellent mechanical property, stable quality and the like.
Claims (10)
1. The preparation method of the super-tough high-temperature-resistant nylon material is characterized by comprising the following steps of:
drying the nylon raw material to obtain a pretreated raw material;
adding the pretreated raw materials into a frequency modulation rotary vacuum kettle, adding a solid-phase tackifier and a toughening agent into the kettle body to perform solid-phase polycondensation reaction, controlling the solid-phase polycondensation time, temperature, vacuum degree and nitrogen purging amount, and cooling to obtain a solid-phase polycondensate;
and adding an antioxidant and a lubricant into the solid-phase polycondensate, and extruding and granulating by an extruder to obtain the super-tough high-temperature-resistant nylon material.
2. The method for preparing the super-tough high-temperature-resistant nylon material according to claim 1, wherein the nylon raw material is a high-temperature-resistant nylon raw material selected from polyterephthalamide or polyisophthalamide;
the solid phase adhesion promoter is selected from one or a combination of two of 4370-20, GY-0609, F-36, ADR4468, ADR4370, Zemac-L65, Zemac-L68, E60P and HK 8850;
the toughening agent is selected from any one or the combination of two of ethylene acrylic acid copolymer, maleic anhydride grafted ethylene octene copolymer MA H-g-POE, maleic anhydride functionalized ethylene octene copolymer MAH-g-POE or polyolefin elastomer grafted maleic anhydride POE-g-MAH;
the antioxidant is selected from any one or the combination of two of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, PW-9225B, BRUGGOLEN H10, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, H3337 and H161;
the lubricant is selected from HW-800P,
One or a combination of two of the components of HyperC181, WE60, PE TS-3 and PTFE-0141.
3. The method for preparing super tough high temperature resistant nylon material according to claim 2, wherein the ethylene acrylic acid copolymer is a560, the maleic anhydride grafted ethylene octene copolymer MAH-g-POE is W1B, the maleic anhydride functionalized ethylene octene copolymer MAH-g-POE is FB521A, and the polyolefin elastomer grafted maleic anhydride POE-g-MAH is selected from any one or combination of CM5805, N216, ST-1 or FZ-07.
4. The preparation method of the super-tough high-temperature-resistant nylon material according to claim 1, wherein the addition amount of the toughening agent is 1-5% of the mass of the pretreatment raw material, and the mass ratio of the pretreatment raw material to the solid-phase tackifier is 1: (0.5-2), the addition amount of the antioxidant is 0.01-1% of the mass of the solid-phase polycondensation, and the addition amount of the lubricant is 0.05-1% of the mass of the solid-phase polycondensation.
5. The method as claimed in claim 1, wherein the drying temperature is 100-120 ℃, the drying time is 6-8h, and the drying device is selected from any one of an electrothermal vacuum oven, an electrothermal blowing oven, a steam oven and a high temperature oven.
6. The method for preparing the super tough high temperature resistant nylon material as claimed in claim 1, wherein the solid phase polycondensation time is 1-3h, the temperature is 200-220 ℃, the vacuum degree is 1-3MPa, and the nitrogen purging amount is 1-5L/min.
7. The method for preparing super tough high temperature resistant nylon material according to claim 1, wherein the pH of the solid phase condensation polymer is controlled to 8.0-9.5.
8. The method as claimed in claim 1, wherein the extrusion temperature of the extruder is 280-320 ℃, the vacuum degree is 0.05-0.08MPa, and the extrusion speed is 4-6 HZ.
9. The method for preparing the super tough high temperature resistant nylon material according to claim 1, wherein the extruder is selected from any one of a single-screw combined extruder and a double-screw combined extruder.
10. The super-tough high-temperature-resistant nylon material is characterized by being prepared by the preparation method of the super-tough high-temperature-resistant nylon material as claimed in any one of claims 1 to 9, and the inherent viscosity of the super-tough high-temperature-resistant nylon material is greater than 0.9dL/g after being dried at the temperature of 100 ℃ and 120 ℃ for 4 to 6 hours.
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| CN113698759A (en) * | 2021-08-26 | 2021-11-26 | 金旸（厦门）新材料科技有限公司 | Reinforced and toughened high-temperature-resistant nylon material and preparation method thereof |
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| US20130338274A1 (en) * | 2012-06-13 | 2013-12-19 | E I Du Pont De Nemours And Company | Thermoplastic melt-mixed compositions with epoxy-amine heat stabilizer |
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