CN112759760A - High-temperature and low-temperature aging resistant toughened polyamide 5X resin and preparation method thereof - Google Patents
High-temperature and low-temperature aging resistant toughened polyamide 5X resin and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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Abstract
The invention discloses a high and low temperature aging resistant toughened polyamide 5X resin, and a preparation method and application thereof. The polyamide 5X resin is terminated by the fatty diacid containing the flexible chain in the polymerization process, and the content of terminal amino groups in the polyamide resin can be reduced, so that the yellowing resistance of the obtained polyamide resin at high temperature in the subsequent processing and injection molding processes is obviously improved, and the aging resistance is good. The formed product prepared by the polyamide 5X resin of the invention has good strength performance and high and low temperature resistance, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of resin synthesis, and particularly relates to high and low temperature aging resistant toughened polyamide 5X resin, and a preparation method and application thereof.
Background
Polyamide resins are excellent in heat resistance, chemical resistance, weathering resistance, mechanical properties, electrical properties, and the like, and are therefore generally used in various industrial applications as injection molding materials, fibers, and films.
However, since the crystalline property is high, if the molded article is injection molded into a thin-walled molded article or a molded article having a non-uniform wall thickness and a complicated shape, warpage occurs and the molded article is deformed. In general, attempts have been made to improve such problems by mixing various inorganic particles, but there are problems that the surface appearance of the product is impaired, anisotropy occurs due to the orientation of fibrous inorganic substances, and the molded body is deformed.
If the subsequent modification is carried out, addition of auxiliary materials such as a toughening agent and a stabilizer requires a separate step or the steps become complicated, and therefore, improvement is desired in the polymerization stage so as to obtain a polyamide resin which has good physical properties and is free from warpage during injection molding. Meanwhile, in the field of engineering plastics, the polyamide needs the defects that engineering parts are easy to brittle fracture at high and low temperatures, the ageing phenomenon is serious after long-term use, the mechanical property retention rate is low at high temperature, and the like.
CN109705342A adopts monofunctional isocyanate to terminate, so that the content of terminal carboxyl and terminal amino in polyamide resin is reduced, however, since isocyanate is easy to generate self-polymerization reaction to form dimer or high molecular weight polymer, impurities are easy to be introduced into polyamide resin, thereby influencing the mechanical property of polyamide.
At present, the research and development of polyamide 5X resin with good high and low temperature aging resistance and toughness performance still remains a problem to be solved urgently in the prior art.
Disclosure of Invention
In order to solve the defects of the prior art and products, the invention provides a polyamide PA5X resin, a preparation method and application thereof.
After intensive research, the inventor of the invention finds that the resin turns yellow due to the fact that a plurality of terminal carboxyl groups and terminal amino groups are remained at the tail end when the polyamide polymerization is completed, particularly the terminal amino groups are easily oxidized at high temperature or oxidized by nitrogen oxide in air to generate yellow substances, and the polyamide resin is terminated by the fatty dibasic acid containing the flexible chain in the polymerization process, so that the content of the terminal amino groups in the polyamide resin can be reduced, and the yellowing resistance of the obtained polyamide resin at high temperature in the subsequent processing and injection molding processes is obviously improved, and the aging resistance is good.
Specifically, the invention provides polyamide PA5X resin, wherein the raw materials of the polyamide PA5X resin comprise 20-80 parts by weight of dibasic acid, 20-80 parts by weight of pentanediamine and 0.1-2 parts by weight of an end-capping agent, wherein the end-capping agent is selected from fatty dibasic acid with the carbon atom number larger than that of the dibasic acid.
In some preferred embodiments of the present invention, the raw materials of the polyamide PA5X resin include pentanediamine and dibasic acid, the pentanediamine can be chemically or biologically derived pentanediamine, preferably biologically derived 1, 5-pentanediamine; and/or the presence of a gas in the gas,
the dibasic acid is selected from one of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid, and is preferably one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid; and/or the presence of a gas in the gas,
the end capping agent is selected from at least one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid and eicosanedioic acid; and/or the presence of a gas in the gas,
the polyamide PA5X resin raw material further comprises 0.01-0.1 weight part of antioxidant, preferably, the antioxidant is selected from at least one of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, antioxidant H10, manganese hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite, and most preferably is calcium hypophosphite.
In some preferred embodiments of the present invention, the difference between the number of carbon atoms contained in the end-capping agent and the number of carbon atoms contained in the dibasic acid is 2 or more.
According to a preferable technical scheme of the invention, the polyamide PA5X resin comprises 30-60 parts by weight of dibasic acid, 30-60 parts by weight of pentamethylene diamine, 0.01-0.097 part by weight of antioxidant and 0.2-1.8 part by weight of end-capping reagent.
In some preferred embodiments of the present invention, the mass of the end-capping agent is 0.5 to 2.0 wt.% of the total mass of the polyamide PA5X resin, for example, the mass of the end-capping agent is 0.5 wt.%, 0.8 wt.%, or 1.0 wt.% of the polyamide PA5X resin.
In some preferred embodiments of the present invention, the polyamide 5X resin further comprises an additive. Such additives include, but are not limited to: any one or more of coupling agent, chain extender, heat-resistant stabilizer, weather-resistant agent, hydrolysis-resistant stabilizer, reinforcing agent, toughening agent, pigment, gloss enhancer, dye, crystal nucleating agent, delustering agent, plasticizer, antistatic agent, flame retardant, catalyst and anti-UV agent.
As a preferred embodiment, the polyamide resin may further include an additive in an amount of 0.1 to 1 wt.% based on the total mass of the raw material dibasic acid, in addition to the polyamide 5X resin.
Specifically, the additive is selected from one or more of a coupling agent, a plasticizer, a chain extender, an anti-hydrolysis stabilizer, a reinforcing agent, a delustering agent, a defoaming agent, a flame retardant, a crystallization nucleating agent and a pigment, and the mass of the additive accounts for 0.1-0.5 wt% of the total mass of the raw material dibasic acid.
Further, the hydrolysis-resistant stabilizer, reinforcing agent, delustering agent, flame retardant, crystallization nucleating agent, pigment in the additive may be those conventionally used in the art as long as the effect of the polyamide resin of the present invention is not adversely affected.
According to a preferable technical scheme of the invention, the yellow index YI value of the polyamide 5X resin is 1.0-5.0, and preferably 1.0-3.0.
According to a preferable technical scheme of the invention, the content of the terminal amino groups of the polyamide 5X resin is 20-70 mol/ton, and preferably 30-60 mol/ton.
In some preferred embodiments of the present invention, the polyamide PA5X has a relative viscosity of 1.6 to 3.4.
In some preferred embodiments of the present invention, the polyamide PA5X resin has a tensile strength of 55 to 125MPa, more preferably 75 to 115 MPa.
In some preferred embodiments of the present invention, the flexural strength of the polyamide PA5X resin is 65 to 125MPa, and more preferably 80 to 130 MPa.
In some preferred embodiments of the invention, the polyamide PA5X resin has a notched impact strength, measured at 23 ℃ in accordance with ISO180-2001, of greater than 5.0KJ/m2More preferably, it is more than 5.5KJ/m2For example, 5.0 to 8.5KJ/m2Or 5.5 to 7.0KJ/m2。
In some preferred embodiments of the invention, the polyamide PA5X resin has a notched impact strength, measured at-60 ℃ in accordance with ISO180-2001, of greater than 4.0KJ/m2More preferably, it is more than 5.0KJ/m2For example, 4.0 to 7.0KJ/m2Or 5.0 to 6.0KJ/m2。
In some preferred embodiments of the invention, the polyamide PA5X resin has a notched impact strength, measured at 150 ℃ in accordance with ISO180-2001, of greater than 4.5KJ/m2More preferably, it is more than 5.0KJ/m2For example, 4.5 to 7.5KJ/m2Or 5.0 to 6.5KJ/m2。
The present invention provides a method for preparing the polyamide 5X resin, the method comprising the steps of:
carrying out amidation reaction on dibasic acid and 1, 5-pentanediamine in the presence of an end-capping agent to obtain a polyamide resin melt, and after the melt is discharged, carrying out strand cutting and dicing to obtain the polyamide PA5X resin.
According to a preferred embodiment of the invention, the starting material of the polyamide PA5X resin further comprises an antioxidant, in particular the antioxidant may be added to the starting material at various stages, for example, before the amidation reaction is started, the antioxidant is added to the reaction vessel. According to a preferred embodiment of the invention, the method comprises the steps of:
(1) under the condition of nitrogen, 1, 5-pentanediamine, dibasic acid and water are uniformly mixed to prepare a nylon salt solution, and an antioxidant and a blocking agent are added into the nylon salt solution; wherein the molar ratio of the 1, 5-pentanediamine to the dibasic acid is (1-1.05): 1;
(2) heating, wherein the pressure in the reaction system is increased to 0.3-2.0 Mpa, the time is controlled to be 1.5-2.0 h, exhausting and maintaining the pressure, the temperature of the reaction system is 232-265 ℃ when the pressure maintaining is finished, then reducing the pressure to 0-0.2 MPa (gauge pressure), the temperature of the reaction system is 245-280 ℃ after the pressure reducing is finished, and vacuumizing to obtain a polyamide melt;
(3) discharging the melt obtained in the step (2), and carrying out bracing and dicing.
Preferably, in the step (1), the concentration of the nylon salt solution prepared by uniformly mixing 1, 5-pentanediamine, dibasic acid and water is 55-65 wt.%, and the percentage is the mass percentage of the nylon salt solution.
Preferably, the step (1) further comprises adding an antioxidant, and after the end-capping reagent is added, adjusting the pH value of the polyamide salt solution to be 7.80-8.20 when the concentration of the polyamide salt solution is 10 wt.%, wherein the percentage is the mass percentage of the nylon salt solution.
Preferably, in the step (1), the antioxidant is used for improving the anti-aging performance of the polyamide slices, and is selected from at least one of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, antioxidant H10, manganese hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite, and is most preferably calcium hypophosphite.
In some preferred embodiments of the present invention, the antioxidant is preferably added in an amount of 100 to 800 ppm by mass, more preferably 200 to 600 ppm by mass, relative to the mass of the nylon salt in the nylon salt solution, when the polyamide 5X resin of the present invention is polymerized;
further, the end-capping agent comprises any one or a combination of more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecane diacid and eicosanedioic acid, and preferably, the end-capping agent is sebacic acid.
In some preferred embodiments of the present invention, the addition amount of the end-capping agent is preferably 0.2% to 1.2 wt.%, more preferably 0.3% to 0.8 wt.%, relative to the mass of the nylon salt in the nylon salt solution.
The addition of a proper amount of the end-capping agent containing a flexible chain is beneficial to increasing the content of flexible groups in the polyamide 5X resin, so that the bending resistance of the polyamide 5X resin is improved, and the polyamide 5X resin has excellent toughness; if the content of the terminal-blocking agent containing a flexible chain is too large, the crystalline properties of the polyamide 5X resin are deteriorated, resulting in a decrease in the mechanical properties of the polyamide 5X resin.
Preferably, in the step (2), the relative vacuum degree is-0.01 MPa to-0.09 MPa, the vacuum time is maintained for 15-75 min, the vacuum finishing temperature is controlled at 265-275 ℃,
preferably, in the step (3), the pelletizing is carried out in water, the water temperature is 20-50 ℃, the rotation speed of a roller is 500-800 rpm, and the pelletizing time is 20-45 min.
In another aspect of the present invention, there is provided a molded article obtained from the above polyamide 5X resin as a raw material.
The molded article may further contain other conventional additives selected from the group consisting of: inorganic stabilizers, antioxidants, organic stabilizers, lubricants, pigments, metallic flaks, metal-coated particles, halogen-containing flame retardants, halogen-free flame retardants, impact modifiers, antistatic agents, conductivity additives, mold release agents, optical brighteners, natural sheet silicates, synthetic sheet silicates, or mixtures of the foregoing additives.
Another aspect of the present invention provides a method for producing a molded article from the above polyamide 5X resin, using injection molding, extrusion, pultrusion, blow molding or other shaping techniques.
Compared with the prior art, the implementation of the invention has at least the following advantages:
1. the polyamide 5X resin synthesized by the method has good high and low temperature resistance, can be well applied to a high-temperature area, can completely meet the requirement of use in a high-temperature environment of 135 ℃, and is particularly suitable for occasions with high requirements on the high and low temperature resistance of nylon, such as automobiles, aerospace, electronic appliances and the like.
2. The polyamide 5X disclosed by the invention has good toughness, particularly has good toughness under both low temperature and high temperature notch impact, and can be applied to the fields of aerospace, automobiles, electrical equipment, mechanical parts and the like which need toughening materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
1. Method for detecting relative viscosity eta r
Concentrated sulfuric acid method with Ubbelohde viscometer: a dried polyamide sample (0.5. + -. 0.0002 g) was accurately weighed, dissolved in 50mL of concentrated sulfuric acid (98%), measured in a thermostatic water bath at 25 ℃ and the time t of passage of the concentrated sulfuric acid was recorded0And the polyamide solution flowing time t.
Relative viscosity calculation formula:
relative viscosity η r ═ t/t0
Wherein: t: the time of solution flow; t is t0: the solvent was run through time.
2. Method for detecting content of terminal amino group
After the sample is dissolved by using trifluoroethanol, titrating by using hydrochloric acid standard solution and sodium hydroxide standard solution respectively, and calculating.
3. The molecular weight and the detection method comprise the following steps:
the number average molecular weight of the main peak (polymer peak) in the elution curve was calculated from the elution curve (vertical axis: signal intensity by detector, horizontal axis: elution time) of each sample obtained by Gel Permeation Chromatography (GPC) based on the calibration of a standard sample, polymethyl methacrylate (PMMA), and the measurement was performed under the following conditions.
A detector: RI detector
A chromatographic column: 2 × PSS 7 μ PFG Linear M column 300 × 8.0mm solvent: hexafluoroisopropanol containing sodium trifluoroacetate at a concentration of 0.05 mol/L
Temperature: 40 deg.C
Flow rate: 1mL/min
Injection amount: 100 μ L
Concentration: 3 to 5g/L
Sample preparation: the polyamide resin or the polyamide resin composition obtained in each example and the like was weighed in hexafluoroisopropanol containing 0.01 mol/L of sodium trifluoroacetate so as to be 0.5mg/mL in terms of the polyamide resin, and dissolved by stirring at room temperature for 1 hour, and the resulting solution was filtered through a hydrophobic membrane filter (pore size: 0.22 μm) to prepare a sample.
PMMA standard: a STANDARD elution curve (calibration curve) was prepared using STANDARD81506-1EA (number average molecular weight range: 500-27000000) prepared by Fluka.
4. Yellow Index (YI)
Testing according to HG/T3862.
5. Tensile strength
The tensile rate at the time of the test was 50mm/min as determined according to ISO 527-2.
6. Bending strength
The test conditions were 2mm/min, determined according to ISO 178.
7. Notched impact strength
And (3) testing the notch impact strength of the material by adopting a cantilever beam pendulum bob impactor. The impact strength was determined according to ISO180-2001 method, notch depth 2mm, pendulum energy 2.75J.
8. The heat resistance is determined according to the standard of section 9.5 in UL62275, the target temperature required by the UL62275 standard is 105 ℃/135 ℃, and the difference between the experiment and the UL62275 standard is as follows: humidity at 120 ℃/150 ℃: and (3) under the environment of 50 +/-5, carrying out a tensile strength test after aging for 1000 hours and standing for 21 days at normal temperature, and calculating the tensile strength retention rate before and after the aging test.
9. The high and low temperature resistance test method comprises the following steps:
(1) testing equipment: a vertical high-temperature oven and a cold and hot impact test box;
(2) the test method comprises the following steps: adding distilled water according to the proportion of 2.5 percent of the mass percent of the nylon sample strip, sealing by a PE film bag in a heat sealing way, detecting the high temperature resistance, the low temperature resistance and the tripping force after placing for 7 days, and recording the result.
And (3) high temperature resistance test: and (3) placing the product in an oven at 150 ℃ for 72h, wherein the surface of the product has no crack, and the product is qualified if the product is manually bent at 90 degrees and has no fracture, otherwise, the product is unqualified.
And (3) low temperature resistance test: and (3) placing the product in a cold and hot impact test box at the temperature of-40 ℃ for 72h, marking the product as qualified if the product has no crack after being manually bent at 90 degrees and has no fracture, and otherwise marking the product as unqualified.
10. Bending resistance experiment test method
(1) Testing equipment: a constant temperature and humidity test chamber;
(2) the test method comprises the following steps: a bandage (3.0X 180mm, thickness 1.5mm) formed by injection molding of polyamide 5X resin is sealed in an aluminum plastic packaging bag and placed in a constant temperature and humidity test box with the temperature of 25 +/-2 ℃ and the relative humidity of 60 +/-5% RH for 1 h. Then, 50 bands made of the same polyamide 5X resin were tested as a set, wherein the gear face of the bands was manually folded in half toward the outside for a total of 5 times at every interval of the bands, and if one breakage or crack occurred in the bands, the band was counted as 1 band breakage.
And counting the number of the brittle-broken ribbons in the ribbon group, and calculating the proportion of the number of the broken ribbons in a group of 50 ribbons to obtain the brittle failure rate. If the brittle failure rate is less than 5 percent, the polyamide 5X resin is marked as qualified, otherwise, the polyamide 5X resin is marked as unqualified.
1, 5-Pentanediamine, Decanedioic acid, tetradecanedioic acid, and octadecanedioic acid were obtained from Kaiser (Jinxiang) biomaterials Co., Ltd., and adipic acid was obtained from Chemicals, Inc., national drug group. Other raw materials and reagents such as calcium hypophosphite and sodium hypophosphite can be prepared by methods known in the literature or can be commercially available.
Example 1
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of calcium hypophosphite and 0.5% of sebacic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, and after uniform mixing, the pH value is adjusted to 7.97 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure to 268 ℃ after the pressure reducing is finished and the pressure for 1 h. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 273 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 25 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 20 min.
The polyamide 56 resin obtained was subjected to a relative viscosity test, and the result was 2.75. The amino end group test result is 52.4 mol/ton; yellowness index YI result was 2.45; the number average molecular weight of the polyamide 56 resin was obtained by GPC measurement54062, respectively; and the polyamide 56 resin is tested for tensile strength of 102.4MPa by adopting an ISO 527-2 method, bending strength of 125.5MPa by adopting an ISO 178 method and notched impact strength (23 ℃) of 6.8KJ/m by adopting an ISO180-2001 method2The notched impact strength (-60 ℃) was measured according to ISO180-2001 at 5.4KJ/m2Notched impact strength (150 ℃ C.) of 5.8KJ/m was measured according to ISO180-20012The test results are shown in Table 1.
Example 2
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 600 mass ppm of calcium hypophosphite and 0.8% of sebacic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, after uniform mixing, the pH value is adjusted to be 7.92 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure for 1h at 264 ℃ after the pressure reducing is finished. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 272 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Example 3
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of calcium hypophosphite and 1.0% of sebacic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, and after uniform mixing, the pH value is adjusted to be 7.94 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure maintaining time to 3 h, reducing the pressure to 265 ℃ after the pressure reducing is finished, and reducing the pressure for 1 h. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 273 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Example 4
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of sodium hypophosphite and 0.5 percent of octadecanedioic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, and after uniform mixing, the pH value is adjusted to 7.93 when the concentration of the nylon salt solution is 10 percent, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, reducing the pressure to 265 ℃ after the pressure reducing is finished, and reducing the pressure for 1 h. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 275 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Example 5
(1) Under the condition of nitrogen, 1, 5-pentanediamine, dodecanedioic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the dodecanedioic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, then 300 mass ppm of calcium hypophosphite and 0.8 percent of tetradecanedicarboxylic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, and after uniform mixing, the pH value of the nylon salt solution is adjusted to be 7.93 when the concentration of the nylon salt solution is 10 percent, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure is reduced to 3 h after the pressure is maintained, and reducing the temperature of the reaction system to 262 ℃ after the pressure is reduced, wherein the pressure is reduced for 1 h. Vacuumizing at-0.05 Mpa for 30min at 274 deg.C.
(3) Melting, discharging, bracing and dicing to obtain polyamide 512 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 512 resin obtained was subjected to the relevant tests, and the results of the measurements are shown in tables 1 and 2.
Example 6
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of calcium hypophosphite, 0.5 mass percent of dodecanedioic acid and 0.5 mass percent of tetradecanedioic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, and after uniform mixing, the pH value of the nylon salt solution with the concentration of 10 percent is adjusted to be 7.93, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, reducing the pressure to 265 ℃ after the pressure reducing is finished, and reducing the pressure for 1 h. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 275 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Example 7
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of calcium hypophosphite (relative to the mass of the nylon salt in the nylon salt solution) is added into the nylon salt, and after uniform mixing, the pH value of the nylon salt solution is adjusted to be 7.97 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure to 268 ℃ after the pressure reduction is finished and the pressure for 1 h; adding 0.5% sebacic acid (relative to the mass of nylon salt in the nylon salt solution) through a feeding port under the protection of nitrogen, stirring for 5min, and vacuumizing; vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 273 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 25 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 20 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Example 8
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 0.5 percent of sebacic acid (relative to the mass of the nylon salt in the nylon salt solution) is added into the nylon salt, and after uniform mixing, the pH value of the nylon salt solution is adjusted to be 7.97 when the concentration of the nylon salt solution is 10 percent, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure to 268 ℃ after the pressure reducing is finished and the pressure for 1 h. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 273 deg.C.
(3) Melting, discharging, feeding into a melt pump, uniformly adding 300 mass ppm (relative to the mass of the nylon salt in the nylon salt solution) of antioxidant calcium phosphite into the melt of the polyamide 56 by weight, and carrying out bracing and granulating to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 25 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 20 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Comparative example 1
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, the pH value is 7.92 when the concentration of the nylon salt solution is adjusted to 10%, and the percentage is the mass percentage of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure for 1h at 264 ℃ after the pressure reducing is finished. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 272 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Comparative example 2
1461.4g of adipic acid, 1138.9g of hexamethylenediamine, 1g of catalyst sodium hypophosphite and 1600g of deionized water are weighed and added into a high-pressure reaction kettle, the high-pressure reaction kettle is vacuumized and filled with nitrogen, the steps are repeated for three times to remove residual air in the reaction kettle, and after the replacement is finished, the high-pressure reaction kettle keeps the micro-positive pressure of 25 kPa.
Heating the high-pressure reaction kettle to 80 ℃ under the stirring condition of 100r/min, reacting at a constant temperature for 1.5h, then continuously heating to 220 ℃, continuously increasing the temperature while starting to enable the interior of the high-pressure reaction kettle to be in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle after the pressure reaches 2.0MPa, and slowly releasing the pressure of the high-pressure reaction kettle to the normal pressure within 1.5h when the temperature is increased to 275 ℃.
And (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 0.8MPa, extruding, bracing and cutting the materials from a die head to obtain PA66 polyamide resin particles.
5g of m-toluene isocyanate is dissolved in 200mL of N, N-dimethylformamide, and then the prepared PA66 polyamide resin particles (the mass ratio of the m-toluene isocyanate to the PA66 polyamide resin particles is 1:450) are added, the temperature is raised to 90 ℃, the mixture is stirred for 5 hours, a Buchner funnel is vacuumized and filtered, and the mixture is dried in a vacuum oven at 80 ℃ for 10 hours, so that the anti-yellowing PA66 polyamide resin is obtained, and the performance test results are shown in tables 1 and 2.
Comparative example 3
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 2000 mass ppm of calcium hypophosphite and 0.5% of sebacic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, after uniform mixing, the pH value is adjusted to be 7.92 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure for 1h at 264 ℃ after the pressure reducing is finished. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 272 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Comparative example 4
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of calcium hypophosphite and 3.0% of sebacic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, after uniform mixing, the pH value is adjusted to be 7.92 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure for 1h at 264 ℃ after the pressure reducing is finished. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 272 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Comparative example 5
(1) Under the condition of nitrogen, 1, 5-pentanediamine, dodecanedioic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the dodecanedioic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of calcium hypophosphite and 0.8% of adipic acid (relative to the mass of the nylon salt in the nylon salt solution) are added into the nylon salt, and after uniform mixing, the pH value of the nylon salt solution is adjusted to be 7.93 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure is reduced to 3 h after the pressure is maintained, and reducing the temperature of the reaction system to 262 ℃ after the pressure is reduced, wherein the pressure is reduced for 1 h. Vacuumizing at-0.05 Mpa for 30min at 274 deg.C.
(3) Melting, discharging, bracing and dicing to obtain polyamide 512 slices; the granulation is carried out in water, the water temperature is 30 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 22 min.
The polyamide 512 resin obtained was subjected to the relevant tests, and the results of the measurements are shown in tables 1 and 2.
Comparative example 6
1461.4g of adipic acid, 1001.5g of pentanediamine, 1g of calcium hypophosphite and 1510g of deionized water are weighed and added into a high-pressure reaction kettle, the high-pressure reaction kettle is vacuumized and filled with nitrogen, the steps are repeated for three times to remove residual air in the reaction kettle, and the micro-positive pressure of 25kPa is reserved in the high-pressure reaction kettle after the replacement is finished.
Heating the high-pressure reaction kettle to 80 ℃ under the stirring condition of 100r/min, reacting at a constant temperature for 1.5h, then continuously heating to 220 ℃, continuously increasing the temperature while starting to enable the interior of the high-pressure reaction kettle to be in a constant pressure state by a method of releasing water vapor in the high-pressure reaction kettle after the pressure reaches 2.0MPa, and slowly releasing the pressure of the high-pressure reaction kettle to the normal pressure within 1.5h when the temperature is increased to 275 ℃.
And (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 0.8MPa, extruding, bracing and cutting the materials from a die head to obtain PA56 polyamide resin particles.
5g of m-toluene isocyanate is dissolved in 200mL of N, N-dimethylformamide, and then the prepared PA66 polyamide resin particles (the mass ratio of the m-toluene isocyanate to the PA56 polyamide resin particles is 1:450) are added, the temperature is raised to 90 ℃, the mixture is stirred for 5 hours, a Buchner funnel is vacuumized and filtered, and the mixture is dried in a vacuum oven at 80 ℃ for 10 hours, so that the anti-yellowing PA56 polyamide resin is obtained, and the performance test results are shown in tables 1 and 2.
Comparative example 7
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, a 60 wt.% nylon salt solution is prepared, the percentage accounts for the mass percent of the nylon salt solution, 300 mass ppm of calcium hypophosphite (relative to the mass of the nylon salt in the nylon salt solution) is added into the nylon salt, and after uniform mixing, the pH value of the nylon salt solution is adjusted to be 7.97 when the concentration of the nylon salt solution is 10%, and the percentage is the mass percent of the nylon salt solution.
(2) Heating the solution, increasing the pressure in the reaction system to 1.8Mpa, controlling the time to 1.5h, exhausting, maintaining the pressure, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) after the pressure maintaining is finished and the pressure for 3 h, and reducing the pressure to 268 ℃ after the pressure reducing is finished and the pressure for 1 h. Vacuumizing at-0.05 Mpa for 30min, and maintaining the temperature at 273 deg.C.
(3) Melting, discharging, bracing and cutting into granules to obtain polyamide 56 slices; the granulation is carried out in water, the water temperature is 25 ℃, the rotating speed of a roller is 500rpm, and the granulation time is 20 min.
The polyamide 56 resin thus obtained was subjected to the relevant tests, and the results of the tests are shown in tables 1 and 2.
Application example
Using the polyamide PA5X resins obtained in examples 1 to 8 and comparative examples 1 to 7 as raw materials, specimens and bands were prepared and tested for properties as follows.
a) The test specimen was produced as follows:
1. the production equipment is an injection molding machine (model: SUMITOMO DEMAG SE350 HSZ).
2. The production process comprises the following steps: first 285 ℃ is the first section, second 285 ℃ is the second section, third 285 ℃ is the third section, fourth 285 ℃ is the fourth section, fifth 280 ℃ is the fifth section, and sixth 250 ℃ is the third section; the injection pressure during injection molding is 130MPa, and the production cycle is 12 s.
3. The nylon strips were dried at 105 ℃ for 8 h.
The performance of the spline product was tested as follows:
distilled water was added in an amount of 2.5% by mass of the sample piece and heat-sealed with a PE film bag, and after standing for 7 days, the high temperature resistance and the low temperature resistance were measured and the results were recorded, as shown in Table 2.
b) The ribbon to be tested was prepared according to the formulation and method for preparing the ribbon specific material, the ribbon product disclosed in example 1 of CN 109777098A.
The prepared ribbon is sealed and then stored for 1h at the temperature of 25 +/-2 ℃ and the relative humidity of 60 +/-5 percent RH at constant temperature and humidity, bending resistance tests are carried out, and the results are recorded, and are shown in table 2.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2:
1. by comparing examples 1-8 with comparative examples 1-7, the polyamide PA5X resin in the examples of the invention has excellent comprehensive properties, especially excellent high and low temperature resistance, because the polyamide 5X resin has excellent aging resistance and is not easy to age due to the addition of an effective antioxidant during polymerization. The polyamide PA5X resin prepared by the embodiment of the invention has excellent performance advantages when used in the fields of automobiles and electrical equipment. Meanwhile, compared with the examples 6 and 7, the polyamide PA5X resin has simple process during preparation, and the addition modes of the auxiliary antioxidant and the end-capping reagent have small influence on the resin performance, so that the single addition mode is fixed;
2. by comparing examples 1 to 8 with comparative examples 1 to 7, it can be seen that the introduction of the flexible chain-containing end-capping agent in the polyamide PA5X resin enables the polyamide resin to have excellent high and low temperature impact properties because the addition of a suitable amount of the flexible chain-containing end-capping agent increases the content of flexible groups in the polyamide 5X resin, improves the flex resistance, and enables the polyamide 5X resin to have excellent toughness; in the bending resistance test, the phenomena of fracture and cracking of the cable ties prepared by the polyamide PA5X resin in the examples 1-8 are basically not observed, so that the phenomenon of brittle fracture in the forming process is greatly improved by the polyamide PA5X resin in the invention;
therefore, the polyamide PA5X resin prepared by the method can be widely applied to the fields of aerospace, industry, transportation equipment, textile and the like which need high-toughness materials, particularly to automobile parts.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The polyamide 5X resin is characterized in that the raw materials of the polyamide PA5X resin comprise 20-80 parts by weight of dibasic acid, 20-80 parts by weight of pentamethylene diamine and 0.1-2 parts by weight of end-capping reagent;
wherein the end capping agent is selected from fatty dibasic acids having a greater number of carbon atoms than the dibasic acids.
2. Polyamide 5X resin according to claim 1, characterized in that said pentamethylenediamine may be chemically or biologically derived, preferably 1, 5-pentamethylenediamine of biological origin; and/or the presence of a gas in the gas,
the dibasic acid is selected from one of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid, and is preferably one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid or octadecanedioic acid; and/or the presence of a gas in the gas,
the end capping agent is selected from at least one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid and eicosanedioic acid; and/or the presence of a gas in the gas,
the polyamide PA5X resin further comprises 0.01-0.1 part by weight of an antioxidant, wherein the antioxidant is selected from at least one of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, an antioxidant H10, manganese hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite, and the most preferable is calcium hypophosphite; and/or the presence of a gas in the gas,
the difference between the number of carbon atoms contained in the end-capping agent and the number of carbon atoms contained in the dibasic acid is 2 or more; and/or the presence of a gas in the gas,
the mass of the end-capping agent accounts for 0.5-2.0 wt.% of the total mass of the polyamide PA5X resin.
3. The polyamide 5X resin as claimed in claim 1, wherein the polyamide PA5X resin comprises, as raw materials, 30 to 60 parts by weight of a dibasic acid, 30 to 60 parts by weight of a pentamethylenediamine, 0.01 to 0.097 part by weight of an antioxidant, and 0.2 to 1.8 parts by weight of an end-capping agent; and/or the presence of a gas in the gas,
the polyamide PA5X resin has a notched impact strength, measured at 23 ℃ in accordance with ISO180-2001, of more than 5.0KJ/m2More preferably, it is more than 5.5KJ/m2(ii) a And/or the presence of a gas in the gas,
the polyamide PA5X resin has a notched impact strength, measured at-60 ℃ in accordance with ISO180-2001, of more than 4.0KJ/m2More preferably, it is more than 5.0KJ/m2(ii) a And/or the presence of a gas in the gas,
the polyamide PA5X resin has a notched impact strength, measured at 150 ℃ in accordance with ISO180-2001, of more than 4.5KJ/m2More preferably, it is more than 5.0KJ/m2(ii) a And/or the presence of a gas in the gas,
the relative viscosity of the polyamide PA5X is 1.6-3.4; and/or the presence of a gas in the gas,
the polyamide PA5X resin has a tensile strength of 55-125 MPa, and more preferably 75-115 MPa; and/or the presence of a gas in the gas,
the polyamide PA5X resin has a flexural strength of 65 to 125MPa, and more preferably 80 to 130 MPa.
4. A process for preparing the polyamide 5X resin according to claim 1, characterized in that it comprises the following steps:
carrying out amidation reaction on dibasic acid and 1, 5-pentanediamine in the presence of an end-capping agent to obtain a polyamide resin melt, and after the melt is discharged, carrying out strand cutting and dicing to obtain the polyamide PA5X resin.
5. The method of claim 4,
the end-capping agent comprises any one or combination of more than one of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecane diacid and dodecanedioic acid, preferably, the end-capping agent is sebacic acid; and/or the presence of a gas in the gas,
the polyamide PA5X resin raw material further comprises an antioxidant, wherein the antioxidant is selected from at least one of sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, magnesium phosphite, calcium phosphite, zinc phosphite, antioxidant H10, manganese hypophosphite, sodium hypophosphite, magnesium hypophosphite, calcium hypophosphite and zinc hypophosphite, and is most preferably calcium hypophosphite.
6. The method according to claim 5, characterized in that it comprises the steps of:
(1) under the condition of nitrogen, 1, 5-pentanediamine, dibasic acid and water are uniformly mixed to prepare a nylon salt solution, and an antioxidant and a blocking agent are added into the nylon salt solution; wherein the molar ratio of the 1, 5-pentanediamine to the dibasic acid is (1-1.05): 1;
(2) heating, wherein the pressure in the reaction system is increased to 0.3-2.0 Mpa, the time is controlled to be 1.5-2.0 h, exhausting and maintaining the pressure, the temperature of the reaction system is 232-265 ℃ when the pressure maintaining is finished, then reducing the pressure to 0-0.2 MPa (gauge pressure), the temperature of the reaction system is 245-280 ℃ after the pressure reducing is finished, and vacuumizing to obtain a polyamide melt;
(3) discharging the melt obtained in the step (2), and carrying out bracing and dicing.
7. The method according to claim 6, wherein, in step (1),
the concentration of the nylon salt solution prepared by uniformly mixing 1, 5-pentanediamine, dibasic acid and water is 55-65 wt.%; and/or the presence of a gas in the gas,
the addition amount of the antioxidant is preferably 100-800 mass ppm, more preferably 200-600 mass ppm, and the addition amount is relative to the mass of the nylon salt in the nylon salt solution; and/or the presence of a gas in the gas,
the addition amount of the blocking agent is preferably 0.2 wt.% to 1.2 wt.%, more preferably 0.3 wt.% to 0.8 wt.%, relative to the mass of the nylon salt in the nylon salt solution.
8. The method according to claim 6, wherein in the step (3), the granulation is performed in water, the water temperature is 20-50 ℃, the rotation speed of the roller is 500-800 rpm, and the granulation time is 20-45 min.
9. A molded article produced from the polyamide 5X resin according to any one of claims 1 to 3.
10. A method of making a shaped article according to claim 9, wherein the method utilizes injection molding, extrusion, pultrusion, blow molding or other shaping techniques.
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