CN108503824B - Polyamide 5X melt, resin and preparation method thereof - Google Patents
Polyamide 5X melt, resin and preparation method thereof Download PDFInfo
- Publication number
- CN108503824B CN108503824B CN201710102851.0A CN201710102851A CN108503824B CN 108503824 B CN108503824 B CN 108503824B CN 201710102851 A CN201710102851 A CN 201710102851A CN 108503824 B CN108503824 B CN 108503824B
- Authority
- CN
- China
- Prior art keywords
- polyamide
- resin
- oligomer
- salt solution
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
Abstract
The invention discloses a polyamide 5X melt and polyamide 5X resin prepared from the same. The polyamide 5X melt comprises 0.2 to 2.4 wt% of oligomers. According to the polyamide 5X resin disclosed by the invention, the problems of filament breakage and influence on the granulating effect and resin quality in the granulating process are greatly improved by adjusting the content of the oligomer, so that the granulating effect is greatly improved, and the obtained polyamide 5X resin is full in particles and excellent in quality.
Description
Technical Field
The invention relates to a polyamide 5X melt, resin and a preparation method thereof.
Background
The polyamide is a polymer with an amido repeating unit on a high molecular chain, has excellent comprehensive properties such as mechanical property, forming processability, wear resistance, chemical resistance and the like, is mainly applied to fibers and engineering plastics, and can be used for preparing films in a small amount. In the last 30 th century, DuPont first achieved industrial production of polyamides and applied to the fiber field. In the 80 s of the 20 th century, with the rapid development of the automobile industry and the electronic and electrical industry, the polyamide resin becomes the engineering plastic with the largest consumption and the widest application field. Currently widely used polyamide resins are polyamide 6(PA6) and polyamide 66(PA 66).
Polyamide 5X is a novel polyamide which is polymerized from 1, 5-pentanediamine and a dibasic acid. The prior art polyamide 5X resin can be prepared by the following process: concentration → high pressure pre-polycondensation → flash evaporation → normal pressure or vacuum polycondensation → granulation and molding to obtain the resin. However, in the preparation process of the polyamide 5X resin, the phenomenon of broken filaments during pelletizing is serious, and the pelletizing effect and the resin quality are affected. This phenomenon is urgently to be solved.
Disclosure of Invention
The invention provides polyamide 5X resin and a preparation method thereof, aiming at solving the defects that the yarn breaking phenomenon occurs in the process of pelletizing polyamide 5X resin and the pelletizing effect and the resin quality are influenced.
The inventors have conducted extensive studies on a process for producing a polyamide 5X resin in order to reduce the occurrence of strand breakage during cutting and to obtain polyamide 5X chips having excellent quality. In the research process, the inventor conducts deep research on each step of the polymerization process, conducts a large number of experiments on each parameter, and finds that the pelletizing effect is influenced by a plurality of factors, wherein the content of the oligomer in the polyamide 5X directly influences the quality of the pelletizing effect, the oligomer content is controlled within a specific range, the pelletizing effect can be greatly improved, and the resin with uniform particles and excellent quality is obtained, so that the technical scheme of the invention is obtained.
One object of the present invention is: providing a polyamide 5X melt, wherein the polyamide 5X melt comprises 0.2-2.4 wt% of oligomer, and the percentage is the mass percentage of polyamide 5X resin.
Another object of the invention is: providing a polyamide 5X resin, wherein the polyamide 5X resin is obtained by granulating a polyamide 5X melt; wherein the polyamide 5X melt comprises 0.2-2.4 wt% of oligomer, and the percentage is the mass percentage of the polyamide 5X melt.
The following further explains the preferred embodiments of the present invention:
in a preferred embodiment of the present invention, the polyamide 5X comprises a polyamide polymerized from monomers of 1, 5-pentanediamine and dicarboxylic acid. Wherein the dicarboxylic acid can be short-chain dicarboxylic acid (the number of carbon atoms on a carbon chain is less than 10) or long-chain dicarboxylic acid; wherein the short-chain dibasic acid preferably comprises one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, preferably adipic acid and/or sebacic acid; the long carbon chain dibasic acid preferably comprises one or more of undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, maleic acid and Δ 9-1, 18-octadecenedioic acid.
In a preferred embodiment of the present invention, the oligomer comprises a cyclic oligomer of polyamide, such as: mono-and/or polycyclic oligomers of polyamides; wherein the poly cyclic oligomer may include: one or more of a polyamide binary cyclic oligomer, a polyamide ternary cyclic oligomer, a polyamide quaternary cyclic oligomer, and a polyamide pentabasic cyclic oligomer.
Preferably, the polyamide cyclic oligomer may have the formula:
among them, n is preferably 1 to 8, and more preferably 1 to 5.
Among them, m is preferably 2 to 16, and more preferably 4 to 10.
In a preferred embodiment of the present invention, the oligomer is contained in an amount of 0.4 to 2.0 wt%, more preferably 0.5 to 1.6 wt%, based on the mass of the polyamide 5X melt.
In a preferred embodiment of the present invention, the content of the polyamide mono-cyclic oligomer is 20 to 45%, preferably 30 to 40%, and the percentage is the weight percentage of the oligomer.
According to a preferred technical scheme of the invention, the content of the polyamide binary cyclic oligomer is 15-35%, preferably 20-30%, and the percentage is the mass percentage of the oligomer.
According to a preferred technical scheme of the invention, the content of the polyamide ternary cyclic oligomer is 20-45%, preferably 30-40%, and the percentage is the mass percentage of the oligomer.
In a preferred embodiment of the present invention, the content of the polyamide quaternary cyclic oligomer is 10% or less, preferably 5% or less, and the percentage is a mass percentage of the oligomer.
According to a preferred technical scheme of the invention, the content of the polyamide five-membered cyclic oligomer is less than 10%, preferably less than 5%, and the percentage is the mass percentage of the oligomer.
For example: when the polyamide 5X is polyamide 56, the oligomer included therein may have the formula:
among them, n is preferably 1 to 8, and more preferably 1 to 5.
For another example: when the polyamide 5X is polyamide 510, the oligomer included therein may have the formula:
among them, n is preferably 1 to 8, and more preferably 1 to 5.
The inventor considers that the influence of the oligomer content on the pelletizing effect is probably caused by the following reasons: the volatilization of the oligomer can increase bubbles in the polyamide 5X melt, so that the phenomena of end breakage and filament are generated when the melt is subjected to wire drawing and grain cutting. Controlling the oligomer content within a specific range can greatly improve the pelletizing effect and obtain a resin with uniform particles and excellent quality, but the lower the amount of oligomer, the better, and the more the amount of oligomer is reduced to a certain extent, the more the bubbles rise.
On the other hand, the moisture content in the polyamide 5X melt also has a great influence on the quality of the polyamide 5X resin pellets. Conventionally, it is often considered that: the more the moisture content is, the more the bubble content in the polyamide 5X melt is increased, and the phenomena of end breakage and filament are easily caused during the granulation. And the lower the moisture content, the less the phenomena of broken ends and filaments. However, the inventors have made a number of experiments and found that the results are different from the above prior knowledge and that the results of the experiments show that: on the basis of the oligomer control at a specific content, a certain moisture content rather favors the reduction of bubbles, that is to say: the oligomer content, in combination with the specific water content of polyamide 5X, can further reduce the phenomena of end breakage and filament during the pelletization of polyamide 5X resin. On the basis, the more preferable technical scheme of the invention is obtained.
In a preferred technical scheme of the invention, the moisture content of the polyamide 5X melt is 600-18000ppm, preferably 1200-9000ppm, and the content is the mass percent of the polyamide 5X melt.
Another object of the invention is: provided is a polyamide 5X resin, wherein the polyamide 5X resin comprises 0.2-2.4 wt% of oligomer, and the percentage is the mass percentage of the polyamide 5X resin.
In a preferred embodiment of the present invention, the polyamide 5X resin has a water content of 200-2000ppm, preferably 400-1500 ppm.
In a preferred embodiment of the present invention, the polyamide 5X resin has a terminal amino group content of 20 to 70mol/ton, preferably 30 to 60 mol/ton.
In a preferred embodiment of the present invention, the polyamide 5X resin has a carboxyl end group content of 50mol/ton or more, preferably 60 to 100 mol/ton.
It is another object of the present invention to provide a process for the preparation of a polyamide 5X melt, comprising the steps of:
(1) under the condition of nitrogen, 1, 5-pentanediamine, aliphatic dibasic acid and water are uniformly mixed to prepare a salt solution of polyamide; wherein the molar ratio of the 1, 5-pentanediamine to the aliphatic dibasic acid is (1-1.05): 1;
(2) heating the salt solution of polyamide, raising the pressure in the reaction system to 0.3-2.0Mpa, exhausting, maintaining the pressure, leading the temperature of the reaction system to be 232-265 ℃ when the pressure maintaining is finished, then reducing the pressure in the reaction system to be 0-0.2Mpa (gauge pressure), leading the temperature of the reaction system to be 245-280 ℃ after the pressure reducing is finished, and vacuumizing to obtain a polyamide melt; the polyamide 5X melt comprises 0.2-2.4 wt% of oligomer, and the percentage is the mass percentage of the polyamide 5X resin.
According to a preferable technical scheme of the invention, the vacuumizing time is 10-45 min.
According to a preferable technical scheme of the invention, the vacuum degree after vacuumizing is between-0.01 and-0.08 Mpa (gauge pressure).
According to a preferable technical scheme of the invention, the temperature after the vacuum pumping is 260-280 ℃.
According to a preferred embodiment of the invention, the concentration of the salt solution of the polyamide is between 30 and 90%, preferably between 50 and 75%; the percentage is the mass percentage of the salt solution of the polyamide.
In a preferred embodiment of the present invention, the pH value of the salt solution of polyamide at a concentration of 10% is 6 or more, preferably 7.2 to 8.9, more preferably 7.5 to 8.2, the percentage being based on the mass of the salt solution of polyamide.
Another object of the invention is: provided is a preparation method of a polyamide 5X resin, the preparation method comprising the steps of: and pelletizing the polyamide 5X melt to obtain the resin.
After the pelletization, drying is preferably carried out under conditions conventional in the art.
According to the polyamide 5X resin disclosed by the invention, the problems of filament breakage and influence on the granulating effect and resin quality in the granulating process are greatly improved by adjusting the content of the oligomer, so that the granulating effect is greatly improved, and the obtained polyamide 5X resin is full in particles and excellent in quality.
Detailed Description
The present invention will be described in detail below with reference to examples to make the features and advantages of the present invention more apparent. It should be noted that the examples are for understanding the concept of the present invention and the scope of the present invention is not limited to only the examples listed herein.
In the invention, the detection method of each parameter is as follows:
1. the method for detecting the content of the oligomer comprises the following steps:
drying a polyamide 56 sample in a forced air oven at 130 ℃ for 7 hours, then placing the polyamide 56 sample into an aluminum-plastic bag, sealing the opening of the aluminum-plastic bag, then placing the aluminum-plastic bag into a dryer for cooling, then accurately weighing about 2g of the polyamide 56 sample, placing the polyamide 56 sample into a 250mL round-bottom flask, adding 100mL purified water, heating and refluxing for 24 hours by using a heating jacket, taking the polyamide 56 sample, washing the polyamide 56 sample with the purified water for three times, drying the polyamide 56 sample in the forced air oven at 130 ℃ for 7 hours, then transferring the polyamide 56 sample into an aluminum-plastic bag weighed in advance, sealing the opening of the round-bottom flask, then placing the polyamide 56 sample into the dryer for cooling, subtracting the weight of the aluminum-plastic bag from the total weight of the aluminum-plastic bag and the polyamide 56 sample to obtain the weight of the polyamide 56 sample after being boiled, and calculating the oligomer content by comparing the weight difference of the polyamide sample before and after being boiled. Each sample was tested in duplicate.
2. Amino-and carboxyl-terminal groups: 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 method for detecting the water content of the resin comprises the following steps: taking 1g of resin sample, and measuring by using a Karl Fischer moisture tester, wherein the detection temperature is 200 ℃, and the detection time is 20 min.
Example 1
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare 80 percent salt solution of polyamide, wherein the weight of the salt is 20 kg; the molar ratio of 1, 5-pentanediamine to adipic acid is (1-1.05): 1, the pH value of the salt solution of the polyamide is 8.2 when the concentration of the salt solution of the polyamide is 10 percent, wherein the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.7Mpa, exhausting, maintaining the pressure, reducing the pressure to 0.02Mpa (gauge pressure) when the pressure maintaining is finished, maintaining the temperature of the reaction system at 245 ℃ after the pressure reducing is finished, reducing the pressure in the reaction system to 260 ℃, vacuumizing to-0.01 Mpa for 40min, and maintaining the temperature after the vacuum at 268 ℃ to obtain a polyamide melt;
the polyamide 56 melt included 0.9 wt% of oligomer (percentage being mass% of the polyamide 56 melt);
wherein, the composition and the content of the oligomer are as follows:
(3) cutting into granules, and drying to obtain resin;
the content of the oligomer in the obtained polyamide 56 resin was 0.9 wt% (based on the mass of the polyamide 56 resin).
Example 2
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60% polyamide salt solution, wherein the weight of the salt is 20 kg; the molar ratio of 1, 5-pentanediamine to adipic acid is (1-1.05): 1, the pH value of the salt solution of the polyamide is 7.3 when the concentration of the salt solution of the polyamide is 10 percent, wherein the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.2Mpa, exhausting, maintaining the pressure, reducing the pressure to 0.05Mpa (gauge pressure) when the pressure maintaining is finished, maintaining the temperature of the reaction system at 250 ℃ after the pressure reducing is finished, reducing the pressure in the reaction system to 265 ℃, vacuumizing for 15min, and maintaining the temperature at-0.02 Mpa after the vacuum, thus obtaining a polyamide melt;
the melt of polyamide 56 comprises 1.3 wt% of oligomers (percentage being the mass percentage of the melt of polyamide 56);
wherein, the composition and the content of the oligomer are as follows:
(3) cutting into granules, and drying to obtain resin;
the content of the oligomer in the obtained polyamide 56 resin was 1.3 wt% (based on the mass of the polyamide 56 resin).
Example 3
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare 75% of salt solution of polyamide, wherein the weight of the salt is 20 kg; the molar ratio of 1, 5-pentanediamine to adipic acid is (1-1.05): 1, the pH value of the salt solution of the polyamide is 7.5 when the concentration of the salt solution of the polyamide is 10 percent, wherein the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.6Mpa, exhausting, maintaining the pressure, keeping the temperature of the reaction system at 246 ℃ after the pressure maintaining is finished, then reducing the pressure in the reaction system to 0.01Mpa (gauge pressure), keeping the temperature of the reaction system at 262 ℃ after the pressure reducing is finished, vacuumizing to-0.07 Mpa, vacuumizing for 25min, and keeping the temperature after the vacuum at 270 ℃ to obtain a polyamide melt;
the polyamide 56 melt included 1.5 wt% of oligomer (percentage is mass% of polyamide 5X melt), and the water content in the polyamide 5X melt was 3000 ppm;
wherein, the composition and the content of the oligomer are as follows:
(3) cutting into granules, and drying to obtain resin;
the content of the oligomer in the obtained polyamide 56 resin was 1.5% by weight, and the moisture content was 800ppm (percentage is a mass percentage of the polyamide 56 resin).
Example 4
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60% polyamide salt solution, wherein the weight of the salt is 20 kg; the molar ratio of 1, 5-pentanediamine to adipic acid is (1-1.05): 1, the pH value of the salt solution of the polyamide is 8.1 when the concentration of the salt solution of the polyamide is 10 percent, wherein the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.1Mpa, exhausting, maintaining the pressure, reducing the pressure to 0.01Mpa (gauge pressure) when the pressure maintaining is finished, reducing the temperature of the reaction system to 262 ℃, vacuumizing to-0.04 Mpa, vacuumizing for 35min, and maintaining the temperature after vacuumizing to 271 ℃ to obtain a polyamide melt;
the polyamide 56 melt included 1.2 wt.% oligomer and the water content in the polyamide 5X melt was 5000ppm (the percentages being by mass of the polyamide 5X melt);
wherein, the composition and the content of the oligomer are as follows:
(3) cutting into granules, and drying to obtain resin;
the content of the oligomer in the obtained polyamide 56 resin was 1.2% by weight, and the moisture content was 1200ppm (percentage is a mass percentage of the polyamide 56 resin).
Example 5
(1) Under the condition of nitrogen, 1, 5-pentanediamine, sebacic acid and water are uniformly mixed to prepare a 60% polyamide salt solution, wherein the weight of the salt is 20 kg; the molar ratio of 1, 5-pentanediamine to adipic acid is (1-1.05): 1, the pH value of the salt solution of the polyamide is 7.92 when the concentration of the salt solution of the polyamide is 10 percent, wherein the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.3Mpa, exhausting, maintaining the pressure, reducing the pressure to 0Mpa (gauge pressure) when the pressure maintaining is finished, maintaining the temperature of the reaction system at 235 ℃, reducing the pressure to 258 ℃ after the pressure reducing is finished, vacuumizing to-0.02 Mpa for 28min, and maintaining the temperature after the vacuum at 265 ℃ to obtain a polyamide melt;
the resulting polyamide 510 melt had an oligomer content of 0.4 wt% and a moisture content of 5000ppm (as a mass percentage of the polyamide 56 melt).
Wherein, the composition and the content of the oligomer are as follows:
(3) cutting into granules, and drying to obtain resin;
the resulting polyamide 510 resin had an oligomer content of 0.4 wt% and a moisture content of 1200ppm (percentage being a mass percentage based on the polyamide 56 resin).
Comparative example 1
(1) Under the condition of nitrogen, 1, 5-pentanediamine, adipic acid and water are uniformly mixed to prepare a 60% polyamide salt solution, wherein the weight of the salt is 20 kg; the molar ratio of 1, 5-pentanediamine to adipic acid is (1-1.05): 1, the pH value of the salt solution of the polyamide is 8.38 when the concentration of the salt solution of the polyamide is 10 percent, and the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, increasing the pressure in the reaction system to 1.8Mpa, exhausting, maintaining the pressure, reducing the pressure to 0.01Mpa (gauge pressure) when the pressure maintaining is finished, maintaining the temperature of the reaction system at 250 ℃ after the pressure reducing is finished, reducing the pressure in the reaction system to 275 ℃, vacuumizing to-0.01 Mpa, vacuumizing for 50min, and maintaining the temperature after the vacuum to 285 ℃ to obtain a polyamide melt;
(3) and (4) granulating and drying to obtain the resin.
The content of the oligomer in the obtained polyamide 56 resin was 2.5 wt%.
The cut ends and the number of filaments obtained for the polyamide 5X resin chips obtained in examples 1 to 5 are shown in the following table:
| granulation effect | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Broken end | 5 | 9 | 3 | 4 | 1 | 25 |
| Filament | 3 | 7 | 2 | 3 | 2 | 31 |
| Total of | 8 | 16 | 5 | 7 | 3 | 56 |
The above embodiments are merely illustrative of the technical solutions and do not constitute limitations of the present invention.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (34)
1. A polyamide 5X melt comprising 0.2 to 2.4 wt.% of an oligomer, said percentages being by mass of the polyamide 5X melt, wherein the oligomer is an amide cyclic oligomer having the formula:
wherein n is 1-8;
wherein m is 2-16,
wherein the polyamide 5X melt is prepared by a preparation process comprising the steps of:
(1) under the condition of nitrogen, 1, 5-pentanediamine, aliphatic dibasic acid and water are uniformly mixed to prepare a salt solution of polyamide; wherein the molar ratio of the 1, 5-pentanediamine to the aliphatic dibasic acid is (1-1.05): 1; wherein the concentration of the salt solution of the polyamide is 30-90%, and the percentage is the mass percentage of the salt solution of the polyamide; the pH value of the salt solution of the polyamide is more than 6 when the concentration of the salt solution of the polyamide is 10 percent, and the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, raising the pressure in the reaction system to 0.3-2.0Mpa, exhausting, maintaining the pressure, leading the temperature of the reaction system to be 232-265 ℃ when the pressure maintaining is finished, then reducing the pressure in the reaction system to be 0-0.2Mpa, leading the pressure to be gauge pressure, leading the temperature of the reaction system to be 245-280 ℃ after the pressure reduction is finished, and vacuumizing to obtain polyamide 5X melt; wherein the vacuum degree after vacuum pumping is-0.01 to-0.08 Mpa, and the pressure is gauge pressure;
wherein the vacuumizing time is 10-45min, and the temperature after vacuumizing is 260-280 ℃.
2. Polyamide 5X melt according to claim 1, wherein n-1-5.
3. Polyamide 5X melt according to claim 1, wherein m-4-10.
4. A polyamide 5X resin, wherein the polyamide 5X resin is obtained by granulating a polyamide 5X melt; wherein the polyamide 5X melt comprises 0.2-2.4 wt% of oligomer, the percentage is the mass percentage of the polyamide 5X melt, wherein the oligomer is amide cyclic oligomer, and the structural formula is as follows:
wherein n is 1-8;
wherein m is 2-16,
wherein the polyamide 5X melt is prepared by a preparation process comprising the steps of:
(1) under the condition of nitrogen, 1, 5-pentanediamine, aliphatic dibasic acid and water are uniformly mixed to prepare a salt solution of polyamide; wherein the molar ratio of the 1, 5-pentanediamine to the aliphatic dibasic acid is (1-1.05): 1; wherein the concentration of the salt solution of the polyamide is 30-90%, and the percentage is the mass percentage of the salt solution of the polyamide; the pH value of the salt solution of the polyamide is more than 6 when the concentration of the salt solution of the polyamide is 10 percent, and the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, raising the pressure in the reaction system to 0.3-2.0Mpa, exhausting, maintaining the pressure, leading the temperature of the reaction system to be 232-265 ℃ when the pressure maintaining is finished, then reducing the pressure in the reaction system to be 0-0.2Mpa, leading the pressure to be gauge pressure, leading the temperature of the reaction system to be 245-280 ℃ after the pressure reduction is finished, and vacuumizing to obtain polyamide 5X melt; wherein the vacuum degree after vacuum pumping is-0.01 to-0.08 Mpa, and the pressure is gauge pressure;
wherein the vacuumizing time is 10-45min, and the temperature after vacuumizing is 260-280 ℃.
5. The polyamide 5X resin of claim 4, wherein n-1-5.
6. The polyamide 5X resin according to claim 4, wherein m is 4-10.
7. The polyamide 5X resin of claim 6, wherein the aliphatic dibasic acid comprises one or more 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, octadecanedioic acid, maleic acid, and Δ 9-1,18 octadecenedioic acid.
8. Polyamide 5X resin according to any one of claims 4 to 7, characterized in that: the oligomer comprises polyamide mono-cyclic oligomers and/or poly-cyclic oligomers.
9. Polyamide 5X resin according to any one of claims 4 to 7, characterized in that: the content of the oligomer is 0.4-2.0 wt%, and the percentage is the mass percentage of the polyamide 5X resin.
10. The polyamide 5X resin of claim 9, wherein: the content of the oligomer is 0.5-1.6 wt%, and the percentage is the mass percentage of the polyamide 5X resin.
11. The polyamide 5X resin of any one of claims 4 to 7, the oligomer comprising: one or more of polyamide mono-cyclic oligomer, polyamide bi-cyclic oligomer, polyamide tri-cyclic oligomer, polyamide tetra-cyclic oligomer and polyamide penta-cyclic oligomer.
12. The polyamide 5X resin of claim 11, wherein the polyamide unitary cyclic oligomer is present in an amount of 20 to 45% by weight of the oligomer.
13. The polyamide 5X resin of claim 11, wherein the polyamide unitary cyclic oligomer is present in an amount of 30 to 40% by weight of the oligomer.
14. The polyamide 5X resin of claim 11, wherein the polyamide binary cyclic oligomer is present in an amount of 15 to 35% by weight of the oligomer.
15. The polyamide 5X resin of claim 11, wherein the polyamide binary cyclic oligomer is present in an amount of 20 to 30% by weight of the oligomer.
16. The polyamide 5X resin of claim 11, wherein the polyamide ternary cyclic oligomer is present in an amount of 20 to 45% by weight of the oligomer.
17. The polyamide 5X resin of claim 11, wherein the polyamide ternary cyclic oligomer is present in an amount of 30-40% by weight of the oligomer.
18. The polyamide 5X resin of claim 11, wherein the polyamide quaternary cyclic oligomer is present in an amount of 10% or less, the percentage being by mass of the oligomer.
19. The polyamide 5X resin of claim 11, wherein the polyamide quaternary cyclic oligomer is present in an amount of 5% or less, the percentage being by mass of the oligomer.
20. The polyamide 5X resin of claim 11, wherein the polyamide pentamer cyclic oligomer is present in an amount of 10% or less, the percentage being by mass of the oligomer.
21. The polyamide 5X resin of claim 11, wherein the polyamide pentamer cyclic oligomer is present in an amount of 5% or less, the percentage being by mass of the oligomer.
22. Polyamide 5X resin according to any one of claims 4 to 7, characterized in that: the moisture content of the polyamide 5X melt is 600-18000ppm, and the content accounts for the mass per million of the polyamide 5X melt.
23. The polyamide 5X resin of claim 22, wherein the polyamide 5X melt has a moisture content of 1200-9000ppm, the moisture content being in parts per million by mass of the polyamide 5X melt.
24. The polyamide 5X resin of claim 11, wherein: the polyamide 5X resin has a water content of 200-2000 ppm;
and/or the polyamide 5X resin has an amino end group content of 20-70 mol/ton;
and/or the polyamide 5X resin has a carboxyl end group content of 50mol/ton or more.
25. The polyamide 5X resin of claim 24, wherein the polyamide 5X resin has a water content of 400-1500 ppm.
26. The polyamide 5X resin of claim 24, wherein the polyamide 5X resin has an amino end group content of 30-60 mol/ton.
27. The polyamide 5X resin of claim 24, wherein the polyamide 5X resin has a carboxyl end group content of 60 to 100 mol/ton.
28. A method for preparing a polyamide 5X melt, comprising the steps of:
(1) under the condition of nitrogen, 1, 5-pentanediamine, aliphatic dibasic acid and water are uniformly mixed to prepare a salt solution of polyamide; wherein the molar ratio of the 1, 5-pentanediamine to the aliphatic dibasic acid is (1-1.05): 1; wherein the concentration of the salt solution of the polyamide is 30-90%, and the percentage is the mass percentage of the salt solution of the polyamide; the pH value of the salt solution of the polyamide is more than 6 when the concentration of the salt solution of the polyamide is 10 percent, and the percentage is the mass percentage of the salt solution of the polyamide;
(2) heating the salt solution of polyamide, raising the pressure in the reaction system to 0.3-2.0Mpa, exhausting, maintaining the pressure, leading the temperature of the reaction system to be 232-265 ℃ when the pressure maintaining is finished, then reducing the pressure in the reaction system to be 0-0.2Mpa, leading the pressure to be gauge pressure, leading the temperature of the reaction system to be 245-280 ℃ after the pressure reduction is finished, and vacuumizing to obtain polyamide 5X melt; wherein the vacuum degree after vacuum pumping is-0.01 to-0.08 Mpa, and the pressure is gauge pressure;
wherein the vacuumizing time is 10-45min, and the temperature after vacuumizing is 260-280 ℃;
the polyamide 5X melt comprises 0.2-2.4 wt% of oligomer, wherein the percentage is the mass percentage of the polyamide 5X melt, the oligomer is an amide cyclic oligomer, and the structural formula of the oligomer is as follows:
wherein n is 1-8;
wherein m is 2-16.
29. The method of claim 28, wherein n-1-5.
30. The method of claim 28, wherein m is 4-10.
31. The production method according to claim 28, wherein the salt solution of the polyamide has a pH value of 7.2 to 8.9 at a concentration of 10%, the percentage being a mass percentage based on the salt solution of the polyamide.
32. The production method according to claim 28, wherein the salt solution of the polyamide has a pH value of 7.5 to 8.2 at a concentration of 10%, the percentage being a mass percentage based on the salt solution of the polyamide.
33. A method for preparing a polyamide 5X resin, the method comprising the steps of:
production of a polyamide 5X melt according to the production method of any one of claims 28 to 32,
and pelletizing the polyamide 5X melt to obtain the resin.
34. The method of claim 33, wherein said pelletizing is followed by drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710102851.0A CN108503824B (en) | 2017-02-24 | 2017-02-24 | Polyamide 5X melt, resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710102851.0A CN108503824B (en) | 2017-02-24 | 2017-02-24 | Polyamide 5X melt, resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108503824A CN108503824A (en) | 2018-09-07 |
| CN108503824B true CN108503824B (en) | 2022-02-15 |
Family
ID=63372814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710102851.0A Active CN108503824B (en) | 2017-02-24 | 2017-02-24 | Polyamide 5X melt, resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108503824B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040151B (en) * | 2018-10-15 | 2023-10-13 | 上海凯赛生物技术股份有限公司 | Polyamide 5X resin and preparation method and application thereof |
| CN112410916B (en) | 2019-08-22 | 2022-05-06 | 上海凯赛生物技术股份有限公司 | Polyamide 56 fiber with low boiling water shrinkage rate and preparation method and application thereof |
| CN112759760B (en) * | 2019-11-02 | 2023-09-22 | 上海凯赛生物技术股份有限公司 | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof |
| CN112779622A (en) | 2019-11-07 | 2021-05-11 | 上海凯赛生物技术股份有限公司 | Polyamide 56 industrial yarn and preparation method and application thereof |
| CN115449070B (en) * | 2021-06-09 | 2024-02-23 | 上海凯赛生物技术股份有限公司 | Polyamide resin and preparation method, composition and fiber product thereof |
| CN116144019A (en) * | 2021-11-19 | 2023-05-23 | 上海凯赛生物技术股份有限公司 | Polyamide resin, composition and application thereof in engineering plastics |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006348276A (en) * | 2005-05-17 | 2006-12-28 | Mitsubishi Chemicals Corp | Self-hinging molding |
| JP2006348057A (en) * | 2004-05-21 | 2006-12-28 | Mitsubishi Chemicals Corp | Polyamide resin |
| JP2009191156A (en) * | 2008-02-14 | 2009-08-27 | Mitsubishi Chemicals Corp | Polyamide resin and polyamide resin composition |
| CN102046859A (en) * | 2008-03-26 | 2011-05-04 | 东丽株式会社 | Polyamide 56 filament, and fiber structure and air-bag base cloth each comprising the same |
| CN102449029A (en) * | 2009-03-30 | 2012-05-09 | 东丽株式会社 | Polyamide resin, polyamide resin composition, and molded article comprising same |
| CN103980486A (en) * | 2013-02-07 | 2014-08-13 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon |
| CN104562271A (en) * | 2013-10-28 | 2015-04-29 | 上海凯赛生物技术研发中心有限公司 | Nylon fibers and preparation method thereof |
| CN106147223A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 5X is as the application of fire proofing |
| CN106146831A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 56 material prepared by a kind of bio-based 1,5-pentanediamine |
-
2017
- 2017-02-24 CN CN201710102851.0A patent/CN108503824B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006348057A (en) * | 2004-05-21 | 2006-12-28 | Mitsubishi Chemicals Corp | Polyamide resin |
| JP2006348276A (en) * | 2005-05-17 | 2006-12-28 | Mitsubishi Chemicals Corp | Self-hinging molding |
| JP2009191156A (en) * | 2008-02-14 | 2009-08-27 | Mitsubishi Chemicals Corp | Polyamide resin and polyamide resin composition |
| CN102046859A (en) * | 2008-03-26 | 2011-05-04 | 东丽株式会社 | Polyamide 56 filament, and fiber structure and air-bag base cloth each comprising the same |
| CN102449029A (en) * | 2009-03-30 | 2012-05-09 | 东丽株式会社 | Polyamide resin, polyamide resin composition, and molded article comprising same |
| CN103980486A (en) * | 2013-02-07 | 2014-08-13 | 上海凯赛生物技术研发中心有限公司 | Preparation method of nylon |
| CN104562271A (en) * | 2013-10-28 | 2015-04-29 | 上海凯赛生物技术研发中心有限公司 | Nylon fibers and preparation method thereof |
| CN106147223A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 5X is as the application of fire proofing |
| CN106146831A (en) * | 2015-05-12 | 2016-11-23 | 上海凯赛生物技术研发中心有限公司 | Polyamide 56 material prepared by a kind of bio-based 1,5-pentanediamine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108503824A (en) | 2018-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108503824B (en) | Polyamide 5X melt, resin and preparation method thereof | |
| CN113527668B (en) | Long-chain polyamide and preparation method and application thereof | |
| CN110054772B (en) | Long-carbon-chain polyamide resin and preparation method thereof | |
| CN108503825B (en) | Preparation method of polyamide and prepared polyamide resin | |
| CN114716668A (en) | Semi-aromatic polyamide resin and preparation method and application thereof | |
| CN107513163A (en) | A kind of preparation method of high-transparency high-toughness nylon 66 resin | |
| TWI794146B (en) | High molecular weight polyamides and copolyamides with uniform rv and low gel content | |
| KR20130060216A (en) | Semi-aromatic polyamide | |
| CN108505134B (en) | Polyamide 5X fiber and preparation method thereof | |
| CN108503823B (en) | Polyamide resin and preparation method thereof | |
| WO2015114017A1 (en) | Three-component copolymers having high transparency and low gas permeability and process for the production thereof | |
| CN111621150A (en) | Flame-retardant nylon composition and preparation method thereof | |
| CN110857331B (en) | Copolymer containing polyamide 56 and preparation method thereof | |
| CN110903646A (en) | Preparation method of nylon cable tie material with high and low temperature resistance | |
| CN113845657B (en) | Semi-aromatic polyamide resin and preparation method thereof | |
| KR101672552B1 (en) | Polyamide Resin Composition with Low Melting Temperature | |
| US3211807A (en) | Process for obtaining a blend of a polyamide and a poly(n-vinyl amide) | |
| CN108501247B (en) | Polyamide grain cutting method, resin preparation method and prepared resin | |
| CN111560170B (en) | Antibacterial polyamide and preparation method and application thereof | |
| CN112759760B (en) | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof | |
| CN115612095A (en) | High-temperature-resistant semi-aromatic copolyamide and preparation method, composition and molded product thereof | |
| CN112239537A (en) | Long-acting high-temperature-resistant block polyamide composition and fiber and preparation method thereof | |
| JP4258152B2 (en) | Method for producing polyamide | |
| CN117586624A (en) | Preparation method of ultrahigh-fluidity high-temperature nylon resin | |
| CN115449070B (en) | Polyamide resin and preparation method, composition and fiber product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 4 / F, building 5, No. 1690, Cailun Road, free trade zone, Pudong New Area, Shanghai Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CATHAY INDUSTRIAL BIOTECH Ltd. Address before: 201203 Shanghai Zhangjiang High Tech Park of Pudong New Area Cailun Road No. 5 No. 1690 Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. |
|
| CB02 | Change of applicant information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191101 Address after: 4 / F, building 5, No. 1690, Cailun Road, free trade zone, Pudong New Area, Shanghai Applicant after: CATHAY R&D CENTER Co.,Ltd. Applicant after: CIBT USA Address before: 201203 floor 4, building 5, No. 1690, Cailun Road, free trade zone, Pudong New Area, Shanghai Applicant before: CATHAY R&D CENTER Co.,Ltd. Applicant before: CATHAY INDUSTRIAL BIOTECH Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |