CN112759760B - High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof - Google Patents
High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof Download PDFInfo
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- CN112759760B CN112759760B CN201911062331.7A CN201911062331A CN112759760B CN 112759760 B CN112759760 B CN 112759760B CN 201911062331 A CN201911062331 A CN 201911062331A CN 112759760 B CN112759760 B CN 112759760B
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08G69/28—Preparatory processes
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Abstract
The invention discloses a high-low temperature aging resistant toughened polyamide 5X resin, and a preparation method and application thereof. The polyamide 5X resin is blocked by fatty dibasic acid containing flexible chains in the polymerization process, so that the content of terminal amino groups in the polyamide resin can be reduced, and the yellowing resistance of the obtained polyamide resin is obviously improved at high temperature in the subsequent processing and injection molding processes, and the ageing resistance is good. The molded product prepared from the polyamide 5X resin 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 a high-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, weather resistance, mechanical properties, electrical properties, and the like, and therefore are generally used for various industrial applications as injection molding materials, fibers, and films.
However, since the crystallinity is high, if the molded article is injection molded into a molded article having a thin wall thickness, a molded article having a non-uniform wall thickness and a complicated shape, there is a problem that warpage occurs and the molded article is deformed. In general, such problems can be improved by mixing various inorganic particles, but there are problems in that the surface appearance of the product is impaired or anisotropy is generated by the orientation of fibrous inorganic substances, and the molded body is deformed.
If the auxiliary materials such as a toughening agent and a stabilizer are added for the subsequent modification, a separate process is required, or the process becomes complicated, etc., so that improvement in the polymerization stage is desired to obtain a polyamide resin having good various physical properties and not warping at the time of injection molding. Meanwhile, the polyamide needs to show the phenomenon that engineering parts are easy to brittle fracture at high and low temperatures in the field of engineering plastics, the aging phenomenon is serious after long-term use, and the bad phenomena such as low retention rate of mechanical properties when the engineering parts are used at high temperatures are needed.
CN109705342a employs monofunctional isocyanate blocking to reduce the content of carboxyl and amino ends in the polyamide resin, however, since isocyanate readily undergoes self-polymerization to form dimers or polymers of high molecular weight, impurities are readily introduced into the polyamide resin, thereby affecting the mechanical properties of the polyamide.
At present, the research and development of polyamide 5X resin with good high-low temperature aging resistance and toughness improvement performance is still a problem to be solved in the prior art.
Disclosure of Invention
In order to solve the defects of the prior art and products, the invention provides polyamide PA5X resin, and a preparation method and application thereof.
After intensive studies, the inventors of the present invention have found that, since a large amount of terminal carboxyl groups and terminal amino groups remain at the terminal ends when the polymerization of the polyamide is completed, particularly, the terminal amino groups are easily oxidized at high temperature or oxidized by nitrogen oxides in the air, resulting in yellow substances, which cause yellowing of the resin, and the polyamide resin is blocked with a flexible chain-containing aliphatic dibasic acid during the polymerization, the terminal amino group content in the polyamide resin can be reduced, so that the yellowing resistance of the resulting polyamide resin is remarkably improved at high temperature during the subsequent processing and injection molding, and the aging resistance is good.
Specifically, the invention provides a 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 end capping agent, wherein the end capping agent is selected from fatty dibasic acid with carbon atoms larger than that of the dibasic acid.
In some preferred embodiments of the present invention, the raw materials of the polyamide PA5X resin include a pentanediamine and a dibasic acid, and the pentanediamine may be a chemically or biologically derived pentanediamine, preferably a biologically derived 1, 5-pentanediamine; and/or the number of the groups of groups,
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, 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 number of the groups of groups,
the end-capping agent is at least one selected from 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 number of the groups of groups,
the raw material of the polyamide PA5X resin further comprises 0.01 to 0.1 part by weight of an antioxidant, preferably, the antioxidant is at least one selected from 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, calcium hypophosphite.
In some preferred embodiments of the present invention, the difference between the number of carbon atoms contained in the capping agent and the number of carbon atoms contained in the dibasic acid is 2 or more.
According to a preferred technical scheme of the invention, the raw materials of the polyamide PA5X resin comprise 30-60 parts by weight of dibasic acid, 30-60 parts by weight of pentanediamine, 0.01-0.097 part by weight of antioxidant and 0.2-1.8 parts by weight of end capping agent.
In some preferred embodiments of the present invention, the amount of the capping agent is 0.5 to 2.0wt.% based on the total amount of the polyamide PA5X resin, for example, 0.5wt.%, 0.8wt.%, or 1.0wt.% based on 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 a combination of a plurality of coupling agents, chain extenders, heat stabilizers, weather stabilizers, hydrolysis stabilizers, reinforcing agents, toughening agents, pigments, gloss enhancers, dyes, crystal nucleating agents, delustrants, plasticizers, antistatic agents, flame retardants, catalysts and UV stabilizers.
As a preferred embodiment, the polyamide resin may include 0.1 to 1wt.% of an additive based on the total mass of the raw dibasic acid, in addition to the above polyamide 5X resin.
Specifically, the additive is one or more selected from a coupling agent, a plasticizer, a chain extender, an anti-hydrolysis stabilizer, a reinforcing agent, a delustrant, a defoamer, a flame retardant, a crystallization nucleating agent and a pigment, and the mass of the additive is 0.1-0.5 wt.% of the total mass of the raw material dibasic acid.
In addition, the hydrolysis-resistant stabilizer, reinforcing agent, matting agent, flame retardant, crystallization nucleating agent, pigment in the additive may be those conventionally employed in the art as long as the action of the polyamide resin of the present invention is not adversely affected.
According to a preferred embodiment of the present invention, the yellow index YI of the polyamide 5X resin is 1.0 to 5.0, preferably 1.0 to 3.0.
According to a preferred embodiment of the present invention, the amino group-terminated content of the polyamide 5X resin is 20 to 70mol/ton, preferably 30 to 60mol/ton.
In some preferred embodiments of the 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 115MPa.
In some preferred embodiments of the present invention, the polyamide PA5X resin has a flexural strength of 65 to 125MPa, more preferably 80 to 130MPa.
In some preferred embodiments of the invention, the polyamide PA5X resin has a notched impact strength of greater than 5.0KJ/m, measured at 23℃according to ISO180-2001 2 More preferably greater than 5.5KJ/m 2 For example, 5.0 to 8.5KJ/m 2 Or 5.5-7.0 KJ/m 2 。
In some preferred embodiments of the invention, the polyamide PA5X resin has a notched impact strength of greater than 4.0KJ/m, measured at-60℃according to ISO180-2001 2 More preferably more than 5.0KJ/m 2 For example, 4.0 to 7.0KJ/m 2 Or 5.0 to 6.0KJ/m 2 。
In some preferred embodiments of the invention, the polyamide PA5X resin has a notched impact strength of greater than 4.5KJ/m, measured at 150℃according to ISO180-2001 2 More preferably more than 5.0KJ/m 2 For example, 4.5 to 7.5KJ/m 2 Or 5.0-6.5 KJ/m 2 。
The present invention provides a method for preparing the polyamide 5X resin, the method comprising the steps of:
and carrying out amidation reaction on dibasic acid and 1, 5-pentanediamine in the presence of a blocking agent to obtain a polyamide resin melt, discharging the melt, and then bracing and granulating to obtain polyamide PA5X resin.
According to a preferred embodiment of the present invention, the raw material of the polyamide PA5X resin further comprises an antioxidant, which may be added to the raw material at various stages, for example, before the amidation reaction starts, the antioxidant is added to the reaction vessel. According to a preferred embodiment of the invention, the method comprises the steps of:
(1) Uniformly mixing 1, 5-pentanediamine, dibasic acid and water under the condition of nitrogen to prepare a nylon salt solution, and adding an antioxidant and a blocking agent into the nylon salt solution; wherein, the mol ratio of the 1, 5-pentanediamine and the dibasic acid is (1-1.05): 1, a step of;
(2) Heating, increasing the pressure in the reaction system to 0.3-2.0 Mpa, controlling the time to 1.5-2.0 h, exhausting and maintaining the pressure, enabling the temperature of the reaction system to be 232-265 ℃ when the pressure maintaining is finished, reducing the pressure to 0-0.2 Mpa (gauge pressure) when the pressure reducing is finished, enabling the temperature of the reaction system to be 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 granulating by bracing.
Preferably, in the step (1), the concentration of the nylon salt solution prepared by uniformly mixing the 1, 5-pentanediamine, the dibasic acid and the water is 55-65 wt%, and the percentage is the mass percentage of the nylon salt solution.
Preferably, in the step (1), an antioxidant is further added, and after the end capping agent is added, the pH value is adjusted to 7.80-8.20 when the concentration of the polyamide salt solution is 10wt.%, and the percentage is the mass percentage of the nylon salt solution.
Preferably, in the step (1), the antioxidant is used for improving the ageing resistance of the polyamide chips, and the antioxidant is at least one selected from 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 antioxidant is preferably added in an amount of 100 to 800 mass ppm, more preferably 200 to 600 mass ppm, 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 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, nonadecanedioic acid and eicosanedioic acid, and preferably, the end capping agent is sebacic acid.
In some preferred embodiments of the present invention, the capping agent is added in an amount of preferably 0.2 to 1.2wt.%, more preferably 0.3 to 0.8wt.%, relative to the mass of nylon salt in the nylon salt solution.
The addition of an appropriate amount of the blocking agent containing a flexible chain is beneficial to increasing the content of the 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 end-capping agent containing the flexible chain is excessively large, the crystallization property of the polyamide 5X resin is deteriorated, resulting in a decrease in the mechanical properties of the polyamide 5X resin.
Preferably, in the step (2), the vacuum is carried out at a relative vacuum degree of-0.01 Mpa to-0.09 Mpa, the vacuum time is maintained for 15-75 min, the vacuum ending temperature is controlled at 265-275 ℃,
preferably, in the step (3), the granulating is carried out in water, the water temperature is 20-50 ℃, the rotating speed of the roller is 500-800 rpm, and the granulating time is 20-45 min.
In another aspect of the present invention, there is provided a molded article produced using the polyamide 5X resin as described above as a raw material.
The shaped article may further comprise other additives commonly used from the group consisting of: inorganic stabilizers, antioxidants, organic stabilizers, lubricants, pigments, metallic flakes, metal-coated particles, halogen-containing flame retardants, halogen-free flame retardants, impact modifiers, antistatic agents, conductivity additives, mold release agents, optical brighteners, natural layered silicates, synthetic layered silicates or mixtures of the above additives.
Another aspect of the present invention provides a method for producing a molded article from the polyamide 5X resin described above, using injection molding, extrusion, pultrusion, blow molding or other molding 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 invention has good high-temperature and low-temperature resistance, can be well applied to a high-temperature area, can completely meet the use in a high-temperature environment of 135 ℃, and is especially suitable for occasions with high requirements on the high-temperature and low-temperature resistance of nylon, such as automobiles, aerospace, electronic appliances and the like.
2. The polyamide 5X has good toughness, particularly has good toughness in notch impact at low temperature and high temperature, and can be applied to the fields of aerospace, automobiles, electrical equipment, mechanical parts and the like which need toughening materials.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
1. Method for detecting relative viscosity eta r
Concentrated sulfuric acid process with Ubbelohde viscometer: accurately weighing 0.5+ -0.0002 g of dried polyamide sample, adding 50mL of concentrated sulfuric acid (98%) for dissolution, measuring in a constant temperature water bath at 25 ℃ and recording the flow-through time t of the concentrated sulfuric acid 0 And polyamide solution flow-through time t.
The relative viscosity number calculation formula:
relative viscosity ηr=t/t 0
Wherein: t: the time of the solution flow; t is t 0 : solvent flow-through time.
2. Method for detecting content of terminal amino group
After the sample was dissolved with trifluoroethanol, it was titrated with hydrochloric acid standard solution and sodium hydroxide standard solution, respectively, and calculated.
3. The molecular weight and detection method are as follows:
the number average molecular weight of the main peak (polymer peak) in the elution curve was calculated from the calibration of the polymethyl methacrylate (PMMA) as a standard sample based on the elution curve (vertical axis: signal intensity by detector, horizontal axis: elution time) of each sample obtained by Gel Permeation Chromatography (GPC), and the measurement was performed under the following conditions.
A detector: RI detector
Chromatographic column: 2x PSS 7 μ PFG Linear M column 300 x 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 mu L
Concentration: 3-5 g/L
Sample preparation: the polyamide resin or the polyamide resin composition obtained in each example was weighed in 0.01 mol/L hexafluoroisopropanol containing sodium trifluoroacetate so as to convert the polyamide resin into 0.5mg/mL, and stirred at room temperature for 1 hour to dissolve, and the obtained solution was filtered by a hydrophobic membrane filter (pore size 0.22 μm) to prepare a sample.
PMMA standard sample: 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)
Tested according to HG/T3862.
5. Tensile Strength
The tensile speed at the time of the test was 50mm/min, as determined according to ISO 527-2.
6. Flexural Strength
The test conditions were 2mm/min as determined according to ISO 178.
7. Notched impact Strength
The notched impact strength of the material was measured using a cantilever Liang Baichui impactor. Impact strength was measured according to ISO 180-2001, notch depth 2mm, pendulum energy 2.75J.
8. The heat resistance was measured according to the standard of section 9.5 in UL62275, the target temperature required by the UL62275 standard being 105 ℃/135 ℃, the difference between the present experiment and the UL62275 standard being: at 120 ℃/150 ℃, humidity: and (3) in the environment of 50+/-5, aging for 1000 hours, and then carrying out a tensile strength test after being placed for 21 days at normal temperature, and calculating the tensile strength retention rate before and after the aging test.
9. The method for testing the high and low temperature resistance comprises the following steps:
(1) Test equipment: a vertical high-temperature oven and a cold and hot impact test box;
(2) The testing method comprises the following steps: distilled water is added according to the proportion of 2.5 percent of the mass percentage of the nylon sample strip, and the PE film bag is used for heat sealing, and after the nylon sample strip is placed for 7 days, the high temperature resistance, the low temperature resistance and the release force are detected and the result is recorded.
High temperature resistance test: placing in an oven at 150 ℃ for 72 hours, wherein the surface of the product has no cracks, and if the product is bent by hand at 90 degrees and has no cracks, the product is qualified, otherwise, the product is unqualified.
Low temperature resistance test: placing in a cold and hot impact test box at-40 ℃ for 72 hours, wherein no crack exists on the surface of the product, and if the product is bent by 90 degrees manually and has no fracture, the product is marked as qualified, otherwise, the product is marked as unqualified.
10. Bending resistance experiment test method
(1) Test equipment: constant temperature and humidity test box;
(2) The testing method comprises the following steps: the band (3.0X 180mm, 1.5mm thick) formed by injection molding polyamide 5X resin is sealed, and an aluminum plastic packaging bag is placed into a constant temperature and humidity test box with the temperature of 25+/-2 ℃ and the relative humidity of 60+/-5% RH for 1h. Then, 50 bands made of the same polyamide 5X resin were tested as a group, wherein each band was manually folded in half toward the outside at a distance from each other, and if the band was broken and split once, the band was brittle broken 1 time in total 5 times.
Counting the number of brittle-rupture bands in the group of bands, and calculating the proportion of the number of broken bands to a group of 50 bands to obtain the brittle-rupture rate. If the brittle failure rate is less than 5%, the group of polyamide 5X resins is marked as being acceptable, otherwise, the group of polyamide 5X resins is marked as being unacceptable.
1, 5-pentanediamine, dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid were purchased from Kaiser (Jinxiang) biological materials Co., ltd, and adipic acid was purchased from Guo pharmaceutical Chemicals Co., ltd. Other materials such as calcium hypophosphite and sodium hypophosphite and reagents can be prepared by methods known in the literature or can be obtained commercially.
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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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, after uniform mixing, the pH value is 7.97 when the concentration of the nylon salt solution is 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, wherein the temperature of the reaction system is 243 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the pressure to 268 ℃ when the pressure reducing is finished, and reducing the pressure for 1 hour. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 273 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the granulating is carried out in water, the water temperature is 25 ℃, the rotating speed of the rolling shaft is 500rpm, and the granulating time is 20min.
The relative viscosity of the resulting polyamide 56 resin was measured and found to be 2.75. The amino end test result is 52.4mol/ton; yellow index YI results in 2.45; obtaining the polyamide 56 resin with the number average molecular weight of 54062 by GPC test method; and the polyamide 56 resin is tested by ISO 527-2 method for tensile strength of 102.4Mpa, ISO 178 method for bending strength of 125.5Mpa, ISO180-2001 method for notched impact strength (23 ℃) of 6.8KJ/m 2 Notched impact strength (-60 ℃) 5.4KJ/m was measured according to ISO180-2001 method 2 Notched impact strength (150 ℃) 5.8KJ/m was measured according to ISO180-2001 method 2 Test resultsSee 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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 7.92 when the concentration of the nylon salt solution is 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, wherein the temperature of the reaction system is 241 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the temperature of the reaction system to 264 ℃ after the pressure reducing is finished, and reducing the pressure for 1 hour. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 272 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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, after uniform mixing, the pH value is 7.94 when the concentration of the nylon salt solution is 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, wherein the temperature of the reaction system is 244 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), and reducing the pressure for 1 hour when the temperature of the reaction system is 265 ℃ after the pressure reducing is finished. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 273 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 300 mass ppm of sodium hypophosphite and 0.5% of octadecanedioic 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 7.93 when the concentration of the nylon salt solution is adjusted to be 10 percent, 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, maintaining the temperature of the reaction system at 242 ℃ at the end of the pressure maintaining, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) by reducing the pressure, and reducing the pressure for 1 hour at 265 ℃ at the end of the pressure reducing. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 275 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage 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 is 7.93 when the concentration of the nylon salt solution is 10 percent, 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, maintaining the temperature of the reaction system at 242 ℃ at the end of the pressure maintaining, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) by reducing the pressure, and reducing the pressure for 1 hour at 262 ℃ at the end of the pressure reducing. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 274 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 512 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 512 resin obtained was subjected to the relevant test, and the measurement results 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 300 mass ppm of calcium hypophosphite, 0.5% of dodecanedioic acid and 0.5% of tetradecanedioic 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 7.93 when the concentration of the nylon salt solution is 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, maintaining the temperature of the reaction system at 242 ℃ at the end of the pressure maintaining, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) by reducing the pressure, and reducing the pressure for 1 hour at 265 ℃ at the end of the pressure reducing. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 275 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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, after uniform mixing, the pH value is adjusted to 7.97 when the concentration of the nylon salt solution is 10 percent, 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, wherein the temperature of the reaction system is 243 ℃ when the pressure is maintained, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the pressure to 268 ℃ when the pressure is reduced, and reducing the pressure for 1 hour; 0.5 percent of sebacic acid (relative to the mass of nylon salt in the nylon salt solution) is added through a charging port under the protection of nitrogen, and after stirring for 5min, vacuum pumping is carried out; vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 273 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the granulating is carried out in water, the water temperature is 25 ℃, the rotating speed of the rolling shaft is 500rpm, and the granulating time is 20min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage 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 then added into the nylon salt, after uniform mixing, the pH value is adjusted to 7.97 when the concentration of the nylon salt solution is 10 percent, 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, wherein the temperature of the reaction system is 243 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the pressure to 268 ℃ when the pressure reducing is finished, and reducing the pressure for 1 hour. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 273 ℃.
(3) Melting and discharging, feeding into a melt pump, uniformly adding 300 mass ppm (relative to the mass of nylon salt in the nylon salt solution) of antioxidant calcium phosphite into a polyamide 56 melt according to the weight of the antioxidant calcium phosphite, and granulating by bracing to obtain polyamide 56 slices; the granulating is carried out in water, the water temperature is 25 ℃, the rotating speed of the rolling shaft is 500rpm, and the granulating time is 20min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results are shown in tables 1 and 2.
Comparative example 1
(1) And uniformly mixing 1, 5-pentanediamine, adipic acid and water under the condition of nitrogen, wherein the molar ratio of the 1, 5-pentanediamine to the adipic acid is 1.05:1, and the nylon salt solution with the weight percentage of 60wt.% is prepared, the pH value is 7.92 when the concentration of the nylon salt solution is regulated to be 10%, and the weight 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, wherein the temperature of the reaction system is 241 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the temperature of the reaction system to 264 ℃ after the pressure reducing is finished, and reducing the pressure for 1 hour. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 272 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results are shown in tables 1 and 2.
Comparative example 2
1461.4g of adipic acid, 1138.9g of hexamethylenediamine, 1g of sodium hypophosphite serving as a catalyst 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 process is repeated 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 replacement is completed.
Heating the high-pressure reaction kettle to 80 ℃ under the stirring condition of 100r/min, reacting for 1.5h at constant temperature, then continuously heating to 220 ℃, after the pressure reaches 2.0MPa, continuously heating the high-pressure reaction kettle while starting to enable 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, and slowly decompressing the high-pressure reaction kettle to normal pressure within 1.5h when the temperature is raised to 275 ℃.
And (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 0.8MPa, extruding the materials from a die head, and granulating the extruded braces to obtain PA66 polyamide resin particles.
5g of m-toluene isocyanate was dissolved in 200mL of N, N-dimethylformamide, and then prepared PA66 polyamide resin particles (the mass ratio of the m-toluene isocyanate to the PA66 polyamide resin particles is 1:450) were added, and the mixture was stirred for 5 hours at a temperature of 90℃and filtered under vacuum by a Buchner funnel, and dried for 10 hours at a temperature of 80℃in a vacuum oven, whereby yellowing-resistant PA66 polyamide resins were obtained, and the performance test results thereof are shown in Table 1 and Table 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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 7.92 when the concentration of the nylon salt solution is 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, wherein the temperature of the reaction system is 241 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the temperature of the reaction system to 264 ℃ after the pressure reducing is finished, and reducing the pressure for 1 hour. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 272 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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 7.92 when the concentration of the nylon salt solution is 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, wherein the temperature of the reaction system is 241 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the temperature of the reaction system to 264 ℃ after the pressure reducing is finished, and reducing the pressure for 1 hour. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 272 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, and 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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 is adjusted to 7.93 when the concentration of the nylon salt solution is 10 percent, 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, maintaining the temperature of the reaction system at 242 ℃ at the end of the pressure maintaining, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure) by reducing the pressure, and reducing the pressure for 1 hour at 262 ℃ at the end of the pressure reducing. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 274 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 512 slices; the dicing is carried out in water, the water temperature is 30 ℃, the rotating speed of the rolling shaft is 500rpm, and the dicing time is 22min.
The polyamide 512 resin obtained was subjected to the relevant test, and the measurement results 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 process is repeated 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 replacement is completed.
Heating the high-pressure reaction kettle to 80 ℃ under the stirring condition of 100r/min, reacting for 1.5h at constant temperature, then continuously heating to 220 ℃, after the pressure reaches 2.0MPa, continuously heating the high-pressure reaction kettle while starting to enable 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, and slowly decompressing the high-pressure reaction kettle to normal pressure within 1.5h when the temperature is raised to 275 ℃.
And (3) filling nitrogen into the high-pressure reaction kettle to the pressure of 0.8MPa, extruding the materials from a die head, and granulating the materials in a brace manner to obtain PA56 polyamide resin particles.
5g of m-toluene isocyanate was dissolved in 200mL of N, N-dimethylformamide, and then prepared PA66 polyamide resin particles (the mass ratio of the m-toluene isocyanate to the PA56 polyamide resin particles is 1:450) were added, and the mixture was stirred for 5 hours at a temperature of 90 ℃, filtered by vacuum through a Buchner funnel, and dried for 10 hours at a temperature of 80 ℃ in a vacuum oven, whereby yellowing-resistant PA56 polyamide resin was obtained, and the performance test results thereof are shown in Table 1 and Table 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, 60wt.% nylon salt solution is prepared, the percentage is the mass percentage of the nylon salt solution, then 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, after uniform mixing, the pH value is adjusted to 7.97 when the concentration of the nylon salt solution is 10 percent, 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, wherein the temperature of the reaction system is 243 ℃ when the pressure maintaining is finished, maintaining the pressure for 3 hours, reducing the pressure in the reaction system to 0.005Mpa (gauge pressure), reducing the pressure to 268 ℃ when the pressure reducing is finished, and reducing the pressure for 1 hour. Vacuum-pumping is maintained at-0.05 Mpa for 30min, and the temperature after vacuum is 273 ℃.
(3) Melting and discharging, and bracing and granulating to obtain polyamide 56 slices; the granulating is carried out in water, the water temperature is 25 ℃, the rotating speed of the rolling shaft is 500rpm, and the granulating time is 20min.
The polyamide 56 resin obtained was subjected to the relevant test, and the measurement results 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, bars and ties were prepared and tested for properties as follows.
a) The test specimen production method is as follows:
1. production equipment, an injection molding machine (model SUMITOMO DEMAG SE HSZ 350).
2. The production process comprises the following steps: first-stage 285 ℃, second-stage 285 ℃, third-stage 285 ℃, fourth-stage 285 ℃, fifth-stage 280 ℃ and sixth-stage 250 ℃; the injection pressure during injection molding is 130MPa, and the production period is 12s.
3. Nylon bars were dried at 105 ℃ for 8h.
The performance test of the spline product is as follows:
distilled water is added according to the mass percentage of 2.5% of the sample strip, the sample strip is sealed by a PE film bag in a heat sealing way, the sample strip is placed for 7 days, and then the high temperature resistance and the low temperature resistance are tested and recorded, and the results are shown in Table 2.
b) The tie to be tested was made according to the formulation and method for making tie-specific materials, tie-products disclosed in example 1 of CN 109777098A.
The obtained band was sealed and stored at a constant temperature and humidity at a temperature of 25.+ -. 2 ℃ and a relative humidity of 60.+ -. 5% RH for 1 hour, and the bending resistance was measured and the results were recorded, and the results are shown in Table 2.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2:
1. by comparing examples 1 to 8 with comparative examples 1 to 7, the polyamide PA5X resin in the examples of the present invention has excellent overall properties, particularly excellent high and low temperature resistance, because the polyamide 5X resin has excellent aging resistance due to the addition of an effective antioxidant during polymerization, and is not liable to undergo aging. 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, by comparing the embodiment 1 with the embodiments 6 and 7, the polyamide PA5X resin has simple process in preparation, and the addition mode of the auxiliary agent antioxidant and the end capping agent has less influence on the resin performance, so that the single addition mode is not only 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 capping agent in the polyamide PA5X resin gives the polyamide resin excellent in high-low temperature impact properties, because the addition of an appropriate amount of the flexible chain-containing capping agent increases the content of flexible groups in the polyamide 5X resin, and the bending resistance is improved, resulting in the polyamide 5X resin having excellent toughness; in the bending resistance test, the belts prepared by adopting the polyamide PA5X resin in the examples 1-8 basically have no fracture phenomenon, so that the brittle fracture phenomenon of the polyamide PA5X resin in the invention can be greatly improved in the forming process;
therefore, the polyamide PA5X resin prepared by the invention can be widely applied to the fields of aerospace, industry, traffic equipment, textile and the like which need high toughness materials, in particular to automobile parts.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (16)
1. The polyamide 5X resin is characterized in that the raw materials of the polyamide 5X 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 end capping agent;
wherein the end capping agent is selected from fatty dibasic acids having a carbon number greater than that of the dibasic acid;
the end-capping agent is at least one selected from 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;
the mass of the end capping agent is 0.5 to 2.0wt.% of the total mass of the polyamide 5X resin.
2. The polyamide 5X resin of claim 1, wherein the pentanediamine is a chemically or biologically derived pentanediamine; and/or the number of the groups of groups,
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/or the number of the groups of groups,
The polyamide 5X resin also comprises 0.01 to 0.1 weight part of antioxidant, wherein the antioxidant is at least one selected from 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/or the number of the groups of groups,
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.
3. Polyamide 5X resin according to claim 2, characterized in that the pentanediamine is a 1, 5-pentanediamine of biomass origin;
and/or the diacid is 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 antioxidant is calcium hypophosphite.
4. The polyamide 5X resin according to claim 2, wherein the polyamide 5X resin comprises 30 to 60 parts by weight of dibasic acid, 30 to 60 parts by weight of pentanediamine, 0.01 to 0.097 part by weight of antioxidant, and 0.2 to 1.8 parts by weight of end-capping agent.
5. The polyamide 5X resin according to claim 1, wherein the polyamide 5X resin has a yellowness index YI value of 1.0 to 5.0; and/or the number of the groups of groups,
the polyamide 5X resin has a notched impact strength of greater than 5.0KJ/m, measured at 23℃according to ISO180-2001 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the polyamide 5X resin has a notched impact strength of greater than 4.0KJ/m, measured at-60℃according to ISO180-2001 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the polyamide 5X resin has a notched impact strength of greater than 4.5KJ/m, measured at 150℃according to ISO180-2001 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the relative viscosity of the polyamide 5X is 1.6-3.4; and/or the number of the groups of groups,
the tensile strength of the polyamide 5X resin is 55-125 MPa; and/or the number of the groups of groups,
the bending strength of the polyamide 5X resin is 65-125 MPa.
6. The polyamide 5X resin according to claim 1, wherein the polyamide 5X resin has a yellowness index YI value of 1.0 to 3.0; and/or the number of the groups of groups,
the polyamide 5X resin has a notched impact strength of greater than 5.5KJ/m, measured at 23℃according to ISO180-2001 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the polyamide 5X resin has a notched impact strength of greater than 5.0KJ/m, measured at-60℃according to ISO180-2001 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the polyamide 5X resin has a notched impact strength of greater than 5.0KJ/m, measured at 150℃according to ISO180-2001 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the tensile strength of the polyamide 5X resin is 75-115 MPa; and/or the number of the groups of groups,
the bending strength of the polyamide 5X resin is 80-130 MPa.
7. A process for preparing the polyamide 5X resin of any one of claims 1-6, characterized in that the process comprises the steps of:
and carrying out amidation reaction on dibasic acid and 1, 5-pentanediamine in the presence of a blocking agent to obtain a polyamide resin melt, discharging the melt, and then bracing and granulating to obtain the polyamide 5X resin.
8. The method of claim 7, wherein the capping agent comprises any one or a combination 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, eicosanedioic acid; and/or the number of the groups of groups,
the raw materials of the polyamide 5X resin further comprise an antioxidant, wherein the antioxidant is at least one selected from 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.
9. The method of claim 7, wherein the capping agent is sebacic acid.
10. The method of claim 8, wherein the antioxidant is calcium hypophosphite.
11. The method according to claim 7, characterized in that it comprises the steps of:
(1) Uniformly mixing 1, 5-pentanediamine, dibasic acid and water under the condition of nitrogen to prepare a nylon salt solution, and adding an antioxidant and a blocking agent into the nylon salt solution; wherein, the mol ratio of the 1, 5-pentanediamine and the dibasic acid is (1-1.05): 1, a step of;
(2) Heating, increasing the pressure in the reaction system to 0.3-2.0 Mpa, controlling the time to 1.5-2.0 h, exhausting and maintaining the pressure, enabling the temperature of the reaction system to be 232-265 ℃ when the pressure maintaining is finished, reducing the pressure to 0-0.2 Mpa gauge pressure, enabling the temperature of the reaction system to be 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 granulating by bracing.
12. The method according to claim 11, wherein in the step (1), the concentration of the nylon salt solution prepared by uniformly mixing 1, 5-pentanediamine, the dibasic acid and the water is 55 to 65wt.%; and/or the number of the groups of groups,
The addition amount of the antioxidant is 100-800 mass ppm, and the addition amount is relative to the mass of the nylon salt in the nylon salt solution; and/or the number of the groups of groups,
the addition amount of the end capping agent is 0.2wt.% to 1.2wt.%, relative to the mass of the nylon salt in the nylon salt solution.
13. The method according to claim 12, wherein the antioxidant is added in an amount of 200 to 600 mass ppm relative to the mass of the nylon salt in the nylon salt solution; and/or the number of the groups of groups,
the addition amount of the end capping agent is 0.3wt.% to 0.8wt.%.
14. The method according to claim 12, wherein in the step (3), the dicing is performed in water at a water temperature of 20 to 50 ℃, a rotational speed of the roller of 500 to 800rpm, and a dicing time of 20 to 45 minutes.
15. A molded article obtained by using the polyamide 5X resin according to any one of claims 1 to 6 as a raw material.
16. A method of making the shaped article of claim 15, wherein the method utilizes injection molding, extrusion, pultrusion, blow molding, or other shaping techniques.
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| 成都科学技术大学等.缩聚反应举例.《高分子化学及物理学》.1981,35. * |
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